Industrial Chemistry Library, Volume 10
Used Battery Collection and Recycling
Industrial Chemistry Library Advisory Editor: S.T. Sie, Faculty of Chemical Technology and Materials Science Delft University of Technology, Delft, The Netherlands
Volume 1
Progress in C 1 Chemistry in Japan (Edited by the Research Association for C 1 Chemistry)
Volume 2
Calcium Magnesium Acetate. An Emerging Bulk Chemical for Environmental Applications (Edited by D.L. Wise, Y.A. Levendis and M. Metghalchi)
Volume 3
Advances in Organobromine Chemistry I (Edited by J.-R. Desmurs and B. G6rard)
Volume 4
Technology of Corn Wet Milling and Associated Processes (by P.H. B lanchard)
Volume 5
Lithium Batteries. New Materials, Developments and Perspectives (Edited by G. Pistoia)
Volume 6
Industrial Chemicals. Their Characteristics and Development (by G. Again)
Volume 7
Advances in Organobromine Chemistry II (Edited by J.-R. Desmurs, B. G6rard and M.J. Goldstein)
Volume 8
The Roots of Organic Development (Edited by J.-R. Desmurs and S. Ratton)
Volume 9
High Pressure Process Technology: Fundamentals and Applications (Edited by A. Bertucco and G. Vetter)
Volume 10
Used Battery Collection and Recycling (Edited by G. Pistoia, J.-P. Wiaux and S.P. Wolsky)
Industrial Chemistry Library, Volume 10
Used B attery Collection and Recycling Edited by G. Pistoia
Via G. Scalia 10, 00136 Rome, Italy J.-P. Wiaux
Titalyse S.A., Route des Acacias 54 bis, CH-1227 Carouge, Geneva, Switserland
S.P. Wolsky Ansum Enterprises, 1900 Cocoanut Road, Boca Raton, Florida 33432, USA
2001 ELSEVIER
Amsterdam
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Preface
About 40 billion batteries were produced in the year 2000 and this number is increasing at approximately 5% annually. A large number of these batteries contain hazardous materials. Batteries also contain significant quantities of important materials. Consequently the uncontrolled disposal of batteries presents both a major risk to health and the environment and a significant waste of valuable material resources. Recognizing the importance of controlling battery waste disposal, worldwide government and industry efforts have been initiated to collect and recycle such wastes. Led by the OECD member states, legislation has been put in place mandating the collection and recycling of cadmium, lead and mercury batteries. Industry organizations have been established for the purpose of educating the consumer and developing collection/recycling programs. We may mention the Portable Rechargeable Battery Association (PRBA) and the Rechargeable Battery Recycling Corporation (RBRC) in the U.S.A., and the European Portable Battery Association (EPBA) and CollectNiCad in Europe. As a consequence of these laws and programs, increasing quantities of spent batteries are being collected and recycled. Recycling batteries with their varied chemistries is a difficult task. The success of the industry in meeting this challenge has been important to the advancement of this effort. We wish to express our deep gratitude to the contributors of the various chapters of this book and to the organizations and companies that have provided us general information and encouragement. Many of these groups have also contributed on a regular basis to the annual congresses organized first in the U.S.A. by one of us (S.P. Wolsky) - Seminar on Battery Waste Management - and later by others in Europe - Battery Recycling Congress. Our goal has been to present in one volume a systematic and updated summary of the important aspects of the battery waste issue. As such this book will be of interest to all those working in this important field.
G. Pistoia
J.-P.Wiaux
S.P. Wolsky
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vii
List of Contributors
J. DAVID, SNAM, 9 rue de la Garenne, F-38074, Saint Quentin Fallavier, France N. ENGLAND, The Portable Rechargeable Battery Association, 1000 Parkwood Circle, Atlanta, GA 30339, U.S.A. K. FUJIMOTO, Portable Rechargeable Battery Committee, Battery Association of Japan, Kikai,
Shinkou Kaikan Building 5F, 3-5-8 Siba-Kouen, Minato-ku, Tokyo 105-0011, Japan R. JUNGST, Lithium Battery R&D Department, Sandia National Laboratories, P.O. Box 5800, Albuquerque, NM87185-0613, U.S.A. W. McLAUGHLIN, Solid Team Inc., 148 Limestone, Claremont, CA 91711, U.S.A. D.G. MILLER, Toxco Inc., 3200 E. Frontera, Anaheim, CA 92806, U.S.A. K. L. MONEY, Inmetco, 245 Portersville Road, P.O. Box 720, Ellwood City, PA 16117, U.S.A. H. MORROW, International Cadmium Association, 9222 Jeffery Road, P.O. Box 924, Great Falls, VA 22066-0924, U.S.A. E. PAOLUCCI, Texeco, Via Pomarico 58, 00178 Rome, Italy A. PESCETELLI, Texeco, Via Pomarico 58, 00178 Rome, Italy A. TINE', Texeco, Via Pomarico 58, 00178 Rome, Italy N. WATSON, EPBA, Hazelwick Avenue, Crawley, Mallory House, West Sussex RH 10 1FQ, Great Britain D.B. WEINBERG, Howrey Simon Arnold & White, 1299 Pennsylvania Avenue, Washington, D.C. 20004, U.S.A. J.-P. WIAUX, Titalyse SA, 54bis Route des Acacias, CH-1227 Carouge, Geneva, Switzerland
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Table of Contents Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . List o f Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 1. Environmental and Human Health Impact Assessments of
Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
H. Morrow Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2
Battery R a w Materials Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5
Manufacture o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10
Use and Maintenance o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
15
Disposal o f Spent Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
Environmental and H u m a n Health Impact Assessments . . . . . . . . . . . . . . . 22 Cycle Life Analysis o f Battery Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
Chapter 2. Portable Rechargeable Batteries in Europe: Sales, Uses, Hoarding, Collection and Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 J.-P. Wiaux Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
The European Market o f Portable Rechargeable Batteries . . . . . . . . . . . 39 Hoarding o f Portable Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Batteries in Municipal Solid Waste ( M S W ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 Collection o f Spent Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 Collection Efficiency and Recycling Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
83
Chapter 3. Battery Collection and Recycling in Japan .............................. 87
K. Fujimoto Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 Treatment of Spent Primary Dry Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 Recycling of Spent Lead-Acid Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91 Collection and Recycling Activities for Portable Rechargeable Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Chapter 4. Ni-Cd Battery Collection and Recycling Programs in the U.S.A.
and Canada . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
105
N. England, D.B. Weinberg, K.L. Money and H. Morrow Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 The environmental issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 The NiCd Battery Recycling Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 The Industry NiCd Battery Recycling Program . . . . . . . . . . . . . . . . . . . . . . . 109 The INMETCO NiCd Battery Recycling Process . . . . . . . . . . . . . . . . . . . . 113
Chapter 5. Environmentally Sound Recycling of Ni-Cd Batteries ............... 119 N. England
Introduction and Principal Findings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 The Nature and Implications of Rechargeable Ni-Cd Battery Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121 Ni-Cd Battery Recycling Esperiences Within the OECD ........... 123 The RBRC P r o g r a m - Canada and the U.S . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 Lessons Learned w Recommendations for Action . . . . . . . . . . . . . . . . . . . . 137
Chapter 6. Nickel-Cadmium and Nickel-Metal Hydride Battery Treatments 147
J. David Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147 Treatment of Nickel Cadmium Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150 1. Types of Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
xi 2. Specific Processes for the Treatment o f Nickel C a d m i u m Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
155
T o d a y ' s Battery Recycling Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162 1. Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
162
2.
U.S.A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
171
3.
Korea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
171
4.
Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 7. P r i m a r y
174
Battery Recycling in Europe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
N. Watson Battery Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
177
Battery Collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
177
Battery Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
191
Battery Sorting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
199
Integrating with Existing Recycling Operations . . . . . . . . . . . . . . . . . . .
209
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
222
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
223
Chapter 8. L e a d - A c i d B a t t e r i e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
225
A. Pescetelli, E. Paolucci and A. Tinb Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
225
The Environmental and Health Impact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225 Economical Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
228
Lead Accumulator Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 The Collection o f Spent Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
234
Comparison With Other Countries o f the European Union ..... 239 Collection Modes and Recycling Techniques . . . . . . . . . . . . . . . . . . . . . . 251 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chapter 9.
Recycling The Lithium Battery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
D.G. Miller and W. McLaughlin
261
263
xii
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
The Hazards and Safety Aspects of Recycling Lithium Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
267
Environmental Concerns of Recycling Lithium Batteries ...... 272 Sorting, Packaging, Storage, and Transporting of Lithium Batteries for Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274 Lithium Battery Recycling Technologies . . . . . . . . . . . . . . . . . . . . . . . . . 277 The Toxco's Background and Processing Method . . . . . . . . . . . . . . . 279 Two o f Toxco's Typical Chemical Analyses . . . . . . . . . . . . . . . . . . . . . 282 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Chapter 10. Recycling of Electric Vehicle Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
R.G. Jungst Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
295
Electric Vehicle/Hybrid Electric Vehicle Batteries . . . . . . . . . . . . . . 297 General Recycling Issues, and Drivers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304 Existing Methods for EV Battery Recycling . . . . . . . . . . . . . . . . . . . . . . 308 Optimized Recycling Processes for Advanced Batteries ........ 317 Recycling Prospects for Future Advanced Batteries . . . . . . . . . . . . . 320 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
Appendix A. Most Common Types of Commercial Batteries . . . . . . . . . . . . . . . . 329
Appendix B. Main Legislation on Battery Waste in the U.S.A. and E.U.
341
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
369
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
ENVIRONMENTAL
AND HUMAN HEALTH
IMPACT ASSESSMENTS
OF BATTERY
SYSTEMS
Hugh Morrow International Cadmium Association 9222 Jeffery Road Post Office Box 924 Great Falls, VA 22066-0924 USA
Abstract Total life cycle analyses may be utilized to establish the relative environmental and human health impacts of battery systems over their entire lifetime, from the production of the raw materials to the ultimate disposal of the spent battery. The three most important factors determining the total life cycle impact appear to be battery composition, battery performance, and the degree to which spent batteries are recycled after their useful lifetime. This assessment examines both rechargeable and nonrechargeable batteries, and includes lead acid, nickel cadmium, nickel metal hydride, lithium ion, carbon zinc and alkaline manganese batteries. Battery metals such as lead, cadmium, mercury, nickel, cobalt, chromium, vanadium, lithium, manganese and zinc, as well as acidic or alkaline electrolytes, may have adverse human health and environmental effects. The specific forms of these materials as well as the relative amounts present will establish the risks associated with that particular battery system. However, the degree to which such batteries are collected and recycled after their useful life may largely mitigate any such adverse effects. Landfill or incineration disposal options are not as desirable as recycling, but the risks associated with those options are not so unacceptably high as to require the phase outs of any existing battery technologies. Battery performance characteristics, likewise, are important in establishing the amount of potentially hazardous waste generated per unit of battery energy generated.
Rechargeable battery systems obviously enjoy a great advantage in this respect since they may be recharged and reused many times. However, other factors such as the battery voltage, ampere-hour rating, cycle life, charging efficiency and self-discharge characteristics may also be important in establishing the total amounts of hazardous waste generated per unit of battery energy and thus the total environmental impact per unit of battery energy. Safety issues have also become more important in recent years as more active battery chemistries have been developed. In particular, the presence of corrosive electrolytes and highly ignitable or explosive battery materials under certain conditions has become an issue which the battery industry must address. At present, it appears as if improvement in the recycling rates of spent batteries will produce the most substantial decreases in the environmental and human health impacts of battery systems. Introduction
Total life cycle analysis (LCA) is increasingly being utilized to establish the relative human health and environmental impacts of many products and processes. In these analyses, the total impacts, from the production of the raw materials for the product, through its manufacture, use and ultimate disposal are established, and then usually compared to other similar products. Environmentalists and regulators have used these principles to favor the displacement of one product in the marketplace with an allegedly "more environmentally friendly" product. Very often, however, it has been found that one product may exhibit high negative LCA impacts in one area, while another product may be deficient in another area. Such appears to be the case when various battery chemistries are compared. The components of a total life cycle analysis are generally agreed to consist of the following four basic steps: I.
Scope and Goal Definition
II. III.
Materials and Energy Inventory Environmental and Human Health Impact Assessments
IV.
Improvement Assessment
The scope and goal definition (Step I) is necessary in that most life cycle analyses may be as wide or as narrow as one wishes to make them. For example, one could define a
product life cycle analysis so widely as to include the production of the mining equipment used to mine the ore which produced the metal which went into the manufacture of the battery. Generally, however, these effects become normalized over so many other products as to become secondary effects of little consequence in the specific analysis of, for example, a rechargeable NiCd battery. The major area, however, which should be included, is the energy and emissions associated with the direct production of the raw materials used in the batteries. Thus, it is very important that the scope of a particular life cycle analysis be carefully defined and that comparisons between products be made on the basis of the same scope. In the case of batteries, the following stages are considered to be the major contributors to environmental and human health impacts and would be included in a life cycle analysis: 9
Battery Raw Materials Production
9
Battery Production Process
9
Battery Distribution and Transportation Requirements
9
Battery Use
9
Battery Recharging and Maintenance (Rechargeable Batteries)
9
Battery Recycling or Waste Management Option
Once these stages are established and the scope of the life cycle analysis reasonably well defined, then a complete materials and energy inventory analysis (Step II) must be performed on each of these stages to determine the overall materials and energy balances. As shown in Figure 1, the inputs of energy and materials on the left hand side for every stage in the manufacture, use and disposal of a battery are balanced by the outputs of usable products and environmental releases on the right hand side. To produce the least environmental and human health impacts, the environmental releases from all of these stages should be minimized. In carrying out life cycle analyses for battery systems, it becomes very quickly apparent that the inventory analyses for certain stages are insignificant compared to others. For example, the emissions associated with distribution and transportation of batteries and the appliances they power are spread out over so many billions of units as to be
Inputs
Outputs Battery Raw Materials Water Emissions
Battery& BatteryPack Production Procenes Energy
Airborne Emissions
Battery-Powered Devices & Applications Solid Wastes
Distribution & Transpo~ation Raw
Recycled Materials
Materials
Use, Recharging & Maintenance Usable Products
Recycling
Figure 1. Materials and E n e r g y I n v e n t o r y Analysis for Battery S y s t e m s
insignificant to the LCA of one single battery. Furthermore, sealed batteries have no emissions during normal use, and the emissions associated with the recharging of batteries depends very much upon the power generating infrastructure in a particular country. In countries dependent on high sulfur coals, the impact could be significant, but in countries with hydroelectric, nuclear, solar power or other clean energy sources, the emissions associated with recharging batteries are virtually non-existent. In any
event, these emissions, even in the case of dirty fossil fuels, also appear to be so spread out over so many applications as to have little effect on an individual battery's life cycle analysis. Each one of these stages will be considered in more detail below, but it appears as if battery raw material production, battery manufacture, battery performance during use, and battery recycling or disposal as waste are the most important stages in the comparative life cycle analyses of battery systems. The emissions associated with and the energy consumed during each of these stages will establish the environmental loading resulting from each battery system, which in turn may be converted into a human health and environmental impact analysis by assuming certain impact values for each of the materials emitted and energy consumed. A further factor particular to the evaluation of the life cycle analyses of battery systems is that their human health and environmental impacts must be normalized to the total lifetime energy output of the battery. In other words, impacts are expressed in terms of effects per kilowatt-hour of energy generated. This requirement is necessary since battery systems all differ considerably in their total lifetime energy output. Rechargeable batteries generally have higher total lifetime energy outputs than nonrechargeable batteries, and thus their environmental and human health impacts are lower. Put another way, it requires more non-rechargeable batteries to produce the same total lifetime energy as rechargeable batteries. Because the total lifetime energy of a battery system is important to its life cycle analysis, parameters such as operating voltage, ampere-hour rating, cycle life, charging efficiency and self-discharge characteristics may all become important factors in establishing a battery system's overall life cycle analysis.
Battery, Raw Materials Production Obviously, the first and most important factor in the inventory analysis stage is the overall composition of the battery system. Technically, a life cycle analysis can only be specifically performed on a specific battery composition, and there is often great variety in the compositions for batteries that nominally all belong to the same family. In addition, a rigorous life cycle analysis should consider every material in the battery, no matter how minute the environmental impacts may appear to be. The tendency in most life cycle analyses on battery systems to date has been to concentrate on the "hazardous materials" or "heavy metals" contained in those batteries while ignoring contributions which may arise from greater amounts of less high-profile substances. For example, life
cycle analyses of lead acid batteries usually focus on their lead content and ignore the sulfuric acid electrolyte. Most analyses of nickel-cadmium batteries dwell on the cadmium LCA contribution while minimizing the nickel and cobalt contribution. In a rigorous analysis, the contributions of every material must be considered. Some will indeed be found to be insignificant and have little or no effect on the final total impact, but others may have suprisingly large effects. Another factor which has yet to be properly evaluated and factored into battery life cycle analyses is the form of the material in the battery system itself. When evaluating the environmental and human health effects of battery materials, most analyses have assumed, for example in NiCd batteries, a single environmental impact value for nickel and all of its compounds or a single environmental impact value for cadmium and all of its compounds. Since these single values are usually derived from tests on a highly soluble species, they almost always overstate the environmental and human health impacts of the materials actually used in batteries. For example, in nickel-cadmium batteries, the relatively insoluble cadmium oxide is the compound normally used in the battery whereas the environmental and human health impact values are based on the highly soluble cadmium chloride. Thus, battery life cycle analyses usually represent the worst case scenario as far as human health and environmental impact are concerned. However, it is important to recognize the basis on which the environmental and human health impact values are assigned. In the case of zinc, for example, the surrogate compound used to derive impact values is zinc oxide which is a reasonable choice. In the case of some other metals, such as nickel and cadmium mentioned above, the impact values are based on the highly soluble species as surrogate compounds which very much overstates the relative risk. This problem has yet to be addressed in life cycle analyses of battery systems, and it is difficult to state how much it might affect them when it is addressed. These problems not withstanding, it is possible to examine general battery families and to make some analyses of these families based on generalized or average compositions, recognizing however that individual variations within the battery family may be considerable. The compositions of several such generalized battery families are indicated in Table I. These chemistries vary considerably, as shown by the three sets of data presented below (Fujimoto 1999, Morrow 1998 and Gaines 1994). This wide variation in battery chemistry is one of the primary reasons why it is so difficult to draw generalized conclusions about the relative environmental and human health impacts of one family of batteries compared to another family.
Table I. Various Nominal Compositions of Battery Families Battery, System Alkaline Manganese* Lead Acid* Nickel-Cadmium* Nickel Metal Hydride (ABs)* Nickel Metal Hydride (AB2)*
Nominal Composition, Weight Percent 30Fe - 20Zn - 15Mn 6 5 P b - 25H2SO4 30Fe - 30Ni - 15Cd 45Ni - 10Mg/A1 - 9Ce - 4Co 3 9 N i - 6 V - 6 Z r - 3 C r - 3 T i - 2.5Co
Nickel-Cadmium**
3 2 . 5 F e - 1 7 . 5 N i - 2 2 . 5 C d - 3Co
Nickel Metal Hydride**
4 2 . 5 N i - 1 7 . 5 F e - 7 . 5 C o - 12.5 Rare Earths
Lithium-Ion** Lead Acid*** Nickel-Cadmium(PBE)*** Nickel-Cadmium(FNC)***
2 2 . 5 F e - 1 7 . 5 C o - 7.5A1- 7 . 5 C u - 3Li 6 9 P b - 22H2SO4 14Fe - 26Ni - 18Cd 15Fe - 31Ni - 22Cd
Nickel Metal Hydride(ABs)***
4 4 F e - 2 9 N i - 5 Rare E a r t h s - 2 C o - 1Mn
Nickel Metal Hydride(AB2)***
4 4 F e - 2 4 N i - 7 V - 3 Z r - 2Cr- 1Ti
* Morrow 1998
**Fujimoto 1999
***Gaines 1994
The above data and data from other sources show some interesting trends in battery compositions over time. For example, the older NiCd batteries, which are the ones being collected and recycled now, tend to exhibit lower cadmium and cobalt values than the newer generations of NiCd batteries. There are also distinct differences in nickel and cadmium contents between industrial and consumer batteries. The battery industry generally agrees that consumer NiCds being collected today for recycling contained an average of 15% Cd. Industrial NiCds, on the other hand, may show a much wider variation, and levels from 7% Cd to 24% Cd have been noted in some industrial NiCds. Interestingly enough, a "Li-ion" battery actually contains very little lithium, and should more properly be designated an Fe-Co-A1-Cu-Li battery. These examples, however,
should be sufficient to demonstrate that using nominal compositions for battery life cycle analyses may introduce large factors of uncertainty into such analyses, and the compositional basis for any battery's LCA must be stated as part of the analysis results. The first analysis which obviously must be performed is to establish the emissions produced and the energy consumed during the production of the raw materials used for battery production. In the case of the metals utilized for the electrode materials in most batteries, the mining, smelting, and refining of the base metal, and their subsequent conversion into the specific form of the material utilized in the battery are the processes which must be addressed. Direct emissions of metals from the mining, smelting and refining of battery metals such as lead, cadmium, nickel, cobalt, zinc, manganese and many other metals are generally well-controlled and are subject to stringent regulation today. Metal emissions from the primary nonferrous smelters have diminished
Figure 2. Sources of Human Cadmium Exposure (Van Assche 1998) (the sources listed are arranged clockwise from: fertilizers, 42%)
considerably in the past twenty years as demonstrated by Canada's ARET (Accelerated Reduction and Elimination of Toxics) Program and the U.S. Environmental Protection Agency's TRI (Toxics Release Inventory) and 33/50 Programs. In addition, studies on the sources of human cadmium exposure, for example, indicate that only 6.3% of all human cadmium exposure comes from nonferrous smelting, principally zinc, lead and copper, and that only 2.5% arises from cadmium applications such as NiCd batteries. This data is shown graphically in Figure 2 and is based on studies in Europe (Van Assche 1998, Van Assche and Ciarletta 1992). Thus, it is clear that primary metals production processes do not contribute significantly to the environmental impact of the battery systems. A second environmental impact from the production of nonferrous battery metals arises because of the relative amount of energy utilized to produce a given quantity of the metal. In this case, the amount of energy necessary to produce a metric tonne may be related to the amount of greenhouse gases produced to create that energy. However, again, this may be too simplistic a view in that the amounts of greenhouse gases depend very much upon the types of fossil fuels used, air pollution control devices in place, and the nature of the energy producing combustion mechanisms. The energy consumed in the primary metal production of five common battery metals is summarized in Table II (Schuckert 1997). From an energy consumption standpoint, metals with low melting temperatures such as lead and cadmium, require less energy to produce, and thus have a lower environmental impact with respect to the generation of greenhouse gases. Metals which are produced by electrolytic processes or have high melting temperatures require higher energy inputs to produce and thus have higher environmental impacts with respect to greenhouse gases. Table II. Energy Consumed in Primary Metal Production Battery Metal
Ener~v (GJ/mt)
Manganese Nickel
54 200
Lead
25
Zinc/Cadmium
70
10 Nickel, for example, is produced by electrolytic processes and has a higher melting temperature, and thus requires higher energy to produce per metric tonne. However, in general, the levels of both metal emissions and greenhouse gas emissions which are produced in the production of battery metals are a small fraction of the total weight of the metals used in the battery. Thus, what is far more important in a total environmental impact analysis is whether or not a spent battery is recycled or disposed of by landfilling or incineration. If a battery is recycled, then the vast majority (>95%) of the weight of the battery does not produce an environmental impact. If the battery is landfilled or incinerated, then most of the materials in the battery are capable of producing an environmental impact. If all batteries were recycled to a similar degree, then compositional factors and primary metal production factors, as well as other factors to be subsequently discussed, would be more important. Finally, the conversion of the primary metal into the product and the form which are actually utilized in the battery system should be considered. For example, the electrode materials in lead acid batteries are normally cast lead or lead-alloy grids. The materials utilized in NiCd batteries are cadmium oxide and high surface area nickel foams or meshes. Technically, all of these factors should be considered to produce a detailed life cycle analysis. However, again, these differences are generally quite small compared to the principal variables- composition, performance and spent battery disposal option.
Manufacture of Battery, Systems Similarly, there is ample data available to demonstrate that the emissions associated with the manufacture of battery systems are minimal compared to those associated with the disposal of batteries into the environment. For example, studies have been made on NiCd batteries by both the Organization for Economic Cooperation and Development (OECD) and the Stockholm Environmental Institute (SEI) which indicate that the vast majority of cadmium in the manufacture of NiCd batteries partitions to the product and that only very small amounts are emitted to the environment. This result arises from both stringent regulations in place today, modem pollution control technology, and the general commitment to utilize valuable raw materials to the fullest extent possible. The partitioning of cadmium in the manufacture of NiCd batteries, according to the OECD (Organization for Economic Cooperation and Development 1994) and SEI (Stockholm Environmental Institute 1994) data, is summarized in Table III.
11 The SEI data is based mainly on earlier emission numbers for NiCd battery manufacturing, whereas the OECD monograph data represents updated emissions in the European Union as of 1994 compared to total volumes of cadmium utilized for NiCd battery production, based on information from the International Cadmium Association. All of this data indicates that most of the cadmium remains in the product and is not lost during NiCd battery manufacturing. A similar conclusion can be inferred with respect to nickel and cobalt, the other materials in a NiCd battery which might be likely to be regarded as "hazardous" and contribute to an adverse environmental impact. Iron, of
Table III. Partitioning of Cadmium in NiCd Battery Manufacturing Percent of Total Cadmium SEI Report OECD Monograph Industrial Consumer Industrial Consumer Air Emissions
0.10
0.00
0.01
0.01
Water Emissions
0.15
0.05
0.03
0.03
Solid Waste Product
2.75
2.45
0.50
0.50
97.00
97.50
99.46
99.46
course, is also present in major amounts, and, technically, should also be considered, but, as will be shown later, its environmental impact is quite low and therefore does not contribute significantly to the environmental impact of the NiCd battery system. Another set of data has been provided by a study on aqueous emission factors for cadmium in the Rhine River basin from 1970 to 1990 (Elgersma et al. 1992). This study was performed by the Delft University of Technology in the Netherlands and the International Institute for Applied Systems Analysis (IIASA) in Austria and was presented at the 1992 Seventh Intemational Cadmium Conference. This data, which is shown graphically in Figure 3, clearly shows that aqueous cadmium emissions for industrial NiCd battery manufacture have decreased from approximately 8 grams per kilogram of cadmium processed to less than 1 gram of cadmium per kilogram of cadmium processed in 1988. Similarly, aqueous cadmium emissions for consumer NiCd battery manufacture have decreased from 15 grams of cadmium per kilogram of cadmium processed in 1970 to about 1 gram of cadmium per kilogram of cadmium
12
Figure 3. Aqueous Emission Factors for Rhine River Basin, 1970-1990 processed in 1988. These 1988 aqueous cadmium emission levels correspond to approximately a 0.1% aqueous emission factor, in reasonable agreement with the data shown in Table III, and would probably be lower if based on 1995 or subsequent data. An additional point worth noting is that these significant decreases in NiCd battery manufacturing aqueous emissions were accomplished during the 1980s, the period of the highest growth rate in the NiCd market. In addition, two sets of data from the Battery Association of Japan (BAJ), formerly known as the Japan Storage Battery Association (JSBA), equally clearly demonstrate that the levels of cadmium emissions to air and water in Japan have decreased steadily over the period from 1980 through 1992 in spite of the greatly accelerated production of NiCd batteries in Japan during that same time period (Mukunoki and Fujimoto 1996). Japan is the world's largest producer of NiCd batteries, and currently accounts for over 70% of the world's NiCd battery production. If there is any country where potential environmental contamination by cadmium from NiCd battery manufacture should be
13
Percent of River Water Samples Above 10 ~g Cd/liter
Millions of NiCds Produced in Japan 1000
0.25%
8oc
i~i
.................................. -
600
0.20%
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1982
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Figure 4. Japanese River Water C a d m i u m Concentration and NiCd Battery Production
realized, it is Japan. Yet the data presented in Figure 4 for Japanese river
water
cadmium concentration and in Figure 5 for Japanese ambient air cadmium concentration respectively exhibit decreasing trends over these years in spite of eightfold increases in NiCd battery production. A more proper way of expressing average emissions associated with the manufacture of battery systems is to establish those emissions on the basis of the levels per KW-hr of battery energy provided, as the provision of stored energy is the function of a battery and batteries differ markedly in their ability to store energy. Such an analysis has been carried out (Geomet Technologies 1993) for industrial nickel-cadmium batteries intended for electric vehicle applications. These manufacturing emissions data are presented in Table IV.
14
Figure 5. Japanese Ambient Air Cadmium Concentration and NiCd Battery Production
Table IV. Metal Emissions in Production of NiCd Electric Vehicle Batteries* Grams Metal Emissions per KW-Hour Emission Sink
Nickel
Cadmium
Air
3.15
1.78
0.08
Water
2.28
1.31
0.05
Land Total
Negligible 5.43
*Source: Geomet Technologies
Negligible 3.09
Cobalt
Negligible 0.13
15 Typical industrial NiCd batteries utilized for electric vehicle applications have an energy density of 50 Watt-Hours per kilogram which corresponds to weight per unit energy of 20 kilograms per Kilowatt-Hour. Thus the metal emission levels associated with the manufacture of industrial NiCd batteries are roughly 0.04% of the total weight of the battery, in reasonably close agreement with most present day estimates which place total metal emissions during battery manufacturing between 0.01% and 0.1%. The data sets in Tables III and IV agree reasonably well, particularly if the decreasing levels of metal emissions with time are considered. Finally, a life cycle analysis conducted by SAFT (Comu and Eloy 1995) on nickelcadmium batteries for electric vehicle applications has established results comparable to those cited above. This study indicates that losses during the manufacturing process are likely to be on the order of 0.037% of battery weight for nickel and 0.008 - 0.019% of battery weight for cadmium, depending on the recycling options adopted. Once again, these estimates are consistent with other studies, and indicate very low environmental and human health impacts from the manufacturing stage of a battery's total life cycle analysis. Thus, the emissions associated with the manufacture of battery systems, like those associated with the production of the primary raw materials, are generally quite low, probably less than 1% of the total potential emissions if the spent battery were discarded entirely into the environment after use. While most of the data presented above are relevant mainly to nickel-cadmium batteries, which have been heavily studied because of regulatory and environmental controversy, the same general conclusions apply to other battery systems in general with some variations. Primary raw material production and battery manufacturing , in general, contribute only a small fraction of the environmental or human health impact that might be encountered in unconsidered waste disposal.
Use and Maintenance of Battery. Systems Rechargeable batteries are long-lived products which, in general, may be used many times over if they are charged and discharged properly. Non-rechargeable batteries are shorter lived products, but in some cases have higher initial energy density than rechargeable batteries. Since various battery chemistries, in general, will have different operating voltages, energy ratings and cycle lives (if they are rechargeable), each individual battery system will have different total lifetime energy characteristics. Even
16 within the same battery chemistry family, there will be variations to suit specific applications. Thus, an AA-sized NiCd battery may exhibit energy ratings from 500 milliampere-hours to 1,500 milliampere-hours depending on its intended use. Correspondingly, other properties, such as cycle life, may vary as well. In addition, total battery energy varies with battery size, the larger the battery in general the larger its total lifetime energy, other factors being equal. Therefore, it may be very difficult to establish an average set of performance characteristics for a battery family, but only to establish them for a very specific battery chemistry, size and type. Battery performance is importance because in determining any human health or environmental impacts of battery systems, these must be normalized to a unit energy basis, as previously noted for emissions associated with battery manufacturing. Thus, any emissions during any stage of the life cycle of the battery system must be divided by the total lifetime energy of the battery to obtain results which allow comparison amongst battery systems. The total lifetime energy of a particular battery system is the product of its voltage, capacity and cycle life. Strictly speaking, charging efficiency and self-discharge characteristics should also be taken into account, but in most life cycle analyses to date, they have not been. For example, the basic performance parameters of an AA-sized NiCd battery are summarized in Table V.
Table V. Basic Performance Parameters of AA NiCd Battery Parameter
Voltage Capacity Total Energy Cycle Life (80%DOD) Total Lifetime Energy
Range of Values
1.2 Volts 0.5 to 1.2 ampere-hours 0.6 to 1.4 watt-hours 700 to 1200 cycles 420 to 1680 watt-hours
Nickel-cadmium and nickel metal hydride batteries both operate at 1.2 volts, whereas alkaline manganese batteries produce 1.5 volts and lead acid batteries 2.0 volts. Lithium-ion batteries have an unusually high voltage, above 3.0 volts, which gives them a high energy density. Thus, all three of the parameters mentioned above - voltage, battery capacity, and cycle life - will be instrumental in establishing the life cycle
17 performance of a battery system. It is not just the composition of the battery alone which is important, and, as will be subsequently shown, it is the waste disposal option chosen for the battery which is perhaps even more important than either of these first two characteristics in determining life cycle impact. During the normal use and maintenance of a battery system, they are neither destroyed nor dissipated nor do they emit any harmful substances. Battery systems may be sealed or vented. If they are sealed, then no emissions occur during normal use and maintenance. If they are vented, then water vapor, hydrogen gas or oxygen gas may be vented, depending on the system and whether it is charging or discharging. A 1994 report (Stockholm Environmental Institute 1994), for example estimated that the dissipation rates for both industrial and consumer NiCd batteries were 0.01 percent per year. The International Cadmium Association believes, based on surveys of its NiCd battery producer members, that the dissipation rates are virtually zero, or so low as to be undetectable.
.~
However, a further consideration is the potential life cycle effect of each recharging cycle for the battery. The energy necessary to recharge a battery is generated by the primary power grid which generally operates on some form of fossil fuel. Combustion of fossil fuels result in the generation of greenhouse gases which can have an effect on a complete life cycle analysis, particularly if dirty fossil fuels are used or air pollution emission control devices are inadequate. In general, the emissions and life cycle effects associated with recharging are again small compared to those of battery disposal. One analysis (Schuckert et al. 1997) has measured the primary energy consumption during the production and utilization of both lead acid and nickel-cadmium batteries and their consequent effect upon carbon dioxide emissions and nitrous oxide emissions. In these cases, the amounts of energy required and greenhouse gases generated over the battery system's entire lifetime are lower for NiCd batteries than for lead acid batteries because of their higher cycle life, energy density and total lifetime energy even though the initial energy required to produce the NiCd battery is higher than to produce the lead acid battery.
Disposal of Spent Batteries In a life cycle impact analysis of battery systems, regardless of composition, performance and whether or not they are rechargeable, it is clearly the final disposal of the battery which determines its major environmental and human health impact. The
18 emissions associated with all the stages up to the disposal of the battery are perhaps only 1% to 2% of the total potential emissions if the battery is simply discarded into the environment. This figures changes, of course, if the battery is disposed of in a controlled manner such that emissions are minimized. Nonetheless, disposal is the key step in determining total environmental or human health impact. There are four possible options for the disposal of spent batteries- composting, incineration, land filling or recycling. Composting is obviously not intentionally utilized as most battery systems are simply not biodegradable. Incineration likewise is not a preferred option because of the low calorific value of batteries. They simply do not burn well, and their mass is not substantially reduced by the incineration process. However, incineration is utilized in some countries where land filling is not as viable an option to reduce volumes of combustible wastes. In Japan and some European nations which have little or no available landfill space, incineration of municipal solid waste (MSW) has become a necessity. Batteries which are invariably contained in municipal solid waste will not be reduced in volume by incineration and will most likely partition to the clinker ash or residue from the MSW incineration process. In some cases, small consumer batteries may be broken apart, battery materials oxidized or volatilized, and subsequently recondensed on the fine fly ash from the incinerator. Air emission pollution control devices should capture better than 99% of these fly ash emissions (Chandler 1995), but then the fly ash must generally be subsequently landfilled. All in all, however, incineration is not particularly well suited for the disposal of batteries, although it must be realized that incineration of the small consumer cells will invariably occur in some countries which utilize incineration for a large share of their municipal solid waste disposal. If, in fact, toxic or hazardous materials from batteries do concentrate in the fly ash from incinerators and that fly ash is captured by air emission control devices, then that ash must be disposed of as a hazardous waste in landfills. Ultimately what might be required is the derivation of a statistical probability of a specific chemical release of a specific concentration during a specific time period from the landfilled fly ash. There are, for example, provisional tolerable daily or weekly intakes (PTWIs) for certain materials established by the World Health Organization (WHO) which well might be used to limit the amounts of certain battery metals from land filling. Total life cycle impact analyses may be utilized to help establish those limits. However, it should also be mentioned that the WHO tolerable daily intake levels for cadmium range from 70 lag per day for the average 70-kg man to 60 lag per day for the average 60-kg woman.
19 Cadmium daily intake levels in most OECD nations have been decreasing steadily since the 1970s and today range from 10 to 20 pg per day, well below any levels of human health concem (Intemational Cadmium Association 1999). These relationships are shown in Figure 6.
Figure 6. Daily Cadmium Intake Levels for General Population
Thus, land filling of incinerator ash from batteries may not be a significant problem and releases through this waste disposal option may not be as great as feared by some. The two most likely options for the disposal of spent batteries today are land filling and recycling. Land filling is currently the most widely used option, as it is the most widely used disposal option for all municipal solid wastes in OECD nations. A recent report (OECD 1998) indicated that an average of 63% of the municipal solid waste in OECD
20 nations was land filled, an average of 17% was incinerated, and the balance of 20% was recycled or composted. However, even if batteries are land filled, it is by no means certain that this disposal option poses an immediate threat to human health and the environment. For example, a Swiss review by the University of Berne for the OECD (Eggenberger and Waber 1998) on landfill leachate data from landfills in Canada, Denmark, France, Germany, Italy, Japan and Switzerland indicated that the vast majority of leachate samples passed the World Health Organization's (WHO) recommended cadmium drinking water standard of 3 ~tg per liter. Some of the data included in this survey were obtained from 50-year old unlined landfills, which theoretically should represent a worst case environmental impact scenario. Thus, the present disposal of NiCd batteries in landfills does not appear to pose an unwarranted risk from the perspective of leaching cadmium into the environment and entering the human food chain. Even when considered on a long term basis, there is considerable doubt that the presence of land filled battery metals such as lead, zinc, and cadmium would have the catastrophic environmental effects which some have predicted. Studies on 2000-year old Roman artifacts in the United Kingdom (Thornton 1995) have shown that zinc, lead and cadmium diffuse only very short distances in soils, depending on soil type, soil pH and other site-specific factors, even after burial for periods up to 1900 years. Another study in Japan (Oda 1990) examined nickel-cadmium batteries buried in Japanese soils to detect any diffusion of nickel or cadmium from the battery. None has been detected after almost 20 years exposure. Further, it is unclear given the chemical complexation behavior of the metallic ions of many battery metals exactly how they would behave even if metallic ions were released. Some studies have suggested, for example, that both lead and cadmium exhibit a marked tendency to complex in sediments and be unavailable for plant or animal uptake. In addition, plant and animal uptake of metals such as zinc, lead and cadmium has been found to depend very much on the presence of other elements such as iron and on dissolved organic matter (Cook and Morrow 1995). Until these behavior are better understood, it is unjustified to equate the mere presence of a "hazardous" material in a battery with the true risk associated with that battery. Unfortunately, this is exactly the method which has been too often adopted in comparison of battery systems, so that the true risks remain largely obscured. These caveats notwithstanding, there is still little argument that the most preferred option for the disposal of spent batteries is obviously collection and recycling. Not only does this option greatly reduce any risk which may exist, but it conserves valuable
21 natural resources as well. Today, recycling is viewed as the best human health and environmental option for the disposal of spent batteries, and it is the fastest growing option. Lead acid batteries have already achieved impressive recycling rates, better than 90% in the United States, and growing all over the world. The questions surrounding recycling of NiCd batteries are not whether it is or is not the best disposal option, but only how to improve collection rates, how to finance collection and recycling programs to improve returns, how to label batteries to maximize collection, and how to measure recycling rates. With NiMH and Li-ion batteries, the issues are developing the recycling technologies to improve materials recovery. With the alkaline manganese and carbon zinc batteries, the questions revolve more around the economics of the collection and recovery processes. Obviously collection and recycling of a spent battery prevents the entry of the majority, probably greater than 98%, of the battery's weight into the environment after use. However, there are other environmental impact factors which also must be considered with regard to recycling. For example, when comparing battery systems, it is instructive to compare the relative energies required to recycle various battery systems. Nickeliron, nickel-cadmium and lead acid batteries are relatively easy to recycle because the reduction of nickel, iron, cadmium and lead oxides back to their pure metals requires less energy than the reduction of the oxides of other battery metals such as zinc, manganese, chromium, titanium, zirconium, lithium and the rare earth metals which are constituents of alkaline manganese, nickel metal hydride and lithium-ion batteries. Another factor is the emissions associated with the production of battery metals by the recycling process as opposed to production from virgin ore. There have been many studies to demonstrate that recycling requires far less energy input than production of metal from virgin ore (Gaines 1994), but there are also now studies to indicate that emissions from recycling are lower as well. One report (Geomet Technologies 1993) on electric vehicle NiCd batteries, for example, compares cadmium emissions from production and recycling and finds that recycling emissions are roughly 10 to 100 times lower. These results are summarized in Table VI. Considered from another point of view, three estimates of the degree of materials recovery from the recycling of NiCd batteries all place that recovery rate at greater than 99%. Similarly high recoveries would be expected for the recycling of nickel-iron and lead acid batteries, but recovery rates from recycling of alkaline manganese, nickel metal hydride and lithium ion batteries might be somewhat lower because of the high
22 Table VI. Cadmium Emissions from Production and Recycling NiCd Batteries* Production Emissions
Recycling Emissions
(grams Cd per KW-hr)
(arams Cd per KW-hr)
Air Water
0.28 to 3.6 0.40 to 2.4
0.0062 0.0014
Land
Negligible
Negligible
*Source: Geomet Technologies 1993
energies required and the difficulty of reducing some of the battery metal oxides present in these systems. For example, anywhere from 10% to 20% of the total weight of nickel metal hydride batteries might be lost in the slag during the recycling of these batteries due to the presence of very reactive metals (chromium, aluminum, magnesium, vanadium, zirconium, titanium, rare earth elements) which are strong oxide formers and very difficult to reduce. While it has been suggested that this slag could be utilized for other applications, some environmentalists and regulators argue that such "downgraded" applications do not constitute true recycling. Thus, it is possible to recover a very high percentage of the material in a spent battery, and no doubt recovery technology will improve in the future to allow high degrees of materials recovery from all battery systems. However, the efficiency of the collection process for spent batteries and the efficiency of the metal recovery process are both factors which will affect the overall environmental and human health impacts of battery systems.
Environmental and Human Health Impact Assessments Once a complete energy and materials inventory of all of the various steps in a battery's life cycle has been established, the next steps are to categorize the inventory items into various groups. In general, these impacts have been realized on three areas: 9 Natural Resources 9 Human Health Impacts 9 Ecological or Environmental Impacts
23 Determining the impact assessment requires classification of each impact into one of these categories, characterization of the impact to establish some kind of relationship between the energy or materials input/output and a corresponding natural resource/human health/ecological impact, and finally the evaluation of the actual environmental effects. Many life cycle analyses admit that this last phase involves social, political, ethical, administrative, and financial judgments and that the quantitative analyses obtained in the characterization phase are only instruments by which to justify policy. A truly scientific life cycle analysis would end at the characterization phase, as many of the decisions made beyond that point are qualitative and subjective in nature. The inventory analysis determines all of the energy and materials inputs in a battery's life cycle and all of the outputs which could have an environmental or human health impact. These outputs include direct emissions from all production and manufacturing processes, including emissions from the energy production processes, and from the use, maintenance, recycling or waste disposal of the battery. All of these emissions must then be considered on a normalized basis by dividing by the total lifetime energy of the battery. The results are total amounts of emissions per kilowatt-hour of energy. If the battery is not recycled, then virtually the entire weight of the spent battery must be considered as being dispersed into the environment, although as discussed previously, the true risk or immediate impact of land filled or incinerated and land filled batteries may be released over an extended period of time and only to a limited degree. The great controversy in life cycle analyses arises when specific impact assessment values are assigned for each particular material. There are many systems which have been proposed and the impact values vary widely. Strictly speaking, impact values should be very specific for the specific battery material involved. In practice, most systems employ generic categories such as "nickel and its compounds" or "lead and compounds" and employ human health and environmental impact data from surrogate compounds which are usually those which have been most studied in environmental and human health research. Unfortunately, this practice creates a worst case scenario analysis in that the surrogate compounds are almost always the highly soluble species of a metal compound, designed to yield rapid results in clinical tests, but not indicative of the manner in which battery compounds may behave. Thus, for example, cadmium chloride, the highly soluble cadmium compound and one often utilized in environmental and human health research, may be and often is used as the surrogate for all cadmium
24 metal and compounds, whereas the cadmium compounds present in NiCd batteries are the much less soluble cadmium oxide and cadmium hydroxide. Even worse, in many analyses, impact values appear to be assigned quite subjectively with no justification or methodology specified. Because of this problem, huge variations in environmental impact values exist from one method to another. Essentially, one can obtain any life cycle analysis result one desires simply by arbitrarily selecting artificially high or low environmental impact values. To have any validity at all, a life cycle analysis must be based on environmental and human health impact values which are rooted in quantitative, measurable indices of a material's effect on human, terrestrial or aquatic life. A 1997 comparison (Morrow 1997) compared the normalized life cycle analysis impact values for four rechargeable battery systems utilizing five different impact assessment techniques. Needless to say, the results were very inconsistent except that lead acid batteries consistently fared well because of their high recycling rate. All of the other battery systems ranged over the entire spectrum from relatively benign to the most toxic depending on the environmental impact assumptions chosen. For example, the five impact assessment evaluation methods reviewed in the 1997 comparison (Morrow 1997) were as follows: CML M e t h o d - Developed by The Centre for Environmental Science in Leiden, The Netherlands. The effects of water and air emissions of various chemicals on certain general areas such as eutrophication, energy depletion, greenhouse effect, acidification, winter smog, summer smog, heavy metals and carcinogenicity were expressed in terms of potential rather than real effects. EPS Method- The Environmental Priority in Product Design method was developed in Sweden by the Swedish Environmental Research Institute and the Swedish Federation of Industries. This system sets a value to a change in the environment through impacts on human health, biological diversity, production, resources and aesthetic values. Tellus Method- The Tellus Method is based on control costs of various air pollutants and considers factors such as carcinogenic potency ranking, oral reference dose ranking or a combination thereof.
25 Ecoscarcity M e t h o d - Defines a relationship for a given country of given area
between the critical level of a pollutant set by the limited carrying capacity of the natural environment and the actual anthropogenic emissions of that pollutant.
The
countries
evaluated by the
ecoscarcity method are
Switzerland, Netherlands, Norway and Sweden. 9 U.S. Environmental Protection Agency M e t h o d - Based on an analysis technique developed for EPA by the University of Tennessee, this method considers all major human health and environmental effects of the chemicals including persistence and bioaccumulation. It also includes weighting factors for the actual levels of emissions. These various evaluation schemes produce widely varying results. For example, in rating the metals utilized in various batteries systems, it was generally found that lead, cadmium and mercury consistently were listed as battery metals with the most adverse environmental or human health impacts. However, it was also noted that nickel, cobalt, chromium and even zinc were listed as materials of concern in some systems. Even more remarkable were some of the relative impact assessment values assigned to some battery metals relative to other battery metals. While this variation can be explained to some degree by the different bases used for the techniques, it also clearly indicates that a life cycle evaluation of a battery system will depend to a great extent upon the evaluation system chosen. For example, the relative environmental impact values assigned to six battery metals according to the five different evaluation techniques are summarized in Table VII. These values are all normalized to a maximum value of 100 which is the most adverse environmental impact effect to allow comparison across the five systems. There is really very little consistency across these environmental impact assessment methods except that the Swedish and Dutch systems rate cadmium the battery metal with the most adverse effects, while the Tellus and Ecoscarcity Methods rate mercury the most adverse battery metal. Zinc, manganese, nickel and even lead have relatively low effects except in the U.S. EPA system, which however is the one system which is most closely tied to actual quantitative assessments of environmental and human health toxicological end points. What is very surprising is the relatively low impact values for mercury in the Swedish and Dutch schemes given the general worldwide concern for mercury.
26
Table VII. Relative Environmental Impact Values for Battery Metals Utilizing Various Assessment Evaluation Methods Method
C__d_d
Ha
Pb
Ni
Mn
Z._.qn
CML
100.0
1.9
3.8
2.8
1.9
1.9
EPS
100.0
13.5
2.3
2.9
0.01
0.88
Tellus
65.2
100.0
21.3
5.6
0.15
0.15
Ecoscarcity
7.1
100.0
0.4
8.6
*
0.71
U.S. EPA
74.9
*
95.3
84.4
54.1
22.3
*Not evaluated by this method
Sweden and Netherlands appear to be much more concerned about cadmium and therefore their actions against nickel-cadmium batteries are not surprising. The conclusion must be that life cycle impact assessment values are, at best, estimates which are heavily biased towards particular area's, country's, organization's or individual's points of view and are often not really scientifically based. Of the five techniques considered above, only the U.S. EPA method appears to be largely based on scientifically established toxicological endpoints for human health and the environment, and even in the establishment of those endpoints, there are a considerable number of assumptions and judgments made as to the relative weighting factors utilized and surrogate compounds employed which affect the ultimate impact assessment.
Life Cycle Analysis of Battery Systems If the total energy and emissions of a battery during its entire lifetime production, use, maintenance and disposal are established, then divided by the total lifetime energy of the battery, the total emissions per kilowatt-hour of energy may be derived. These are separated into specific materials, usually elements, compounds or groups of compounds, for which specific environmental and/or human health impact assessment values are available. Utilizing these values, the overall relative life cycle environmental impact of a particular battery system may be established and compared to other battery systems. As previously discussed, these analyses involve many assumptions and
27 generalizations. In point of fact, accurate analyses can only be carried out on a specific battery composition with specific battery performance. Even then, the assumptions inherent in the impact assessment values, the manufacturing processes, the disposal options and all of the other steps discussed in this review create a large area of uncertainty. These uncertainties notwithstanding, it is useful and interesting to carry out an analysis on a specific battery to show how some of these variables will affect the overall analysis. At the 8th Intemational Conference on Nickel-Cadmium Batteries in Prague, Czech Republic, a paper (Morrow 1998) was presented which discussed the relative effects of performance and recycling on the life cycle impact assessment of nickel-cadmium batteries. An AA-sized NiCd battery with an assumed composition of 3 0 % N i - 15%Cd -
1%Co was studied even though the references and data in Table I clearly show that
these compositions could vary widely. The AA-sized consumer cell is, of course, a small (23-gram) sealed consumer cell, and thus there are no emissions during its use, maintenance or recharging, which would be small even if it were a vented cell. The range of performance parameters chosen were those previously presented in Table V. While the voltage for an AA-sized NiCd battery has remained the same over the years, the capacity of this cell and thus its unit energy have increased over the years. In 1990, the best AA-sized NiCd had a capacity of 0.5 ampere-hours, whereas in 2000, the best commercially available NiCd capacity in this size is about 1.2 ampere-hours. In addition, cycle life has generally improved, so that today's batteries have a higher total lifetime energy than yesterday's batteries. This statement is probably true of all battery systems, not just the nickel-cadmium system. If we assume that better than 98% of a battery's total environmental impact is contained in the battery itself and whether or not it is disposed of by incineration, land filling or recycling, then it becomes a relatively simple exercise to compute the environmental impacts of AA-sized NiCd batteries under the compositional and performance assumptions made above. A 23-gram NiCd battery will contain 6.90 grams of nickel, 3.45 grams of cadmium and 0.23 grams of cobalt. From previous analyses, these three materials in the NiCd battery will be the ones which will produce the largest adverse environmental effects even though there may be moderate amounts of steel, plastic, copper and electrolyte present as well. If we assume that the entire weight of the battery upon disposal represents an emission or output to the environment, then the "heavy metal waste" generated per kilowatt-hour of total lifetime battery energy is as
28 summarized in Table VIII. Two figures are shown, one for the lowest lifetime energy (420 watt-hours) and one for the highest lifetime energy (1680 watt-hours). It is immediately obvious that the highest energy NiCd exhibits the lowest amount of heavy metal waste generated when expressed in terms of grams per kilowatt-hour of total lifetime battery energy. The lowest energy NiCd correspondingly exhibits the highest amount of heavy metal waste per unit of lifetime battery energy. As expected, the amounts of the individual heavy metal wastes generated are directly proportional to the battery's assumed composition. If higher or lower nickel, cadmium or cobalt contents are utilized, then the values for those metals will shift in direct proportion.
Table Vlll. Heavy Metal Waste Generated for AA-Sized NiCd* Batteries Waste Generated, grams per KW-hr Element
Hi2hest Energy
Lowest Energy
Cadmium
2.05
8.21
Cobalt
0.14
0.55
Nickel
4.10
16.43
*Assumed Composition: 3 0 % N i - 15%Cd- 1%Co
Once the ranges of heavy metal wastes generated have been established for an AA-sized NiCd battery of an assumed composition, the next step in the analysis is to assess the environmental and human health impacts of those wastes. While there are many different techniques for assessing the environmental and human health impacts of various materials, the preferred method which will be utilized in this analysis is the one developed for the U.S. Environmental Protection Agency by the University of Tennessee (Davis et al. 1994). This method considers all the major human health and environmental effects including persistence and bioaccumulation which are really relevant to organic compounds but not to metals. This method also includes weighting factors for the actual total levels of emissions. Under this ranking and scoring system, "inherent hazard values" are assigned to various chemicals depending on their quantitative effects on human health and environmental toxicological endpoints. These human health endpoints include both acute and chronic effects, ingestion as well as
29 inhalation, carcinogenicity considerations and other effects such as mutagenicity and reproductive effects. A set of appropriate factors for aquatic and terrestrial organisms are similarly incorporated into the scoring system. The human health and environmental factors are then multiplied by the exposure potential which includes parameters expressing biological oxygen demand half-life, hydrolysis half-life and an aquatic bioconcentration factor. It is felt that this system is probably one of the better impact assessment systems available today because it assigns impact values based on quantitative scientific data rather than subjective "concem" over a chemical which is often based on perception rather than scientific data. On the other hand, the bioaccumulation and persistence factors have already been shown to be not particularly relevant to metals per se. In the future, altemative evaluation systems such as solubility and transformation characteristics of metals and metal compounds, and models such as the biotic ligand model will be found to be much more appropriate for evaluating the human health and environmental impacts of battery metals. If the environment impact assessment values for the U.S. EPA method shown in Table VII are combined with the heavy metal waste data for nickel, cadmium and cobalt shown in Table VIII, environmental impact assessment values per unit of total battery energy for each of the three metals may be derived. The sum of these three values then yields an approximate environmental impact value for an AA-sized NiCd battery of an assumed composition and an assumed range of performance and total lifetime energy. The lowest impact values are associated with the highest set of performance parameters of capacity and cycle life, while the highest impact values are associated with the lowest set of capacity and cycle life performance parameters. This data may be further analyzed to establish the respective impact values when various percentages of the NiCd batteries are recycled. Such an analysis is shown in Table IX for two levels of recycling, 0% and 40%. For each level of recycling, the range of impact values for each element corresponding to the highest and lowest performance parameters are shown. As expected, recycling of 40% of the NiCd batteries results in a 40% reduction in the environmental impact values associated with NiCd batteries. What is perhaps more surprising is that performance can have a marked effect on the total life cycle environmental impact associated with NiCd batteries. The data indicate that, if both capacity and cycle life of an AA-sized NiCd battery can simultaneously be realized at the top end of the assumed ranges, then total life cycle risks may be reduced by a factor of four compared to those batteries with performance at the bottom end of the assumed ranges.
30
Table IX. Environmental Impact Values per Kilowatt-Hour Lifetime Energy For AA-Sized NiCd Batteries at Two Recycling Levels Environmental Impact Values p e r K W - h r Element
0 % Recycling
4 0 % Recycling
Nickel
346 - 1384
208 - 831
Cadmium
154 - 614
Cobalt TOTAL
92 - 369
7 - 27
4 - 16
507 - 2025
304 - 1216
The relative contributions to the environmental impact values for AA-sized NiCd batteries are further shown graphically in Figure 7 as functions of both battery
r/3
=
~ g h Performance
2,500
1.620
a * "~.
~
L_ 5.A~;
Cobalt
~~!
Nickel
1,215
1,~0
810
~:~ 500 Z
Low Performance
405
405
3~
203
o 0%
20%
40%
60%
Percentage of NiCd Batteries Recycled
Figure 7. The Effects of Recycling, Performance and Composition on the
Environmental Impact Values for AA-Sized NiCd Batteries
I0!
80%
31 performance ranges, degree of recycling and the individual contributions made by the major battery metals. It is evident that high performance batteries have lower environment impacts than lower performance batteries. It is also clear that increased recycling rates drastically lower the environment impacts associated with these batteries. In the particular environmental impact analysis technique (U.S. EPA) used in this analysis, nickel contributes the greatest impact, followed by cadmium. Cobalt contributes very little environmental impact at all. The lower performance batteries are, in fact, the ones being collected and recycled today, and these results suggest that in today's situation, the most effective way to lower environmental impacts is to increase the recycling rate. Steady improvements in the performance of batteries will also mean that the batteries being produced today and collected 5 to 10 years from now will pose less risk to the environment than those being collected now. Finally, the individual environmental impact contributions of nickel, cadmium and cobalt in this example are based on assumptions and are somewhat fixed by the battery system. It probably will not be possible to vary, for example, NiCd battery chemistry in a manner significant enough to have as major an effect on total life cycle risk as the degree of recycling and battery performance have.
Conclusions
From the foregoing analysis, it is concluded that the most effective methods to reduce total battery life cycle environmental impacts are to increase recycling rates, to improve battery performance, and to lower hazardous material contents provided that this does not compromise battery performance. It is further concluded that the waste battery disposal step is, by far, the single most important factor in determining the total environmental and human health impact of a battery system over its entire life cycle. Finally, it must be noted that present-day environmental impact assessments of battery systems rely on enormous assumptions regarding battery composition, battery performance, and the environment impacts of battery materials. Until such a time as standards are developed for life cycle analyses of battery systems, it will be almost meaningless to compare battery systems on this basis, unless assumptions are clearly stated and analyses are applied in a uniform manner. It will also be necessary to accurately determine the actual contributions made in all of the various life cycle stages of a battery instead of being forced to assume that they are negligible because of lack of accurate and pertinent information.
32 References
Chandler 1995, "Cadmium in Municipal Solid Waste Management Systems," Sources of Cadmium in the Environment, Inter-Organization Programme for the Sound Management of Chemicals (IOMC), Organization for Economic Cooperation and Development, Paris, France. Cook and Morrow 1995, "Anthropogenic Sources of Cadmium in Canada," National Workshop on Cadmium Transport Into Plants, Canadian Network of Toxicology Centres, Ottawa, Ontario, Canada, June 20-21, 1995. Cornu and Eloy 1995, "Nickel Cadmium Batteries: Life Cycle Analysis in the Electric Vehicles Application," The Seventh International Seminar on Battery Waste Management, Deerfield Beach, Florida, November 8, 1995. Davis et al. 1994, "Chemical Hazard Evaluation for Management Strategies: A Method for Ranking and Scoring Chemicals by Potential Human Health and Environmental Impacts," Report prepared by The University of Tennessee, Center for Clean Products and Clean Technologies for the Waste Minimization, Destruction and Disposal Research Division, Risk Reduction Engineering Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio, EPA/600/R-94/177, September 1994. Eggenberger and Waber 1998, "Cadmium in Seepage Waters of Landfills: A Statistical and Geochemical Evaluation," Report of November 20, 1997 for the OECD Advisory Group on Risk Management Meeting, February 9-10, 1998, Paris, France. Elgersma et al. 1992, "Emission Factors for Aqueous Industrial Cadmium Emissions in the Rhine River Basin: A Historical Reconstruction for the Period 1970-1988," Edited Proceedings Seventh International Cadmium Conference- New Orleans, Cadmium Association (London), Cadmium Council (Reston VA) and International Lead Zinc Research Organization (Research Triangle Park NC). Fujimoto 1999, "Collection and Recycling Activities for Portable Rechargeable Batteries in Japan," Proceedings of the 5th International Battery Recycling Congress, Deauville, France, September 27-29, 1999.
33 Gaines 1994, "Energy Use and Emissions in the Production and Recycling of Electric Vehicle Batteries," Report of December 13, 1994, Energy Systems Division, Argonne National Laboratory, United States Department of Energy, Argonne, Illinois. Geomet Technologies 1993, "Nickel-Cadmium Batteries for Electric Vehicles- Life Cycle Environmental and Safety Issues," Final Report No IE-2629 prepared for the Electric Power Research Institute (EPRI), December 1993. International Cadmium Association 1999, "Cadmium- A Problem of the Past, A Solution for the Future," International Cadmium Association, Brussels, Belgium and Great Falls, VA, 1999. Morrow 1997, "The abuse of life cycle analyses for comparison of battery systems," Materials Solutions for Environmental Problems, Proceedings of the International Symposium sponsored by the Materials Science and Engineering Section of The Metallurgical Society of CIM, 36th Annual Conference of Metallurgists of the Canadian Institute of Metallurgists, Sudbury, Ontario, Canada, August 17-20, 1997. Morrow 1998, "The Importance of Recycling and Performance to Life Cycle Analyses of Nickel Cadmium Batteries," 8th International Nickel-Cadmium Battery Conference, Prague, Czech Republic, September 20-21, 1998. Mukunoki and Fujimoto 1996, "Collection and Recycling of used Ni-Cd Batteries in Japan," Sources of Cadmium in the Environment, Inter-Organization Programme for the Sound Management of Chemicals (IOMC), Organization for Economic Cooperation and Development, Paris, France. Oda 1990, "In-Ground Burial Test for Ni-Cd Batteries," 2 nd Intemational Seminar on Battery Waste Management, Deerfield Beach, Florida, November 5-7, 1990. Organization for Economic Cooperation and Development 1994, Risk Reduction Monograph Number 5: Cadmium, OECD Environment Directorate, Paris, France. Organization for Economic Cooperation and Development 1998, Towards Sustainable Development: Environmental Indicators, OECD Group on the State of the Environment, Paris, France.
34 Stockholm Environmental Institute 1994, Accounting for Cadmium, Stockholm Environmental Institute, London, UK. Schuckert et al. 1997, "Life cycle engineering as an environmental management t o o l Comparison of nickel and lead traction battery systems," Materials Solutions for Environmental Problems, Proceedings of the International Symposium sponsored by the Materials Science and Engineering Section of The Metallurgical Society of CIM, 36 th Annual Conference of Metallurgists of the Canadian Institute of Metallurgists, Sudbury, Ontario, Canada, August 17-20, 1997. Thornton 1995, "Heavy metal migration in soils and rocks at historical smelting sites," Environmental Geochemistry and Health (1995), 17, pages 127-138. Van Assche 1998, "A Stepwise Model to Quantify the Relative Contribution of Different Environmental Sources to Human Cadmium Exposure," 8th International
Nickel-Cadmium Battery Conference, Prague, Czech Republic, September 20-21, 1998. Van Assche and Ciarletta 1992, "Cadmium in the Environment: Levels, Trends and Critical Pathways," Edited Proceedings Seventh Intemational Cadmium Conference New Orleans, Cadmium Association (London), Cadmium Council (Reston VA) and Intemational Lead Zinc Research Organization (Research Triangle Park NC).
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
35
P O R T A B L E R E C H A R G E A B L E B A T T E R I E S IN E U R O P E : SALES, USES, HOARDING, COLLECTION
AND RECYCLING
Jean-Pol Wiaux Titalyse SA, Route des Acacias, 54bis, CH-1227 Carouge, Geneva, Switzerland
1. INTRODUCTION During the year 2000, the total worldwide battery market value reached approximately 30-35 billion euros.Four major market segments can be distinguished for the batteries: primary, starting lighting and ignition (SLI), industrial rechargeable and portable rechargeable. The primary battery sales account for one third of this market segment where the main technology is represented by alkaline batteries. This market is increasing on a 5% per year basis with no major change or technology rupture foreseen (Pilot - 2001). The second largest market segment is represented by industrial batteries where the leadacid battery used for stand-by in telecommunication or industry, railways, aviation is dominating. Nickel-cadmium batteries are expected to gain market shares thanks to their greater reliability and safety but also because of their uses in advanced applications with higher added value. The third market fraction is the traditional SLI battery application field which is under development due to an increasing demand for electrical and electronic applications in cars, like air conditioning systems and alterno-starters. To compensate the related demand for DC power, major car manufacturers have decided to increase the voltage of the battery unit from 12 volts to 42 volts. The last market fraction is represented by portable rechargeable batteries (PRB).
1.1.
Portable Rechargeable Batteries
The portable rechargeable battery market account for 20% of total batteries sales. It is a
36 market driven by the most advanced electrical and electronic equipment (EEE) in the fields of computing, communication, household equipment and all the portable electrical devices like cordless power tools, tooth brushes, dust busters, CD and MD players and the future generations of portable electronic equipment. This market segment was multiplied by a factor greater than 3 in the last ten years and is foreseen to maintain a significant growth in the near future. It is worth mentioning that nickel-cadmium (Ni-Cd) batteries have been the first type of portable rechargeable battery to take advantage of this market evolution. If a cumulative value is considered for the sales of Ni-Cd batteries from 1980, one reaches a total value of more than 150,000 tonnes of portable Ni-Cd batteries introduced in Europe between 1980 and 2000 (CollectNiCad- 2000). Until 1995, the largest fraction of Ni-Cd batteries introduced into the market was in household and electronic equipment. The emergency lighting units market has been in constant but moderate growth during the 1990's. From 1995, the cordless power tools application has taken a dominant position for these batteries (see also Figure 4) both in consumer and professional applications. A ten to twenty percent annual market increase has been observed during the last three years (Black&Decker 2001). Finally, the market share of Ni-Cd batteries in the electronic appliances has been replaced by Ni-MH and Li-Ion technologies as a consequence of a market driven evolution. One of the main features of this market is that the largest fraction (95%) of portable rechargeable batteries is sold incorporated in electrical and electronic equipment. Only a minor fraction ( ,.-, (, ,-Retailers ~ ~::. : I
Collection
Eqt. & Batt. '
[The
(Distributors-/Retailers, -
,,
,,
CommunitieS) ,
,
~,,
,
,
,
,,J
t
,,,
!
,,
:ManufactEmm:::;/ . .9. .
+
/
[: Eqt, il~ / M a f i ~ / i ~ r i ~ i : ] ! 1
........
Primary:baRerNs;i &Accumulators I ' .manUfacturers - i
t
[Materialsl
95
Germany France
80 70
Sweden
>95
Norway
>95
The Netherland
90
Greece Portugal
90 75
Austria
80
The data mostly refer to the number of replacement batteries, which is equivalent to that of the spent ones. Data on spent batteries are not always available, as the collection system is often irregular as it is managed by private operators. Furthermore, spent batteries often cross borders, e.g. France-Germany, East EuropeGermany or Austria, France-Spain, Scandinavian Countries-United Kingdom, and this factor determines some uncertainty as to whether the figures are correct.. The collection costs are summarized in table 12. 9 Recycling
The costs for lead recycling are reported in table 13.
249 Table 12
Country Italy France Germany Austria United Kingdom
Cost (E/kgPb) 0.10 0.15 0.15 0.15 0.13
Table 13
Country Italy France Germany United Kingdom
Cost (C/kgPb) 0.32 0.29 0.34 0.28
These recycling costs refer to lead for the production of ingot lead or standard Pb/Sb alloy; other alloys have extra costs. ,
Sulphuric Acid Disposal
The above costs include disposal of the acid. The acid contained in a spent battery is accepted in all countries but is not paid; its weight is not taken into account when determining the dry total weight of the spent batteries. Only in Italy, "free" acid is accepted, i.e. the acid that leaks from broken batteries and accumulates at the bottom of the containers. Its acceptance is imposed by COBAT with the aim to limit acid dispersion in the environment, although the collectors prefer to sell acid-free batteries to the recyclers.
250 9
Slag Disposal
As previuosly mentioned, there are two types of slag: from smelting (iron and sulphur compounds, silica and soda from rotary kilns) and from plastic materials (ebonite, PVC, PE). The disposal costs depend on the slag volume rather than its weight. Accordingly, disposing of a given weight of smelting slag will be cheaper than disposing of the same weight of plastics which are lighter and need more space. In table 14, the cost given is average for both types of slag. Table 14
Country
Cost (•/kgPb)
Italy France Germany United Kingdom
0.02 0.01 0.02 0.01
9 Total Recovering Costs
It is now possible to calculate the total costs for battery recovering (table 15). A complete comparison among european countries is rather diffult due to the lack of reliable official data and since there is no entity such as COBAT, controlling the phases and costs of recycling. Information is directly provided by the operators who have some difficulties in obtaining the right figures.
Table 15
Country Italy France Germany United Kingdom
Cost (C/kgPb) 0.44 0.45 0.51 0.42
251 From this comparison, it is evident that the free-market regime is not always able to ensure lower costs. Furthermore, it has to be considered that, in this regime, only what is economically convenient is collected. For a complete comparison, one has to take into account such factors as power, ecological costs, taxes, facility maintenance, etc. Looking at table 11, it can be noted that the recycling rate is higher in those countries with a consortia-based system. Lower rates in other countries are explained because the collection is directly linked to lead price; therefore, when the lead price diminishes, collection becomes less attractive as in this case the impact of transport cannot be further reduced, and the overall collection cost vis a vis lead price is higher. Free competion may therefore show some negative aspects, especially if one considers that acid-free batteries are paid better than others. On the contrary, the overpricing-based system is able to meet the costs of a complete recovery and, at the same time, to protect the environment.
6. C O L L E C T I O N MODES AND RECYCLING TECHNIQUES Collection Modes
The systems used to collect and store spent accumulators are not the same in the various countries. The lack of uniformity has to be ascribed mainly to the nature and small dimensions of the operators. However, as an example the italian situation is described below. 9
Primary holders
Primary holders storing spent batteries are obliged to hand them free of charge to authorised companies. The primary holders are fined if batteries are left in a public space. Secondary holders (such as scrap-metal operators and car electricians) assure their storing in safe conditions, i.e. the batteries will not be broken and acid and/or Pb compounds not spilled. 9 Collection Authorised transportation companies take back the used batteries from secondary holders. These companies should have available a truck fleet to be able to reach
252 secondary holders everywhere, especially in the big towns. Furthermore, the trucks must be equipped in such a way to grant loading and transportation without any spillage of dangerous substances from the batteries. To this end, all trucks are equipped with stainless-steel acid-resistant containers shaped so as to contain any spilled acid. Once the batteries are collected, the trucks reach the collection center and the batteries are stockpiled in storage areas whose floors are lined with acidresistant materials. These areas must be sheltered and aerated, and located so to allow an easy loading of the batteries on bigger trucks for delivery to the recycling plants. Any acid spilled during the loading/tmloading operations is collected in special containers and sent to the recycling plants.
9 Transport to the Recycling Plants Battery transport is carried out according to the criteria indicated below: 9 location of the recycling plants; 9 volume of batteries assigned by COBAT; 9 volume of batteries received by the collection centres; 9 transport cost minimisation: The COBAT databank allows monitoring of the flow of spent batteries to the recycling plants. In this way, it is possible to meet the recyclers' requirements and to optimise the number of voyages to reduce the risk of environmental damage.
The Production Cycle- Recovery Technologies The current recycling technology used world-wide involves various steps. The first operation requires the non-metallic components to be separated from the metallic fraction by crushing and physical sorting. In this way, reusable organic components are recovered and dangerous substances, such as PVC, are not fed into the furnace. Attempts to treat the batteries bypassing this preliminary step have been made at the industrial level (shaft furnace); however, no advantageous result from both economical and environmental points of view was achieved. The treatment process involves the following steps: 9 physical treatment;
253 9 smelting/reduction of lead-bearing products; 9 refining the lead obtained by smelting to meet the market specifications; 9 alloying. 9
Physical T r e a t m e n t Facilities
Until the early 60's, Pb recovery from spent batteries was carried out by shredding the battery manually and detracting the plates along with the separators and part of the ebonite cover. The plates were delivered to the lead reduction plant. The ebonite case was washed in a drum and lead sulphate recovered. After drying, the lead sulphate was fed into a reduction furnace. The washed ebonite was dumped. This method was unsatisfactory in terms of workers' health (prolonged exposure to lead) and lead recovery (as plates treated were not clean since they contained 8-10% plastic materials, and due to the simultaneous reduction of Pb/Sb grids along with the active mass). In the middle 60's, the major italian producers of secondary lead patented and operated an automated battery shredding facility. This technology, later modified to take into account the increasing use of polypropylene cases containing more electrolyte, was in use till late 70's-early 80's. Since then, the same producers have modified the existing shredding facility to adapt it to the new battery type
(as
mentioned, with a polypropylene case and more acid) and to comply with the more restrictive regulations. 9
Sink and Float Separation
This process takes place in two phases. In the first, the batteries are shredded, the active matter is separated and dried, and the acid is neutralised. In the second, lead is separated from ebonite (or polypropylene) with the so-called 'sink and float' process.
Battery Shredding A payloader feeds a hopper with batteries. From the hopper, by means of a conveyor belt, the batteries fall into a rotating cylinder were the cases are broken with the help of big iron beams inside. In the same cylinder, the resulting scrap is dried by a gas burner. The end of the cyclinder is provided with two sieves. The first sieve allows
254 the recovery of the dried active mass, which is sent through a belt to a series of containers. The second sieve allows the retention of the coarse parts, such as partly broken cases also sent to containers. The part containing ebonite (polypropylene), separators and lead is conveyed to the 'sink and float' unit.
Separation of the Components A slurry made of the active battery mass is fast stirred in a pool. Its density and viscosity are frequently checked. This slurry is conveyed to a separating drum, flowing upstream with respect to the scrap. Then, the slurry drags the shredded containers and the plastic separators which begin to float because of their low specific weight as compared to the slurry. At the end of the drum a rotating sieve separates the slurry from the plastic materials. The shredded containers proceed to the second section were they are washed by recycled water. On the other hand scrap-lead leaves the drum and reaches a rotating sieve for washing. After that it falls onto a conveyor belt and is stockpiled. Periodically and altematively, the slurry carrying also the active matter is drawn from the tank and sent to a couple of draining tanks, of which one is continually being replenished and the other depleted. Here, water drains the material and is then eliminated into a sewer, while the active mass is from time to time collected, dried and added to the one already separated by the rotating sieve. 9 Hydrodynamic Separation and Carbon
This unit has two sections, the first allowing shredding and separation, and the second allowing sulphur elimination from the active mass. Sulphur is present as lead sulphate and is recovered as sodium sulphate, used in the soap industry.
Battery Shredding and Separation of the Components The incoming batteries are stored in a special concrete place lined with acid-resistant asphalt, having a storage capacity is 4,000-6,000 tons of batteries. Here, acid drains from those batteries broken during the unloading operations. Sometimes, the batteries are crushed on purpose by means of a crawler. The drained electrolyte is collected in one or more pits, from which it is conveyed to reservoirs. The batteries now partly emptied (6-12% residual electrolyte) are fed to a hopper, from which they are belt-conveyed to a special hammer mill for shredding. The resulting lead paste,
255 mostly PbOx and PbSO4, is transferred from the mill to a wet sieve (mesh: 1-1.5 mm) were it is separated from other components. The mixture of grids, polyethylene (PE) separators, polypropylene (PP), PVC, wood and other materials is sent to the hydrogravimetric separator. Due to a strong water flow, PP floats at the top of the equipment, while the grids sink to the bottom. PE, PVC and other residues leave the separator through an opening and can possibly be treated to obtain a further separation. At this stage, the following products have been obtained: 9 active mass+water: about 60% of the incoming battery weight; 9 grids (95% lead): 28%; 9 PP (its percentage depends on the type of case): 97% of initial PP weight; 9 PE+PVC+other residues (variable percentage): The grids are stored and then sent to feed the kiln. PP flakes can be marketed as such or extruded by special equipment to obtain granules, later sold to manufacturers of plastic products. In Europe, the commercial value of extruded PP reaches about 6080% of its original value. The PE/PVC mixture is land filled. Several plants limit the physical treatment to this phase and send to fumaces the lead mixture Carbonatation process
The lead paste is pumped into a reaction vessel. By adding Na2CO3, the following reaction occurs: Na2CO3 + PbSO4 ") PbCO3 + Na2SO4 Once the reaction is finished, the paste passes through a filter-press and a desulphurated material with 12% water is obtained. The solution containing sodium sulphate is crystallized to obtain anhydrous Na2SO4 and the hot water is recycled. This second phase has the advantage of transforming lead sulphate into carbonate, minimising SOx emissions and making unnecessary the use of special scrubbers. Furthermore, the lead sulphate requires large amounts of reactants in the furnace, while the lead carbonate only needs coal. Therefore, the advantages are:
256 9 no SOx emission; 9 few reactants needed; 9 increased kiln productivity: 30%; 9 proceeds from selling Na2SO4 to soap and glass industry allow the compensation of about 85% of the cost of Na2CO3 used. This technique is still in use in several plants. However, marketing Na2SO4 is becoming more and more difficult, especially as far as the soap industry is concerned. So, the use of this technique depends on the economical, technological and environmental conditions of a recycling plant. A flowchart describing all the treatment steps carried out in the plant is reported on page 33. Metallurgical Plants 9 Smelting/Reduction
Smelting is the key process in the cycle of spent lead batteries recovery. The fumace can be of different types: reverberatory fumace, used in the metallurgical industry not only for lead, but also for copper, steel, etc. These furnaces have a radiant vault and a refractory lining of chromium-magnesium bricks, with lateral oxy-fuel burners and are fed by a loading hopper. The feed made of metallic lead, lead compounds, reducing agents and slagging agents is carefully pre-mixed; rotary kilns, widely used by virtue of their flexibility in terms of operation and maintenance. In a plant, normally two such kilns of different sizes are installed. The number of batteries to be treated determines the one to be used. The burner is set on one of the kiln headers and is made retractable as the charge is introduced through the same opening. The combustion fumes leave the side opposite the bumer. Since rotary kilns are widely used, the following description of the process refers to them.
257
BATTERY MIX
u I CRUSHER I INDUSTRIAL WATER
I GR DS
I
POLYPROPILENE
I SULPHATED PASTE
r I
RECYCLING WATER I
I HYDROGRAVIMETRIC I SEPARATOR
I
t~ -~
PRESS FILTER
P.V.C. + WASTE
J .......
PASTE
Na2CO3 WASHING WATER INDUSTRIAL
u
I
v
I
REACTIONTANK
PASTE + SOLUTION u
WARM WATER TO WASHING
! PRESS FILTER
I
u
I SOLUTION TANK I~[ I CONDENSATOR I
H20 VAPOR
I
q WARM WATER ; TANK
I MOTHER LIQiOR
BURGE
CRYSTALLIZER 2" I
u
I EVAPORATION AND I CRYSTALLIZER 1"
VAPOR
CRYSTAL + MOTHER LIQUOR
CRYSTAL +
MOTHE~LIQUOR
I CENTRIFUGE I DR ....
FVAPOR
ICENTRIFUGEI ~
LIQUOR
DR ER FVAPOR
~
DESULPHATED PASTE
I
258 The amount of charge introduced in the kiln, especially in terms of reactants and slagging agents, is a function of whether the lead paste carbonatation was made before smelting. In the absence of carbonatation, the feed mix is made up of metallic lead, lead sulphate, coal, soda, scrap-iron, silica (sand) and/or glass. These materials are charged without pre-mixing but sequentially, according to their function: soda, lead and its salts, carbon, scrap-iron. The charge is fed from the burner side keeping the kiln slowly rotating. The oxy-fuel burner is stoked with methane. The charge components give rise to reactions eventually leading to metallic lead: NazCO3 + 2PbSO4 + Fe + 9C "-) 2Pb + FeS + Na2S + 9CO + CO2 The maximum temperature is 1000~
The yield in terms of lead is about 90%.
Fe and Na2CO3prevent the formation of SO2 (sulphides are formed instead), thus the combustion fumes have SO2 levels below the permitted limit. Once the reaction is over, lead and slag are sequentially cast from the casting hole in the middle of the kiln. Molten lead and slag are cast in ladles on a train perpendicular to the kiln and kept under suction.The whole cycle- charging, reactions and casting lasts about 3 hours. The fumes are conveyed to a fume scrubber, before sending them to a filter. Sometimes, a special scrubber for SO2 is also used, to eliminate possible excess. The plants equipped with a carbonatation unit benefit a great deal from the production. In fact, as the charge is mainly made of metallic Pb and PbCO3, the amount of necessary Fe, C and slagging agents is lower. Furthermore, reaction time and temperature are also reduced, lead yield is higher and SO2 emissions are negligible. An increase in the production capacity by 30-35% may be estimated with respect to the treatment based on sulphur-containing lead. However, as mentioned above, carbonatation brings about higher operation costs and the need to sell sodium sulphate. Nevertheless, the last-generation plants designed for the production of primary lead are able to treat sulphur-bearing lead from spent batteries. These are direct-smelting plants which are suitable to treat lead sulphates, which, after the addition of lead concentrates, are directly reduced to metallic lead without problems. In Europe, there are three plants of this kind. Although based on different technologies, a feeding mix
259 made up of lead concentrates and lead sulphate from batteries is used in all cases. A plant built with Kivcet technology is operating in Italy; another one (QSL technology) is in Germany; a third (Ausmelt technology) is in France. 9
Refining/Alloying
From the smelting of lead ores or spent batteries a metallic lead is obtained which has to be refined, i.e. purified from other metals, so as to obtain 99.9% grade lead. Those metals are treated in special facilities to recover them. Usually, lead concentrate carries precious metals, sometimes in economic concentrations. Lead can be refined either electrolitically or thermally. 9
Electrolytic Refining
With this process, the smelted lead is cast as anode and electrolysed in a fluosilicic acid solution. By this process pure lead is collected as cathode, while any other metals remain on the anode and are recovered as anodic slurry, further treated to recover single metals. 9
T h e r m a l Refining
With this method, the refming process takes place in open kettles, usually quite large, heated by a direct flame underneath. Plants producing lead from spent batteries prefer this process because the investment and direct costs are lower and there is a small quantity of secondary metals. Refining can be performed either continuously or in batches, according to the production requirement of the plant. In particular, smelted lead is cast into ingots and sent to a kettle were it is smelted again to free it from copper (decopperizing) by skimming the surface with a bucket. Afterwards, the molten lead is channeled to other kettles were it is further separated from other impurities/metals, again by skimming. Each kettle
is provided with
stirrers and pumps to pour molten lead into the next kettle. The phases of the continuous process are: 9 Decopperizing; 9 detinning (with soda and NaNO3, with or without Harris' machine); 9 deantimoning (with oxygen and Harris' machine); 9 alloying (Pb/Ca, Pb/Sb, Pb/Sn);
260 9 final refining and casting. The ashes generated during the ref'minig phase, after sorting, are recycled to the kilns. Lead metal is cast into ingots, after checking its grade, using an automatic casting machine. At the end of this machine an automatic machine stakes the ingots.
Comparison of the Production Technologies The technological advances in the recycling plants cannot be understood without considering the advances that have involved the batteries they are treating. Batteries have undergonemajor changes in their performance and materials. The replacement of ebonite with PP for the case and of PVC with PE for the separator has been quite an important step. The new generation of batteries has allowed the recyclers to reduce the amount of material to be land filled, to improve working conditions within their plants and to to recover and market organic products, so that the overall costs can be reduced. All modem technologies are based on the following phases: crushing the battery, sorting non-metal components and treating the metal. The technological differences as to the first and second phases are not so relevant, as such facilities are now well known and easy to get in the market. As to the third phase, possible alternatives are: 9 direct treatment of lead and its compounds in the smelting/reducing kilns. This solution cuts the costs, but limits the capacity of the kilns, while increasing the costs of ecological facilities; 9 carbonatation of the lead salts before smelting. This solution calls for higher expenses for equipment and their management, with the risk of not getting back a satisfactory revenue from the sale of sodium sulphate. Nevertheless, this alternative allows for a 30-35% increase in production capacity and a reduced cost for ecological facilities; 9 sale of lead sulphate to primary smelters, and also its partial or total tolling by reduction plants (i.e. treatment cost for recyclers account). If sold, lead sulphate would dramatically reduce recyclers' expenses; if tolled, the production capacity of the recyclers would increase, as it would only depend on the shredding facility size, which however is usually oversized in this kind of plant. On the other hand, should the lead sulphate be sold, the recyclers would lose market shares for the trmal product and their production would become less
261 autonomous. In case of partial or total tolling, the recyclers should pay not only for smelting, but also for delivering the sulphate to the plant and taking back the refined metal. These considerations highlight how the right choice stems on economical rather than technical parameters. Therefore, the final choice is up to the management. If only the technical aspects were considered, the last two options (carbonatation, sale/toll) would appear more reliable.
CONCLUSIONS The growing interest of government, industry and ordinary people toward the environmental problems has made possible the issue of regulations to protect the environment and human health. In this respect, the high collection rate of spent batteries in the developed countries (European Union for instance) is a significant achievement. It is everyone's hope that the developing countries can soon bridge the gap, as lead pollution is not halted by the country borders. The lead market has undergone major changes, so that great attention is devoted to its recovery and recycling. The technological advances in the lead/acid accumulators field have made lead recovery easier and safer for the environment. At the same time, the lead metallurgy has become environmentally friendly as well. Lead is a material with excellent electrochemical properties. As long as its toxicity is kept under control, and this is entirely possible, lead will be useful and used for many years to come.
This Page Intentionally Left Blank
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
RECYCLING
263
THE LITHIUM BATTERY
D a v i d G. Miller a and Bill M c L a u g h l i n b
a Toxco Inc., 3200 E. Frontera, Anaheim, CA 92806, U.S.A. b Solid Team Inc., 148 Limestone, Caremont, CA 91711, U.S.A.
INTRODUCTION Prior to discussing the practicalities of recycling lithium batteries, it is necessary to first provide a background illustrating the types and characteristics of lithium batteries. Following the background section, this chapter will focus on: 9 9 9 9 9 9
The hazards and safety aspects of recycling lithium systems The environmental concerns of lithium recycling Sorting, packaging, and transporting the batteries for recycling Components of the batteries with regard to recycling Current recycling techniques Typical chemical analyses
BACKGROUND
The never-ending search for the most efficient battery (lightest weight, highest energy) has gone on since the batteries were initially developed. The LeClanche cell, lead acid and carbon zinc batteries sustained the portable electric world until the latter part of the 20 th century. During this period the technology base of electronics began drastically expanding due to breakthroughs in microelectronics, software, digital systems, communications technology, and electric transportation. It seems that each year brings us the conveni~ence of some new device that is battery powered. In the past 20 years the desire for a better battery has turned into a necessity. In the past 40 years this quest for the perfect battery has had amazing results. The development and refinement of many battery types such as the alkaline, silver zinc,
264 lithium primary, nickel metal hydride, and lithium secondary systems has made tremendous progress. In addition to consumer types, many other systems are also evidence of intensified battery development efforts. These include, but are certainly not limited to, nickel hydrogen, magnesium silver chloride, zinc air, and several types of lithium and calcium based thermal systems, only to name a few.
This search however, is limited by certain restrictions. Among these restrictions, are the fundamental laws of physics and chemistry. One such rule is that each element (or compound) can only achieve its well defined maximum, positive or negative, electrical potential. Lithium and sodium, are the two lightest metals and also have the
265 highest electrochemical potentials at 3.04 and 2.71V, respectively. This makes both appear to be great candidates as an anode material. Under this premise, much interest and emphasis was placed on the development and design of some of the earlier sodium sulfur batteries in military applications and electric vehicles. The sodium and sulfur couple was, in fact, very good but, in a practical battery, very poor. The downfall of the sodium based battery was the high heat generated (and necessary) for normal operation. The battery case breached in many situations releasing molten sodium and resulting in a flaming mass of burning metal. In a nutshell, sodium was found to be too reactive for any battery purpose other than very specialized low vibration, remote military applications. Throwing out sodium as the perfect anode, lithium is the next obvious choice. Thus the lithium generation of batteries was born. The military was in many ways the test bed for this high-energy lightweight electrical system. In primary (nonrechargeable) systems the lithium anode was tried with many cathodes including thionyl chloride, sulfur dioxide, manganese dioxide, carbon monofluoride, sulfuryl chloride, iron disulfide, as well as many that never made it into practical applications. Some of these proved successful and are still used today, many proved to be failures for one reason or another and development ceased. Along with the benefits of the light lithium metal come several disadvantages. One of the inescapable characteristics of elemental lithium is that it will react with air or water exothermically. The batteries also were found to react violently when heated too much, when charged, when pierced, when over discharged, or when short-circuited. The contents were sometimes violently reactive in air and water and generated highly flammable hydrogen gas. It was also found that the reason the lithium primaries could not be charged was based on the plating characteristics of the lithium metal. Indeed, it does not plate evenly and begins to form tiny spikes or dendrites. As the charge is continued, these dendrites can grow long enough to pierce the separator material causing a direct internal short. This pinpoint short is believed to create a tiny area of molten lithium which quickly spreads throughout the anode surface. There is a thermal runaway followed by venting (the battery over heats and ejects the inner cell contents, sometimes violently). This physical characteristic seemed to be an impasse for the development of a rechargeable lithium battery system. For over thirty years lithium primary batteries gained consumer and industrial awareness. They became well known for their performance in very diverse military
266 applications. They gained a reputation for their long shelf life, constant voltage, wide operating temperature range, and low self-discharge characteristics. They provided the highest voltages for the longest duration at half of the weight of many other conventional systems. Unfortunately, these earlier primary batteries (especially the liquid cathode cells) also became known for their reactivity and obvious safety concerns. During the 90's came one of the biggest breakthroughs in rechargeable batteries since the development of the Nickel Cadmium: lithium ion batteries, with liquid or polymeric electrolytes, were developed. These lithium rechargeable batteries operate on the premise that the electrical potential of lithium metal is approached, but lithium metal is not present. Indeed, Li § from one lithium compound in the anode is transferred to another lithium compound at specific sites on the cathode during discharge. The reverse occurs during charge but the adverse plating of the lithium metal does not occur because the lithium ion is not allowed to form lithium metal. There is only approximately 0.1 V difference between the fully charged battery voltage and the voltage necessary to plate lithium metal. If charging of the battery is continued beyond the fully charged voltage, Li § begin to plate on the surface of the anode in metallic form and can result in venting similar to primary lithium batteries. It is for this reason that successful lithium rechargeable systems have charge control circuitry. Lithium batteries can be categorized into many types. Several of the most common types are listed below. This is not a complete list nor is it meant to be. Soluble Cathode:
Lithium/Thionyl Chloride Lithium/SulfurDioxide Lithium/Sulfuryl Chloride
Solid Cathode:
Lithium/Manganese Dioxide Lithium/Iron Disulfide Lithium/Carbon Monofluoride Lithium/Iodide
Thermals:
Lithium/Iron Disulfide
Lithium Rechargeable:
Carbon/LithiumCobalt Oxide
267 Carbon/LithiumManganese Oxide Carbon/LithiumNickel Cobalt Oxide Lithium Metal/Polymer Each type is unique in electrical and chemical characteristics. Each type also has special recycling techniques that must be considered. By over looking a difference in chemical composition, size, or reactivity, tragic environmental and safety concerns can be quickly realized.
It is also necessary to understand the battery types to
maximize an efficient and cost effective commercial business. Lithium batteries are not all the same, they are not an inert waste even if lithium is not in elemental form, and they require special packaging, storage, handling, processing, and personnel training.
THE
HAZARDS
AND
SAFETY ASPECTS
OF
RECYCLING
LITHIUM
BATTERIES As seen in the previous section there are numerous types of lithium batteries. In this section, we shall look at the generic hazards of primary (with liquid or solid cathode) and rechargeable batteries. There is much controversy over the reactivity of several individual chemistry types. It is the authors opinion that there are inherent hazards associated with any battery type or energy source and in most situations the hazards and size are directly related. In a similar scenario, lithium batteries in general cannot be categorized into being more or less hazardous than any other chemistry without knowing the exact type and size of the systems to be compared. The hazards of any battery system increase with size (as mentioned above), but in contrast, depending on the type, a smaller lithium system may be much more reactive than a larger lithium system of a different type.
Hazards of Primary Batteries In the case of the primary lithium systems, the hazards for the most part involve the safe processing and management of the elemental lithium and associated hydrogen gas. Eliminating the random very violent reactions is paramount when considering the safe processing of the batteries for recycling. Once lithium and hydrogen are controlled, the components within the battery can be exposed, separated, neutralized, reprocessed, and
268 separated again or re-manufactured into marketable materials. Primary lithium batteries exhibit the following hazards.
1) Because the reaction of lithium with water quickly generates hydrogen and heat, and because a lithium battery can spark if shorted, there is extreme risk for fire, flames, and violent deflagration. Violent deflagration simply means that the destructive pressure wave generated when a battery vents has a slight rise-time when plotted versus time. A pressure wave from an explosion, on the other hand, has zero rise-time. It should be noted that to the common observer, under abusive circumstances, lithium primary batteries may certainly look like explosive. 2) Soluble-cathode lithium primary batteries most times contain very toxic cathodes and flammable solvents. These types of batteries are seldom seen outside of the military in sizes larger than a button/coin cell. They are common in some heavy industrial or remote processes including oil-drilling operations. many military forces throughout the world.
They are extremely common in
269 3) Any lithium primary battery under the right (or wrong) circumstances can vent fire and flames similar to a torch. 4) The hazards of a lithium primary system increase by magnitudes as the size of the battery increases.
Large lithium primary batteries or cells of any type can be very
dangerous if not handled properly.
Hazards of Secondary Batteries Recycling lithium rechargeable battery systems does not involve elemental lithium under normal conditions. It is the authors belief that a fully charged large nickel metal-hydride battery has the potential to be much more reactive than a comparably sized lithium secondary. The metal-hydride battery worst-case hazards include the possibility of very high hydrogen concentrations within the battery case. In certain situations this could result in a violent hydrogen reaction (this violent reaction, by the way, would not be considered deflagration but instead is an actual explosion). Because there is no elemental lithium, many of the hazards of processing lithium ion systems are similar to other non-lithium battery systems. There are also new hazards and, as in the case of the primary lithium batteries, each type must be evaluated. The lithium ion rechargeable systems are much less reactive than lithium primary systems for several reasons: 1) There is no elemental lithium (under normal use scenarios), thus there is very little hydrogen generated. There is the possibility of elemental lithium being produced if the charge control circuitry has failed. This possibility cannot be overlooked in the case of a commercial recycling facility. 2) The electrolytes are less reactive than most soluble-cathode primary batteries. Sulfur dioxide, thionyl chloride and sulfuril chloride are extremely toxic and quickly fume when exposed to moisture (forming very acidic mists). 3) There is very little free electrolyte in lithium secondary systems, thus reducing the possibility of spilling acidic liquids. The hazards of the lithium secondary systems are described below and must be considered in any recycling process.
270 1) The non-aqueous electrolyte is primarily composed of flammable organic solvents. 2) Large heavy batteries can consist of many cells with high cumulative voltages. This naturally increases the risks of electric shock and crushing injuries. 3) The battery electrolyte is toxic. 4) The presence of elemental lithium can sometimes occur if the charge control circuitry fails. Hazards Considerations
Lithium batteries when new or fully charged are capable of possessing large amounts of electrical energy (as do many types of batteries).
When received at a
recycling facility, most of this energy should be dissipated since the majority of batteries sent for recycling should be depleted. A commercial recycling facility cannot count on this being the situation in all cases. Consumers and industry alike mix new and used batteries in many applications. They change the batteries of several systems (i.e. radios, flashlights etc.) even though only one actually needs new batteries or they replace one or two cells instead of replacing all of the cells from a system. As a result, batteries received for processing vary in depths of discharge from fully depleted to fully charged. Multi-cell batteries should always be treated as fully charged to avoid serious injury. This electrical energy can also (and will eventually) create a spark. Sparking can occur under abusive circumstances such as terminal-to-terminal shorting or internal shorting due to piercing or crushing the case. In the presence of a spark the electrolyte, packaging material and other combustible material will cause a fire. Some organic electrolytes have a low vapor pressure and will quickly evaporate into the air. The organic vapors must be managed to reduce the risk of personnel exposure as well as to prevent the formation of extremely flammable environments. In a similar scenario, there is no sorting equipment available that can distinguish between the various chemistries of lithium batteries. Consumer collection or recycling facility efforts many times depends on manually sorting the various types of batteries. Batteries are shipped with the wrong shipping or safety documents and may even be mistaken for other types of batteries all together. The point is that a recycling facility must be prepared for the worst case scenario when it is least expected. A facility must put a high priority on screening, quality control and safety.
271 Worker and personnel safety should always be considered in a recycling environment.
Battery safety consists of many common sense concepts as well as
several that are not common sense. 1) Wear eye protection. 2) Wear safety shoes. 3) Wear long sleeves when working with neutralization chemicals or battery electrolytes. 4) Use chemical resistant gloves, apron, and face shield when working with the electrolyte or vented batteries. 5) When working with a large battery disconnect the cells. 6) Do not wear metal rings, watches, or necklaces that may come in contact with the electrical terminals of the batteries. 7) If cutting electrical wiring, cut one wire at a time to prevent shorting the battery. Use care when disconnecting cells not to short-circuit the terminals with wrenches or other metal objects. The cell cases in many situations are one side of the electrical circuit. With this in mind, never remove the protective plastic cell coating. 8) Remove all non-essential combustible material from the processing area. Remember that secondary fires cause most damage resulting from a lithium battery fire. 9) Always work in pairs or keep in contact with other workers via intercom. 10) Practice fire response in accordance with an approved response plan. 11) Practice spill response in accordance with an approved response plan. 12) Make sure fire extinguishers are accessible, clearly marked, and are the correct class for the types of fires anticipated. Graphite powder based extinguishers are the correct class for lithium primaries and can also be used for lithium ion. Copper fire extinguishers should not be used for soluble-cathode lithium primary batteries. Make sure personnel are familiar with extinguisher locations. 13) Supplied air or respirators with organic filters (for lithium secondary batteries), and acid filters (for lithium primaries), should be readily available if exposed to battery electrolytes. Respirators are not recommended for long term exposure or exposure to unknown concentrations of electrolytes. 14) Always have a copy of the battery Material Safety Data Sheet (MSDS) on file and available. 15) When disassembling a battery into cells, always refer to an electrical schematic if at all possible.
272 16) In most situations it is best to store the batteries in a sprinkler-controlled area. The batteries can and will start the fire but only vent reactive materials for a brief period. The chance of water actually coming in contact with elemental lithium is very remote. The water will cool most batteries in close proximity to the fire and also will prevent secondary fires as a result of the battery fire. Water should not be used on very large lithium batteries (above 1000 Ah per cell) but these batteries comprise much less than 1% of the lithium battery population and are only used in military and government applications.
ENVIRONMENTAL CONCERNS OF RECYCLING LITHIUM BATTERIES All batteries should be recycled. Lithium batteries are no exception. Even when discharged, the batteries contain some form of lithium, organic solvents, and other chemicals most of which are toxic. When not fully discharged, the batteries have the potential to start fires. Aside from the known environmental concerns of today, it is not unlikely that in the future new environmental requirements or concerns may evolve from the disposal of batteries. In one eastern block country there is a huge problem with lead acid batteries contaminating ground water. One middle eastern country had a landfill f'tre that burned out of control for many days due to lithium batteries. In North America several lithium-recycling facilities have been shut down for environmental reasons. The only sure solution is appropriate recycling. Everything in the battery when new is still contained in it when completely discharged. Incineration, pyrometallurgical and hydrolysis methods eliminate reactivity but in many situations ultimately generate a hazardous waste. This may be wastewater, sludge, bag house waste, or ash. Prior to the processing of any lithium battery for recycling, the battery's material safety data sheet should be reviewed, and, if necessary, a complete analysis should be performed to determine the waste products. Components and chemicals are unique to each manufacturer and not each type of lithium battery. Many are similar but none are identical. Compounds that can cause serious concern if overlooked include chrome, arsenic, fluorine, mercury, organic solvents, asbestos, lithium, and others. At the end of this chapter are two typical battery analyses performed by Toxco Inc., exemplifying the
273 in-depth planning which must occur prior to receiving batteries for recycling. A similar analysis of the anticipated reactions has been developed for each lithium battery type.
So, if one is trying to select a lithium battery recycling facility, what does he look for to make sure the facility is in compliance with environmental requirements? It should have: the required approvals/permits from the designated authority; air discharge permits (if there is any form of air emission), and water discharge permits (if there is any effluent being released). If a recycler states that a facility permit is not necessary he should be able to provide proof of such, in writing, from the competent environmental authority. If one plans on processing larger volumes or extremely hazardous systems the best method of evaluation is a site visit to review the facility and environmental permits. A typical visual audit should include: 1) A review of environmental approvals and permits. 2) 3) 4) 5) 6) 7)
An inspection of the general cleanliness and housekeeping of the facility. A review of the receiving log and hazardous waste manifest log (if applicable), A review of personnel training and qualifications. A review of emergency accident/incident plans. A review of the background and facility history. A review of the corporate structure.
274 SORTING, PACKAGING, STORAGE, AND TRANSPORTING OF LITHIUM BATTERIES FOR RECYCLING Sorting, packaging, storage, and transporting of lithium batteries is discussed in detail since the success of all battery waste management facilities can be quickly affected by these practices.
These processes seem trivial to the actual recycling
methodologies but they are not. The liabilities, safety concerns, and physical damage can be very great if certain steps are not strictly adhered to. authors
opinions and interpretations.
The following are the
Governmental requirements
should be
investigated for the packaging and transportation in your area for your specific needs. There is no automatic mechanism that can sort the various types of lithium batteries. There are expensive automated systems that can sort lithium from nickel, alkaline, etc.
As a result, lithium types must be either sorted by the user or at the
processing facility. This is usually a very tedious and time-consuming process. This process is necessary since some lithium systems can and will contaminate processes. Several types and sizes of lithium batteries and other also have the potential to react violently. If not properly sorted, facilities, personnel, and equipment can be placed at high risk. Improper sorting can be extremely costly at a minimum. Packaging is probably the most overlooked cause of fire or incident. The batteries must be packaged according to strict requirements. The cells or terminals must be insulated with a nonconductive material to prevent short-circuiting against each other or against the sides of metal packaging. The batteries are then placed into an approved metal drum, wooden box, fiberboard box or other approved packaging group II container. The batteries must also be suitably cushioned to reduce vibration and shock during transport. The cushioning recommended is absorbent vermiculite. The inside of the packaging should be lined with a heavy plastic/polypropylene liner. The outside of the package should be labeled with a "Miscellaneous" Class 9 label. Leaking or vented cells must be packaged separately to prevent spills. The transport of lithium batteries varies from country to country.
In most
countries the batteries must be shipped as a hazardous waste UN3091. Only transport companies approved and permitted are allowed to transport hazardous waste and the waste must be labeled and manifested as hazardous waste.
There are exceptions
depending on the type of battery and the quantity of lithium contained within the
275 battery.
In the US several types of common household have been classified as
Universal Waste.
The Universal Waste rule allows the batteries to be shipped via
common carrier using a standard bill of lading. With the development of the lithium ion battery the transport rules are being modified or at least reviewed.
The current
argument is that lithium ion batteries do not have the same characteristics of reactivity
as the lithium primaries of earlier years. Authors note: It is the belief of the authors that the secondary lithium batteries should have been named "light metal" vs. "lithium" rechargeable. They have been scrutinized regarding safety when in fact they do not exhibit the same violent properties of their primary lithium cousins. As the newer lithium rechargeable batteries are evaluated and worst case scenarios are reviewed this fact will be proven and incorporated into transport requirements (hopefully soon). Requirements for the transport between countries involves the import and export authorizations of the environmental agencies of the respective countries involved. The storage requirements for lithium batteries are very similar to those of other batteries. They should be kept out of direct sunlight or high heat. They should be kept covered and clearly marked. In a recycling environment safeguards must be taken to reduce the risk of fire. All combustible material that is not essential should be removed from the area. Batteries should not be stored near explosives, flammable liquids or other non-compatible materials. The storage area should be made of metal or concrete
276 and all materials in the storage area such as insulation, roofing etc. should be reviewed and replaced with a non-flammable substitute. For many years the storage of lithium batteries was considered to be the same as for lithium metal. Sprinkler-type water fire suppression systems were not recommended.
Through experience it is known that
although there is lithium metal in many batteries, this does not cause the most fire damage. In most cases it is the combustible packaging or building materials that cause the majority of battery-related fire damage. For this reason it is recommended that the storage (and processing area) be controlled with sprinklers. Most batteries are small and vent quickly. They also are contained in metal outer battery eases. The reaction from water with a small amount of lithium is considered negligible compared to secondary fire damage. The water will eliminate secondary fires in storage and will act to cool the cases of other batteries within the immediate area. An example of the ideal storage area (used by Toxco Inc as well as many facets of the military) is seen below. This structure is made completely of poured concrete and has an earthen covered roof. For extremely large volumes of batteries another good idea is to store batteries in several such areas vs. storing in one large area. This prevents catastrophic incidents. The areas should also be away from processing equipment and located in a remote site away from personnel.
277 LITHIUM BATTERY RECYCLING TECHNOLOGIES In the recent past most lithium batteries were either put into a landfill or incinerated. Many of the larger lithium primary systems had no known method of disposal, much less recycling. The older large primary lithium batteries were, many times, so reactive that open detonation was used as an effective disposal method. The recycling technologies are only now being fully developed.
The
marketability of the components and the labor dollars invested to process the batteries are the driving considerations. Many research oriented agencies have proposed recycling methodologies which consider the battery chemicals as simply chemicals. Usually the battery characteristics are either overlooked completely or given inadequate planning. The neutralization of chemicals is the primary focus and either economics or safety is limited (at best). For these reasons many lithium battery recycling operations have started but most could not sustain either economic or physical losses. Some of the secondary lithium cells produced today contain cobalt compounds. Cobalt is a valuable metal openly traded for $10-$15 per pound on the open market. At this price, cobalt recovery is the primary goal of several recycling facilities that only accept lithium ion batteries. The authors fear that as other cheaper materials are found, many of these types of facilities may lose their economic justification. Currently, there is only one company in the world that has a long history of recycling all types and sizes of lithium batteries. There are two common types of lithium battery recycling. One type involves processing smaller primary lithium and lithium ion cells in an existing or modified pyrometallurgical processes.
Batteries are fed into an electric arc furnace or metal
smelting type operation. A facility of this type may accept many types of metal wastes and simply blend in batteries. In a pyrometallurgical process electrolytes, paper, plastics, and most other non metal components are burned off and the combustion products are captured in fume scrubbers, bag houses, and other pollution control devices. The primary goal of the pyrometallurgical recycling facility is the recovery of cobalt, ferrous, and some non-ferrous metals. The final product will usually be an ingot containing a mixture of metals. This ingot, free of many battery impurities, is usually sold to downstream secondary metal smelters who specialize in the refining and separation of unique metals. The advantages of a pyrometallurgical process are:
278 1) It is very economical especially when batteries are blended with other waste streams. Recycling costs are similar to incineration costs. 2) Flammable electrolytes pose no threat and may actually add to the efficiency of the process by supplementing the fuel source. 3) Some marketable metal, cobalt, and/or electricity are usually gained from the process. The disadvantages of this type of facility include: 1) The process produces large volumes of ash and air emissions similar to any large smelting operation. 2) The process operates only with the input of large amounts of fuel or electricity. 3) Items not recycled include aluminum (which will be oxidized), lithium, organic electrolytes, carbon, paper, and plastics. 4) Some of the waste products from the process must be disposed of as hazardous waste. 5) The process is not suitable for many primary systems due to the corrosive characteristics of the electrolyte/cathode as well as the reactivity of the battery. Facilities that do not fall into the pyrometallurgical category involve wet chemistry processes. Only two such processes are known and only one has processed high volumes of all types of lithium batteries. These processes generally produce cleaner recycled products, less waste from the process, and are dedicated strictly to processing lithium batteries. Advantages of this type of process are (these advantages have been verified only for the Toxco Inc process since little is known about a developing european wet chemistry process): 1) Recycling of more materials (lithium, aluminum, plastics, and electrolyte solutions) is possible since combustion of the battery is not part of the process. 2) There are negligible air emissions from the process. 3) There is no hazardous waste generated from the process. 4) The process can be used for all types and sizes of lithium batteries. The disadvantages to this process are: 1) Large volumes of chemicals must be handled by properly trained personnel.
279 2) Special batch processing is necessary for some types of batteries or other lithium wastes.
THE TOXCO'S B A C K G R O U N D AND PROCESSING M E T H O D
Toxco, a Southern California environmental firm, developed the most successful lithium recycling processing technique for all lithium batteries regardless of size or type. The process was developed and brought to commercial use in 1992 to meet the need for lithium battery recycling in military systems. It has been strongly improved over the years and has resulted in many U.S. patents. The essence of the processes is the lowering of the reactivity by reducing the temperature of the batteries. Typical chemical reaction rates are halved for every 10~ C (17 ~
drop in temperature. So lowering the batteries to 15~ C reduces the reactivity in
half. Further lowering to 5 ~
reduces the reactivity to 88of its original reactivity.
Placing the batteries in liquid argon or liquid nitrogen reduces the reactivity to less than 1/250,000th of their room temperature reactivity. At these temperatures the batteries are close to inert and can be safely handled regardless of their specific chemistry. Once frozen the batteries are mechanically reduced in size either by shearing, cutting, or shredding. At this point the battery materials are basically divided into three paths: the soluble components including virtually all the lithium possible pass into the bath; the insoluble constituents float, sink, or remain in suspension. Those constituents that sink are primarily recoverable metals. Those that float or remain in suspension are largely waste such as fiberglass, paper, carbon, etc. with no residual value. The dissolved material is then processed through a series of wet chemistry baths and filters to yield lithium carbonate which is a basic building block compound for the lithium industry. Cobalt is recovered in a similar manner and is sold with the lithium carbonate and scrap metal on the open market. The overall process provides an effective technique for recycling lithium batteries. As time passes, if the materials within the batteries can be standardized, there may be opportunities for an even greater percentage of recyclable materials possibly to include the plastic casing or the electrolyte. It should be noted that recovering a useable form of energy from the electrolyte is currently very optimistic. Recovering battery grade electrolyte is currently considered neither cost effective nor efficient. The objectives of the Toxco process were to:
280 1) Recycle all types of spent lithium batteries regardless of size; 2) Recover marketable lithium and other materials such as nickel, case metals (both ferrous and non ferrous), cobalt, and other valuable components in the batteries; 3) Provide an environmentally sound and legal recycling method thus protecting future generations; 4) Provide a safe disposition for the batteries; and, 5) Generate positive revenue for the company that would sustain growth and continued operation. These requirements have all been met. When the company began, acquiring the necessary environmental approvals and permits for a site using a brand new method to recycle a potentially explosive material was quite a challenge. After failing several times to obtain permits in 20 different U.S. states in 1992, Toxco obtained a temporary permit from the Province of British Columbia in Canada. This initial permit was conditional on the success of the methodology. Obviously, the process was a success and the permit was soon made permanent. The U.S. EnvironmentalProtection Agency and Department of Defense, the Canadian Ministry of the Environment, and similar groups around the world currently approve of the facility. There is no hazardous waste generated when lithium batteries are recycled at Toxco Inc. There is no municipal sewer system in the processing area and air emissions are collected via a direct-capture-system over each of the reaction areas. These fumes are processed through three air filters connected in series; the first is a wet bed fume scrubber which removes particulate material, the second is a traveling bed filter to further remove particulate material, and the third treats the emissions chemically. Each year Toxco is required to hire an outside environmental audit firm to test the emissions for conformance with their permit. The 1999 results are presented in Table 1. As one can see the emissions are quite minor in comparison to the allowable limits. The original Toxco facility near Trail, British Columbia began as a 33,000 square foot warehouse on 11 acres of land. Only 15,000 square feet was used as battery processing and the rest remained storage space. This facility has since grown to over 40,000 square feet of processing area dedicated to lithium battery recycling. A second Toxco facility has also been set up in Baltimore (Ohio) and a third is planned in the near future.
281
282
Table 1: Average 1999 Toxco Emissions Data Constituent
Allowable Limits
Li/SO2
Li/SOC12
Li/Cobaltite
MK-50
mg/m 3
Batteries
Batteries
Batteries
Torpedo
50
10.1
Boilers Particulate FI*
1.59
Li+ + e MnIVO2 + Li ++ e _ m > (Li+)MnInO2
Total cell reaction:
Li + MnWOz ~-----> (Li+)Mnrnoz
Anode reaction:
2.2. Recycling Process During shredding, there may be some fumes formed if lithium metal remaining in the cells is ignited. These will be lithium oxide fumes. Some fine particulates (dust) may be carried in the ventilation stream. However, the components of the cells are nonvolatile solids or low-volatile liquids and are not expected to produce significant emissions during shredding. The following reactions are likely to occur when the batteries are shredded and immersed in an alkaline water bath. Un-reacted lithium metal will react with the water,
fw
2Li + 2(6.94)
2H20--=> 2(18.0)
2LiOH + 2(23.94)
H2 2.0
13.88
36.0
47.88
2.0
289 The amount of hydrogen produced will depend on the state of discharge of the battery. The hydrogen formed will be ignited by lithium burning on the surface of the treatment solution to form water. MnO2 is insoluble in caustic solution and will precipitate. The discharge product Li MnO2 will react in the alkaline bath to form lithium hydroxide and manganic oxyhydroxide: 2LiMnO2 2(93.87) 187.74
+
2H20 _ m > 2LiOH + 2(18.0) 2(23.94) 36.0 47.88
2Mn(OH)O 2(87.94) 175.88
The quantity of LiMn02 present will be governed by the degree of discharge of the battery. Mn(OH)O is insoluble in water and is stable to disproportionation. The same products will be formed in the reaction bath whether the batteries are charged or discharged except for the relative proportions of MnO2 and Mn(OH)O. The Mn(OH)O will only be formed from discharged batteries. Propylene carbonate will hydrolyze in alkaline solution to propylene glycol and lithium carbonate: C2H6CO3 +
2LiOH ~ >
C3H6(OH)2
102.09 102.09
2(23.94) 47.88
76.11 76.11
+
Li,CO3
73.89 73.89
The propylene glycol is totally miscible with water. The lithium carbonate is insoluble and will precipitate with other lithium salts. 1,2-dimethoxyethane is soluble in water but is essentially non-reactive. As the concentration of the 1,2-dimethoxyethane builds up in the reaction tank solution, some may start to volatize. However, it is expected that any that does volatize will be ignited by the lithium burning on the surface. The combustion products will be carbon dioxide
290 and water. The carbon dioxide will be absorbed in the caustic scrubber solution to form lithium carbonate which will precipitate with other lithium salts. 2C2H4(OCH3)2 + 1102 ~ >
8CO2 + 10H20
Lithium trifluoromethane sulphonate is a very stable and soluble salt. It will dissolve in the reaction tank solution until its solubility limit is reached, then precipitate with the other lithium salts. 2.3. Air Emissions The shredding and treatment of Li/MnO2 batteries will result in minimal air emissions. Some Li20 may form from metallic lithium igniting on the surface of the reaction tank solution or in the shredder. Some MnO2 may be carried in the exhaust stream as a dust. pressure.
Propylene carbonate is a high boiling liquid with a low vapour
Any vapour that does form will be readily absorbed in the air emission
scrubbers. 1,2-dimethoxythane is a moderately volatile liquid. Any vapour that does form will be captured in the scrubbers and retumed to the reaction tank.
Any that
volatilizes from the reaction tank will be ignited along with the hydrogen given off from the lithium reaction. It is expected that only minor quantities of sub-micron sized fume will pass through the air emission scrubbers. No gases are expected.
2.4. Biological Effects The components and reaction by-products of Li/MnOz batteries have generally low toxicities. 9
Lithium metal is a hazard because of its violent reaction with water. No
toxicological data is available. Exposure can cause severe bum. 9
Lithium oxide (LizO) is corrosive. Exposure or inhalation causes severe
irritation or bums. No toxicological data is available.
291 9 Lithium triofluoromethane sulphonate has low toxicity but may cause mild skin or upper respiratory irritation. 9
Manganese dioxide and manganic oxyhydroxide have low toxicity but may
cause respiratory irritation. 9
1,2-dimethoxythane has low toxicity but may cause dizziness, difficult
breathing or nausea if handled. Skin contact may cause irritation. Propylene carbonate is non-toxic but may cause irritation with prolonged contact. 9
Propylene glycol is non-toxic and has been used to replace glycerol in food
products and cosmetics. Normal safe-handling procedures should prevent any risk to workers dealing with the solids or solutions. Air emissions will be controlled through the ventilation system. No environmental risks are expected.
CONCLUSION Lithium batteries have developed over the past 30 years to become one of the most promising new battery systems. Primary and secondary lithium batteries have gained widespread use in communications, portable tools, military devices, and industry. The next five to ten years will continue to show heavy lithium battery growth in standard uses as well as development into new applications such as electric and hybrid electric vehicles. Although lithium batteries have been shown to be safe in many applications, there are many conditions that will increase the hazards.
These hazards can be
overcome during recycling by any commercial facility through diligent continuous review of handling and processing. The successful facility must not allow recycling, storage, handling, and transportation procedures to become routine. These procedures must be continually revised and checked to verify accuracy and efficiency.
Once a
recycling facility considers their processes as perfect and without flaw, an accident or incident becomes possible.
292 Each type of lithium battery requires slightly different processing/handling. The specific reasons for differing processes may be due to the environmental concems of the materials within the batteries, the size of the batteries, the reactivity of the batteries, safety concerns, differing states of charge of the batteries, and/or different materials to be recovered. An analysis of each battery type should be performed and the results should be reviewed for chemical compatibility of the process, flammability, toxicity, reactivity, safety, and for environmental concerns. The recycling of lithium batteries regardless of size or chemistry is a complicated process. There have been many incidents involving these high-energy batteries and the simplest most obscure aspects of the procedure usually cause these incidents. Toxco Inc., to date, is one of the oldest and most successful lithium battery recycling companies in the world. Although many companies recycle some types or sizes of lithium batteries recovering one or two materials from the battery, Toxco Inc.
293 has the only process in the world that recovers case metals, lithium, and cobalt (if present) from any type or size of primary or secondary lithium battery.
Recycling
lithium and all other batteries is quickly becoming a necessity. As the natural resources of the Earth become scarcer, reutilization of materials will be required. As landfills are used and space becomes limited conservation of this space is required.
As ground
water, soil, and the air become more contaminated alternatives to landfills and incinerators must be developed.
Our sons/daughters and their sons/daughters will
appreciate the progress our generation made to overcome recycling obstacles in an effort to safeguard their future well being.
This Page Intentionally Left Blank
Used Battery Collection and Recycling G. Pistoia, J.-P. Wiaux and S.P. Wolsky (Editors) 9 2001 Elsevier Science B.V. All rights reserved.
RECYCLING
OF ELECTRIC
295
VEHICLE BATTERIES
Rudolph G. Jungst Lithium Battery R&D Department, Sandia National Laboratories, Albuquerque, NM, 87185-0613, U.S.A.
INTRODUCTION Electric vehicles (EVs) first appeared in the late 19th century at about the same time that internal combustion (IC) engine-powered vehicles were introduced. Electric motor and steam technologies were actually more advanced and more reliable than the early gasoline engine [1 ]. William Morrison of Des Moines, Iowa, built the first successful electric car produced in America in 1890 [2], and by 1900, 38 percent of U.S. automobiles were electric. Almost 34,000 electric cars were registered in the U.S. in 1912, the year of their peak acceptance [3]. Quiet operation, reliability, and easy starting and operation were their major selling points. Nevertheless, the limited range and speed of electfics combined with the lower purchase price and low fuel cost for cars powered by gasoline led to a rapid decline in use of electric cars, particularly as the IC engine was improved. By the 1930s, gasoline-powered vehicles dominated the market. With the oil crisis of the 1970s, interest in altemative fuels for vehicles, including electricity, experienced resurgence and serious development efforts resumed. However, these efforts were difficult to sustain during a period of fluctuating oil prices, and only small numbers of EVs that were conversions of IC-powered cars were produced. In the early 1990s, regulatory requirements emerged for the first time as a major factor with the establishment of the California Zero Emission Vehicle (ZEV) initiative. The United States Advanced Battery Consortium (USABC) and more recently the Partnership for a New Generation of Vehicles (PNGV) were formed to address technical challenges to the commercialization of viable electric and hybrid electric vehicle (HEV) power sources and systems. The active participants in these groups have included the major U.S. automobile manufacturers, the U.S. Department of Energy (DOE), and the Electric Power Research Institute (EPRI). As a result of these and other efforts, small numbers of advanced, purpose-built EVs have been offered to consumers in certain areas (e.g.,
296 under manufacturer memoranda of agreement in California). The limited range of pure EVs, particularly with lead-acid batteries (the only option available at first), and their high
capital
cost
continue
to
be
the
major
impediments
to
wide-scale
commercialization. Therefore, much research has been and continues to be directed toward advanced batteries, fuel cells, and other energy storage devices (capacitors, flywheels, etc.), as well as hybrid power plant designs. Advanced batteries include those technologies that were not commercialized by about 1990 (e.g., nickel/metal hydride, lithium-ion). The U.S. DOE, as a major participant in the USABC and PNGV programs, has been working to address infrastructure barriers to the commercial acceptance of EVs since the early 1990s. As an outgrowth of a workshop held in 1991 on sodium-beta batteries [4], a Working Group was established to identify and recommend solutions to commercialization barriers in the areas of battery shipping, battery reclamation and recycling, and in-vehicle safety [5]. The Advanced Battery Readiness Ad Hoc Working Group, as it is now known, continues to provide a forum for discussion of these issues. The purpose of this chapter is to review the current state of recycling technologies for EV and HEV battery power sources. We will use the term recycling to include materials that are reclaimed for use in different products as well as the materials that are reclaimed and transformed into new batteries. A practical method for recycling batteries and other energy storage components from EVs is viewed as essential for the successful implementation of this transportation technology. Toxic materials are found in many battery technologies (e.g., lead, cadmium, nickel). Disposal of EV batteries may be allowable by regulations in some cases, but is likely to be costly and detracts from the environmental benefits of a zero-emission vehicle. The battery is a major cost component for EVs, and therefore disposal is doubly expensive, especially if the waste contains valuable materials. Recycling provides an opportunity to reduce life cycle costs through recovery of high-value materials and avoidance of the cost of hazardous waste disposal. Most developers of power sources for EVs therefore have a goal of recycling as much material as possible at the end of life. Less demanding, secondary uses for the energy storage device may extend its term of operation, or in some cases refurbishment could also be considered. Eventually, however, the battery must be processed in such a way that all the valuable and/or hazardous components and materials can be recycled.
297 E L E C T R I C VEHICLE/HYBRID ELECTRIC VEHICLE BATTERIES EVs depend entirely on the battery system for their power, while HEVs combine a battery system with some other power source (e.g., internal combustion engine, fuel cell) in order to maximize efficiency and increase range. Batteries for EVs and HEVs are much different in scale than those commonly used in portable consumer electronics such as cell phones or laptop computers. EV battery packs typically generate 300 to 350 volts, with 10 to 30 kWh of stored energy for EVs and 1 to 5 kWh for HEV applications. The power to energy ratio is 2 to 4 times greater for the HEV-battery design than that for EVs. The batteries are usually made up of multi-cell modules connected in series/parallel arrangements, although the number of individual cells, battery mass, and battery volume vary somewhat with the design and the type of battery chemistry used. Relatively few consumers would be expected to perform their own battery maintenance, and almost none could replace one of these large batteries themselves. The problem of handling is compounded by the fact that large numbers of EVs and HEVs may come into widespread use. Nominal characteristics for several recent types of EV/HEV battery packs and their associated vehicles are shown in Table 1. Originally, most of the battery packs were of the valve-regulated lead-acid (VRLA) type, which suffers from the disadvantage of a relatively low specific energy (Wh/kg). VRLA-powered vehicles therefore usually exhibit more limited range and payload capacity than those using advanced battery systems. As shown in Table 1, more than a 40% improvement in battery pack energy can be realized by substituting a nickel/metal hydride (Ni/MH) battery for VRLA in the same vehicle. This can be achieved with no increase in battery weight or volume. For most four-passenger family size EVs, the battery weighs about 500 kg and occupies a 200-L volume. HEV batteries only need to be about 10 to 20% of this size and weight because of their lower energy storage needs and the exclusive use of advanced battery chemistries. The configuration of the battery also varies widely with the vehicle design. In some instances (e.g., the EV 1 battery shown in Figure 1), the battery fits in a T-shaped tunnel within the vehicle. In other vehicles (trucks and vans), a fiat battery pack is placed beneath the floor so as not to take up so much of the internal cargo space. Typical configurations of some of the current or proposed battery packs are shown in Figures 1 through 7.
Table 1 Typical EV/HEV Battery Pack Characteristics
298
Vehicle
Battery Type
EVMEV
Pack Power (kW) 83 88 90 83 88 90
Pack Pack Pack Modules/ Calculated Total Pack Energy Voltage Capacity Pack Pack Mass (kg) (Ah) Volume (L) (kWh) (V) GM EV1 26 16.5 VRLA EV 473 205 53 312 GM EV1 546 205 26 60 312 18.7 VRLA EV GM EV1 468 193 26 77 343 26.4 NiMH EV Chevrolet S 10 473 205 26 53 312 16.5 VRLA EV Chevrolet S10 546 205 26 60 312 18.7 VRLA EV Chevrolet S 10 26 27.4 468 193 85 343 NiMH EV 18.7 Ford Ranger 870 39 60 312 VRLA EV Ford Ranger 25 28.5 Ni/MH EV 485 95 300 Chrysler Epic 27 27.5 85 324 VRLA EV Chrysler Epic 30 31.2 Ni/MH EV 62 1 93 336 Mercedes A Class 1 30 370 104 289 Na/NiC12 EV 24 Toyota Ecom 43 144 77 28 288 8.4 Ni/MH EV 24 Toyota RAV4 90 449 189 288 28.3 Ni/MH EV 95 12 32.4 Nissan Altra 360 230 94 345 Li-ion EV 4 41 Nissan Hyper-Mini Li-ion 116 77 90 120 10.8 EV 21 Toyota Prius Gen 1 Ni/MH 44 40 1.8 HEV 15 6.5 288 Toyota Prius Gen 2 NUMH 22 38 274 1.8 HEV 25 39 6.8 GM Precept 45 90 60 28 12.5 350 4.4 NiMH HEV Li-Polymer HEV 43 GM Precept 81 70 7 10.4 350 3.6 Ni/MH Honda Insight HEV 20 0.9 12 22 7 6.5 144 NilMH = nickehetal hydride, VRLA = valve-regulated lead-acid, Na/NiC12= sodium/nickel chloride, Li-ion = lithium-ion, Li polymer = lithiumpolymer
299
Fig. 2. GM Ovonic Ni/MH Battery for the Chevrolet S10 Pickup Truck.
300
Fig. 3. Ford Ranger Truck Ni/MH Battery.
Fig.4. DaimlerChrysler Epic Minivan Advanced Lead-Acid Battery.
301
Fig. 6. Nissan Altra EV Li-lon Battery Module
302
Fig.7. Second Generation Toyota Prius Ni/MH Battery Pack.
The types of batteries predominantly in use at this point are lead-acid and Ni/MH, although a few lithium-ion (Li-ion) systems are starting to appear. As the number of HEVs increases in the near term, the number of Ni/MH systems is also expected to increase. It is the standard energy storage unit in the later models of the GM EV1. Nickel/metal hydride batteries are also used in Ford Ranger and DaimlerChrysler EPIC EVs and in the Toyota and Honda HEVs. However, a niche market for lead-acid systems is likely to remain for lower cost EVs used for commuting short distances. Lithium-ion batteries are used in the Nissan Altra EV, but their use has not expanded as significantly to date as has the N i g H battery system. Although Ni/MH systems appear to offer the best prospects for near-term implementation in spite of high costs, Li-ion or lithium-polymer may eventually provide better performance with a lower battery weight. This assumes questions regarding safety issues associated with the reactivity of lithium and life expectancy issues can be resolved satisfactorily. In the long term, lithium batteries may therefore replace Ni/MH as lithium battery costs are reduced and performance improves. Safer versions of the lithium battery such as lithium-polymer are also being developed and are already available in small cells. Other battery chemistries (e.g., soditma/nickel chloride (Na/NiC12), nickel/zinc (Ni/Zn)) may be found in small numbers, but will
303 probably not be dominant factors in the market over the next 5 to 10 years. Fuel cells are another type of power source that may find increased use in alternative-fuel vehicles in the future, but will not be commercially available in automobiles for several years. Growth of the EV market is a key factor that will determine which power sources are available for recycling over the next 10 to 15 years. The onset of the anticipated exponential growth in the number of EV/HEVs on the road has proved difficult to predict, and this has made developers and recyclers reluctant to invest in establishing dedicated recycling facilities. The changing mix of power sources over time could render a dedicated recycling process obsolete before a significant increase in the number of vehicles occurs. An approach that uses an existing recycling process that is not solely dependent on the EV battery waste stream has been the primary strategy used thus far. However, these processes are not always able to reclaim all of the valuable battery materials. Projections of the number of EVs that will be sold in the U.S. vary considerably depending on the source. An EV population in the U.S. of several hundred thousand has been predicted to occur within a few years ever since the mid-1990s [6]. In 1997, one estimate for 2005 totaled 320,000 vehicles, based on ZEV-mandated programs in California and other states [7]. More recent projections, however, estimate 50,000 EVs per year starting in 2005. This lower projection reflects vehicle estimates resulting from the California Memoranda of Agreement Program, as well as a court decision precluding other states from implementing ZEV programs more restrictive than that in California. Early in the year 2000, the actual EV population in California, the state with the most active ZEV program, was 2300 [8]. The total EV population in the U.S. was about 5,000 late in the year 2000 according to the Electric Vehicle Association of the Americas. This situation may begin to change soon because the ZEV program in place in California in late 2000 requires about 22,000 EVs to be offered for sale by 2003. In addition, the commercial introduction of HEVs by Toyota and Honda could add substantially to these numbers if they become popular. Honda increased the number of Insight vehicles that would be made available for sale in the year 2000 to 6500 based on strong early demand [9]. Clearly, however, an EV population of several hundred thousand in the U.S. is still years away and more time will elapse before the batteries in those vehicles reach end-of-life. Incentives to commit resources toward development of dedicated recycling facilities will therefore likely remain low for some time.
304 GENERAL RECYCLING ISSUES, AND DRIVERS
Economics and Planning Economics is an important consideration when designing a recycling process. Some generic constraints that determine whether recycling is economically viable have been discussed [5]. These include the ability of the market to absorb the large quantity of recycled material that could result in the long term assuming that it is not recycled directly into new batteries. Market size is likely to differ for each of the specific materials that can be recovered. Price collapse or possibly an inability to sell the reclaimed products at all could be the result if a limited market is flooded with recycled material. A fundamental precept of chemical process economics (the Exclusion Principle) states that high-priced materials tend to have limited markets, while high volume materials have low unit prices [ 10]. It is therefore unrealistic to expect to enter a large size market for a particular commodity and command a high unit price. Another general expectation is that the establishment of a new, large scale recycling process dedicated to a particular advanced battery chemistry will most likely take a long time. This is due to two factors: 1) the time required to obtain operating permits from the Environmental Protection Agency (EPA) for an unfamiliar process, and 2) the fact that financing will be difficult to obtain for such a project until there is an established waste stream. In fact, a recycling process that is capable of handling a variety of waste streams is much more likely to be implemented since the EV market and the types of power sources that will be used in EVs are relatively uncertain at this point.
Partnerships Because of the necessity for innovative approaches in the recycling arena, partnerships involving waste processors have begun to emerge. For example, Toxco, Inc., a major recycler of lithium batteries world wide, has formed an alliance with Kinsbursky Brothers, Inc., the largest non-lithium battery management firm in the U.S. By joining forces, battery and vehicle manufacturers can be offered a comprehensive and efficient battery management program through a single source. Automobile and recycling companies have also formed alliances. Because of its use of the Li-ion battery in its Altra EV, Nissan reviewed future recycling capacity for spent Li-ion batteries. The company formed a partnership with Toxco after finding that a significant lithium battery recycling capacity shortfall could be anticipated. Toxco would share a percentage of its long-range processing capacity with Nissan, and also
305 provide additional capacity in Califomia as larger quantities of Nissan EVs appear on the California highways. An additional benefit derived from the Nissan-Toxco agreement is that it has provided renewed enthusiasm for a lithium recycling facility in California. In 1992, it was difficult to obtain a permit for a lithium recycling facility in California because of strict solid and hazardous waste disposal regulations. However, the current regional director of the California Department of Toxic Substances Control has visited the Toxco facility in British Columbia (BC) and met with the BC Ministry of Environment regulators [17]. As a result of that review, a lithium battery recycling facility in California is now considered feasible.
Environment, Safety, and Health Another important consideration for recycling is the toxicity and reactivity of materials. Because EV batteries are large, heavy, operate at high voltages, and frequently contain toxic, corrosive, or reactive materials, health and safety issues must be considered when handling them and may present limits on how to recycle them as well. These issues are all manageable as long as careful planning is done in advance. Most battery maintenance will be performed by trained personnel while the system is in the vehicle, and replacement batteries will most likely only be available through auto dealers or specialty shops. The control provided by the need to use trained installers and the significant cost of the battery means that virtually all batteries will be returned for recycling at end-of-life. A training package to address accident scenarios, including a video, has been prepared for emergency response personnel [11]. This kind of safety information will become more available as the number and types of EVs proliferate. Chemical hazards broadly fall into two categories: 1) physical and health hazards from exposure to these materials during battery handling and dismantlement, and 2) environmental hazards from disposal. If these materials are considered hazardous waste because they are listed by the EPA or categorized as characteristic wastes, then they can only be disposed of in specially designated landfill facilities. Characteristic wastes are classes of materials that are identified as exhibiting leachability, flammability, and corrosivity/reactivity. This adds to the cost and could justify further expenditures to reclaim or recycle these materials even if they are not inherently valuable. An assessment of the health impacts from reclamation of automotive batteries was completed for the California EPA, and a report was issued in 1999 [12]. This study compares the relative impact of recycling nine different types of EV batteries in terms
306 of cancer, toxicity, and ecotoxicological potential. The methodology is semiquantitative and was based on the protocol developed by the Office of Environmental Health Hazard Assessment, a division of the California EPA. Table 2 shows the health and environmental impact score that was developed for each battery constituent. Antimony, arsenic, cadmium, lead, and nickel are the five materials with the highest scores (i.e., the most negative impacts). A health/hazard score for each battery type was then determined by multiplying the constituent score by the estimated amount of emissions to the air and a battery life factor in terms of grams per mile of battery pack usage. The scores were then totaled for each battery type and recycling process as described in Reference 12. These health~azard scores are primarily determined by the human health impacts.
A log-scale graph of the normalized
healtl~azard scores is shown in Figure 8 for different battery types and recycling processes. Generally, the healtl~azard score is highest for batteries containing significant amounts of materials with a high health impact or that are potentially emitted in large amounts by the recycling process. The advanced battery chemistries such as Ni/MH and Li-ion appear to offer improvement over conventional battery systems because they incorporate less hazardous materials and may use hydrometallurgical rather than pyrometallurgical or smelting processes for recycling. A closer examination of hazardous waste characteristics of battery materials does reveal differences between battery chemistries. The toxicity of conventional battery materials such as lead, antimony and cadmium are well known, and therefore they are usually recovered as much as possible rather than disposing of them. Strict emission controls are required to prevent their release into the air or water. The problems with advanced battery systems in this regard are not quite so severe, but there still may be reactive, corrosive, or toxic materials present that must be dealt with during the recycling process. Both Ni/MH and Li-ion batteries do contain hazardous materials. Nickel/metal hydride battery packs, of course, contain nickel, which is a suspected carcinogen in some forms. However, the only hazardous material in a Ni/MH battery, as defined by federal regulations, is the potassium hydroxide (KOH)-based electrolyte (corrosive). The only characteristic hazard of any consequence for the electrode materials in these batteries is toxicity. The hazard level is determined by a test called the toxicity characteristic
307
Table 2. Relative Health Impact of Major Battery Components Material
Health Impact Score
Material
Health Impact Score
Arsenic
65
Fluorine
22
Cadmium
57
Zinc
21
Lead
56
Aluminum
20
Antimony
51
Carbon Black
20
Nickel
45
Vanadium
18
Cobalt
35
Tin
13
Manganese
33
Sulfuric acid
11
Phosphorus
33
Sulfur
9
Copper
31
Iron
8
Chromium
30
Zirconium
7
Lithium
25
KOH
5
Chlorine
23
Titanium
4
Sodium
23
Plastic
3
Note: A higher number indicates a greater effect.
leaching procedure (TCLP) that measures the tendency of metals to leach from the waste under conditions that could be encountered at a landfill. TCLP tests on two different types of AB2 metal hydride alloys showed that the metals in the leachate were either unregulated or below EPA standard limits (chromium) [13]. In regions such as the State of California, however, stricter regulations are in place, and the batteries would be considered hazardous waste there because of the presence of a standard for nickel (20 mg/L). European Community (EC) standards for nickel (2.0 mg/L) are also exceeded. Similar results were found in a more recent measurement where only Ni and Zn, which have no EPA standards, were found in significant concentrations in the TCLP leachate from Ni/MH batteries [14]. Lithium-ion batteries also contain hazardous materials. While lithium intercalated in carbon is somewhat less reactive than lithium metal, it still does react with water to produce lithium hydroxide (LiOH) and hydrogen (H2). Moreover, cycled Li-ion cells could contain lithium metal plated on the surface of the anode if they have been
308
Fig. 8. Normalized Health/Hazard Scores for Various Battery Types and Recycling Processes. subjected to overcharge conditions. The hazard posed by the remainder of the Li-ion battery is mainly in the toxicity area and depends on the specific battery design. The Liion chemistry is not as mature as Ni/MH and several variations of the cathode and electrolyte could be found. Metal oxide cathode materials could contain cobalt, nickel, manganese or, more rarely vanadium. Mixed metal cathodes are becoming more common. Electrolytes are composed of fairly innocuous organic carbonates and a lithium salt. TCLP testing has been done on several types of lithium batteries, and the results show that they would not be considered hazardous waste by EPA standards [14,15].
EXISTING METHODS FOR EV BATTERY RECYCLING As part of a broad assessment of the general recyclability of automotive batteries done in the mid-1990s, a report on recycling technology was prepared for the California Environmental Protection Agency Air Resources Board [ 16]. Ten different EV battery technologies were ranked based on their performance and recyclability. The battery chemistries that were included in this study are presented in Table 3. Because the recycling capacity available for some of these batteries was minimal in 1995 and the
309 market for some of the materials that would be recovered was also too small and unstable to support the recycling effort alone, a mandatory deposit of $100 to $150 per battery was suggested. This figure was believed to be large enough to ensure return of the batteries to central collection sites, but not so large as to trigger theft or a battery black market.
Table 3. Battery Chemistries Included in Recycling Technology Assessment Lead-acid (all types)
Lithium/iron disulfide
Nickel/cadmium
Lithium-ion
Nickel/iron
Lithium-polymer
Nickel/metal hydride
Zinc (zinc-air, zinc/bromine)
Sodium/sulfur Sodium/nickel chloride
performance and recycling technology. The recycling attribute categories of technology, infrastructure, market conditions, and regulatory constraints were used to rank battery technologies and the associated weighting factors assigned to each specific attribute are shown in Table 4. Each battery was scored on a scale of one to five for each recyclingrelated attribute. A score of five indicates the best performance characteristics, and a one indicates the worst performance or characteristic. A total score was calculated by multiplying the individual score for each attribute by the weighting factor for that attribute, and then summing the products. A summary of the final recycling score received by each of the batteries included in the study is presented in Table 5. The higher scores indicate better recycling characteristics.
Lead-acid batteries received a high score by virtue of being a commercial product with an established recycling infrastructure. Nickel/metal hydride and nickel/cadmium are also widely available commercially and are routinely recycled. Zinc batteries are sold in large quantities and little or no hazardous waste and pollutants are produced by processing. Most of the battery technologies farther down the list are ranked lower because the batteries are not commercial products and recycling processes are not developed any further than a bench scale. In the case of sodium/sulfur batteries, the market outlook for recovered products is unfavorable.
310 Table 4. Recycling Attributes used to Rank Battery Technologies
Recycling Attribute
Weighting Factor
Ease of battery dismantling Fraction of output that is recyclable/reusable Fraction of output as hazardous waste Scale of existing technology Size of batteries currently handled Existing recycling facilities Existing collection infrastructure Distance to recycler Market for recycled product Value of product Disposal costs Hazardous material status Toxic metals content Difficulty in permitting new or expanded facilities Effect of air emissions on permitting
Conventional Batteries 9 Lead-acid (Pb-acid)
The lead-acid battery has been the rechargeable energy storage technology of choice since the earliest development of EVs because of its widespread availability, relatively low cost, and generally user friendly characteristics. Consequently, an infrastructure for collection and recycling of these batteries already exists. In fact, recycled lead forms a significant percentage of the lead used in fabricating new batteries. Because the market for lead-acid batteries is already extremely large, even a significant penetration of the EV application by this battery chemistry is not expected to have a noticeable impact on the ability of industry to continue the present high recycling rate. A study was conducted in 1996 and confirmed this low impact of increased EV use on
311 the lead-acid battery recycling infrastructure by projecting the increased amount of recycled lead that would result [ 18]. Although most of the regulations that are currently spurring market development are viewed as encouraging advanced batteries rather than
Table 5. Summary of Scores for Battery Recycling Battery Technology
Total Score (180 Maximum)
Conventional lead-acid
153
Sealed bipolar lead-acid
153
Nickel/metal hydride
147
Nickel/cadmium
146
Zinc-air
146
Zinc/bromine
140
Lithium/iron sulfide
135
Lithium/iron disulfide
135
Lithium-ion
132
Sodium/sulfur
119
Sodium/nickel chloride
114
Aluminum-air
114"
Iron-air
112"
Lithium-polymer
101
* All attributes could not be ranked. lead-acid, lead-acid will likely have a niche role to play in coming years. The annual amount of waste expected from EV batteries in the U.S. was projected out to the year 2005 based on a set of reasonable assumptions in order to compare with the capacity for secondary lead recovery. The long-term trend in U.S. secondary lead recovery capacity is slowly upward, but the existing capacity in 1996 was taken as a conservative estimate. The following assumptions were used in arriving at this projection: 9 A total U.S. EV population of 2000 in 1994 [19] 9 EV sales of 200,000 in 2003 [20] 9 A 3-year replacement schedule for lead-acid batteries in EVs 9 Market share for lead-acid batteries decreasing from 100% in 1995 to 30% for 2000 and beyond
312 9 Improved energy density for lead-acid batteries from 30 Wh/kg in 1995 to 50 Wh/kg in 2005 9 Battery mass per EV of 500 kg in 1995 and decreasing with improved energy density 9 Battery mass is 73% lead In retrospect, most of these assumptions were good, but there were a few that were not. It now appears that EV sales in 2003 will more likely be 10 to 15% of the 200,000 predicted by the Energy Information Agency in 1996. Since a large fraction of these vehicles could well be hybrids using advanced battery technology, the constant 30% market share for lead-acid batteries beyond 2000 is probably also too high. A less important factor is the predicted decrease in battery mass per vehicle as energy density improves. Although this trend may occur at some point, it is probable that the desire for more on-board energy storage will continue unabated for at least the near term. The introduction of advanced batteries with higher energy density has not led to consistently lower weight batteries, but more otten than not the incorporation of more battery capacity. Nevertheless, the assumptions were conservative in the sense that the predictions based on them likely represent an upper limit for the impact on the lead-acid battery recycling industry. The mass of lead in scrap EV batteries is projected to increase as shown in Figure 9, reaching about 16,000 metric tons in 2005. This can be compared to Figure 10, which shows the amount of lead from battery scrap and the total amount of lead recovered from scrap in the U.S. through the year 1995 from U.S. Bureau of Mines data. Total secondary lead is nearing 1M metric tons per year. The predicted EV battery lead mass in 2005 is only about 1.5% of the secondary lead recovery capacity in 1996 and will actually be less than that in 2005 once the future growth in secondary lead recovery is included. Clearly EV battery waste will remain a very small portion of secondary lead production well beyond 2005. Nearly all of the secondary lead is recovered by thermal smelting, which does raise concerns regarding air and water pollution. Emission control devices are necessary to prevent the release of lead particulate to the environment, and in at least one case a backup battery has been installed to ensure that these emission controls continue to operate in the event of a power outage from the local electric utility [21]. However,
313
16000
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
14000 12000 .~. 10000 8000 6000 =[
4000 2000 0 1996
1997
1998
1999
2000
2001
Year
2002
2003
2004
2005
Fig. 9. Projected Mass of Lead in EV Batteries to 2005.
Sec~
1200
1000
o c
"~
800
t
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
TotalScrap
...............................................................
600
I
,I=
4OO
r:S:r::
200
..................
Year Fig. 10. Lead from Battery Scrap, Total Lead Scrap, Secondary Lead Recovery Capacity, and Lead Scrap Export in the U.S. when such a large mass of lead is processed, it is virtually impossible to prevent the release of small amounts during the processing. Nonthermal methods such as electrowinning have been investigated for secondary lead recovery and in some cases
314 have been shown to be technically feasible [22], but these methods have not been widely adopted, mainly due to high costs. More detailed information on recycling processes for lead-acid and other batteries can be found in other sections of this volume. 9 Nickel/Cadmium (Ni/Cd) Another conventional battery technology that has been considered for EVs is Ni/Cd. Although capable of somewhat better performance than lead-acid in some respects, this battery is also more costly and does not equal the performance levels possible with advanced battery systems. It is unlikely to see widespread use in EV applications in the U.S. although there are reported to be more than 10,000 EVs using Ni/Cd batteries presently on the road in Europe [23].
Because of the toxicity of cadmium, which
precludes disposal, and the value of the nickel, there are well-developed processes for recycling of Ni/Cd batteries. Most of the facilities in Europe are dedicated Ni/Cd battery recycling plants. The combined recycling capacity world wide was about 25,000 metric tons of Ni/Cd batteries per year in 1993, but this was significantly underutilized because of inefficient collection systems and low prices for nickel and cadmium. Both pyrometallurgical and hydrometallurgical methods are used to recycle cadmium from a variety of waste materials in plants in North America, Europe, and Japan [24]. Cadmium is relatively easy to separate from other materials because of its low melting point and chemical activity. Since 1995, consumer and industrial Ni/Cd battery recycling in the U.S. has been primarily done at the International Metals Reclamation Company, Inc. (INMETCO) using a process licensed from SAFT NIFE. The cadmium is distilled from the plates using a low temperature thermal process, and the material is used for new battery production. The nickel content of the battery goes into the standard INMETCO stainless steel remelt alloy production. In general, this thermal recovery process makes up the majority of the world recycling capacity. The cadmium is recovered and purified as the metal or can be converted to cadmium oxide. Hydrometallurgical recovery processes operate on a broader variety of waste products and frequently recover other metals in addition to cadmium. They generally employ dissolution by acid treatment followed by selective extraction methods such as precipitation or ion exchange to separate the products. The economics in the
315 hydrometallurgical case may depend on materials other than cadmium, which may not be the major species present. Cadmium recycling appears to be well developed and capacity is more than adequate to handle any near-term growth that could reasonably be expected due to growth in the EV market.
Advanced Batteries
9 Nickel/Metal Hydride (Ni/MH) Nickel/metal
hydride
batteries
can
be
partially
reclaimed
today
through
pyrometallurgical processing, although the focus is primarily on the nickel, chromium and iron fractions. Rare earths and other metals typically contained in the hydride alloy are not separated and form part of a slag that is eventually sold as aggregate for road construction. The principal facility of this type in the U.S. that accepts Ni/MH battery waste is operated by INMETCO. A variety of wastes from the stainless steel industry have been processed in rotary hearth and electric arc furnaces by INMETCO to produce a standard remelt alloy that can be used by stainless steel producers. Nickel/metal hydride batteries are compatible with the INMETCO process due to their high nickel and iron content. Because batteries are only a fraction of the waste stream, the amount of battery waste that is available is not important to continued operation of the process. This recycling process is thus well suited to the current period of uncertainty while EV/HEVs establish a foothold in the market. At present levels of waste generation, there is no fee levied to process Ni/MH scrap, but none of the inherent value is returned to the waste generator, either. In Europe, S.N.A.M. has developed several processes to separate and recycle AB5 hydride alloy from Ni/MH batteries [25]. One process separates 60 to 85 percent of the hydride alloy for reuse in batteries, while the remainder and other metalic components are recycled as nickel-iron scrap. Another simpler process deactivates the hydride alloy and the residue can then be sold for production of nickel or nickel-cobalt alloy. 9 Lithium-ion (Li-ion)
Recycling capabilities for lithium batteries have advanced significantly since the early 1990s. Initial methods focused mainly on deactivation and safe disposal rather than material recovery because of the prevalence and well known reactivity of lithium metal in the primary batteries that made up the bulk of the commercial product at that time
316 [26,27]. The tremendous growth in the rechargeable lithium battery market has stimulated efforts to reclaim the most valuable components of Li-ion cells such as cobalt, and progress has also been made in finding ways to reuse the lithium salts. Although EV-size Li-ion batteries have not been fielded in significant numbers, other opportunities to dispose of very large lithium primary batteries have required development of handling techniques that should also be useful for EV battery modules. For example, a four-year project to dispose of more than 4,500 large lithium batteries for the U.S. Navy and Air Force was begun by Toxco in 1998 [28]. The Li/thionyl chloride primary batteries each weigh 570 pounds, which is the same general size as an EV battery. The first commercial Li-ion battery technology was produced by Sony and they are also the only Li-ion battery manufacturer to develop their own recycling process [29]. Production of Li-ion batteries by Sony began in 1991 and a battery-recycling project began the next year in conjunction with Sumitomo Metals and Mining Co., Ltd. The Sony Li-ion cell contains a lithium cobalt dioxide (LiCoO2) cathode and cobalt comprises 15 to 20% of the battery weight. Since cobalt is a relatively expensive material compared to the other battery constituents, its recovery is the primary objective in the recycling process. Besides the cobalt, which is recovered as cobalt chloride, iron and copper are also recycled from the used Li-ion cells, but the lithium is not reclaimed in the Sony process. If the cathode is changed to another material at some point, a major impact on the recycling economies could occur. Toxco, Inc. has developed processes to recover lithium as lithium carbonate from lithium batteries and other types of lithium-containing wastes [30]. As much as 98% of the available lithium can be recovered, along with a similar fraction of the available cobalt (Co) and much of the aluminum (A1), iron (Fe), and nickel (Ni). The lithium carbonate can be returned to lithium production and Pacific Lithium, Ltd. has done this. More recently, Toxco has acquired facilities to convert the lithium carbonate back into electrolyte salts for lithium batteries. Clearly, it is feasible and profitable to recycle the cobalt cathode and lithium components of these batteries. Recycling of the more valuable constituents of Li-ion EV battery modules should follow in a straightforward manner using the processes developed on the strength of the rapidly growing market for the smaller Li-ion batteries in portable electronic devices. A preview of the handling constraints that will be posed by larger EV modules has been obtained from the work on large lithium/thionyl chloride cells [28,31]. These must be
317 sliced apart under cryogenic conditions to reduce and safely control reactivity until the lithium is deactivated.
OPTIMIZED RECYCLING PROCESSES FOR ADVANCED BATTERIES
9 Nickel/Metal Hydride (Ni/MH) Preliminary studies have been conducted on altematives to the pyrometallurgical processing of N i g H batteries. Hydrometallurgical treatment provides metal salts as products, which may offer market stability benefits in certain circumstances compared to the primary metals produced by smelting. Another advantage is that the separation and recovery of other valuable constituents such as titanium, vanadium, zirconium, and rare earths may become possible. The U.S. Bureau of Mines (USBM) conducted exploratory research on hydrometallurgical processing options for several years [32,33], concluding that these options are indeed feasible for battery scrap containing either AB2 or AB5 hydride alloys. AB2 metal hydride electrodes typically contain about 54% Ni + Co, 42% Ti + V + Zr, and 4% other elements (A1, Cr) by weight. The AB5 electrode consists of a LaNi5 type alloy on a nickel substrate. The alloy contains about 33% rare earths, 10% Co, 50% Ni, 0.12% Fe, and 6% other metals (Mn, Al). USBM evaluated several different leaching protocols and acid solutions for extraction efficiency on whole batteries, cracked batteries, and components. A two-stage leaching process was found to be particularly effective for concentrating the titanium (Ti), vanadium (V), zirconium (Zr), and chromium (Cr) species in solution. Preliminary precipitation tests to recover partially separated metals from solution were run using pH adjustment, carbonate precipitation or oxalate precipitation, although the optimum methods for producing the highest purity products were not determined. Nickel and cobalt could be recovered by electrowinning or solvent extraction as well as by precipitation techniques. Operating revenue that could be generated from chemical separation or physical/chemical separation processes for recycling Ni/MH batteries was compared to a pyrometallurgical process in a report prepared for the National Renewable Energy Laboratory (NREL), a DOE facility located in Golden, Colorado [34]. The pyrometallurgical process has similarities to the process operated by INMETCO. Revenues (or costs) were estimated for both AB2 and AB5 hydride alloy battery designs. Other general assumptions in the cost calculations were that the plant was sited in California and was processing 30,000 metric tons of EV batteries annually.
The
chemical process is based on an acid leach of the battery materials, followed by
318 precipitation of all but the nickel and cobalt, which are recovered by electrowinning. The major products recovered are nickel-iron scrap, steel scrap, polypropylene and nickel metal. In the physical/chemical separation process, the battery electrodes are physically separated prior to chemical processing and the metal hydride alloy powder is recovered and returned to hydride alloy producers. The rest of the procedure is very similar to the chemical process. For the pyrometallurgical process, all of the battery electrodes and powders are smelted to form a ferronickel product and a slag that is enriched in hydride alloy constituents. Slag from batteries containing AB2 alloy could be smelted further to produce ferrovanadium while rare earth producers may be interested in the enriched rare earth content of the slag from AB5 batteries. The only other products are steel scrap and a very low-grade ftmaace slag remaining after the smelting of the ferrovanadium product. In the most favorable case (physical separation/chemical process), the revenue from the recovered products obtained by the recycling process was predicted to be between $16.70/kWh of batteries processed for the AB5 alloy and $18.50/kWh for the AB2 alloy. This is largely because of the value of the credit assumed for the physically separated hydride alloy scrap, although the process is still predicted to generate a small amount of revenue without it. The revenue of $9.50/kWh from the chemical process is second best for the AB5 alloy, and the pyrometallurgical process comes in third at $4.15/kWh. For the AB2 alloy, the pyrometallurgical process looks better at $7.50/kWh, but the chemical process does not generate revenue at -$.50/kWh. The better cost performance of the chemical process in the case of the AB5 alloy is a result of both somewhat lower processing costs and a significantly higher product credit because of the cobalt content. Little follow-on evaluation has occurred for Ni/MH battery recycling processes since the earlier studies described above were completed in about 1994 in spite of the potential benefits that were shown [35]. Mitsui Mining and Smelting Company Limited reported one additional study in 1995 [36]. Nickel, cobalt and rare earth elements were the major materials that were targeted for recovery from the battery. Following mechanical processing, a sulfuric acid leach was applied as the first step in a hydrometaUurgical process. Rare earth elements can be separated by the double salt method and then other impurities (copper, zinc) removed by solvent extraction or sulfide precipitation. The f'mal solution contains nickel and cobalt, which are recovered in high purity by electrowinning. A conceptual flow diagram of the process was presented, but continuous testing and other evaluations had not yet been done.
319 Optimization of the hydrometallurgical-type processes is far from complete, and feasibility and pilot scale-up experiments must still be performed. In order to capitalize on the value of cobalt in the AB2 battery system (worth approximately $18 per pound), and the value of rare earth materials for industrial applications (worth approximately $8 to $10 per pound) [7], a more detailed examination of the economics associated with hydrometallurgical processes is needed. Two factors that seem to be contributing to the low level of interest are the current low prices in the primary metals market and the slow increase in the number of fielded EV batteries. Operators of existing commercial smelting operations are unwilling to accept small, infrequent shipments of battery manufacturing scrap, and returns of end-of-life batteries from the field are expected to be miniscule for some time yet. Even waste processors that are willing to accept small waste shipments, such as INMETCO, will not pay for the scrap at the current level of volume and price. Research on improved, more comprehensive recycling processes is not occurring because profits in the near term will be too low to justify the investment. However, the relatively high cost of the Ni/MH battery system makes it important to maximize the recycling credit that can be obtained, and this will only happen with the development of a more comprehensive recycling process. 9 Lithium-ion (Li-ion) and Lithium-polymer (Li-polymer) One of the future recycling needs for the Li-ion battery chemistry involves testing of improved methods for recovering alternative cathode materials. Because the economic incentive to reclaim these materials will likely be less than for cobalt, it will be important for the processes to be highly efficient and necessary to use inexpensive reagents. Other opportunities are in recovery of carbon anodes. It is preferable to process them back into new battery anodes because this would be the most valuable use for the carbon material. However, this will be a difficult task requiring extensive study before feasibility can be proven. The lithium-polymer version of these batteries is another area where work is needed. Lithium-polymer batteries are being rapidly developed for portable consumer electronics applications and may be used in the future for EV/HEVs since the polymer design mitigates safety concerns regarding lithium metal in large cells. Some work to develop recycling processes is under way, but no details have been published and no process test data have been made available. Although many of the constituents are shared in common with the Li-ion battery system, the presence of a solid polymer
320 electrolyte introduces new materials with unique properties. This may complicate physical disassembly of cells if that is needed as part of the recycling process, but also may present opportunities to increase revenues from recycling. Investment in recycling process improvement will continue to be difficult to obtain for lithium batteries since most of the high-value constituents are already accounted for, and there are only small numbers of prototype lithium-polymer batteries in the field.
RECYCLING PROSPECTS FOR FUTURE ADVANCED BATTERY SYSTEMS 9
S o d i u m / S u l f u r (Na/S)
Much of the effort to develop the Na/S battery was aimed at its use in electric vehicles. Current applications of this advanced battery system are now mainly in the stationary battery area, but feasibility studies were done on the recycling of this system before the EV development efforts were suspended. Sodium/sulfur batteries contain reactive and corrosive materials, but not toxic ones. By treatment of the battery waste, the reactivity problems can be removed. The major difficulty in recycling this chemistry is that most of the constituents have low value or are difficult to recover in a form that could be used in a high-value application (e.g., the beta" alumina electrolyte). A patented proposed recycling scheme has been evaluated on a pilot scale and found to be acceptable from a cost and technical standpoint [37]. This process replaced incineration, which was used earlier in the development program, but judged too expensive for large numbers of batteries. In the recycling process, the batteries are shredded and the soluble constituents extracted with water. The resulting sodium polysulfide solution is acidified to generate hydrogen sulfide, which can be converted to sulfur in a small-scale Claus process reactor. The remaining Na2SO4 solution can be converted to sulfuric acid and sodium hydroxide, which are sold or used in the process. Insoluble ceramic, graphite and metal cell case materials are also recovered. Sulfur recovered in this way was recycled into new Na/S cells that showed identical performance to cells built with virgin sulfur. Estimated processing costs were deemed acceptable at $6 to $10/kWh of batteries based on a 5,000 (metric) ton per year plant size. This compares favorably to the $40 to $60/kWh incineration cost. The relatively low value of the recovered materials prevents this recycling process from being completely self-supporting. Other more valuable forms of sulfur could be recovered with a modified process, but markets for them may
321 be limited because of the Exclusion Principle. A detailed examination of the cost benefits in this area has not been done. A specification was drawn up for a pilot recycling plant (250 tons/year) that would meet German safety and environmental standards, but the plant was not constructed because the quantity of returned batteries was insufficient to support it. Analyses of solution from laboratory-scale recycling were carried out for chromium, which is regulated for toxicity, and levels were found to be below EPA limits. TCLP tests on cells also show amounts of leachable chromium that are within EPA standards. 9
Sodium/Nickel Chloride (Na/NiCI2)
The Na/NiCI2 or ZEBRA battery is another high temperature system that resembles Na/S in some respects. However, the design of the system reduces operational hazards from certain failure modes such as cell shorting. This battery has been road tested in about 90 vehicles [38] including the Mercedes A-class EV, although it is not currently slated for commercialization. A recycling process for the battery has been outlined and appears to be feasible. Detailed cost analyses have not been done, but the presence of nickel offers a stronger possibility of recovered value than for Na/S. The sodium/nickel chloride cell, if completely discharged, no longer contains dangerous (reactive) materials since the products of the cell reaction are NaC1 and nickel [39]. The battery is therefore shorted before beginning the recycling process. Soluble components such as NiC12, NaC1, and NaAIC14 are leached out aider slicing the cells into pieces. These soluble components are further separated by precipitating the nickel as nickel sulfide and subsequent crystallization of NaC1 and NaA1Cl4 from the solution. The insoluble case material and ceramics undergo mechanical sieving and magnetic separation, and the valuable components such as the metals are recovered for metallurgical processing and subsequent reuse. Unfortunately, the relatively expensive beta" alumina ceramic electrolyte would most likely go to very low-value uses at first or be sent to disposal. The cost would likely be strongly influenced by the price of nickel, since that is the most valuable constituent. Recovery of all the nickel is important if the process is to be carried out in locations that regulate nickel for disposal. A preliminary evaluation of recycling costs showed that these are just about offset by the value of the recovered materials [40].
322 9
Nickel/Zinc (Ni/Zn)
Ni/Zn batteries with reasonable cycle lives for motive power applications are being developed. Enough progress has been made that small batteries have been proposed for electric scooters and other light transportation applications. Upgrading to larger packs for EVs may occur with further development and experience since the battery would be relatively inexpensive and environmentally friendly. A detailed recycling plan has not been formulated for this technology, but the battery does not contain any particularly hazardous materials. The untreated batteries would be considered hazardous waste because of the corrosive alkaline electrolyte, but this could be recovered or treated to eliminate that problem. Although no TCLP tests are known to have been done on this battery, it seems likely that enough nickel could leach to cause the waste to be considered hazardous due to toxicity in regions where nickel is regulated. Since there are no other regulated materials in this battery, the waste would not be hazardous according to EPA regulations. The only impediment to recycling could be economic in that the single high-value material is nickel. However, the INMETCO smelting process fits well with the battery system because it recovers both nickel and zinc. Nickel/zinc batteries have been recycled by INMETCO with no apparent difficulty. *
Zinc-air
Mechanically rechargeable, zinc-air batteries have been tested in Europe in postal trucks [41]. In this system, spent zinc anodes are removed from the battery and electrochemically reprocessed. A replacement battery containing charged anodes is loaded into the vehicle to minimize refueling time. Although a recycling process has not been designed, the battery materials are non-toxic and should be easy to handle. The cells do contain KOH electrolyte that would have to be neutralized. Besides the zinc anodes, which are continually recycled during the life of the battery, the materials of construction are steel, carbon, plastic, copper, and nickel. No recycling cost estimates have been made, but the recovered materials would not be very high in value so the process would have to be inexpensive to be economically viable.
SUMMARY Electric vehicle batteries present recycling challenges because of their large size, potentially large numbers, uncertain timetable for implementation, and varied chemistries. Most battery chemistries contain materials that would be considered
323 hazardous waste by virtue of reactivity, corrosivity, or toxicity. On disposal, reactivity and corrosivity can generally be dealt with by appropriate treatment of the battery waste. However, toxicity can cause problems and additional cost for waste disposal if the offending species cannot be reclaimed to a high degree by a recycling process. Ultimately, the choice of the recycling process and its effectiveness is shaped by economics. The goal is always to recycle as much as possible, but it may be too expensive to recover some materials or they may have little value to begin with. Disposal may ultimately be the most cost-effective solution for those low-value materials that do not have hazardous waste characteristics. Batteries that do not contain a large percentage of valuable or reusable materials are particularly vulnerable to these issues. A review of the battery chemistries in use in EVs today or that possibly could be used in the future shows that nearly all have some rudimentary recycling potential. Many can be recycled to a high level, at least on a laboratory or pilot scale. There appear to be no situations that totally preclude recycling. What is presently missing is the optimization of the recycling processes needed to recover maximum value and scale up to a high material feed rate. This is perhaps unavoidable given the past history and continued uncertainty regarding the development of the EV market. Battery recyclers have proven resourceful in the past and just as in the case of the lead-acid technology, the advent of large numbers of EVs and HEVs will stimulate development of improved recycling technology. However, the dominant EV power source 10 to 20 years from now may use different materials or even be a new technology, so much remains to be done.
ACKNOWLEDGEMENTS Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DEAC04-94AL85000. Funding for this work was provided by the DOE Office of Transportation Technologies. The author gratefully acknowledges Thomas Evashenk, California Air Resource Board; David Hermance, Toyota; Paul Gifford, GM Ovonic; Gary Roque, Nissan; George Shishkovsky, DaimlerChrysler; Larry Simmering, Ford; Laura Vimmerstedt, NREL; Carol Hammel, NREL; Members of the Reclamation/Recycle Sub-Working Group; and Imelda Francis, Technical Editor, Just Do Information Technologies (Just Do IT).
324 REFERENCES
1. E.J. DeWaard, and A.E. Klein, "Electric Cars," Doubleday & Co., Inc., Garden City, NY, 1977. 2. P.A. Hughes, "A History of Early Electric Cars," Electric Transit Vehicle Institute, World Wide Web site http://www.etvi.org. 3. "Transportation," Macropaedia, Vol. 28, Encyclopedia Britannica, 15th Ed., p. 775, 1989. 4. P. Patil, G.L. Henriksen, D.R. Vissers, and C. Christianson, "Shipping, Use and Disposal/Recycle Considerations for the Sodium/Beta Batteries in EV Applications," presented at the DOE/EPRI Beta (Sodimn/Sulfur) Battery Workshop VIII, Chester, England, June 1990. 5. R.G. Jungst, and R.P. Clark, "Progress in the Development of Recycling Processes for Electric Vehicle Batteries," presented at the 12th International Electric Vehicle Symposium, Anaheim, CA, December 1994. 6. R.G. Jungst, "Recycling Readiness of Advanced Batteries for Electric Vehicles," presented at the 9th International Seminar on Battery Waste Management, Deerfield Beach, FL, October 1997. 7. C.J. Hammel, G.H. Cole, K.L. Heitner, G. Henriksen, G. Hunt, and R.G. Jungst, "Government-Industry Partnerships and Environmental and Safety Solutions," presented at the SAE 2000 Future Car Congress, April 2000. 8. Executive Summary to the Staff Report, "2000 Zero Emission Vehicle Program Biennial Review," Air Resources Board, California Environmental Protection Agency, State of California, August 7, 2000. 9. Electric Vehicle Progress, Vol. 22 #9, p. 7, May 1, 2000. 10. J. Happel, and D.G. Jordon, "Chemical Process Economics," Marcel Dekker, Inc., New York, NY, pp. 12-13, 1975. 11. American Coalition of Traffic Safety (ACTS), presented at the Ad Hoc Electric Vehicle Battery Readiness Working Group, ACTS Foundation, 1110 Glebe Rd., Suite 1020, Arlington, VA, 22201, January 20-21, 1994. 12. M. Montano, S. Unnasch, P. Franklin, J. Rut, and S. Bendix, "Reclamation of Automotive Batteries: Assessment of Health Impacts and Recycling Technology, Task 2: Assessment of Health Impacts," ARCADIS Geraghty & Miller, April 1999. 13. C.R. Knoll, S.M. Tuominen, J.R. Peterson, L.M. Metz, and T.R. McQueary, "Environmental Impact Status of Select Battery Alloys in 1991," presented at the Third International Seminar on Battery Waste Management, Deerfield Beach, FL, November 4-6, 1991.
325 14. P. Klimek, "Solid Waste Characterization of 'New' CECOM Rechargeable Batteries," presented at the Advanced Battery Readiness Ad Hoc Working Group, February 18-19, 1999. 15. D. Smith, "Sony Electronics Incorporated-Update on Li-ion Battery Environmental Issues," presented at the Advanced Battery Readiness Ad Hoc Working Group, March 4-5, 1998. 16. S. Unnasch, M. Montano, and P. Franklin, "Reclamation of Automotive Batteries: Assessment of Health Impacts and Recycling Technology, Task 1: Assessment of EV Battery Recycling Technology," Acurex Environmental Corporation, March 1995. 17. G.M. Roque, W.J. McLaughlin, "Preparing for the EV's and the Electric Vehicle Batteries," presented at the 11th Seminar on Battery Waste Management, Deerfield Beach, Florida, November 1999. 18. Vimmerstedt L., Jungst R.G., and Hammel C. "Impact of Increased Electric Vehicle Use on Battery Recycling Infrastructure," presented at the 8th International Seminar on Battery Waste Management, October 1996. 19. Electric Vehicle Association of the Americas (EVAA), EVAA World Wide Web site http://www.evaa.org. 20. "Supplement to the Annual Energy Outlook, 1996," Energy Information Agency, U.S. Department of Energy, Washington, DC, EIA tip site (flp://flp.eia.doe.gov), 1996. 21. G.W. Hunt, and C.B. John, "A Review of the Operation of a Large Scale, Demand Side Energy Management System Based on a Valve-Regulated Lead-Acid Battery Energy Storage System," presented at the Electric Energy Storage Applications and Technologies Conference (EESAT 2000), Orlando, FL, September 2000. 22. R.D. Prengaman, "Recovering Lead from Batteries," JOM: Journal of the Minerals, Metals, and Materials Society, Vol. 47, pp. 31-33, 1995. 23. Electric Vehicle Progress, Vol. 22 # 12, p. 2, June 15, 2000. 24. H. Morrow, "The Recycling of Nickel-Cadmium Batteries," The Battery Man, October 1993. 25. J. David, "Battery Recycling '99," presented at the 1l th International Seminar on Battery Waste Management," Deerfield Beach, FL, November 1999. 26. J.P. Guptil, "Disposal of Lithium Batteries and the Potential for Recycling of Lithium Battery Components," presented at the 5th International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1993.
326 27. W.J. McLaughlin, "Recycling of Large Lithium Batteries," presented at the Advanced Battery Readiness Working Group Meeting, Washington, DC, March 1998. 28. W.J. McLaughlin, "Lithium Recycling and Disposal Techniques," presented at the 5th International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1993. 29. K. Murano, "Recycling of Lithium Ion Batteries," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 30. W.J. McLaughlin, "Recycling of Lithium Batteries and Other Lithium Wastes," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 31. W.J. McLaughlin, "Deactivation, Disposal, and Recycling of Large Lithium Batteries," presented at the Ad Hoc Advanced Battery Readiness Working Group Meeting, Washington, DC, April 1997. 32. J.W. Lyman, and G.R. Palmer, "Investigating the Recycling of Nickel Hydride Battery Scrap," J. of Metals, pp. 32-35, May 1993. 33. J.W. Lyman, and G.R. Palmer, "Recycling of Nickel-Metal Hydride Battery Scrap," presented at the 186th Meeting of the Electrochemical Society, Miami Beach, FL, October 1994. 34. J.C. Sabatini, E.L. Field, I-C. Wu, M.R. Cox, B.M. Barnett, and J.T. Coleman, "Feasibility Study for the Recycling of Nickel Metal Hydride Electric Vehicle Batteries," Golden, CO: National Renewable Energy Laboratory, TP-463-6153, January 1994. 35. R.G. Jungst, "Recycling of Advanced Batteries for Electric Vehicles," presented at the 1lth International Seminar on Battery Waste Management, Deerfield Beach, FL, November 1999. 36. T. Yoshida, H. Ono, and R. Shirai, "Recycling of Used Ni-MH Rechargeable Batteries," Proceedings of the Third International Symposium on Recycling of Metals and Engineered Materials, pp. 145-152, 1995. 37. J. Rasmassen, "Sodium Sulfur Battery Disposal and Reclamation at Silent Power Limited," presented at the DOE Ad Hoc Electric Vehicle Battery Readiness Working Group, August 30-31, 1994. 38. C.-H. Dustman, "ZEBRA| for the U.S.," presented at the DOE Ad Hoc Advanced Battery Readiness Working Group, April 3-4, 1997. 39. H. Hammerling, "Recycling of Sodium/Nickel Chloride Batteries," presented at the DOE Ad Hoc Advanced Battery Readiness Working Group, August 30-31, 1994.
327 40. C.-H. Dustman, "Latest Advancement on the ZEBRA Battery," presented at the DOE Ad Hoe Advanced Battery Readiness Working Group, March 4-5,1998. 41. R. Putt, "Zinc-air Battery System," presented at the Ad Hoc Advanced Battery Readiness Working Group, March 21-22, 1996.
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APPENDIX A MOST C O M M O N TYPES OF C O M M E R C I A L BATTERIES*
* The information contained in this appendix has mainly been taken from: "Handbook of Batteries", D. Linden Ed., McGraw-Hill, Inc., New York, 1994. "Handbook of Battery Materials", J.O. Besenhard, Ed., Wiley-VCH, Weinheim, 1999.
330 Batteries can be divided into two broad categories:
Primary batteries: 9Zn-carbon 9Alkaline Zn-MnO2 9Zn-silver oxide 9Lithium
Secondary batteries: 9Lead-acid 9Sealed Lead-acid 9Vented industrial Ni-Cd 9Sealed Ni-Cd 9 9Li and Li-ion
Major Applications of the Batteries Listed Above. Primary batteries 9Zn-carbon: portable radios, instruments, toys, watches, flashlights. *Alkaline Zn-MnO2: calculators, radios, tape and cassette recorders; in general, replacement of Zn-carbon whenever a better performance is required. *Zn-Ag20: watches, calculators, hearing aids, cameras, space applications (in large
sizes). 9Lithium: watches, calculators, cameras, memory backup, toys, pacemakers, military applications. Secondary batteries 9Lead-acid: vehicles (SLI and traction), aircrats, submarines, forklifts, uninterruptible power sources, telephone exchange stations. 9Sealed Lead-acid: power tools, portable electronic equipment. 9Vented Ni-Cd: industrial power applications, communication equipment. 9Sealed Ni-Cd: power tools, portable electronic equipment, cameras, railroad equipment. 9Ni-MeH: several portable applications, e.g. computers and cellular phones, EV traction. 9Li and Li-ion: as for Ni-MeH.
331 In figure 1, the world market by battery type is presented.
A S u m m a r y of the Characteristics of Commercial Batteries
Primary batteries 9 Zn-Carbon
These batteries are the most widely used, also by virtue of their low cost. The anode is high-purity Zn and the cathode is battery-grade manganese dioxide. The electrolyte may be either a solution of ammonium chloride (Leclanch~ cell) or zinc chloride. The overall cell reaction may be written, in simplified form, as: Zn + 2 Mn02
-)
ZnO'Mn203
However, the products which can be found in spent batteries reveal more complicated reactions involving the electrolyte. For instance, in cells with NH4C1 as primary electrolyte, such products as MnOOH, Zn(NH3)2C12, Zn(OH)C1 can be found, whereas in cells with ZnC12 the formation of MnOOH, Zn(OH)C1, ZnC12.xZnO is possible. Leclanch6 cells may be divided into general purpose (intermittent low-rate discharge) and industrial heavy duty (intermittent medium/heavy rates) grades. Zinc-chloride cells also afford continuous discharge and have, in addition, an extra/superheavy duty grade for continuous medium/heavy rates. The zinc-carbon battery is made in two basic shapes, cylindrical and flat, and is available in many sizes. The weight can range from 6g to 900g and the capacity from 300 mAh to 40 Ah *
Alkaline Zn-MnO2
This battery has several advantages over the Zn-carbon battery: higher energy density, better performance at low and high rates, longer shelf life, and better dimensional stability.
332 The anode is powdered Zn metal, the cathode is electrolytic UnO2 and the electrolyte is a concentrated solution of KOH (35-45%). The total reaction on continuous discharge and to 1e/mole MnO2 is: Zn + 2 MnO2 + H20 "-) Zn(OH)2 + 2 MnOOH At low rates or intermittent discharges, the reaction is: Zn + 3 UnO2 "-) 2 ZnO + Un304 The initial voltage of these batteries, as well as the one of Zn-carbon cells, is about 1.5 V. To prevent Zn corrosion and passivation, mercury has long been used to amalgamate the anode. As is well known, Hg has been eliminated or greatly reduced, and replaced with indium, bismuth or other additives. Alkaline batteries are constructed as cyclindrical or button cells. The capacities of the former range from 0.6 to 22 Ah, while those of the latter vary from 35 to 160 mAh. 9
Zn-Silver
Oxide
This high-energy density battery is ideal for use, as button cell, in such electronic devices as cameras, calculators and watches. It features a fiat, constant voltage of 1.5 V and a very low self-discharge The anode is Zn metal, the cathode silver oxide (most commonly as Ag20) and the electrolyte an alkaline solution (20-45% KOH or NaOH). The overall reaction is: Zn + Ag20 --) 2 Ag + ZnO Button Zn-Ag20 cells have capacities ranging from 10 to 200 mAh. 9 Li
Li primary batteries have entered the market in the 70's and have since gained increasingly high market shares in a variety of applications. Li batteries have several pleasant characteristis, such as: high voltage, high energy density, wide temperature range, good power density, flat discharge curves, excellent shelf life. Li batteries can be divided into 3 categories:
333 soluble cathode (SO2, SOC12) solid cathode (MnO2, CFx, FeS2, AgV2Os) solid electrolyte (LiI) The first category features high to moderate power, and sizes ranging from 0.5 to an impressive 20,000 Ah. The second category is useful for low to moderate power, with sizes ranging from 0.03 to 5 Ah. Finally, the third category (where the solid electrolyte LiI is formed in situ when Li is contacted by I2) is useful for very low power applications, with sizes of 3 to 500 mAh. The highest market share is for the Li/MnO2 system, mainly used for automatic cameras. The Li/FeS2 system, with an operating voltage of 1.5 V, is a direct replacement for alkaline batteries. In the growing area of batteries for medical use, Li primary batteries play a major role. Li/I2 is still very important for pacemakers, while Li/AgV205 has taken over many high-rate applications, e.g. defibrillators and neurostimulators.
Secondary batteries 9 Lead-Acid
After 150 years, the lead-acid accumulator is still the most successful one with about 50% of the sales of all batteries in the world and an annual growth of 5%. This is explained by considering that this accumulator is always the cheapest one in any application, while granting a good performance. It can be produced in a variety of sizes. Small individual cells can power electric appliances and electronic devices. Through a full range of intermediate capacities, an accumulator can reach the dimensions of the one used in Chino, California, for the electric grid: 40 MWhr, 10 MW, 2,000 V, 5,000 A. The lead-acid battery has high-surface area Pb as a negative electrode and PbO2 as a positive. In the concentrated (37%) H2SO4 electrolyte solution, the reactions occurring at the electrodes lead to the overall process: Pb + PbO2 + 2 H2804 ~ " ~ 2 PbSO4 + 2 H20
334 Details on the electrodes construction and on the technological evolution are given in chapter 8. 9 Sealed Lead-Acid
These are small, maintenance-free batteries which are sealed as the electrolyte is not depleted during operation. The electrolyte is absorbed in a porous separator or in a gel, so that the battery can be operated in different orientations without spilling. This allows the batteries to be used in portable devices. The chemistry of these batteries is that of conventional lead-acid batteries. However, they have a unique characteristics. The oxygen generated on overcharge is recombined in the cell and there is no water loss. Indeed, oxygen reacts at the negative electrode: Pb + HSO4- + I-I+ + 8902 ~ " ~ PbSO4 + H20 This reaction is possible insofar as there is a very limited amount of electrolyte in the cell, this allowing quick gas diffusion between the plates. Sealed lead-acid batteries are in both cylindrical and prismatic shapes. The cyclindrical ones (usually designed as SLA batteries) have excellent high-rate characteristics. Other than in portable devices, sealed batteries can be used in standby applications, e.g. telephone exchange stations, were they are kept in float charge. In this case too, oxygen recombination is possible. Small lead-acid batteries lag behind other systems in terms of electrochemical performance. However, they have a notably high shelf-life and an attractive price. .
Vented Industrial Ni-Cd
Industrial Ni-Cd batteries are rugged, long-life, cheap batteries capable of operating at high rates. The so-called pocket-plate battery can stand overcharge, polarity reversal and short-circuits. To better utilize the electrode materials, two other structures have been developed: the fiber plate and the plastic-bonded plate. The latter has afforded improved performance characteristics (e.g. an energy density of 110 Wh/1). The negative electrode is Cd, the positive NiOOH, and the electrolyte is a concentrated solution of KOH (with additions of LiOH). The overall reaction is:
335 Cd + 2 NiOOH + 2 H20 4[--) Cd(OH)2 + 2 Ni(OH)2 The discharge voltage is about 1.2 V. Under normal conditions, an industrial battery can reach 2,000 cycles and lifetimes of 8-25 years. This battery can practically be used in all industrial applications, with capacities ranging from 10 to 1,000 Ah. A recent development of the Ni-Cd system is the sintered-plate battery having an energy density higher (up to 50%) than that of the pocket-plate one. It is used in highpower applications,e.g, in turbine engines and many military uses. 9 Sealed Ni-Cd
These batteries, as the sealed lead-acid ones, allow oxygen recombination on overcharge, so that they can be sealed and need no maintenance. The electrodes reactions are those mentioned for conventional batteries. However, in this case, the negative electrode has a higher capacity than the positive. During charge, the latter is fully oxidized first and starts to evolve 02, which migrates to the negative electrode and reacts: Cd + 8902 + H20 ")' Cd(OH)2 As for the sealed lead-acid, a thin electrolyte layer is used to help oxygen transfer. The most common cells are cylindrical (0.05 to 35 Ah) or button-type (0.02 to 0.5 Ah). However, sealed Ni-Cd batteries of 200-400 Ah have been built for EV applications. 9 Ni-MeH
In these batteries, the cadmium used in Ni-Cd batteries is replaced by the hydrogen absorbed in a metal alloy. In comparison with Ni-Cd, the Ni-MeH battery has a higher capacity and is environmentally friendly. On the other hand, its rate capability is lower and overcharge may cause problems. In many portable devices, such as cellular phones and laptop computers, Ni-MeH batteries have replaced Ni-Cd also in view of the similar costs. Large batteries are now being developed for EV traction.
336 The negative electrode, in the charged state, is hydrogen in the form of metal hydride, the positive is nickel oxyhydroxide and the electrolyte is a KOH solution. The overall reaction is: MeH + NiOOH (""~ Me + Ni(OH)2 In the sealed cell, an oxygen recombination reaction occurs during charge. At the positive electrode, oxygen is evolved: 2 OH- -'-) H20 + 8902 + 2e Then, 02 migrates to the negative through the thin electrolyte layer and gives rise to the reaction: 02 + 4 MeH --)
H20 + 4 Me
Water is produced and no overpressure builds up. Two types of metallic alloys are used: a) rare-earth (misch metal) alloys, known as ABs, based on lanthanum and nickel (LaNi5 plus some substituents); b) alloys based on titanium and nickel, plus V, Zr, Cr, known as AB2. The first type is the most widely used. A hydrogen-absorbing alloy must allow quantitative absorption-desorption at relatively high rates and for hundreds of cycles. These batteries are built in cyclindrical, button
or prismatic configurations. The
capacities of portable cells vary from 35 to 2,400 mAh. Their discharge characteristics are similar to those of Ni-Cd batteries. The discharge voltage is around 1.2 V. 9 Li a n d L i - l o n
A traditional rechargeable lithium battery uses a Li anode, a solid cathode (e.g. thermally treated MnO2) and a non-aqueous solution based on a Li salt dissolved in aprotic solvents. Today, the only commercial batteries of this type are the small Li/MnO2 coin cells developed at Sanyo. Research on alternative batteries with sulphur cathodes (normally as organic sulphides) is in progress. However, the known rechargeability problems of the Li anode and the related safety concern have shifted the choice towards the Li-ion batteries. These have such anodes as
337 crystalline graphite or carbon, where Li can be reversibly intercalated. The cathodes are ternary oxides of the type: LiCoO2, LiCoxNil_xO2, LiMn204. The electrolyte can be liquid, e.g. LiPF6 in ethylenecarbonate-dimethylcarbonate, or polymeric. Since 1999, polymer Li-ion batteries have appeared in the market. Such cells, with an in-situ crosslinked polymer, are now used in cellular phones of thin profile. However, at present, the market is dominated by the liquid-electrolyte batteries. The proliferation of portable devices is favouring their rapid growth. Early batteries were of the cylindrical type, but now the prismatic design represents 50% of the production, because of the demand for small sizes. Li-ion cells have superior electrochemical performance, as shown in Table 1, while the initially high costs are slowly being reduced. Furthermore, this type of battery is becoming satisfactorily safe and environmentally benign. Typical voltages are around 3 V and typical capacities in the range 0.5-2 Ah. Large batteries for EV traction have been built and tested. The evolution of the market of portable rechargeable batteries in reported in Table 2.
338
Figure 1. The World Battery Market by Type (Courtesy: Avicenne)
339 Table 1;. Comparison of Portable Rechargeable Batteries
Specific Energy (Whkg "1) Energy Density (Wh1-1) OCV (V) Operating Voltage (V) Peak Charge/ Discharge Rate (C) Charging Time (h) Overcharge Permitted Cycle Life 30% DOD 80% DOD Calendar Life (years) Self Discharge (%/month, RT) Component Toxicity Cost (S/KWh)
Lead-Acid
Ni-Cd
Ni-MeH
Li-lon
30
50
60
100
50 2.1 2.0-1.8
100 1.3 1.2-1.0
180 1.3 1.2-1.0
200 4.1 3.8-3.0
6 2-20 Limited
10 1-3 Yes
5 2-5 No
1 3-20 No
500 200 3
2000 800 5
800 600 3
ca. 2000 800 3-5
3-5 High 0.25
15-20 High 0.40
20-30 Medium 0.45
8-15 Medium 1.25
Table 2. Worldwide Production of Portable Rechargeable Batteries (%)*
Battery
1997
2000
Ni-Cd NiMeH Li-Ion Li-Polymer Lead-Acid
55.7 25.0 7.6 11.7
39.0 34.7 17.3 0.3 8.7
* Adapted from Table 1 in Chapter 2 of this book
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APPENDIX B MAIN LEGISLATION ON BATTERY WASTE IN THE U.S.A. AND E.U.
342 COUNCIL DIRECTIVE of 18 March 1991 on batteries and accumulators containing certain dangerous substances (91/157/EEC)
THE COUNCIL OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Economic Community, and in particular Article 100a thereof, Having regard to the proposal from the Commission (1), In cooperation with the European Parliament (2), Having regard to the opinion of the Economic and Social Committee (3), Whereas any disparity between the laws or administrative measures adopted by the Member States on the disposal of batteries and accumulators could create barriers to trade and distort competition in the Community and may thereby have a direct impact on the establishment and functioning of the internal market; whereas it therefore appears necessary to approximate the laws in the field; Whereas Article 2 (2) of Council Directive 75/442/EEC of 15 July 1975 on waste (4), as amended by Directive 91/156/EEC (5), provides that specific rules for particular instances or supplementing those of the said Directive in order to regulate the management of particular categories of waste shall be laid down by means of individual Directives; Whereas the objectives and principles of the Community's environment policy, as set out in the European Community action programmes on the environment on the basis of the principles enshrined in Article 130r (1) and (2) of the EEC Treaty, aim in particular at preventing, reducing and as far as possible eliminating pollution and ensuring sound management of raw materials resources, on the basis also of the 'polluter pays' principle; Whereas, in order to achieve these objectives, the marketing of certain batteries and accumulators should be prohibited, in view of the amount of dangerous substances they contain; Whereas, to ensure that spent batteries and accumulators are recovered and disposed of in a controlled manner, Member States must take measures to ensure that they are marked and collected separately; Whereas collection and recycling of spent batteries and accumulators can help avoid unnecessary use of raw materials; Whereas appliances containing non-removable batteries or accumulators may represent an environmental hazard when they are disposed of; whereas Member States should therefore take appropriate measures; Whereas programmes should be set up in the Member States to achieve the various objectives set out above; whereas the Commission should be informed of these programmes and of the specific measures taken; Whereas recourse to economic instruments such as the setting up of a deposit system may encourage the separate collection and recycling of spent batteries and accumulators; Whereas provision should be made for consumer information in this field; Whereas provision should be made for appropriate procedures to implement the provisions of this Directive, particularly the making system, and to ensure that the
343 Directive can be easily adapted to scientific and technical progress; whereas the committee referred to in Article 18 of Directive 75/442/EEC should be instructed to assist the Commission in these tasks, HAS ADOPTED THIS DIRECTIVE: Article 1 The aim of this Directive is to approximate the laws of the Member States on the recovery and controlled disposal of those spent batteries and accumulators containing dangerous substances in accordance with Annex I. Article 2 For the purposes of this Directive: (a) 'battery or accumulator' means a source of electrical energy generated by direct conversion of chemical energy and consisting of one or more primary (nonrechargeable) batteries or secondary (rechargeable) cells, as listed in Annex I; (b) 'spent battery or accumulator' means a battery or accumulator which is not re-usable and is intended for recovery or disposal; (c) 'disposal' means any operation, provided that it is applicable to batteries and accumulators, included in Annex II A to Directive 75/442/EEC; (d) 'recovery' means any operation, provided that it is applicable to batteries and accumulators, included in Annex IIB to Directive 75/442/EEC; (e) 'collection' means the gathering, sorting and/or grouping together of spent batteries and accumulators; (f) 'deposit system' means a system under which the buyer, upon purchase of batteries or accumulators, pays the seller a sum of money which is refunded when the spent batteries or accumulators are returned. Article 3 1. Member States shall prohibit, as from 1 January 1993, the marketing of: alkaline manganese batteries for prolonged use in extreme conditions (e.g. temperatures below 0 ~ C or above 50 ~ C, exposed to shocks) containing more than 0,05 % of mercury by weight, - all other alkaline manganese batteries containing more than 0,025 % of mercury by weight. Alkaline manganese button cells and batteries composed of button cells shall be exempted from this prohibition. 2. Paragraph 1 shall be inserted in Annex I to Council Directive 76/769/EEC of 27 July 1976 on the approximation of the laws, regulations and administrative provisions of the Member States relating to restrictions on the marketing and use of certain dangerous substances and preparations (6), as last amended by Directive 85/610/EEC (7). Article 4 1. In the context of the programmes referred to in Article 6, Member States shall take appropriate steps to ensure that spent batteries and accumulators are collected separately with a view to their recovery or disposal. 2. To this end, Member States shall ensure that batteries and accumulators and, where appropriate, appliances into which they are incorporated are marked in the appropriate manner. The marking must include indications as to the following points: separate collection, where appropriate, recycling, the heavy-metal content. -
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344 3. The Commission shall draw up, in accordance with the procedure referred to in Article 10, the detailed arrangements for the marking system. These arrangements shall be published in the Official Journal of the European Communities. Article 5 Member States shall take measures to ensure that batteries and accumulators cannot be incorporated into appliances unless they can be readily removed, when spent, by the consumer. These measures shall enter into force on 1 January 1994. This Article shall not apply to the categories of appliance included in Annex II. Article 6 Member States shall draw up programmes in order to achieve the following objectives: reduction of the heavy-metal content of batteries and accumulators, promotion of marketing of batteries and accumulators containing smaller quantities of dangerous substances and/or less polluting substances, gradual reduction, in household waste, of spent batteries and accumulators covered by Annex I, promotion of research aimed at reducing the dangerous-substance content and favouring the use of less polluting substitute substances in batteries and accumulators, and research into methods of recycling, separate disposal of spent batteries and accumulators covered by Annex I. The first programmes shall cover a four-year period starting on 18 March 1993. They shall be communicated to the Commission by 17 September 1992 at the latest. The programmes shall be reviewed and updated regularly, at least every four years, in the light in particular of technical progress and of the economic and environmental situation. Amended programmes shall be communicated to the Commission in good time. Article 7 1. Member States shall ensure the efficient organization of separate collection and, where appropriate, the setting up of a deposit system. Furthermore, Member States may introduce measures such as economic instruments in order to encourage recycling. These measures must be introduced after consultation with the parties concerned, be based on valid ecological and economic criteria and avoid distortions of competition. 2. When notifying the programmes to which Article 6 refers, Member States shall inform the Commission of the measures they have taken pursuant to paragraph 1. Article 8 In the context of the programmes referred to in Article 6, Member States shall take the necessary steps to ensure that consumers are fully informed of: (a) the dangers of uncontrolled disposal of spent batteries and accumulators; (b) the marking of batteries, accumulators and appliances with permanently incorporated batteries and accumulators; (c) the method of removing batteries and accumulators which are permanently incorporated into appliances. Article 9 Member States may not impede, prohibit or restrict the marketing of batteries and accumulators covered by this Directive and conforming to the provisions laid down herein. Article 10 The Commission shall adapt Articles 3, 4 and 5 and Annexes I and II to technical -
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345 progress in accordance with the procedure laid down in Article 18 of Directive 75/442/EEC. Article 11 1. Member States shall take the measures necessary to comply with this Directive before 18 September 1992. They shall forthwith inform the Commission thereof. 2. Member States shall communicate to the Commission the texts of the provisions of national law which they adopt in the field governed by this Directive. The Commission shall inform the other Member States thereof. Article 12 This Directive is addressed to the Member States. ANNEX I BATTERIES AND ACCUMULATORS COVERED BY THE DIRECTIVE 1. Batteries and accumulators put on the market as from the date laid down in Article 11 (1) and containing: more than 25 mg mercury per cell, except alkaline manganese batteries, more than 0,025 % cadmium by weight, more than 0,4 % lead by weight. 2. Alkaline manganese batteries containing more than 0,025 % mercury by weight placed on the market as from the date laid down in Article 11 (1). ANNEX II LIST OF CATEGORIES OF APPLIANCE EXCLUDED FROM THE SCOPE OF ARTICLE 5 1. Those appliances whose batteries are soldered, welded or otherwise permanently attached to terminals to ensure continuity of power supply in demanding industrial usage and to preserve the memory and data functions of information technology and business equipment, where use of the batteries and accumulators referred to in Annex I is technically necessary. 2. Reference cells in scientific and professional equipment, and batteries and accumulators placed in medical devices designed to maintain vital functions and in heart pacemakers, where uninterrupted functioning is essential and the batteries and accumulators can be removed only by qualified personnel. 3. Portable appliances, where replacement of the batteries by unqualified personnel could present safety hazards to the user or could affect the operation of the appliance, and professional equipment intended for use in highly sensitive surroundings, for example in the presence of volatile substances. Those appliances the batteries and accumulators of which cannot be readily replaced by the user, in accordance with this Annex, shall be accompanied by instructions informing the user of the content of environmentally hazardous batteries and accumulators and showing how they can be removed safely. -
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346 Commission Directive 93/86/EEC of 4 October 1993 adapting to technical progress Council Directive 91/157/EEC on batteries and accumulators containing certain dangerous substances
THE COMMISSION OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Economic Community, Having regard to Council Directive 75/442/EEC of 15 July 1975 on waste (1), as last amended by Directive 91/692/EEC (2), and in particular Article 18 thereof, Having regard to Council Directive 91/157/EEC of 18 March 1991 on batteries and accumulators containing certain dangerous substances (~), and in particular Article 10 thereof, Whereas detailed arrangements should be established for the making system provided for in Article 4 of Directive 91/157/EEC; Whereas appliances need not be marked, since Annex II to Directive 91/157/EEC provides for a special information system for appliances from which the consumer cannot easily remove the battery or accumulator; Whereas there is a need for a symbol clearly showing that batteries or accumulators covered by Directive 91/157/EEC should be collected separately from other household waste; Whereas the use of this symbol for batteries and accumulators covered by Directive 91/157/EEC must be protected; Whereas the measures provided for in this Directive are in accordance with the opinion delivered by the Committee for the Adaptation to Scientific and Technical Progress of Community Legislation on Waste, HAS ADOPTED THIS DIRECTIVE: Article 1 1. This Directive establishes the detailed arrangements for the marking system envisaged in Article 4 of Directive 91/157/EEC on batteries and accumulators covered by that Direcctive and manufactured for sale in, imported into, the Community on or after 1 January 1994. 2. The batteries and accumulators referred to in paragraph 1 which are produced in, or imported into, the Community before 1 January 1994 may be marketed without the symbols provided for in Articles 2 and 3 until 31 December 1995. Article 2 The symbol indicating separate collection shall consist of one of the roll-out containers crossed through, as shown below: The decision on the choice of symbol to be used on batteries and accumulators covered by Directive 91/157/EEC shall be made by the person responsible for marking as described in Article 5 of this Directive. The use of the two symbols shall be considered equivalent throughout the Community. Member States shall inform the public of the meaning of both symbols and grant them equal status in their national provisions regarding batteries and accumulators covered by Directive 91/157/EEC. The use of either symbol shall not constitute a means of arbitrary discrimination or a disguised restriction on trade between Member States. Article 3 The symbol indicating the heavy-metal content shall consist of the chemical symbol for the metal concerned, Hg, Cd or Pb according to the type of battery or accumulator concerned, as described in Annex I to Directive 91/157/EEC.
347 Article 4 1. The symbol described in Article 2 shall cover 3 % of the area of the largest side of the battery or accumulator, up to a maximum size of 5 x 5 cm. For cylindrical cells the symbol shall cover 3 % of half the surface area of the battery or accumulator and shall have a maximum size of 5 x 5 cm. Where the size of the battery or accumulator is such that the symbol would be smaller than 0,5 x 0,5 cm, the battery or accumulator need not be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. 2. The symbol referred to in Article 3 shall be printed beneath the symbol referred to in Article 2. It shall cover an area of at least one quarter the size of the symbol described in paragraph 1 of this Article. 3. The symbols shall be printed visibly, legibly and indelibly. Article 5 Member States shall take the necessary steps to ensure that the marking complies with the provisions of this Directive and is carried out by the manufacturer or his authorized representative established in the Member State concemed or else by the person responsible for placing the batteries or accumulators on the national market. Article 6 Member States shall adopt appropriate measures to ensure full implementation of all the provisions of this Directive, in particular as regards observance of the symbols referred to in Articles 2 and 3. Member States shall lay down the penalties to be applied in the event of an infringement of the measures adopted to comply with this Directive; such penalties must be effective, proportionate and deterrent in their effect. Article 7 Member States shall take the measures necessary to comply with this Directive no later than 31 December 1993. They shall immediately inform the Commission thereof. When Member States adopt these provisions, these shall contain a reference to this Directive or shall be accompanied by such reference at the time of their official publication. The procedure for such reference shall be adopted by Member States. Article 8 This Directive is addressed to the Member States.
348 Commission Directive 98/101~C of 22 December 1998 adapting to technical progress Council Directive 91/157/EEC on batteries and accumulators containing certain dangerous substances (Text with EEA relevance)
THE COMMISSION OF THE EUROPEAN COMMUNITIES, Having regard to the Treaty establishing the European Community, Having regard to Council Directive 91/157/EEC of 18 March 1991 on batteries and accumulators containing certain dangerous substances (1), and in particular Article 10 thereof, Whereas within the framework of the Act of Accession of Austria, Finland and Sweden, in particular in Articles 69 and 112, it is foreseen that during a period of four years from the date of accession the provisions concerning the mercury containing batteries referred to in Article 3 of Directive 91/157/EEC should be reviewed in accordance with EC procedures; Whereas, in order to achieve a high level of environmental protection, the marketing of certain batteries should be prohibited, in view of the amount of mercury they contain; whereas that prohibition, in order to achieve its full effect for the environment, must cover appliances into which such batteries and accumulators are incorporated; whereas such prohibition may have a positive impact in facilitating the recovery of batteries; Whereas the technical development of alternative heavy-metal-free batteries should be taken into account; Whereas Directive 91/157/EEC should be adapted accordingly; Whereas the measures provided for in this Directive are in accordance with the opinion expressed by the Committee established pursuant to Article 18 of Council Directive 75/442/EEC of 15 July 1975 on waste (2), as last amended by Commission Decision 96/350/EC (3), HAS ADOPTED THIS DIRECTIVE: Article 1 Directive 91/157/EEC is amended as follows: 1. Article 3(1) is replaced by the following: '1. Member States shall prohibit, as from 1 January 2000 at the latest, the marketing of batteries and accumulators, containing more than 0,0005 % of mercury by weight, including in those cases where these batteries and accumulators are incorporated into appliances. Button cells and batteries composed of button cells with a mercury content of no more than 2 % by weight shall be exempted from this prohibition.'; 2. Annex I is replaced by the text in the Annex to this Directive. Article 2 Member States shall adopt and publish, before 1 January 2000, the provisions necessary to comply with this Directive. They shall forthwith inform the Commission thereof. When Member States adopt those provisions, they shall contain a reference to this Directive or be accompanied by such a reference on the occasion of their official publication. Member States shall determine how such reference is to be made. Article 3 This Directive shall enter into force on the 20th day following its publication in the Official Journal of the European Communities.
349 ArtMe 4 This Directive is addressed to the Member States. ANNEX 'ANNEX I The following batteries and accumulators are covered by this Directive: 1. Batteries and accumulators put on the market as from 1 January 1999 containing more than 0,0005 % of mercury by weight. 2. Batteries and accumulators put on the market as from 18 September 1992 and containing: more than 25 mg of mercury per cell, except alkaline manganese batteries, more than 0,025 % of cadmium by weight, more than 0,4 % of lead by weight. 3. Alkaline manganese batteries containing more than 0,025 % of mercury by weight placed on the market as from 18 September 1992." -
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350 Draft Proposal of a New Directive of the European Commission on Batteries and Accumulators (with a view to replacing Directives
91/157/EEC and 93/86/EEC) EUROPEAN PARLIAMENT AND COUNCIL DIRECTIVE ../.../EC of .............
on batteries and accumulators
THE EUROPEAN PARLIAMENT AND THE COUNCIL OF THE EUROPEAN UNION, . ........... HAVE ADOPTED THIS DIRECTIVE: Article 1 Objectives
1. The aim of this Directive is to harmonise national measures concerning batteries and accumulators and the management of their wastes in order, on the one hand, to prevent or reduce the negative impact thereof on the environment, thus providing a high level of environmental protection, and, on the other hand, to ensure the functioning of the internal market and to avoid obstacles to trade and distortion and restriction of competition within the Community. 2. To this end, this Directive lays down measures aiming at preventing or reducing the hazardous nature of waste from batteries and accumulators, at ensuring the separate collection of all types of spent batteries and accumulators with a view to recovering their content and at reducing the final disposal of such waste. Article 2 Scope
3. This Directive shall cover all types of batteries and accumulators, as well as the appliances into which they are incorporated as regards marketing, marking and battery removal requirements, whether new or spent, whether they are used for consumer, automotive or industrial purposes, regardless of their shape, volume, weight or material composition. 4. This Directive shall apply without prejudice to other Community legislation, in particular as regards health, quality and safety standards.
Article 3 Definitions
For the purposes of this Directive:
351 1. "battery" means any source of electrical energy generated by direct conversion of chemical energy and consisting of one or more primary battery cells (non-rechargeable); 2. "accumulator" means any source of electrical energy generated by direct conversion of chemical energy and consisting of one or more secondary battery cells (rechargeable); 3. "battery pack" means any set of batteries or accumulators encapsulated in an outer casing into one complete unit, not intended to be opened by the consumer; 4. "portable battery or accumulator" means any battery or accumulator being used in products for private or professional use; 5. "button batteries and accumulators" means small button-shaped cells, normally with a weight of less than 50 g, used for special purposes such as hearing aids, watches and small portable equipment; 6. "industrial and automotive batteries or accumulators" means any battery or accumulator used for industrial purposes, for instance as standby or traction power, or for automotive starter power for vehicles; 7. "spent battery or accumulator" means any battery or accumulator which is a waste within the meaning of Article 1(a) of Directive 75/442/EEC; 8. "separate collection" means the gathering, sorting and/or grouping together of spent batteries and accumulators, separately from any other waste stream; 9. "recovery" means any of the applicable operations provided for in Annex IIB of Directive 75/442/EEC; 10. "recycling" means the reprocessing in a production process of the waste materials for the original purpose or for other purposes but excluding energy recovery. Energy recovery means the use of combustible waste as a means to generate energy through direct incineration with or without other waste but with recovery of the heat; 11. "disposal" means any of the applicable operations provided for in Annex IIA of Directive 75/442/EEC.
Article 4
Prevention
1. Member States shall prohibit the marketing of all batteries and accumulators, with the exception of button batteries and accumulators, containing more than 0.0005% of mercury by weight as well as the appliances into which they are incorporated.
352 2. Member States shall prohibit the marketing of all button batteries and accumulators containing more than 2% of mercury by weight as well as the appliances into which they are incorporated. 3. a) Without prejudice to Article 4 (2) of Directive 2000/53/EC on end of life vehicles, Member States shall prohibit, as from 1 January 2008, the marketing of batteries and accumulators containing more than 0.002% of cadmium by weight as well as the appliances into which they are incorporated. b) Paragraph (a) shall not apply to applications listed in Annex III. d) Member States shall take the necessary measures to ensure that, without prejudice to the requirements contained in Article 8, producers of nickel/cadmium batteries used in applications listed in Annex III provide for the setting up and the financing of the registration, collection, treatment, recovery, safe disposal and monitoring of these spent batteries. Such measures shall ensure a closed loop system and shall be communicated to the Commission. 4. In accordance with the procedure laid down in Article 16, the Commission shall revise paragraph 2 of this Article and Annex III by the end of 2005, taking into account new scientific evidence and technical developments. This revision exercise shall be repeated every three years thereafter. Article 5
Removal of batteries and accumulators from appliances Member States shall ensure that batteries and accumulators cannot be incorporated into appliances unless they can be readily removed, when spent, by the consumer. This provision shall not apply to the categories of appliance included in Annex I. All appliances into which batteries and accumulators are incorporated shall be accompanied by instructions showing how they can be removed safely and, where appropriate, informing the user of the content of the incorporated batteries and accumulators. Article 6
Marking requirements Member States shall ensure that all batteries and accumulators and battery packs are appropriately marked with the symbol shown in Annex II according to the technical requirements laid down in that Annex. Annex II shall be adapted to technical progress in accordance to Article 16. Article 7
Freedom to place on the market
353 Member States may not impede, prohibit or restrict the marketing in their territory of batteries and accumulators conforming to the provisions laid down in this Directive. Article 8
Separate Collection 1. Member States shall ensure that systems are set up so that last holders can return spent batteries and accumulators. They shall take the necessary measures to ensure that portable batteries and accumulators can be returned free of charge. 2. Member States shall aim at achieving no later than 31 December 2004 the following targets for separate collection covering their whole territory: (a) a minimum of 75% by weight of all spent consumer batteries and accumulators; this target shall also apply as a minimum to batteries containing more than 5 ppm mercury and to accumulators containing lead or cadmium considered individually. (b) a minimum of 95% by weight of all spent industrial and automotive batteries and accumulators; this target shall also apply to accumulators containing cadmium considered individually. 3. In line with the information required under Article 14, the targets shall be based on the weight of batteries sold taking into account the lifetime of the batteries. The Commission shall establish, in accordance with the procedure referred to in Article 16 and no later than the date by which this Directive must be implemented in national law, the reference elements on the basis of which the above targets shall be calculated. 4. No later than 31 December 2008 the collection targets shall be reviewed in accordance with the procedure by which this Directive is adopted. Article 9
Recovery and disposal 1. Member States shall ensure that all spent batteries and accumulators collected according to the provisions laid down in Article 8 are recovered or disposed of in accordance with Article 4 of Directive 75/442/EEC. 2. Member States shall ensure that any establishment or undertaking carrying out treatment operations obtains a permit from the competent authorities, in compliance with Articles 9 and 10 of Directive 75/442/EEC. 3. Member States shall aim at achieving no later than 31 December 2004 a minimum recycling rate of 55% by weight of the materials contained in the collected spent batteries and accumulators. No later than 31 December 2008 this recycling target shall be reviewed in accordance with the procedure by which this Directive is adopted.
354 Article 10
Collection and recovery systems Collection and recovery systems shall be open to the participation of the economic operators of the sectors concerned and to the participation of the competent authorities. They shall also apply to imported products under non-discriminatory conditions, and shall be designed so as to avoid barriers to trade or distortions of competition. Article 11
Consumer information Member States shall ensure that consumers are fully informed of: (a) the possibilities to prevent and minimise the use of batteries and accumulators (b) the most environmentally friendly batteries and accumulators for the various applications (c) how to choose appliances operating with environmentally friendly batteries or accumulators (d) the risks of disposing of spent batteries, accumulators and appliances into which they are incorporated together with the ordinary household waste; (e) the collection and return systems available to them;
(f) the meaning of the symbol and the chemical signs (Hg, Cd and Pb) laid down in Annex II; (g) the method of removing batteries and accumulators which are incorporated into appliances. 2. The targets referred to in Article 8 shall be published by the Member States and shall be the subject of an information campaign for the general public and economic operators. Article 12
Programmes Member States shall draw up programmes in order to achieve the following objectives: -promotion of research on and marketing of batteries and accumulators substituting those containing mercury, cadmium and where possible those containing lead
355 -promotion and development of collection and, where appropriate, deposit systems in order to improve separate collection of batteries and accumulators including the reduction of spent batteries stored at home -promotion of research on environmentally friendly and cost-effective recycling methods for all types of batteries These programmes shall be communicated to the Commission at the same time and covering the same period as the reports requested in Article 15. The report which is to be drawn up under Article 15 shall refer to these programmes. Article 13
Economic instruments 1. Member States may, in accordance with the principles governing Community environmental policy, inter alia, the polluter-pays principle, adopt economic instruments to promote the achievement of the objectives of this Directive. Member States shall ensure that these instruments do not distort internal market and competition rules. 2. Member States shall communicate to the Commission the draft measures which they intend to adopt concerning the use of economic instruments to achieve the objectives of this Directive. Article 14
Data collection 1. Member States shall ensure that databases on the quantities of batteries and accumulators including those incorporated in appliances are established in order to allow monitoring of the implementation of the objectives of this Directive for every calendar year. The database shall contain the units and weight of each type of battery and accumulator marketed within the Member States, as well as collected, recycled and disposed of as spent battery or accumulator. 2. Member States shall ensure that the information required under paragraph 1 is provided in a format, which shall be established in accordance with the procedure referred to in Article 16 and no later than the date by which this Directive must be implemented in national law. Article 15
Reporting obligation At three year intervals Member States shall send a report to the Commission on the implementation of this Directive. The report shall be drawn up on the basis of a questionnaire or outline drafted by the Commission in accordance with the procedure
356 laid down in Article 6 of Council Directive 91/692/EEC 13 of 23 December 1991 standardising and rationalising reports on the implementation of certain Directives relating to the environment. The questionnaire or outline shall be sent to the Member States six months before the start of the period covered by the report. The report shall be made available to the Commission within nine months of the end of the three-year period covered by it. The first report shall cover the period of three full calendar years starting from [ 18 months after the date of entry into force of this Directive]. Article 16
Committee procedure 1. The Commission shall be assisted by the committee instituted by Article 18 of Directive 75/442/EEC 14. 2. Where reference is made to this Article, the regulatory procedure laid down in Article 5 of Decision 1999/468/EC 15 shall apply, in compliance with Article 7 and Article 8 thereof. 3. The period provided for in Article 5(6) of Decision 1999/468/EC shall be three months. Article 17
Transposition 1. Member States shall bring into force the law, regulations and administrative provisions necessary to comply with this Directive by ..... [18 months after the date of adoption] at the latest. They shall immediately inform the Commission thereof. 2. When Member States adopt those provisions, they shall contain a reference to this Directive or be accompanied by such a reference on the occasion of their official publication. Member States shall determine how such reference is to be made. 3. Member States shall communicate to the Commission the text of all existing laws, regulations and administrative provisions adopted in the field covered by this Directive. 4. Member States shall lay down the penalties to be applied in the event of an infringement of the measures adopted to comply with this Directive; such penalties must be effective, proportionate and deterrent in their effect.
357 Article 18
Existing Community legislation on batteries and accumulators Directive 91/157/EEC and 93/86/EEC are hereby repealed with effect from the date referred to in Article 17.
ANNEX I LIST OF CATEGORIES OF APPLIANCE EXCLUDED F R O M THE SCOPE OF ARTICLE 5 1. Reference cells in scientific and professional equipment, and batteries and accumulators placed in medical devices designed to maintain vital functions and in heart pacemakers, where uninterrupted functioning is essential and the batteries and accumulators can be removed only by qualified personnel; 2. Portable appliances with an intended lifetime exceeding that of the original set of batteries or accumulators, where their replacement by unqualified personnel could present safety hazards to the user or could affect the operation of the appliance; 3. Appliances in respect of which legal safety standards require the use of tools for battery removal or which are designed and sold as waterproof; 4. Batteries and accumulators incorporated into professional equipment intended for use in highly sensitive surroundings, for example, in the presence of volatile substances.
ANNEX II
SYMBOLS AND TECHNICAL ASPECTS FOR THE MARKING OF BATTERIES AND ACCUMULATORS, BATTERY PACKS AND APPLIANCES WITH A VIEW TO SEPARATE COLLECTION 1. The symbol indicating separate collection for all batteries and accumulators shall consist of the crossed out wheeled bin, as shown below:
358 2. As regards batteries and accumulators as well as button batteries and accumulators containing cadmium or mercury above the levels indicated in Article 4.1 and 4.3 or lead above 0,1% of the weight of the battery, the chemical symbol for the metal concerned, Cd, Hg, Pb, shall be indicated. The symbol indicating the heavy metal content shall be printed beneath the symbol referred to in paragraph 1 of this Annex. 3. The symbol referred to in paragraph 1 of this Annex shall cover 3% of the area of the largest side of the battery, accumulator or battery pack, up to a maximum size of 5 x 5 cm. For cylindrical cells the symbol shall cover 1.5% of the surface area of the battery or accumulator and shall have a maximum size of 5 x 5 cm. Where the size of the battery, accumulator or battery pack is such that the symbol would be smaller than 0.4 x 0.4 cm, the battery, accumulator or battery pack need not to be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. 4. The symbol referred to in paragraph 1 of this Annex shall cover 3% of the area of the largest side of appliances which are required to be marked pursuant to Article 6 of this Directive, up to a maximum size of 5 x 5 cm. Where the size of the appliance is such that the symbol would be smaller than 0.4 x 0.4 cm, the appliance need not to be marked but a symbol measuring 1 x 1 cm shall be printed on the packaging. Where batteries, accumulators or battery packs are incorporated into appliances in such a way that the symbol referred to in paragraph 1of this Annex is fully visible without having to remove the batteries, accumulators or battery packs from the appliance, the appliance need not to be marked. 5. The symbols shall be printed visibly, legibly and indelibly.
ANNEX IH
NICD BATTERY APPLICATIONS, WHICH ARE EXEMPTED FROM THE REQUIREMENT OF ARTICLE 4(3)(A) -Railway and metro (locomotive starting and braking, lighting, signalling) -Aviation (airports, starting, emergency power for aircraft controls) -Stationary (uninterrupted power supply for hospitals, utilities, telecom))
359
The Mercury-Containing and Rechargeable Battery Management Act (The "Battery Act") Public Law 104-142 104th Congress An Act To phase out the use of mercury in batteries and provide for the efficient and cost-effective collection and recycling or proper disposal of used nickel cadmium batteries, small sealed lead-acid batteries, and certain other batteries, and for other purposes. SECTION 1. SHOT TITLE. This Act may be cited as the "'Mercury-Containing and Rechargeable Battery Management Act". SEC. 2. FINDINGS. The Congress f'mds that-- (1) it is in the public interest to-- (A) phase out the use of mercury in batteries and provide for the efficient and cost-effective collection and recycling or proper disposal of used nickel cadmium batteries, small sealed lead-acid batteries, and other regulated batteries; and (B) educate the public concerning the collection, recycling, and proper disposal of such batteries; (2) uniform national labeling requirements for regulated batteries, rechargeable consumer products, and product packaging will significantly benefit programs for regulated battery collection and recycling or proper disposal; and (3) it is in the public interest to encourage persons who use rechargeable batteries to participate in collection for recycling of used nickel-cadmium, small sealed lead-acid, and other regulated batteries. SEC. 3. DEFINITIONS. For purposes of this Act: (1) Administrator.--The term "'Administrator" means the Administrator of the Environmental Protection Agency. (2) Button cell.--The term "'button cell" means a button- or coin-shaped battery. (3) Easily removable.--The term "'easily removable", with respect to a battery, means detachable or removable at the end of the life of the battery-- (A) from a consumer product by a consumer with the use of common household tools; or (B) by a retailer of replacements for a battery used as the principal electrical power source for a vehicle. (4) Mercuricoxide battery.--The term "'mercuric-oxide battery" means a battery that uses a mercuric-oxide electrode. (5) Rechargeable battery.--The term "'rechargeable battery"-(A) means 1 or more voltaic or galvanic cells, electrically connected to produce electric energy, that is designed to be recharged for repeated uses; and (B) includes any type of enclosed device or sealed container consisting of 1 or more such cells, including what is commonly called a battery pack (and in the case of a battery pack, for the purposes of the requirements of easy removability and labeling under section 103, means the battery pack as a whole rather than each component individually); but (C) does not include-- (i) a lead-acid battery used to start an internal combustion engine or as the principal electrical power source for a vehicle, such as an automobile, a truck, construction equipment, a motorcycle, a garden tractor, a golf cart, a wheelchair, or a boat; (ii) a lead-acid battery used for load leveling or for storage of electricity generated by an alternative energy source, such as a solar cell or wind-driven generator; (iii) a battery used as a backup power source for memory or program instruction storage, timekeeping, or any similar purpose that requires uninterrupted electrical power in order to function if the primary energy supply fails or fluctuates momentarily; or (iv) a rechargeable alkaline battery. (6) Rechargeable consumer product.--The term "'rechargeable consumer product"-- (A) means a product that, when sold at retail, includes a regulated battery as a primary energy supply, and that is primarily intended
360 for personal or household use; but (B) does not include a product that only uses a battery solely as a source of backup power for memory or program instruction storage, timekeeping, or any similar purpose that requires uninterrupted electrical power in order to function if the primary energy supply fails or fluctuates momentarily. (7) Regulated battery.--The term "'regulated battery" means a rechargeable battery that-(A) contains a cadmium or a lead electrode or any combination of cadmium and lead electrodes; or (B) contains other electrode chemistries and is the subject of a determination by the Administrator under section 103(d). (8) Remanufactured product.-The term "'remanufactured product" means a rechargeable consumer product that has been altered by the replacement of parts, repackaged, or repaired after initial sale by the original manufacturer. SEC. 4. INFORMATION DISSEMINATION. The Administrator shall, in consultation with representatives of rechargeable battery manufacturers, rechargeable consumer product manufacturers, and retailers, establish a program to provide information to the public concerning the proper handling and disposal of used regulated batteries and rechargeable consumer products with nonremovable batteries. SEC. 5. ENFORCEMENT. (a) Civil Penalty.--When on the basis of any information the Administrator determines that a person has violated, or is in violation of, any requirement of this Act (except a requirement of section 104) the Administrator-- (1) in the case of any violation, may issue an order assessing a civil penalty of not more than $10,000 for each violation, or requiring compliance immediately or within a reasonable specified time period, or both; or (2) in the case of any violation or failure to comply with an order issued under this section, may commence a civil action in the United States district court in the district in which the violation occurred or in the district in which the violator resides for appropriate relief, including a temporary or permanent injunction. (b) Contents of Order.--An order under subsection (a)(1) shall state with reasonable specificity the nature of the violation. (c) Considerations.--In assessing a civil penalty under subsection (a)(1), the Administrator shall take into account the seriousness of the violation and any good faith efforts to comply with applicable requirements. (d) Finality of Order; Request for Hearing.--An order under subsection (a)(1) shall become final unless, not later than 30 days after the order is served, a person named in the order requests a hearing on the record. (e) Hearing.--On receiving a request under subsection (d), the Administrator shall promptly conduct a hearing on the record. (f) Subpoena Power.--In connection with any hearing on the record under this section, the Administrator may issue subpoenas for the attendance and testimony of witnesses and for the production of relevant papers, books, and documents. (g) Continued Violation After Expiration of Period for Compliance.-- If a violator fails to take corrective action within the time specified in an order under subsection (a)(1), the Administrator may assess a civil penalty of not more than $10,000 for the continued noncompliance with the order. (h) Savings Provision.--The Administrator may not take any enforcement action against a person for selling, offering for sale, or offering for promotional purposes to the ultimate consumer a battery or product covered by this Act that was-- (1) purchased ready for sale to the ultimate consumer; and (2) sold, offered for sale, or offered for promotional purposes without modification. The preceding sentence shall not apply to a person-- (A) who is the importer of a battery covered by this Act, and (B) who has knowledge of the chemical contents of the battery when such chemical contents make the sale, offering for sale, or offering for promotional purposes of such battery unlawful under title II of this Act.
361 SEC. 6. INFORMATION GATHERING AND ACCESS. (a) Records and Reports.--A person who is required to carry out the objectives of this Act, including-- (1) a regulated battery manufacturer; (2) a rechargeable consumer product manufacturer; (3) a mercury-containing battery manufacturer; and (4) an authorized agent of a person described in paragraph (1), (2), or (3), shall establish and maintain such records and report such information as the Administrator may by regulation reasonably require to carry out the objectives of this Act. (b) Access and Copying.--The Administrator or the Administrator's authorized representative, on presentation of credentials of the Administrator, may at reasonable times have access to and copy any records required to be maintained under subsection (a). (c) Confidentiality.--The Administrator shall maintain the confidentiality of documents and records that contain proprietary information. SEC. 7. STATE AUTHORITY. Nothing in this Act shall be construed to prohibit a State from enacting and enforcing a standard or requirement that is identical to a standard or requirement established or promulgated under this Act. Except as provided in sections 103(e) and 104, nothing in this Act shall be construed to prohibit a State from enacting and enforcing a standard or requirement that is more stringent than a standard or requirement established or promulgated under this Act. SEC. 8. AUTHORIZATION OF APPROPRIATIONS. There are authorized to be appropriated such sums as are necessary to carry out this Act. TITLE I--RECHARGEABLE BATTERY RECYCLING ACT SEC. 101. SHORT TITLE. This title may be cited as the "'Rechargeable Battery Recycling Act". SEC. 102. PURPOSE. The purpose of this title is to facilitate the efficient recycling or proper disposal of used nickel-cadmium rechargeable batteries, used small sealed leadacid rechargeable batteries, other regulated batteries, and such rechargeable batteries in used consumer products, by-- (1) providing for uniform labeling requirements and streamlined regulatory requirements for regulated battery collection programs; and (2) encouraging voluntary industry programs by eliminating barriers to funding the collection and recycling or proper disposal of used rechargeable batteries. SEC. 103. RECHARGEABLE CONSUMER PRODUCTS AND LABELING. (a) Prohibition.-- (1) In general.--No person shall sell for use in the United States a regulated battery that is ready for retail sale or a rechargeable consumer product that is ready for retail sale, if such battery or product was manufactured on or after the date 12 months after the date of enactment of this Act, unless the labeling requirements of subsection (b) are met and, in the case of a regulated battery, the regulated battery-- (A) is easily removable from the rechargeable consumer product; or (B) is sold separately. (2) Application.--Paragraph (1) does not apply to any of the following: (A) The sale of a remanufactured product unit unless paragraph (1) applied to the sale of the unit when originally manufactured. (B) The sale of a product unit intended for export purposes only. (b) Labeling.--Each regulated battery or rechargeable consumer product without an easily removable battery manufactured on or after the date that is 1 year after the date of enactment of this Act, whether produced domestically or imported shall bear the following labels: (1) 3 chasing arrows or a comparable recycling symbol. (2)(A) On each regulated battery which is a nickel-cadmium battery, the chemical name or the abbreviation "'Ni-Cd" and the phrase "'BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY.". (B) On each regulated battery which is a lead-acid battery, "'Pb" or the words "'LEAD", "'RETURN", and "'RECYCLE" and if the
362 regulated battery is sealed, the phrase "'BATTERY MUST BE RECYCLED.". (3) On each rechargeable consumer product containing a regulated battery that is not easily removable, the phrase "'CONTAINS NICKEL-CADMIUM BATTERY. BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY." or "'CONTAINS SEALED LEAD BATTERY. BATTERY MUST BE RECYCLED.", as applicable. (4) On the packaging of each rechargeable consumer product, and the packaging of each regulated battery sold separately from such a product, unless the required label is clearly visible through the packaging, the phrase "'CONTAINS NICKEL-CADMIUM BATTERY. BATTERY MUST BE RECYCLED OR DISPOSED OF PROPERLY." or "'CONTAINS SEALED LEAD BATTERY. BATTERY MUST BE RECYCLED.", as applicable. (c) Existing or Alternative Labeling.-- (1) Initial period.--For a period of 2 years after the date of enactment of this Act, regulated batteries, rechargeable consumer products containing regulated batteries, and rechargeable consumer product packages that are labeled in substantial compliance with subsection (b) shall be deemed to comply with the labeling requirements of subsection (b). (2) Certification.-- (A) In general.--On application by persons subject to the labeling requirements of subsection (b) or the labeling requirements promulgated by the Administrator under subsection (d), the Administrator shall certify that a different label meets the requirements of subsection (b) or (d), respectively, if the different label-- (i) conveys the same information as the label required under subsection (b) or (d), respectively; or (ii) conforms with a recognized intemational standard that is consistent with the overall purposes of this title. (B) Constructive certification.--Failure of the Administrator to object to an application under subparagraph (A) on the ground that a different label does not meet either of the conditions described in subparagraph (A) (i) or (ii) within 120 days after the date on which the application is made shall constitute certification for the purposes of this Act. (d) Rulemaking Authority of the Administrator.-- (1) In general.--If the Administrator determines that other rechargeable batteries having electrode chemistries different from regulated batteries are toxic and may cause substantial harm to human health and the environment if discarded into the solid waste stream for land disposal or incineration, the Administrator may, with the advice and counsel of State regulatory authorities and manufacturers of rechargeable batteries and rechargeable consumer products, and after public comment-- (A) promulgate labeling requirements for the batteries with different electrode chemistries, rechargeable consumer products containing such batteries that are not easily removable batteries, and packaging for the batteries and products; and (B) promulgate requirements for easy removability of regulated batteries from rechargeable consumer products designed to contain such batteries. (2) Substantial similarity.--The regulations promulgated under paragraph (1) shall be substantially similar to the requirements set forth in subsections (a) and (b). (e) Uniformity.--After the effective dates of a requirement set forth in subsection (a), (b), or (c) or a regulation promulgated by the Administrator under subsection (d), no Federal agency, State, or political subdivision of a State may enforce any easy removability or environmental labeling requirement for a rechargeable battery or rechargeable consumer product that is not identical to the requirement or regulation. (f) Exemptions.-- (1) In general.--With respect to any rechargeable consumer product, any person may submit an application to the Administrator for an exemption from the requirements of subsection (a) in accordance with the procedures under paragraph (2). The application shall include the following information: (A) A statement of the specific basis for the request for the exemption. (B) The name, business address, and telephone
363 number of the applicant. (2) Granting of exemption.--Not later than 60 days after receipt of an application under paragraph (1), the Administrator shall approve or deny the application. On approval of the application the Administrator shall grant an exemption to the applicant. The exemption shall be issued for a period of time that the Administrator determines to be appropriate, except that the period shall not exceed 2 years. The Administrator shall grant an exemption on the basis of evidence supplied to the Administrator that the manufacturer has been unable to commence manufacturing the rechargeable consumer product in compliance with the requirements of this section and with an equivalent level of product performance without the product-- (A) posing a threat to human health, safety, or the environment; or (B) violating requirements for approvals from governmental agencies or widely recognized private standard-setting organizations (including Underwriters Laboratories). (3) Renewal of exemption.--A person granted an exemption under paragraph (2) may apply for a renewal of the exemption in accordance with the requirements and procedures described in paragraphs (1) and (2). The Administrator may grant a renewal of such an exemption for a period of not more than 2 years after the date of the granting of the renewal. SEC. 104. REQUIREMENTS. (a) Batteries Subject to Certain Regulations.--The collection, storage, or transportation of used rechargeable batteries, batteries described in section 3(5)(C) or in title II, and used rechargeable consumer products containing rechargeable batteries that are not easily removable rechargeable batteries, shall, notwithstanding any law of a State or political subdivision thereof governing such collection, storage, or transportation, be regulated under applicable provisions of the regulations promulgated by the Environmental Protection Agency at 60 Fed. Reg. 25492 (May 11, 1995), as effective on May 11, 1995, except as provided in paragraph (2) of subsection (b) and except that-- (1) the requirements of 40 CFR 260.20, 260.40, and 260.41 and the equivalent requirements of an approved State program shall not apply, and (2) this section shall not apply to any lead acid battery managed under 40 CFR 266 subpart G or the equivalent requirements of an approved State program. (b) Enforcement Under Solid Waste Disposal Act.--(1) Any person who fails to comply with the requirements imposed by subsection (a) of this section may be subject to enforcement under applicable provisions of the Solid Waste Disposal Act. (2) States may implement and enforce the requirements of subsection (a) if the Administrator finds that-- (A) the State has adopted requirements that are identical to those referred to in subsection (a) governing the collection, storage, or transportation of batteries referred to in subsection (a); and (B) the State provides for enforcement of such requirements. TITLE II--MERCURY-CONTAINING BATTERY MANAGEMENT ACT SEC. 201. SHORT TITLE. This title may be cited as the "'Mercury-Containing Battery Management Act". SEC. 202. PURPOSE. The purpose of this title is to phase out the use of batteries containing mercury. SEC. 203. LIMITATIONS ON THE SALE OF ALKALINE- MANGANESE BATTERIES CONTAINING MERCURY. No person shall sell, offer for sale, or offer for promotional purposes any alkaline-manganese battery manufactured on or after the date of enactment of this Act, with a mercury content that was intentionally introduced (as distinguished from mercury that may be incidentally present in other materials), except that the limitation on mercury content in alkaline-manganese button cells shall be 25 milligrams of mercury per button cell.
364 SEC. 204. LIMITATIONS ON THE SALE OF ZINC- CARBON BATTERIES CONTAINING MERCURY. No person shall sell, offer for sale, or offer for promotional purposes any zinc-carbon battery manufactured on or after the date of enactment of this Act, that contains mercury that was intentionally introduced as described in section 203. SEC. 205. LIMITATIONS ON THE SALE OF BUTTON CELL MERCURIC-OXIDE BATTERIES. No person shall sell, offer for sale, or offer for promotional purposes any button cell mercuric-oxide battery for use in the United States on or after the date of enactment of this Act. SEC. 206. LIMITATIONS ON THE SALE OF OTHER MERCURIC-OXIDE BATTERIES. (a) Prohibition.--On or after the date of enactment of this Act, no person shall sell, offer for sale, or offer for promotional purposes a mercuric-oxide battery for use in the United States unless the battery manufacturer, or the importer of such a battery-- (1) identifies a collection site in the United States that has all required Federal, State, and local government approvals, to which persons may send used mercuric-oxide batteries for recycling or proper disposal; (2) informs each of its purchasers of mercuric-oxide batteries of the collection site identified under paragraph (1); and (3) informs each of its purchasers of mercuric-oxide batteries of a telephone number that the purchaser may call to get information about sending mercuric-oxide batteries for recycling or proper disposal. (b) Application of Section.--This section does not apply to a sale or offer of a mercuric-oxide button cell battery. SEC. 207. NEW PRODUCT OR USE. On petition of a person that proposes a new use for a battery technology described in this title or the use of a battery described in this title in a new product, the Administrator may exempt from this title the new use of the technology or the use of such a battery in the new product on the condition, if appropriate, that there exist reasonable safeguards to ensure that the resulting battery or product without an easily removable battery will not be disposed of in an incinerator, composting facility, or landfill (other than a facility regulated under subtitle C of the Solid Waste Disposal Act (42 U.S.C. 6921 et seq.)). Approved May 13, 1996.
365 EPA's Document on the States Adopting Advanced Legislation for Battery Management (December 14, 2000) State Legislation Affecting Rechargeable Batteries The 1996 Battery Act eased the burden on battery recycling programs by mandating national, uniform labeling requirements for Ni-Cd and certain small sealed lead-acid batteries and by making the Universal Waste Rule effective in all 50 states. The Battery Act preempts state labeling requirements for these battery types and state legislative and regulatory authority for the collection, storage, and transportation of Ni-Cd and other covered batteries. States can, however, adopt standards for battery recycling and disposal that are more stringent than existing Federal standards. States can also adopt more stringent requirements concerning the allowable mercury content in batteries. Several states have passed legislation mandating additional reductions in mercury beyond those in the Battery Act and prohibiting or restricting the disposal in MSW of batteries with the highest heavy metal content (i.e., Ni-Cd, small sealed lead-acid, and mercuric-oxide batteries). A handful of states have gone further, placing collection and management requirements on battery manufacturers and retailers to ensure that certain types of batteries are recycled or disposed of properly. Among the states and regional organizations that have developed far-reaching legislation for battery management--beyond the scope of Federal law--are: Florida A Florida law, effective April 1998, requires manufacturers, importers, and marketers (excluding retail marketers) of Ni-Cd, small sealed lead-acid, and certain mercuric oxide batteries to develop and implement management programs for collecting and taking back spent batteries. Under the law, manufacturers have the sole responsibility for reclaiming or disposing of the batteries returned to them. Manufacturers are also required to accept brands other than their own, as long as the retumed battery is of the same general type. The same law includes labeling requirements for rechargeable batteries and bans their disposal in the mixed solid waste stream. The law also bans the sale of mercury button cell batteries and limits the mercury content in other nonrechargeable batteries sold in the state. Iowa
Iowa has a comprehensive collection, transportation, and recycling or disposal program for Ni-Cd, household small sealed lead-acid, and mercuric-oxide batteries. Each of these battery types is banned from disposal in MSW. Manufacturers must provide a telephone number to consumers, offering information on returning batteries for recycling or proper disposal. Costs of the program may be built into the original cost of the battery.
Minnesota Minnesota law requires manufacturers of rechargeable Ni-Cd batteries or products containing those batteries to take responsibility for the costs of collecting and managing waste batteries to ensure that they do not enter the waste stream. Consumers are responsible for returning spent batteries to the collection points, which include retail
366 stores and Minnesota's household hazardous waste facilities. New Jersey New Jersey legislation passed in 1992 bans rechargeable batteries from the municipal waste stream and requires that manufacturers take back these batteries for recycling or proper disposal. The legislation also requires that rechargeable batteries be easily removable from products and labeled as to their content and proper disposal. For batteries that aren't currently being recycled, such as alkaline batteries containing mercury, the legislation limits the content of heavy metals. Rhode Island Rhode Island law prohibits the disposal of Ni-Cd, mercuric-oxide, and small sealed lead-acid batteries in municipal or commercial solid waste. Manufacturers of these battery types must ensure that a system exists for the proper collection, transportation, and processing of waste batteries (this requirement pertains only to manufacturers whose batteries are used by a government agency or an industrial, communications, or medical facility). Manufacturers must accept waste batteries returned to their facilities for proper processing. Vermont Vermont law bans the disposal of Ni-Cd, non-consumer mercuric-oxide, and small sealed lead-acid batteries in any district or municipality where an ongoing program exists for treating these wastes. Govemment agencies and industrial, communications, and medical facilities may not dispose of these battery types in MSW. Battery manufacturers must implement a system for the proper collection, transportation, and processing of these battery types and include the cost of collection in the sales transaction. Manufacturers must accept waste batteries retumed to their facilities. Northeast Waste Management Officials' Association The Northeast Waste Management Officials' Association (NEWMOA), a coalition of state waste program directors from New England and New York, has developed draft model legislation meant to reduce mercury in waste. The model legislation proposes a variety of approaches that states can use to manage mercury-containing products (such as batteries, thermometers, and certain electronic products) and wastes, with a goal of instituting consistent controls throughout the region. The proposed approaches focus on notification; product phase-outs and exemptions; product labeling; disposal bans; collection and recycling programs; and a mechanism for interstate cooperation. Bills based on the model legislation have been under consideration by legislators in New Hampshire and Maine. In April 2000, NEWMOA released a revised version of the model legislation following a series of public meetings and the collection of comments from stakeholders. New England Governors' Conference The New England Governors' Conference passed a resolution in September 2000 recommending, among other things, that each New England state work with its legislature to adopt mercury legislation based on the NEWMOA model (see above). The NEWMOA model legislation is meant to reduce the amount of mercury in waste
367 through strategies such as product phase-outs, product labeling, disposal bans, and collection and recycling programs. Certain types of mercury-containing batteries are among the products targeted by the model legislation. State Legislation Affecting Lead-Acid Batteries Most states have passed legislation prohibiting the disposal of lead-acid batteries (which are primarily automotive batteries) in landfills and incinerators and requiring retailers to accept used batteries for recycling when consumers purchase new batteries. For example, Maine has adopted legislation that requires retailers to either: l) accept a used battery upon sale of a new battery, or 2) collect a $10 deposit upon sale of a new battery, with the provision that the deposit shall be returned to the customer if he or she delivers a used lead-acid battery within 30 days of the date of sale. This legislation is based on a model developed by the lead-acid battery industry. Lead-acid batteries are collected for recycling through a reverse distribution system. Spent lead batteries are returned by consumers to retailers, picked up by wholesalers or battery manufacturers, and finally taken to secondary smelters for reclamation. These recycling programs have been highly successful: the nationwide recycling rate for leadacid batteries stands at roughly 95 percent, making them one of the most widely recycled consumer products.
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369 SUBJECT INDEX
ACCUREC GmbH, 163 Advanced battery systems recycling, 315 Advanced Lead Acid Battery Consortium (ALABC), 233,295 Accelerated Reduction and Elimination of Toxics (ARET), 9 Australian Mobile Telecommunications Association (AMTA), 127 Battery Act, 133 Battery Association of Japan (BAJ), 12, 87 Batteries annual acquisition rate, 56 collection efficiency, 55 and recycling rate, 76 collection methods, 184 collection, future options, 190 effect on human health, 307 and environment, 9 european legislation, 178 national legislation, 179, 181 emissions, 11-14 from MSW incinerators, 64 life cycle analysis, 2, 26 in MSW, 61-64 nominal compositions, 7 production in Japan, 88 raw materials production, 3, 5 rechargeable, european market, 39, 42 worldwide production, 41 recycling hydrometallurgical processes, 192 pyrometallurgical processes, 194 recycling score, 311 systems, use and maintenance, 15 sorting, 199 stages in, 202 UV sensing, 203 Efficiency, 205 systems, manufacture, 10 Big River Zinc, 149 British ECTEL, 125
Cadmium concentration in air, 14 in water, 13 in MSW, 37 daily intake levels, 19 emissions during production of NiCd, 22 for EV, 14 emissions during recycling, 22, 65 emissions from landfills, 66 hydrometallurgical separation, 150 partitioning in NiCd battery, 11 pyrometallurgical separation, 154 sources of human exposure, 8 COBAT (Italy), 235 institution, 235 collection network, 236 spent battery assignment to the recycling companies, 237 CollectNiCad, 37 Compositions of battery families, 7 Department of Energy (DOE), 296 Department of Transportation (DOT), 132 Disposal os spent batteries, 17 Dry cells and mercury, 88, 178, 183 composition, 90 recycling techniques, 90 Energizer, 149 Energy consumed in primary metal production, 9 Electric and electronic equipment, 36, 57-61 penetration rate, 46 timeframe for aquisition, 48 Electric arc furnaces, 209 recycling in, 215 Electric vehicle (EV) batteries for, 298 market, 297 general recycling issues, 308 pack characteristics, 298
370 Ecological and environmental impacts, 1,225 Energy to produce primary metals, 9 Environmental Protection Agency (EPA), 132, 305 Environmental impact values for battery metals, 26 for AA NiCd batteries, 30 Euro-Bat-Tri, 207 European Battery Directive EEC 91/57, 178, 234 European Portable Battery Association (EPBA), 182 European Union legislation on waste, 77 EV batteries environment/safety/ health issues, 305 recycling, 304 methods for, 308 Federal Resource Conservation and Recovery (RCRA), 130 GRS Batterien, 150
H2SO4 environmental impact, 227 health impact, 226 Human health impacts of battery components, 307 Heavy metal waste from AA NiCd batteries, 28 Hg in dry cells, 88, 179 Hoarding rate, 50 Hybrid Electric Vehicle (HEV) batteries, 297 International Cadmium Association, 11 International Metals Reclamation Company (INMETCO) NiCd battery recycling, 113, 171, Impact assessment evaluation methods, 24 KOBAR, 162 Lead-acid batteries collection in the European Union consortia-based, 246 non consortia-based, 239 rates, 248 costs, 249 collection in Japan, 92
components, 230 economical aspects, 228 environmental and health impact, 225 European Union regulations, 234 evolution of the market, 229 in EV, 310 recycling costs in Italy, 238 in the European Union, 239 recycling in Japan, 92 industrial, 93 small-size sealed, 94 recycling technologies, 252 comparison of, 260 fusion/reduction, 256 rotary kilns, 256 physical treatments, 253 "sink and float" separation, 253 hydrodynamic separation, 254 carbonatation, 255 flowchart, 257 Pb refining, 259 shipments (from Japan), 91 slag disposal costs, 250 transport to the recycling plants, 252 technological evolution in car accumulators, 231 in industrial accumulators, 233 VRLA, 233
Li2CO3from Li batteries, 289, 316 Lithium batteries Co recovering from, 277 components, 266 current recycling technologies, 277 wet methods, 278 pyrometaUurgical methods, 277 Toxco's cryoscopic technique, 279 economics of recycling, 277 environmental concerns, 272 hazards in recycling, 267, 270 primary batteries, 267 rechargeable batteries, 269 Li/SO2 analysis, 282 air emissions during recycling, 286 battery constituents, 284 chemical reactions, 286 recycling process, 284 Li/MnO2 analysis, 287
371 air emissions during recycling, 290 battery constituents, 287 biological effects, 290 recycling process, 288 safety measures during recycling, 271 sorting/packaging/transporting, 274 types, 266 Lithium-ion batteries, 7 in EV, 315 toxicity, 307 Lithium-polymer batteries, 267, 319 Manufacture of battery systems, 10 Mitsui Mining, 149 NiCd batteries, "Charge Up to Recycle Program", 109 collection of industrial, 68 closed processes, 160 hydrometallurgical process, 150 INMETCO HTMR process, 114 labeling, 111 market for industrial, 43 open processes, 157 performance parameters, 16 pyrometallurgical process, 154 recycling in Europe, 80, 148, 162, 163, 175, 176 Australia, 127 Mexico, 128 U.S.A., 105, 129 Canada, 105, 133 recycling rate formula, 80 sales in Europe, 42 sorting, 67 specific processes, 155 mechanical, 155 hydrometallurgical, 156 thermal, 157 transboundary movement within the OECD, 135, 139 transportation costs, 138 NiMH batteries in EV, 315 recycling, 317, toxicity, 306 Nippon Recycle Center, 148, 172 Optimized battery recycling processes
for NiMH, 317 for Li-ion, 319 for Li-polymer, 319 Organization for Economic Cooperation and Development (OECD), 10, 119 Members, 145 Partnership for a new Generation of Vehicles (PNVG), 295 Pb applications, 230 health impact, 225 mass in EV batteries, 312 reference dose, 226 Portable rechargeable batteries collection and recycling in Japan, 94 collection rates corrected with hoarding, 103 collection results in Japan, 100 collection schemes in Europe, 71 collection volumes in Europe, 68 color coding, 98 elimination modes, 51 hoarding issue, 43, 100 definitions, 45 hoarding rate, 50 in EEE: collection, 73 list of japanese recyclers, 99 market trends (Europe), 42 market trends (Japan), 95 metal contents, 97 quantity available for collection, 53 discarded in MSW, 54 Primary batteries additions to a steel melt, 211 definitions, 177 collection, 177 industry, 180 mercury in, 178, 183 recycling in the metals industry, 209 in the EAF, 210, 215 treatment os spent, in Japan, 88 waste stream analysis, 195 Rechargeable Battery Recycling Corporation (RBRC) in U.S.A. and Canada, 134 Charge Up to Recycle Program, 109, 112
372 Replacement batteries, 46 SAFT AB, 164 SNAM, 167 SORTBAT battery sorting, 204 Spent batteries, collection programs in Europe, 69 Starting, Lighting, Ignition (SLI) batteries, 35 Soci6t6 de Collecte et Recyclage du Mat6riel Electrique (SCRELEC), 74-76 Sources of human Cd exposures, 8 Toho Zinc, 149 Total life cycle analysis (LCA), 2 Toxco-Kinsbursky partnership, 304 Toxco-Nissan partnership, 305 Toxicity Characteristic Leaching Procedure (TCLP), 129, 307 UN environmental indicators, 77 Union Mini~re, 149 Universal Waste Rule, 132 United States Advanced Battery Consortium (USABC), 295 Valdi process, 219 Waelz kilns, 221 Waste from electric and electronic Equipment, 37 World Health Organization (WHO), 18, 226 Zero Emission Vehicle (ZEV) programs in California, 295
