used battery collection and recycling

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 sy

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

(Edited by D.L Wise, Y.A Levendis and M Metghalchi)

Advances in Organobromine Chemistry I (Edited by J.-R Desmurs and B G6rard)

Technology of Corn Wet Milling and Associated Processes (by P.H B lanchard)

Lithium Batteries New Materials, Developments and Perspectives (Edited by G Pistoia)

Industrial Chemicals Their Characteristics and Development (by G Again)

Advances in Organobromine Chemistry II (Edited by J.-R Desmurs, B G6rard and M.J Goldstein)

The Roots of Organic Development (Edited by J.-R Desmurs and S Ratton)

High Pressure Process Technology: Fundamentals and Applications

(Edited by A Bertucco and G Vetter)

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

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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

This Page Intentionally Left Blank

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,

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

This Page Intentionally Left Blank

Table of Contents

Preface

List o f Contributors

Chapter 1 Environmental and Human Health Impact Assessments of Battery Systems 1

H Morrow A b s t r a c t 1

Introduction 2

Battery R a w Materials Production 5

M a n u f a c t u r e o f Battery Systems 10

U s e and M a i n t e n a n c e o f Battery S y s t e m s 15

D i s p o s a l o f Spent Batteries 17

E n v i r o n m e n t a l and H u m a n Health I m p a c t A s s e s s m e n t s 22

C y c l e Life A n a l y s i s o f Battery S y s t e m s 26

C o n c l u s i o n s 31

R e f e r e n c e s 32

Chapter 2 Portable Rechargeable Batteries in Europe: Sales, Uses, Hoarding, Collection and Recycling 35

J.-P Wiaux Introduction 35

The E u r o p e a n M a r k e t o f Portable R e c h a r g e a b l e Batteries 39

H o a r d i n g o f Portable R e c h a r g e a b l e Batteries 43

Batteries in M u n i c i p a l Solid W a s t e ( M S W ) 61

Collection o f Spent R e c h a r g e a b l e Batteries 66

Collection Efficiency and R e c y c l i n g Rate 76

C o n c l u s i o n s 81

R e f e r e n c e s 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

N i c k e l C a d m i u m Batteries 155

T o d a y ' s Battery R e c y c l i n g C o m p a n i e s 162

1 Europe 162

2 U.S.A 171

3 K o r e a 171

4 Japan 172

C o n c l u s i o n 174

Chapter 7 P r i m a r y Battery Recycling in Europe 177

N Watson Battery Definition 177

Battery Collection 177

Battery R e c y c l i n g 191

Battery Sorting 199

Integrating with Existing R e c y c l i n g Operations 209

C o n c l u s i o n s 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 E n v i r o n m e n t a l and Health I m p a c t 225

E c o n o m i c a l Aspects 228

L e a d A c c u m u l a t o r Structure 230

The Collection o f Spent Batteries 234

C o m p a r i s o n W i t h Other Countries o f the E u r o p e a n U n i o n 239

Collection M o d e s and R e c y c l i n g Techniques 251

C o n c l u s i o n s 261

Chapter 9 Recycling The Lithium Battery 263

D.G Miller and W McLaughlin

xii

Introduction 263

Background 263

The Hazards and Safety Aspects o f Recycling Lithium Batteries 267

Environmental Concerns o f Recycling Lithium Batteries 272

Sorting, Packaging, Storage, and Transporting o f Lithium Batteries for Recycling 274

Lithium Battery Recycling Technologies 277

The T o x c o ' s Background and Processing Method 279

Two o f T o x c o ' 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

S u m m a r y 322

References 324

A p p e n d i x 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

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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:

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

Battery-Powered Devices & Applications

Figure 1 Materials and E n e r g y I n v e n t o r y A n a l y s i s 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 non- rechargeable 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

Alkaline Manganese*

Lead Acid*

Nickel-Cadmium*

Nickel Metal Hydride (ABs)*

Nickel Metal Hydride (AB2)*

30Fe - 20Zn - 15Mn

6 5 P b - 25H2SO4 30Fe - 30Ni - 15Cd 45Ni - 10Mg/A1 - 9Ce - 4Co

Nickel Metal Hydride(ABs)***

Nickel Metal Hydride(AB2)***

6 9 P b - 22H2SO4 14Fe - 26Ni - 18Cd 15Fe - 31Ni - 22Cd

4 4 F e - 2 9 N i - 5 Rare E a r t h s - 2 C o - 1Mn

4 4 F e - 2 4 N i - 7 V - 3 Z r - 2Cr- 1Ti

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

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 land- filling 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 land- filled 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

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

Figure 4 J a p a n e s e River W a t e r C a d m i u m Concentration

and N i C d 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 eight- fold 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*

Emission Sink

Grams Metal Emissions per KW-Hour

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 nickel- cadmium 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 Range of Values

Voltage

Capacity

Total Energy

Cycle Life (80%DOD)

Total Lifetime Energy

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

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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

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

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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 b a t t e r i e s - 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

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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

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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

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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 Nickel- iron, 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

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Table VI Cadmium Emissions from Production and Recycling NiCd Batteries*

Production Emissions (grams Cd per KW-hr)

Recycling Emissions (arams Cd per KW-hr)

*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

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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

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 M e t h o d - 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 M e t h o d - 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

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Ecoscarcity M e t h o d - Defines a relationship for a given country of given

a r e a

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

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Table VII Relative Environmental Impact Values for Battery Metals

Utilizing Various Assessment Evaluation Methods

*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

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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 8 th 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