HAZARD ASSESSMENT OF MANAGEMENT OF WASTE LITHIUM BATTERIES
by
B.C. Vincent
Factory Mutual Research Corporation
Norwood, Massachusetts 02062
Contract No. 68-01-6698
Project Officer
Florence Richardson
Office of Solid Waste
Environmental Protection Agency
401 M Street SW
Washington, D.C. 20460
FMRC J.I. OH1N6.RG
070(A)
June 1983
OFFICE OF SOLID WASTE
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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DISCLAIMER
This report has been reviewed by the Office of Solid Waste, U. S. Environ-
mental Protection Agency, and approved for publication. Approval does not
signify that the contents necessarily reflect the views and policies of the
U. S. Environmental Protection Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use.
ii
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ABSTRACT
The purpose of this study was to assess the hazards associated with the
disposal of waste lithium batteries using existing lithium battery safety test
and accident data. First, a survey was conducted to determine 1) basic cell
constituents and electrochemical reaction by-products of the various lithium
batteries, and 2) products of reactions between cell constituents and water or
heat. Next, a survey of solid waste disposal techniques was conducted. This
involved the identification of both waste lithium battery management practices
and conventional solid waste disposal techniques. Using the information from
this survey, the hazards associated with the collection, processing, and dis-
posal of waste lithium batteries were assessed.
A survey of lithium battery safety test and accident data indicated that
abuse test procedures for lithium cells frequently simulated hazardous conditions
anticipated in disposal operations. Abuse test data were then used in evaluating
the behavior of lithium batteries during disposal operations. However, published
results of abuse tests and toxicity data were incomplete for several generic
electrochemical systems, and did not take into account manufacturer variations
in cell construction and safety features. For this reason, it is recommended
that standardized abuse tests be used for testing lithium batteries to deter-
mine their hazard potential. In the interim, until such data can be generated
and reviewed, the following conclusions were made.
1) Lithium-thionyl chloride and lithium-sulfur dioxide batteries should
be considered potential safety hazards if processed using conventional waste
disposal methods.
2) Several lithium battery systems, (lithium-sulfur dioxide, lithium-
thionyl chloride, lithium-manganese dioxide and lithium vanadium pentoxide)
contain highly toxic compounds which may contaminate the environment if re-
leased. These systems should be considered potentially dangerous to the
environment.
3) Because of safety and environmental considerations, lithium bat-
teries, as a class, should not be incinerated.
This report was submitted in fulfillment of Contract No. 68-01-6698 by
Factory Mutual Research Corporation, Norwood, Massachusetts 02062, and sponsored
by the Environmental Protection Agency. This report covers the period
October 1982 - March 1983 and work was completed as of March 31, 1983.
iii
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TABLE OF CONTENTS
Section
ABSTRACT
1
2
3
4
Title
INTRODUCTION
SUMMARY
CONCLUSIONS AND RECOMMENDATIONS
IDENTIFICATION OF LITHIUM BATTERY MATERIALS
Lithium-Sulfur Dioxide (Li/S02)
Lithium-Thionyl Chloride (Li/SOCl2)
Lithium-Polycarbon Monofluoride (Li/(CF) )
X
Lithium-Manganese Dioxide (Li/MnO.)
Lithium-Iodine (Li/I-PVP)
Lithium-Iron Sulfide (Li/FeS)
Lithium Copper-Oxide (Li/CuO)
Lithium-Silver Chromate (Li/Ag2CrO.)
Lithium-Vanadium Pentoxide (Li/V^)
QUANTIFICATION OF WASTE LITHIUM BATTERY DISPOSAL HAZARDS
Lithium Battery Waste Disposal Techniques
Conventional Waste Disposal Techniques
Correlation Of Abuse Test Data To Conventional Waste
Disposal Hazards
Mechanical Shock
Short Circuit
Immersion Tests
Cell Deformation Test (Crush Test)
Elevated Temperature/Incineration Tests
Foreign Object Penetration Test
DISCUSSION
REFERENCES
APPENDIX A
GENERALIZED ABUSE TESTS
Page
iii
1
2
5
7
13
16
18
20
20
22
22
23
23
24
24
24
27
29
30
30
31
31
32
33
37
41
iv
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SECTION 1
INTRODUCTION
Like most battery systems, lithium primary cells are constructed using a
variety of materials which are either toxic, reactive, corrosive, or combustible.
(1 2)
Since their introduction in 1970 ' , attention has been drawn to lithium
batteries as the result of several accidents which have occurred during the use
or test of these cells. In view of this, much of the lithium battery research
in recent years has been directed toward improving lithium battery operational
safety. The result has been chemistry modifications and the development of
low pressure vents, fuses, and diodes which significantly reduce the operational
hazards. However, the basic electrochemical components of these cells remain
the same and therefore the accident potential of these systems must still be
recognized. As these cells find increasing use in military, Industrial, and
consumer applications, it becomes necessary to determine whether the hazards
associated with their disposal warrant their classification and control as
"hazardous wastes." This is the basic objective of this study.
To accomplish this objective, it was necessary to 1) identify potentially
hazardous lithium cell components and their properties, 2) characterize conven-
tional waste disposal hazards as they relate to lithium batteries, and 3) de-
velop a methodology for Interpreting existing lithium battery safety test data
to evaluate the anticipated disposal hazards. The scope of work required that
the program objective be executed without the conduct of tests.
Nonrechargeable cells
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SECTION 2
SUMMARY
The objective of this study was to assess the hazards associated with the
disposal of waste lithium batteries and to make the determination as to whether
or not they should be classified as "hazardous wastes" for disposal purposes.
To accomplish the cited program objective, it was first of all necessary
to identify the hazards of the various chemicals in lithium primary battery sys-
tems. This entailed not only the identification of basic cell constituents but
also the identification of those compounds occurring as by-products of electro-
chemical reactions taking place within a given cell during discharge. Further,
to assist in the quantification of safety and environmental hazards, it was also
necessary to determine the products of reactions between cell constituents and
water or heat for those situations where the structural integrity of the cell is
compromised. Once cell materials and reaction by-products were identified,
f 3—8)
safety and toxicity classification data were consulted to assess safety
and environmental hazards.
The data indicated that the lithium-thionyl chloride, lithium-sulfur dioxide,
lithium-manganese dioxide, lithium-iodine, and lithium-vanadium pentoxide systems
contain at least one highly toxic chemical or compound as a basic cell component.
Five systems, lithium-thionyl chloride, lithium-sulfur dioxide, lithium-polycarbon
monofluoride, lithium-iron sulfide, and lithium-vanadium pentoxide contain ele-
ments which will produce hazardous by-products when contacted by water. All
nine lithium battery systems surveyed during this study have components which
will generate hazardous gases when heated to decomposition.
Next, a survey of solid waste disposal techniques was conducted. This sur-
vey was executed in two phases.
First, a survey of lithium battery disposal techniques used by battery
manufacturers and specialty organizations was made. The survey included a review
of processing techniques, battery neutralization and disposal methods, and
accident experience. Most of this information came from personal communication
with battery industry manufacturers or their representatives since very little
information existed in the literature.
The second phase was an assessment of conventional municipal and industrial
waste disposal techniques, specifically geared toward determining the equipment
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and processes used for handling solid waste and rubbish. Using the information
from this survey, the hazards associated with the collection, processing, and
disposal of waste lithium batteries via conventional waste disposal operations
were determined.
Hazardous situations created by conventional waste processing operations
are: 1) mechanical shock - caused by throwing, dropping, or rough handling
during collections or explosion in a processing unit (baler, compactor or shred-
der) during processing; 2) external short circuit - the result of bridging bat-
tery terminals by electrically conductive materials contained in the trash;
3) immersion in water or moist material; 4) crushing - caused by shredding or
compacting operations (during collection or processing) or grading equipment at
the disposal site; 5) elevated temperature/fire - caused by spontaneous heating
of organic matter in the trash or an incineration operation; and 6) foreign ob-
ject penetration - rupture or puncture by adjacent material during compacting
or landfilling operations. The hazardous situations may result in lithium bat-
tery explosion, fire, internal exothermic reactions, or hazardous material re-
leases.
Once potential hazards were defined, efforts were made to assess the effects
of these hazards during disposal operations. These hazard assessments were
based upon published physical abuse test (incineration, mechanical shock, crush-
ing, etc.) data for various lithium cells. The test procedures frequently
simulated hazardous situations anticipated in disposal operations. By cor-
relating abuse test data to potential accident scenarios, a reasonable assess-
ment of the behavior of lithium batteries in conventional waste disposal op-
erations was made.
The review of abuse test data revealed the following:
1) External short circuit tests of unfused lithium-sulfur dioxide, lithium-
thionyl chloride and lithium-polycarbon monofluoride cells resulted in the
activation of vent mechanisms. Certain lithium-thionyl chloride cells also de-
formed and exploded under external short circuit conditions.
2) Immersion (in fresh or salt water) and drop tests of intact cells at
approximately 25°C produced no hazardous situation.
3) Cell deformation (crush) tests resulted in the venting of lithium-
sulfur dioxide cells.
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4) Foreign object penetration tests caused minor heating (10°-20°C) in
lithium-copper oxide cells and explosion in lithium-thionyl chloride cells.
5) Explosions are likely if the internals of lithium cells are allowed
to reach the melting point of lithium (approximately 180°C).
Conclusions based upon this hazard evaluation are presented in Section 3
of this report.
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SECTION 3
CONCLUSIONS AND RECOMMENDATIONS
Lithium battery disposal hazards can be divided into two broad categories:
1) immediate hazards for disposal workers handling the batteries, and 2) long-
range hazards to the environment and the neighboring populace.
Hazards to disposal workers can best be determined from standardized abuse
tests similar to those described in Appendix A. Some published abuse test data
results are available, but further testing is needed to provide a comprehensive,
updated data base covering all lithium cell designs, i.e., including important
variations among manufacturers. In lieu of a standardized abuse test data base,
the following interim generic hazard classifications are offered based on bat-
tery component toxicity/flammability/reactivity data, accident reports, and the
correlation of available abuse test data to abuses incurred during disposal.
1) Lithium-thionyl chloride and lithium-sulfur dioxide batteries should
be temporarily classified as hazardous because they can explode, burn, and/or
vent toxic fumes during conventional municipal solid waste disposal operations.
If and when manufacturers of these batteries submit documented evidence that
their particular cells should be rated low hazard or nonhazardous when sub-
jected to the types of abuse tests in Appendix A, their cells should be ex-
empted from this hazardous classification.
2) The remaining lithium battery systems surveyed (lithium-carbon
monofluoride, lithium-manganese dioxide, lithium-iodine, lithium-iron sulfide,
lithium-copper oxide, lithium-silver chromate and lithium vanadium pentoxide)
should not be classified as hazardous to disposal workers because they do not
present the same safety hazard as do the thionyl chloride and sulfur dioxide
systems. During this study no cases of fire or explosions initiated by these
systems were documented. With possible exception of incineration, the abuse
test data reviewed gave virtually no indication of safety problems with these
systems.
3) All lithium battery systems are hazardous to nearby personnel and
the environment when they are incinerated; therefore, incineration should be
prohibited.
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With regard to the long-range hazard to the environment and surrounding
populace it was determined that six of the lithium battery systems surveyed in
this study (lithiumsulfur dioxide, lithium-thionyl chloride, lithium-manganese
dioxide, lithium-iodine, lithium-polycarbon monofluoride and lithium-vanadium
pentoxide) may contain highly toxic compounds which will contaminate the en-
vironment if released. The actual environmental impact will be a function of
the concentration of cells disposed in a given location, as well as the (cur-
rently unspecified) quantities of these toxic materials in individual cells.
The decision as to whether to classify these batteries as environmentally haz-
ardous should be delayed until data on material quantities, case corrosion
rates, pollutant leach rates, and transport (dispersal paths in the soil) are
acquired. In the interim, treatment and disposal of waste lithium batteries
as an environmentally hazardous waste would be prudent.
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SECTION 4
IDENTIFICATION OF LITHIUM BATTERY MATERIALS
Initially, a survey of battery manufacturers was conducted to determine the
types of lithium anode battery systems currently being produced and distributed
in this country. The results of this survey are presented in Table 4-1. At
least 18 companies are currently producing or marketing lithium batteries.
(Companies which produce batteries for specialized applications, or those which
custom design batteries according to customer specifications, may not be in-
cluded in the table.) Lithium battery systems discussed in this report are:
lithium-sulfur dioxide, lithium-thionyl chloride, lithium-polycarbon monofluoride,
lithium-manganese dioxide, lithium-iodine, lithium-iron sulfide, lithium-copper
oxide, lithium-silver chromate, and lithium-vanadium pentoxide. Lithium battery
systems which are in production but not discussed, due to lack of data, are the
lithium-sulfuryl chloride and lithium-lead bismuthate systems.
Table 4-2 lists the lithium battery systems investigated during this study.
Of these, a limited number are currently available for over-the-counter purchase
but they represent a very small percentage of total battery sales. Lithium bat-
teries currently available for over-the-counter purchase are: lithium-polycarbon
monofluoride, lithium-iron sulfide, and lithium-manganese dioxide. Lithium-copper
oxide, lithium-iodine and lithium-silver chromate cells were not available for
over-the-counter purchase, but are utilized by consumers in specialty appli-
cations, such as consumer electronics, heart pacemakers, and fire alarm equip-
ment. The lithium-sulfur dioxide, lithium-thionyl chloride and lithium-vanadium
pentoxide systems are used primarily for military and industrial applications
and are frequently designed and manufactured according to customer specifications.
To fully assess lithium battery safety and environmental hazards, it was
necessary to identify 1) hazardous chemicals and compounds found in waste
lithium cells, and 2) any new products created as the result of disposal pro-
cesses.
The common component of all electrochemical systems'investigated in this
study is the lithium which is used to construct the anodes. Lithium is the
lightest and least reactive alkali metal and is, in fact, the lightest of all
solid elements. Of the alkali metals, it possesses the largest negative
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TABLE 4-1 LITHIUM BATTERY MANUFACTURERS
00
1. Altus Corporation
San Jose, CA
2. Battery Engineering
Newton, MA
3. Catalyst Research
Baltimore, MD
4. Duracell International
Elmsford, NY
S. Eagle-Picher
Joplln, Missouri
6. Electrochem Industries
Clarence , NY
7. General Electric
Gainesville, FL
8. GTE
Waltham, MA
9. Honeywell
Horsham, PA
10. Lockheed
Palo Alto, CA
11. Matsushita (Panasonic)
Secaucus, NJ
12. Power Conversion
Elmwood Park, NJ
13. Ray-0-Vac
\laA1ann UT
Type(B)
Llthium-thionyl chloride
(L1/SOC12)
L1/SOC1,
t.
Lithium-sulfur dioxide
(Li/S02)
Lithium- Iodine
(Li/I)
Li/SO,
Lithium-manganese dioxide
(Ll/MnO-)
Li/I
Li/SOCl,
Carbon-monofluoride (Ll/CF)
Li/MnO,
I
Li/SOCl, (Bromine Complex)
Li/Mn02
Li/SOCl,
Llthium-sulfuryl chloride,
(L1/SO,C12)
L1/SOCI2, L1/S02,
LI thlum-vanad lum
pentoxide (Li/V 0 )
& j
Lithium- a liver oxide
(Ll/Ag20)
Ll/CF, Li/Mn02
LI/SO., Ll/MnO,
L1/SOCL2, Ll/CF*
Ll/Mn02, Ll/CF
Slze(a)
Custom
AA.C.DD, Custom
Button, Prismatic
C.D,
Cylindrical cells
1/2AA,AA,A,C,D,DD,
Custom, Prismatic
Button, 1/2AA.AA.2/3A
2/3C,l/2C,D,DD
Custom
C.D
1/2AA,AA,C,D,DD
Prismatic
Custom
C.D.DD,
Prismatic, Custom
Custom
Paper sizes, Button
1/2A.2/3A.C,
Cylindrical
1/2AA,AA,1/2A
2/3A.3/4C.C,! 1/4C.C
Button, C,D
Rated
Cell Volt ages (s)
3.6V
3.6V
2.8V
3.0V
3.0V
3.0V
1.9V
3.6V
2.8V
3.0V
3.9V
3.0
3.6V
2.9V
3.6V
3.4V
-
3.0V
6.0V
2.8V
3.0V
3.4V
2.9V
3.6V
Applications
Military, CMOS Circuits, Industrial
Military, Industrial
Electronic Circuits, Cardiac Pace-makers, Military
Military, Industrial Consumer Products (Ll/MnO,
Li/I)
Electronic Circuitry, Military, Industrial, Consumers
Products
Electronic Circuits, Military, Industrial
Military. Electronic Circuits, Industrial
Military, Industrial, Medical
Military, Space rocket propulsion applications
Industrial, Electronic Circuits,
Consumer Products
Military, Consumer, Medical
Consumer, Medical
*CMOS - Complementary Metal Oxide Semiconductor
Includes bathtub shapes and flat cells
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Manufacturer
Type(s)
TABLE 4-1 (Concluded)
Size(s)
Raced
Cell Voltages(3)
Applications
14. SAFT
Valdosta, CA
15. Sanyo
Little Ferry, NJ
16. Tadiran-Israel
Plainview, NY
17. Union Carbide
New Uork, NY
18. Wileon Greatbatch
Clarence, NY
L1/SOC12, Ll/MnO
Lithium-copper oxide
(Ll/CuO)
Lithium-silver chromate
(Ll/Ag,CrO.)
Lithium-lead bismuthate
Button, 1/2AA.AA
Prismatic*
Complimentary Metal Oxide Semiconductor
Includes bathtub shapes and flat cells
3.5V
3.0V
1.5V
Ll/Mn02
L1/SOC12
Li/MnO,, Ll/CF
Lithium- iron sulfide
(Ll/FeS)
Li/I
Y, N, 2N, C, D, Button,
Prismatic
1/2AA,C,D,AA
Button
Button, Prismatic
3.0V
6.0V
3.6V
1.5V
2.8V
Military (L1/SOC1,), Medical
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TABLE 4-2 HAZARD CHARACTERISTICS OF LITHIUM BATTERY MATERIALS
System
Li/S02
L1/SOC12
Li/(CF)x
Li/MnO,
2
*«.
NA'
Sulfur Dioxide
Aceconitrlle
Propylene Carbonate
Lithium Bromide
Thionyl Chloride
Lithium Tetrachloraluminate
Aluminum Chloride
Lithium Sulfide
Sulfur Dioxide
Lithium Chloride
Sulfur
Carbon Mono fluoride
Methyl Acetate
Lithium Hexafluroarsenate
Dimethyl Sulfite
Methyl Formate
Lithium Fluoride
Manganese Dioxide
Lithium Perchlorate
Propylene Carbonate
1 , 2-Dimethoxy ethane
Methyl Acetate
1,2-Propanediol
Carbon Dioxide
ice 4 G - Gas; L = Liquid;
a Not Available
Phase"
20°C:
1 atm
G
L
L
S
L
S
S
S
G
S
g
S
L
S
L
L
S
S
S
L
L
L
L
G
S - Solid
**
NFPA Classification
Health Flamm. React
2
3
1
NA
HA
NA
3
NA
2
NA
2
NA
1
NA
NA
2
NA
NA
NA
1
2
1
0
NA
0
3
1
NA
NA
NA
0
NA
0
NA
1
NA
3
NA
NA
4
NA
NA
NA
1
2
3
1
NA
0
2
0
NA
NA
NA
2
NA
0
NA
0
NA
0
NA
NA
1
NA
NA
NA
0
0
0
0
NA
**NFPA classifications. -'
Numbers from 0 to 4
Toxicity Rating
High
Moderate
None
Unknown
High
NA
Moderate
Unknown
High
Moderate
Very Low
NA
Moderate
NA
Unknown
Moderate
High
High
Unknown
None
Unknown
Moderate
None
Asphyxiant
Health, Flammabllity
e increasing hazard.
Comments
Irritating gas. Toxic in high concentration.
Dangerous when exposed to heat or flame.
Slight fire hazard.
Corrosive. Emits toxic fumes when exposed
to air.
Exposure to moisture produces toxic or
corrosive fumes.
Irritating gas. Toxic in high concentrations
Emits toxic fumes during burning.
Fire/explosion hazard when exposed to heat.
Emits toxic fumes upon heating.
Fire/Explosion/Toxic fume hazards when
exposed to heat .
High toxicltyvia inRostion.
HiRh toxicitv via intravenous route.
Irritant
Slight fire hazard.
Moderate fire/explosion hazard when exposed
to heat
Fire/explosion hazard when exposed to heat.
Low fire/explosion hazard when exposed
to heat.
Asphyxiating gas.
and Reactivity (stability).
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TABLE 4-2 (Continued)
System
Li/I
Li/FeS
Li/CuO
Li/Ag2
Li/V20
Material
Iodine
Poly-2-Vinylpyridin
Zirconium
Lithium Iodine
Iron Sulfide
Tetrahydrofuran
1 , 2-Dimethoxyethane
Lithium Perchlorate
Propylene Carbonate
Butyrolactone
Lithium Sulfide
Copper Oxide
Lithium Perchlorate
CrO^Silver Chromate
Lithium Perchlorate
Fropylene Carbonate
Lithium Chromate
, Vanadium Pentoxide
Nitromethane
Ethylene Carbonate
Lithium Perchlorate
Aluminum Chloride
Lithium Hexaf luoroarsenate
Lithium Tetrafluoroborate
Methyl Formate
Phase
20°C:
1 atm
S
L
S
S
S
L
L
S
L
L
S
S
S
S
S
L
S
S
L
S
S
S
S
S
L
NFPA Hazard Classification
Health Flamm. React.
NA
NA
NA
NA
NA
2
2
NA
1
0
NA
NA
NA
NA
NA
X
NA
NA
1
2
NA
3
NA
NA
2
NA
NA
NA
NA
NA
3
2
NA
1
1
NA
NA
NA
NA
NA
1
NA
NA
3
1
NA
0
NA
NA
4
NA
NA
NA
NA
NA
0
0
NA
0
0
NA
NA
NA
NA
NA
0
NA
NA
4
1
NA
2
NA
NA
1
Toxiclty Rating
High
Unknown
Unknown
NA
Unknown
Moderate
Unknown
Unknown
None
Unknown
Unknown
Unknown
Unknown
Unknown
Unknown
None
Unknown
High
Moderate
Unknown
Unknown
Moderate
NA
NA
Moderate
Comments
Emits toxic fumes when heated.
Fire/explosion hazard.
Moderate fire/explosion hazard when
exposed to heat.
Irritant
Slight fire hazard.
Slight fire hazard.
Moderate fire/exploaion hazard when
exposed to heat.
Irritant
Irritant
Slight fire hazard.
Slight fire hazard.
Dust has high toxicity properties via
inhalation. Also toxic via injection.
Fire/explosion hazard when exposed
to heat
Slight fire hazard.
Irritant
Exposure to moisture produces
toxic or corrosive fumes.
Fire/Explosion/Toxic fume hazards when
exposed to heat.
Lithium Vanadium Pentoxide
NA
NA
NA
NA
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electrode potential. This makes it ideal for use in high energy density bat-
tery systems. Lithium melts at approximately 179°C and will ignite in air near
that temperature. Traditional fire suppression agents may not be entirely ef-
fective against lithium and in some cases will intensify the fire. Lith-X, a
graphite-based, dry chemical fire suppression agent, is recommended for the
extinguishment of lithium fires. However, extinguishment becomes more compli-
cated 1) if the lithium is mixed with Class A materials (such as would be
found in typical rubbish) which require cooling together with fire suppression;
or 2) if the burning lithium surface is inaccessible to direct application of
the suppression agent. The difficulty in extinguishing the fire is directly
related to the amount of lithium involved and ignited. However, for most ap-
plications, the amount of lithium used in the production of a cell is extremely
small, generally less than 1/2 gram.
Lithium is extremely reactive with water, nitrogen (at high temperatures),
carbon dioxide, acids, or oxidizing agents. Lithium reacts with water to form
lithium hydroxide (LiOH) and hydrogen (H2). The LiOH by-product of this reaction
is both caustic and toxic. Hydrogen is explosive in air at concentrations of
4 to 75 percent by volume. However, no instance of ignition of either lithium
metal or hydrogen gas as the result of the lithium-water reaction was noted
in the literature reviewed for this study. Finally, an explosion hazard can
exist when lithium is used to form compounds with heavy metals such as silver
oxide, silver chloride, mercury oxide, etc.
Basic cell components and electrochemical reaction by-products for the
various lithium cells were identified using published battery research data
(3—8)
and manufacturers' product bulletins. Existing safety and toxicity data
were consulted to determine the hazard characteristics of these materials. These
data are presented in Table 4-2. Table 4-2 shows the material phase (gas,
liquid, or solid) at 20°C and 1 atmosphere pressure, its National Fire Protection
Association (NFPA) Hazard Classification , and its Sax Toxicity Rating^ '.
The identification of by-products created as the result of disposal processes
required making the assumption that unprocessed waste lithium batteries are
placed in an ordinary land disposal area (either above or below ground). Cells
assigned to these areas, even if unopened, will eventually release their contents
without benefit of neutralization
12
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to the surroundings. When this occurs, the released chemicals and compounds
become free to react with the environment (soil, water, air) and produce ad-
ditional compounds which may pose new environmental and safety threats. To
/o_g\
assess this problem, available toxicity datav ~ ' were consulted to determine
reaction products between lithium battery components and these materials. Data
identifying the by-products of reactions between lithium battery materials and
soils were not available. Reactions between identified lithium battery com-
pounds and air were predicted upon the existence of moisture, and are, therefore,
equivalent to those reactions solely involving water.
The effect of water upon exposed lithium battery components is also of in-
terest because precipitation or subsurface waters will eventually'combine with
lithium battery components to produce leachates which could enter water supplies.
(3-8)
According to sources surveyed during this study , a number of lithium bat-
tery materials react with water to produce hazardous elements. These materials,
and their reaction products are presented in Table 4-3.
Spontaneous heating of trash often occurs at land disposal areas as the
result of the biochemical decay of organic matter. For this reason, it was
desirable to determine the effects of elevated temperatures upon lithium bat-
tery chemicals and compounds. Lithium battery components which produce hazard-
ous substances when heated are also presented in Table 4-3. Components which
do not produce hazardous by-products when exposed to either water or heat are
not included in this table.
LITHIUM-SULFUR DIOXIDE (Li/S(>2)
Lithium-sulfur dioxide (L1/SO-) battery systems have been commercially avail-
able for approximately ten years. The system has undergone various evolutionary
changes precipitated by valid concerns regarding its electrochemical stability.
Basic components of Li/S02 cells are the lithium anode, a polytetrafluoroethylene
(TEFLON)-bonded carbon cathode on an expanded aluminum screen, and an organic
electrolyte. The electrolyte can be either acetonitrile (AN) or a propylene
carbonate (PC) solvent containing a salt such as lithium bromide (LiBr) or
lithium hexafluoroarsenate (LiAsFg); the AN-LlBr solvent-salt combination is
more commonly used. The active cathode material, sulfur dioxide (SO,,), is in-
cluded in the electrolyte. The concentration of SO in the electrolyte attenu-
ates as the cell discharges. Standard cells utilize an electrolyte/depolarizer
13
-------
TABLE 4-3 COMPONENTS OF LITHIUM BATTERY SYSTEMS WHICH REACT WITH WATER OR HEAT
Cell Type
Component
Produces of Reaction with
Products of Reaction with Heat
LI/SO, Basic Components
Sulfur Dioxide (SOj)
Acetonltrlle (Mechyl cyanide-CHjCN)
L1/SOC12 Basic Components
Thlonyl Chloride (SOC12)
Aluminum Chloride (A1C1)
Electrochemical Reaction By-products
Lithium Sulflde (L12S)
Sulfur Dioxide (SOj)
Sulfur (S)
Li/(CF)x Basic Components
Methyl Acetate (CH3C02CH3)
Dimethyl Sulflte ((CH3>2S03)
Methyl Formate (HCOOC«3)
Li/MnO_ Basic Components
Manganese Dioxide (Mn02)
Lithium Perchlorate (LiClO.)
1.2-Dlmethoxyethane(CHjOCHjCHjOCH^)
Methyl Acetate (CH3C02CH3)
Electrochemical Reaction By-products
1,2 Propanediol (CHjOHCHOHCH.,)
Li/I Basic Components
Poly-2-vinylpyridlne I(-CH(C5H4N)-CH2
Li/FeS Basic Components
Tetrahydrofuran (OCH2CH2CH2CH2>
1,2-Dlmethoxyethane (CH3OCH2CH2OCH3)
Lithium Perchlorate (L1C10.)
Electrochemical Reaction By-products
Lithium Sulfide (LiS)
Sulfurlc acid (H2SOA)
Cyanides
Hydrogen Chloride(HC1) ,
Sulfur Dioxide(S02)
Violent exothermic reactions,
Hydrogen chloride (HC1)
Hydrogen sulfide (H2S)
Sulfuric acid (H.SO.)
Sulfuroua Acid (HS0>
Sulfur dioxide
Hydrogen Sulfide
Exothermic reactions, Hydrogen cyanide gas
Sulfur dioxide, Sulfur chloride
Chlorides
SO gasea
Exothermic reactions, Sulfur dioxide
Exothermic reactions
Exothermic reactions
Exothermic reactions
Chlorides (L1C1)
Exothermic reactions
Exothermic reactions
Exothermic reactions
Exothermic reactions, cyanides
Peroxides
Exothermic reactions
Chlorides (L1C1)
SO gases
t Refei
3 4-8
-------
TABLE 4-3 (Concluded)
Cell Type
Component
Products of Reaction with H.O
Products of Reaction with Heat
Ll/CuO
Li/V205
Baalc Components
1,2-Diaethoxyethane (CH3OCH2CH2OCH3>
Lithium Perchlorate (L1C10.)
Basic Components
Lithium Perchlorate (L1C10, )
Electrochemical Reaction By-products
Lithium Chromate (LiCrO, )
Baalc Components
Nitromethane (CH.NO.)
Ethylene Carbonate (C.H^O.)
Lithium Perchlorate (L1C1O.)
Aluminum Chloride
Violent exothermic reactions,
Hydrogen chloride (HC1) -
Methyl Formate (HCOOCHj)
Exothermic reactions
Chlorides (LiCl)
Chlorides (L1C1)
Exothermic reactions
Exothermic reactions
Exothermic reactions
Chlorides (LiCl)
Chlorides (LiCl)
Exothermic reactions
-------
combination consisting (approximately) of 70% S02 (liquid) + 10% AN + 20% LiBr
by weight^ '. Cells which use a propylene carbonate (PC) solvent have
electrolyte/depolarizer combinations of 70% S02 + 20% AN/PC 4- 10% LiBr by
weight. When LiAsF, is employed as the electrolyte salt, the electrolyte/
depolarizer combination is likely to be 70% S02 + 21% AN + 9% LiAsFg by weight.
A typical cell is constructed using a "jelly roll" configuration (see Figure 4-1).
This involves creating a "sandwich" of the anode material (Li), polypropylene
separator, and carbon cathode/current collector. The "sandwich" is then spirally
wound and inserted in a steel can with the lithium side in contact with the in-
ternal wall of the can. Rupture vents or pressure-relieving diaphragms are in-
corporated in the design of these batteries as safety features.
(12)
The cell accepted basic reaction is :
2Li + 2S02 ->• Li2S20^ (Lithium dithionite)
In addition to the production of lithium dithionite, Li/S02 cells have been known
to produce methane (CH,), lithium cyanide (LiCN), and B-amino-n-butyronitrile
/i o 1 o N
under certain circumstances ' . On occasion, usually under conditions of
thermal stress, either internal or external in origin, Li/S02 cells will vent
S00 to the surroundings . SO, is an irritating gas in concentrations of
6-12 ppm and requires 400-500 ppm to be considered life-threatening. It can
react with water and steam to produce sulfuric O^SO^) and sulfurous (H2S03)
acids. The acetonitrile used in these cells is both toxic and flammable .
Acetonitrile can react explosively with sulfuric acid, which could be produced
by the H.O-SO- reaction in or near a breached cell. When heated to decompo-
sition acetonitrile will also emit toxic cyanide fumes.
LITHIUM-THIONYL CHLORIDE (Li/SOCl2)
The lithium-thionyl chloride (Li/SOCl2) cell has the highest energy density
of all commercially available lithium anode battery systems. The cell consists
of a lithium anode, a TEFLON-bonded carbon cathode, a nonwoven or felted fiber-
glass separator, and the inorganic liquid SOC12 as the electrolyte solvent and
AN/PC in a 3:1 combination
The cell is initially pressurized to 3-4 atmospheres by the S02 contained in
its electrolyte.
Department of Transportation (DOT) definition of flammable and combustible
16
-------
Terminal tob
Epoxy clear
Hermetic gloss
•to metal seal
Hermetically
sealed can
Insulator
Separator
Lithium
anode
Carbon cathode
Cell case
Insulator
Rupture vent
Fill eyelet
Figure 4-1 Internal structure of a lithium-sulfur dioxide cell
(Duracell International, Inc.)(ref. 11)
17
-------
active cathode material. Included in the thionyl chloride is lithium tetra-
chloroaluminate (LiAlCl, ) , or one of two specially prepared salts of chemical
formulation— Li2B10Cl10 and LijOCAlCl-^ ' . Cells can be constructed
either using a "jelly roll" configuration similar to that used for Li/S0_ cells
(Figure 4-1) or employing a cylindrical, highly porous carbon cathode, contain-
ing the electrolyte, surrounded by a current collector (Figure 4-2). Thionyl
chloride cells utilize low pressure vents and fuses to prevent conditions which
might lead to thermal runaway reactions. The most commonly cited cell reaction
is:
2 SOC1, + 4 Li -»• 4 Lid + SO, + S,
(17)
although two others have been proposed , namely:
3 SOC12 + 8 Li -»• Li2S03 + 6 LiCl + 2 S
SOC12 + 2 Li •* 2 LiCl + SO* (unstable state)
2 SO* •»• S02 + S.
Thionyl chloride is more toxic than sulfur dioxide and is classified as a
corrosive liquid. In the presence of moisture, it violently decomposes into
hydrogen chloride and sulfur dioxide.
The production of sulfur dioxide and sulfur during the electrochemical
process is noteworthy because: 1) sulfur dioxide produces sulfuric acid (H-SO.)
and sulfurous acid (H.SO.) when it contacts water and 2) the mixture or sulfur
(18}
and molten lithium is potentially explosive v .
LITHIUM-POLYCARBON MONOFLUORIDE (Li/(CF) )
X
The lithium-polycarbon monofluoride (Li/(CF) ) cell was developed in 1968
X
and appears to be an attractive system for many low-current consumer appli-
cations. The Li/(CF) cell consists of a solid lithium foil anode rolled onto
A
a nickel collector; a TEFLON-bonded polycarbon monofluoride cathode; and an
organic electrolyte composed of lithium hexafluoroar senate (LiAsF,) dissolved
o
in either methyl formate (HCOOCH-) , methylacetate (CH,C00C-_H,0) , or dimethyl-
20}
sulfite ((CH3)2S03)V * '. Cylindrical cells can be constructed using the
"jelly roll" configuration, with polypropylene as the separator. In button
cells, the anode and cathode materials are formed into disks which are separated
by another disk of polypropylene.
18
-------
Note: The system is
imexsed in electrolyte
KEY:
1 - CAN
2 - ANODE
3 - BOTTOM INSULATOR
4 - SEPARATOR
5 - CATHODE
6 - COLLECTOR
7 - GLASS-TO-METAL SEAL
8 - TOP INSULATOR
9 - COVER
10 - EPOJrt FILLING
11 - HERMETICALLY WELDED SEAM
12 - POSITIVE TERMINAL
Figure 4-2 Lithium-thionyl chloride cell (Tadiran Israel
Electronics Industries, Ltd.)(ref. 32)
19
-------
The cell reaction is:
(CF) + nLi •»• nC + nLiF (lithium fluoride).
n
Resultant products are carbon and lithium fluoride, which are formed without
the production of gases or heat in low rate cells. Larger, high rate cells
(•\a\
must be vented to reduce the probability of explosion . Lithium fluoride
(4)
is considered to be highly toxic . Other materials of interest are the sol-
vents used for electrolytes. Dimethyl sulfite is an irritant which, upon heat-
ing, emits toxic fumes of SO ; it can also react with water or steam to produce
x t
sulfur dioxide. Methyl formate and methyl acetate are flammable liquids.
LITHIUM-MANGANESE DIOXIDE (Li/Mn02>
High energy density and economical fabrication are the positive aspects of
lithium-manganese dioxide (Li/MnO^) battery systems. These systems are very
attractive for consumer applications. Li/MnO- cells utilize a lithium anode,
a manganese dioxide (MnO_) cathode, and an organic electrolyte in various con-
(21)
figurations . A typical electrolyte consists of a mixture of two organic
solvents, propylene carbonate and 1,2-dimethoxyethane (CH_OCH.CH~OCH,), to which
lithium perchlorate (LiClO.) has been added. Separators of polypropylene are
used. Cylindrical cells are constructed using either the "jelly roll" or
inside-out (external cathode, see Figure 4-3) configurations. Prismatic and
(22)
button cells are also available. The cell reaction is :
Li + MnIV02 * Mnm02 (Li+) .
By-products of the electrochemical reaction have been suggested to be
(22)
1,2-propanediol (CH2OHCHOHCH_) and carbon dioxide . The propanediol can
further react with the lithium to produce lithium oxide and hydrogen or it can
be absorbed by the MnO, and be oxidized to propylaldehyde and water.
(4)
Manganese dioxide is considered to be highly toxic if ingested . Both
propylene carbonate and 1,2-dimethoxyethane are combustible.
LITHIUM-IODINE (Li/I-PVP)
Various designs using this chemistry are currently on the market, primarily
for use in cardiac pacemaker applications. A typical lithium-iodine (Li/I) cell
will consist of a lithium anode, a cathode/depolarizer composed of iodine and
DOT definitions of flammable and combustible
20
-------
sepa'ato' and
organic electrolyte
-anode
negative terminal
Figure 4-3 Cross-sectional view of cylindrical
inside-out Li/Mn02 cell
(Sanyo Electric Company, Ltd.)(ref-
21
-------
polyvinylpyridine (PVP) , and an electrolyte/separator of solid Lil which is formed
when the PVP is added prior to sealing the cell. Zirconium (Zr) serves as the
(23)
current collector and holder for the anode . The cell reaction is:
2 Li + I2 + PVP •* 2 Lil (PVP).
During service, the Lil electrolyte/separator increases in size as the cell dis-
charges, Cells are hermetically sealed and do not employ venting mechanisms.
Both iodine and zirconium are slightly radioactive, and iodine has a high toxicity
(4)
rating according to Sax .
LITHIUM-IRON SULFIDE (Li/FeS)
Small button-type 1.5 volt organic electrolyte Li/FeS cells are currently
produced by Union Carbide. The components of these cells, according to the
product bulletin, include a lithium anode; an FeS cathode and a separator/
electrolyte of unspecified composition . Experimental cells developed by
(25)
Uetaniv of Hitachi Maxell Ltd. utilized organic electrolytes of lithium
perchlorate plus one or more of the following: propylene carbonate, y-
rolactone, tetrahydrofuran (THF) or 1,2-dimethoxyethane (DME) . The cell re-
action is:
FeS + 2 Li •* Fe + Li2S .
The lithium sulfide (Li2S) produced during the electrochemical reaction may
yield hydrogen sulfide when it contacts water. When heated, Li-S will emit
SO gases as it decomposes. Propylene carbonate, Y-butyrolactone , tetrahydro-
t
furan and 1,2-dimethoxyethane are combustible liquids; the tetrahydrofuran
being extremely flammable.
LITHIUM COPPER-OXIDE (Li/CuO)
The Li/CuO cell is in limited production and as a result there is very
little information regarding its composition. However, the Li/CuO cell should
be similar in construction to the Li/FeS system.. Basic constituents are a
lithium anode, copper oxide cathode plus an organic electrolyte. The electro-
lyte used is probably 1,2-dimethoxyethane (DME) solvent to which lithium
perchlorate has been added. The 1,2-dimethoxyethane is a combustible* liquid.
Lithium perchlorate may emit chloride fumes when exposed to elevated temperatures
fDOT definitions
22
-------
LITHIUM-SILVER CHROMATE
The lithium-silver chromate (Li/AgjCrO^) cell consists of a lithium anode
a silver chromate/acetylene black cathode, and an organic electrolyte. One
such cell developed by SAFT utilizes an organic electrolyte which is prepared
by dissolving lithium perchlorate in propylene carbonate. The overall cell
/ofi 27}
reaction has been reported to be ' :
2 Li + AgCrOA -»• Li2Cr04 + 2 Ag .
A secondary reaction has been reported as :
2 Li + Li2Cr04 -»• 2 Li20 + CrOj.
Although the exact cell "recipe" could not be determined from the product liter-
ature, the hazards associated with these cells should be similar to those of the
lithium-iron sulfide and copper oxide systems in which the primary hazard (s)
are due to the use of flammable and combustible electrolytes such as DME and
tetrahydrofuran.
LITHIUM-VANADIUM PENTOXIDE
The basic cell consists of: a lithium anode constructed by attaching
lithium foil to a nickel screen current collector; an active cathode of
vanadium pentoxide (V205) mixed with carbon pressed around a stainless steel
grid; and an organic electrolyte. The electrolyte is produced by dissolving
lithium hexafluoroarsenate (LiAsF,) and lithium tetrafluoroborate (LiBF.) salts
/•oo ooV (31)
in methyl formate (HCOOCHg) v ' or methyl acetate (CH3C02CH3)
The accepted cell reaction for the Li/LiBF, :MA/V20,. system has been
(31}
reported to bev ' :
Li + V205 -*• LiV205.
Hazards presented by Li/V^O, cells involve the methyl formate and methyl
acetate solvents used in electrolytes. Both solvents are extremely flammable
and represent an explosion hazard, if air is present in the cell.
23
-------
SECTION 5
QUANTIFICATION OF WASTE LITHIUM BATTERY DISPOSAL HAZARDS
LITHIUM BATTERY WASTE DISPOSAL TECHNIQUES
The survey of battery industry disposal practices yielded only one organ-
ization, Battery Disposal Technology, Inc. located in Clarence, N.Y., which has
as its sole function the disposition of waste lithium batteries. The facility
is fully licensed and sanctioned by the U.S. Department of Transportation for
receiving and handling lithium batteries. To effect disposal, this facility
uses a process in which cell cases are breached and the contents neutralized
in the same operation. To accomplish this, a rotating hammermill is used to
crack cell cases in the presence of an unspecified aqueous spray which hydro-
lyzes the lithium and possibly other reactive components. After shredding,
the reacted material is funneled through a screen into a holding tank where it
is completely wetted with the same aqueous solution to insure that all materials
are completely reacted. The wetted residues are subsequently pumped from the
holding tank by a private contractor and, as a precautionary measure, deposited
in a secured landfill. The Battery Disposal Technology facility processes all
types of lithium cells but the bulk of those batteries processed are either
lithium-sulfur dioxide or lithium-thionyl chloride.
Most manufacturers and large commercial and military users of lithium bat-
teries who must dispose of the batteries do take specific precautions in the dis-
position process. Usually, this involves a neutralization procedure, such as
breaching cell cases and reacting internal components with an aqueous solution,
followed by disposal in a hazardous waste disposal facility. However, it is
possible that manufacturers may not employ a neutralization procedure but in-
stead seal waste lithium cells in containers (drums, barrels, etc.) which are
then buried. The Environmental Protection Agency's classification of lithium
batteries will determine future practices for these manufacturers.
CONVENTIONAL WASTE DISPOSAL TECHNIQUES
Conventional waste disposal operations are conducted in three phases:
collection, processing (baling, compacting or shredding), and ultimate disposal
via burial or incineration. The hazards associated with these various opera-
tions are summarized in Table 5-1.
-------
TABLE 5-1 HAZARDS ASSOCIATED WITH DISPOSAL OPERATIONS
Operation
Hazardous Situation
Resultant Hazard
Collection
External short circuit
Mechanical shock
- dropped
- thrown
Crushing of cell
- pickup vehicle compacting
Foreign object penetration
- pickup vehicle compacting
Moisture Intrusion
Exploslon/fire/lnternal exothermic
reactions
Mechanical shock
- dropped
- thrown
Crushing of cell
- pickup vehicle compacting
Foreign object penetration
Hazardous material release
(cell breached)
External short circuit
Mechanical shock
- dropped
- thrown
Moisture intrusion
Hazardous gas release (cell Intact)
Processing
External short circuit
Crushing of cell
- shredding, compacting
Mechanical shock
- explosion in processing unit
Foreign object penetration
Elevated temperature/fire
- heating or Ignition by
adjacent materials
- incineration
Explosion/fire/internal exothermic
reactions/hazardous material release
(cell breached)
External short circuit
Elevated temperature/fire
Hazardous gas release (cell intact)
Disposal External short circuit
Crushing of cell
- dump and filling operations
Moisture Intrusion
Elevated temperature/fire
Exploslon/fire/internal exothermic
reactions
Crushing of cell
- dump and filling operations
Elevated temperature/fire
Hazardous material release
(cell breached)
External short circuit
Moisture Intrusion
Elevated temperature/fire
- heating or ignition by
adjacent materials
Hazardous gas release (cell intact)
25
-------
During normal collections, waste batteries and cells may be subjected to
1) external short circuit - the result of electrical bridging of cell terminals
by electrically conductive objects contained in the trash, 2) mechanical shock -
caused by dropping or rough handling, 3) crushing - caused by the shredding or
compacting operations of pickup vehicles, and 4) immersion in water or moist
material. These situations could initiate hazardous incidents such as ex-
plosion, fire, internal exothermic reactions, and hazardous material releases.
Internal exothermic reactions may result in elevated wall temperatures which
could ignite adjacent refuse. Hazardous material releases may involve either
the release of cell gases via operation of a safety vent (cell remains intact)
or a serious failure of the cell container which potentially exposes all in-
ternals.
Processing operations may entail baling (or compacting), shredding, in-
cineration, or a combination thereof. Baling/compacting operations may be per-
formed on previously processed or unprocessed material, at the collection site
or in a processing facility. Waste batteries processed through baling/compacting
equipment may be subjected to: 1) external short circuit - as cells contact
electrically conductive materials, 2) mechanical/shock - through the action of
the compactor or an explosion in the processing unit, 3) crushing, 4) fire - in-
itiated within the processing unit, and 5) foreign object penetration. During
shredding operations, cells are crushed, their cases torn open, and contents
released. In the shredder, exposed cell constituents may be subjected to
spark ignition sources produced by the impact of shredding hammers striking
metallic or abrasive waste material. The basic hazards encountered when pro-
cessing waste lithium batteries will be the same as those associated with
collection operations, i.e., explosion, fire, internal exothermic reactions,
and hazardous material releases.
Strict environmental pollution regulation has forced the closing of many
incineration operations in the United States. There are, however, some units
still in operation. Unopened batteries and cells disposed of using incinerators
may present an explosion hazard.
The final stage of the waste disposal process is the assignment of residual
products to a permanent location. This is usually land burial or disposal at
secured or sanitary landfills. During dumping and filling operations unopened
26
-------
cells may be subjected to crushing and foreign object penetration. After com-
pletion of these operations, waste lithium cells are intermingled with assorted
rubbish and may also be subjected to 1) immersion in water or moist material,
and 2) elevated temperatures caused by the spontaneous heating of organic
matter in the trash. The hazards associated with the final disposition of
waste lithium cells are explosion, fire, release of hazardous material (in-
cluding gases), and internal exothermic reactions.
CORRELATION OF ABUSE TEST DATA TO CONVENTIONAL WASTE DISPOSAL HAZARDS
The approach used in making determinations of hazards associated with the
management of waste lithium batteries was the correlation of existing abuse
test data to hazardous situations anticipated by conventional waste disposal
operations. Available abuse test data on lithium'batteries frequently dupli-
cate hazards which are likely to occur during conventional waste disposal meth-
ods. By correlating abuse test data reported in the literature to those hazard-
ous situations, hazard assessments were made. Correlations between abuse tests
and hazardous situations are presented in Table 5-2. Numerous lithium battery
safety tests were surveyed for applicability in making assessments. Seven tests
were finally selected: 1) mechanical shock (drop test), 2) external short cir-
cuit, 3) immersion, 4) cell deformation (crush test), 5) elevated temperature,
6) incineration, and 7) foreign object penetration. Since data from many sources
were reviewed, thereby yielding a variety of test procedures and test results,
a set of minimum criteria for the conduct and evaluation of test data for each
of the seven tests had to be established. The results are the generalized test
procedures and evaluation criteria for each of the seven tests which are pre-
sented as Appendix A. The procedures for each of the outlined abuse tests are,
for the most part, generalized composites of one or more existing tests. Evalu-
ation criteria are stated in general terms since the bulk of existing abuse
test data are reported that way. For example, quantities of either gases or
electrolytes released during abuse tests were usually not defined, therefore
no attempts were made to quantify such losses. Changes in the physical appear-
ance of cells after test were also described in general terms such as cracked
seals, crimp failures, or swollen and corroded cases.
27
-------
TABLE 5-2 CORRELATION OF ABUSE TESTS TO DISPOSAL HAZARDS
Hazard
1. Cell dropped, thrown or
involved in explosion
from adjacent cell
Abuse Test
1. Mechanical shock
2. Terminals bridged via
electrically conductive
material
1. External short circuit
3. Cell submerged in water
or moist material
1. Immersion test
4. Cell crushed or shredded
1. Cell deformation test
5. Cell exposed to heat or
flame, including
incineration
1. Elevated temperature test
2. Incineration test
6. Object penetrates cell
casing
1. Foreign object penetration
test
28
-------
The basis for hazard assessments are the results of abuse tests on C- and
D-cells (ANSI designations) since these data were more universally available.
Unfortunately, the hazards associated with cells of different sizes may also
be different and prevent the extrapolation of hazard potential between dif-
ferent battery sizes within a given chemistry. Abuse tests reviewed during
this study are as follows.
MECHANICAL SHOCK
During collection and processing, waste lithium batteries may be dropped,
thrown, or subjected to forces created by exploding waste material in close
proximity. Because of this, efforts were made to determine the effects of me-
chanical shock upon lithium battery systems. Manufacturers such as Tadiran
and Power Conversion^ ' adopted deceleration tests designed to conform with
requirements set forth by the Federal Aviation Administration (FAA)^34^ and the
United States Army1 . In these tests, lithium batteries are subjected to
forces ranging from 100 to 1000 g's for durations of 0.5 to 23 ms. While the
results of these tests provide useful information regarding the ability of in-
ternal components to withstand acceleration or deceleration, they provide no
information on the cells' ability to withstand physical impact.
The Environmental Protection Agency (EPA) employs a Structural Integrity^36^
Test for making determinations for hazardous waste. This test, while providing
some impact data, appears to be much too lenient for making a determination as
to the structural integrity of steel-clad battery cells. The EPA test involves
impacting a cell 15 times with a 0.33 kg mass (,0.73 Ib) from a height of
15.24 cm (6 in.). This is an insufficient challenge. However, drop tests such
/37\ (38^
as those performed by Shahv ' and Baumanv ' do provide sufficient challenge
for testing a cell's ability to withstand mechanical shock expected during waste
collection and processing. Such tests duplicate the real-world situation in
which a cell is either dropped or thrown from a height. The test by Shah re-
quires that a cell be dropped from a height of 5 meters onto a concrete pad.
Bauman used a height of 12.2 meters and a steel plate anvil instead of the con-
crete pad. The Bauman test is probably too severe since it is unlikely that a
cell or battery would be dropped or thrown from a height of 12 meters or more
during routine collection operations. Therefore, the Shah test (i.e., a drop
29
-------
test from 5 meters) was used as the minimum requirement for evaluating the ability
of a cell to withstand the mechanical shocks likely to be incurred during waste
disposal operations.
Abuse test data reviewed during this study showed no instance of a com-
mercial lithium battery or cell posing a hazard when dropped from a height of
5 meters or more. However, explosions did occur in several Li/S0_ specialty
cells during the conduct of the drop tests performed by Shah.
SHORT CIRCUIT
When lithium cells and batteries are mixed together with rubbish and other
trash, the possibility exists that contact with electrically conductive materials
may cause short circuiting. It was, therefore, necessary to determine whether
or not a cell could be short circuited without presenting a safety hazard.
(32) (39)
Several organizations, including Tadiran and Factory Mutual routinely
use tests designed to assess the hazards associated with short circuiting of a
cell or battery. Tests require bridging of battery terminals with a low-resis-
tance electrical conductor, then observing the behavior for a period of time
between 30 minutes and 24 hours.
(14 40-45)
Short circuit tests of lithium-thionyl chloride ' , lithium-sulfur
dioxide^ ' ' and lithium-polycarbon monofluoride^ revealed that these
systems were affected to varying degrees by this condition. All of these bat-
teries have vented under short circuit conditions, and explosions were docu-
(40 45)
mented for the lithium-thionyl chloride system ' . These batteries have
also successfully passed short circuit tests.
IMMERSION TESTS
Since waste lithium cells are likely to be disposed of along with moist
materials or left in containers which collect water, it becomes necessary to
define the hazards presented when these cells are immersed in water. This is
particularly true of those cells which have vents or which are not hermetically
sealed. Some cells contain components which are extremely reactive with water
and the ability of the cell to withstand moisture intrusion is a significant
protection requirement. Immersion tests in fresh and salt water have been per-
formed by Brooks J on lithium sulfur dioxide batteries, and McCartney
30
-------
using llthium-thionyl chloride, with varying results. Immersion in salt
water is the more severe test, primarily because of the possibility of acceler-
(40 47)
ated corrosion of the cell casev ' .
None of the data reviewed gave indication of safety problems with any of
the nine systems under study.
CELL DEFORMATION TEST (CRUSH TEST)
Compacting and baling operations could cause cell deformations which, in
turn, may result in internal shorts or the release of toxic or flammable electro-
lyte. Internal shorts can cause exothermic reactions and explosions in certain
(18)
types of lithium cells . The cell deformation test involves the gradual
crushing of the lower portion (bottom one-half, one-third or one-quarter) of a
cell using a compression device (e.g., vise, mechanical clamps, etc.) while
simultaneously monitoring the open circuit voltage and the cell wall temperature.
The ability of the cell to withstand deformation without explosion or exothermic
reaction was of primary interest.
(33)
With the exception of one lithium-sulfur dioxide cell which vented ,
no particular safety problems were noted in the data reviewed.
ELEVATED TEMPERATURE /INCINERATION TESTS
There are essentially two scenarios. The first involves the situation in
which waste lithium cells are subjected to elevated temperatures but not to the
extent required for incineration. Spontaneous heating of organic material, the
dumping of hot material onto the batteries or solar heating of closed trash con-
tainers are all possibilities. These exposures will in all likelihood produce
temperatures somewhat lower than the melting point of lithium (179°C). Elevated
(32) (43)
temperature tests performed by Tadiranv ' (150°C for 3 hr) , Babai and Zak
(63°C for 4 hr) and Roaansky and Watson (71°C for 2 weeks and 54°C for 30 days)
were examined.
The second scenario is that in which the lithium cell is incinerated. When
lithium cells are included with other rubbish or trash, there exists the pos-
sibility that they can be either purposely or accidentally incinerated. Although
most incineration equipment is designed to withstand minor explosions, the effect
of a quantity of lithium cells exploding within such equipment has yet to be
31
-------
determined. It would, therefore, be beneficial to know which cells represent an
explosion hazard during incineration. To make this determination, a simple
incineration test described in Table A-6 can be performed. What is required
(49)
is the exposure of the cell to flame or high temperature and maintaining
this exposure until the cell is consumed. What is of interest is whether or not
the cell explodes, produces toxic or corrosive gases, or significantly intensifies
the fire. Taylor and McDonald^ used both an explosionproof furnace at 540°C
and direct flame for incineration tests.
The tests performed by Taylor and McDonald gave no indication of a signi-
ficant safety hazard for lithium-sulfur dioxide cells in a furnace, However,
(39)
incineration tests reported by Bajpai and Zalosh indicate that lithium-
polycarbon monofluoride batteries will burn violently and rocket under these
conditions. Tests conducted at Factory Mutual for a private client demonstrate
that the behavior of lithium batteries under elevated temperature and incin-
eration conditions is a function of 1) cell packaging (soft-sided, steel can,
single cell or multiple-cell arrangements, etc.), and 2) failure mode of cell
casing (cells undergoing pressure relieving failures usually do not rocket or
explode), as well as 3) its chemical composition.
FOREIGN OBJECT PENETRATION TEST
One of the more serious situations which might be encountered is that in-
volving the penetration of a cell by an electrically conductive object. In this
instance, there exists the potential for 1) release of flammable, toxic, or
corrosive liquid and gas, or 2) Internal short reactions (fire, explosion, etc.).
Numerous foreign object penetration test procedures have been reported in the
(33)
literature. Basically, these involve either boring with a high-speed drill
or puncturing^ ' ' ' ' ' the case with manually- or mechanically-driven nails.
In addition to determining if a fire or explosion hazard existed, checks of cell
venting, physical changes and escaping electrolyte were made.
The most violent reaction documented involved the explosion of high power
i naii
.(50)
lithium-thionyl chloride cells when punctured by a nail. Some minor heating
(10-20°C) was documented in lithium-copper oxide cells
32
-------
SECTION 6
DISCUSSION
The assessment of hazards associated with the disposition of waste lithium
batteries is based upon four factors: 1) the toxicity of cell materials, in-
cluding those formed as the result of electrochemical reactions or reactions
with water or heat; 2) the probability of the material escaping containment;
3) the quantity of toxic material escaping containment; and 4) the personnel
safety hazard, i.e^, the potential for fire, explosion, or toxic substance re-
lease during waste disposal operations. The author's evaluation of these four
factors for the various lithium systems is described here.
Perusal of Table 4-3 reveals that five of the lithium battery systems sur-
veyed utilize the following basic components which are classified highly toxic
substances : 1) thionyl chloride, 2) sulfur dioxide, 3) manganese dioxide,
4) iodine, and 5) vanadium pentoxide. Furthermore, the lithium-polycarbon mono-
fluoride battery produces a toxic compound, lithium fluoride, as the by-product
of the electrochemical reaction taking place in the cell, However, of these
six compounds, only the thionyl chloride and sulfur dioxide are hazardous by
skin contact or inhalation. The other four toxic materials found in the other
batteries must either be ingested, injected or placed under the skin to produce
toxic effects. This is significant from a (personnel) handling viewpoint,
since human ingestion, injection, or subcutaneous application of these toxic
materials is not likely to occur during normal collection, processing, or dis-
posal operations. These materials may, therefore, escape containment and still
not represent a significant personnel hazard. However, specific precautions
must be taken by waste processing personnel when handling either thionyl chloride
or sulfur dioxide. These materials may represent a significant personnel haz-
ard if they escape containment.
Lithium-thionyl chloride, lithium-sulfur dioxide, lithium-polycarbon mono-
fluoride, and lithium-vanadium pentoxide systems have basic components which
will react with water to produce hazardous substances (Table 4-2). From a per-
sonnel safety point of view, the thionyl chloride and sulfur dioxide system
require special handling. Thionyl chloride may react violently when it con-
tacts water while sulfur dioxide produces suffocating corrosive fumes. Accord-
ing to toxicity data in Table 4-2, all lithium batteries surveyed in this
33
-------
study will produce toxic or corrosive gases when heated to decomposition. This
suggests that lithium batteries should not be incinerated.
The probability of toxic materials escaping containment as well as a pre-
diction of the quantity of material escaping are basically nonquantifiable
parameters. The key issues are 1) whether or not cell cases remain intact,
and 2) the number and size of cells which are used and eventually disposed of.
The outer cases of lithium cells disposed of using conventional, nonhazardous,
waste disposal techniques will eventually corrode, exposing the internal com-
ponents. Although consistent placements of total lithium battery sales at
"less- than one percent of total battery sales" were encountered throughout this
study, sales figures and distribution patterns were not available. The environ-
ment impact of lithium batteries will depend upon the type of cell (toxic chem-
ical involved) and the localized concentration of cells. The lithium from a
single cell will probably represent little or no environmental hazard. However,
a large number of breached cells releasing their contents to the environment
may pose a significant problem. These problems have not been fully studied and
addressed. A single relevant study by Crumrine et al provides a model which
can be used to measure environmental impact of breached lithium cells. However,
this model requires the knowledge of the amount and purity of the toxic sub-
stance under study. These data were not available from the manufacturers. The
Crumrine study addressed the problem of cyanide production in lithium-sulfur
dioxide cells. The study concluded that lithium-sulfur dioxide cells be dis-
posed of in sanitary landfills. The study further recommended that large numbers
of cells be disposed of at either sanitary or secured landfills which practice
leachate monitoring.
An evaluation of personnel safety hazards was performed by 1) examining
the behavior of various lithium battery systems under abuse conditions, and
2) reviewing accident data.
The results of abuse tests should provide some indication of inherent safety
hazards. During this study, abuse test data were reviewed for this purpose.
The review of existing abuse test data yielded the following information:
1) External short circuit tests of unfused lithium-sulfur dioxide, lithium-
thionyl chloride and lithium-polycarbon monofluoride cells resulted in the acti-
vation of vent mechanisms. Gases vented by thionyl chloride and sulfur dioxide
-------
cells may contain hydrogen cyanide, sulfur dioxide or sulfur chloride. Lithium-
thionyl chloride cells have also deformed and exploded under external short cir-
cuit conditions.
2) Immersion (in fresh or salt water) and drop tests of intact cells at
approximately 25°C produced no hazardous situation.
3) Cell deformation (crush) tests resulted in the venting of lithium-
sulfur dioxide cells. It is significant that sulfur dioxide gas is irritating
and toxic.
4) Foreign object penetration tests caused minor heating (10°-20°C) in
lithium-copper oxide cells and explosion in lithium-thionyl chloride cells.
5) Explosions are likely if the internals of lithium cells are allowed
to reach the melting point of lithium (approximately 180°C). This is particu-
larly true of those cells which produce elemental sulfur (some lithium-sulfur
dioxide chemistries) during discharge.
From this information the conclusion might be drawn that lithium-thionyl
chloride, lithium-sulfur dioxide, lithium-carbon monofluoride and lithium-copper
oxide cells have significant safety problems. However, the absence of sufficient
abuse test data preclude such a conclusion. This information is based on a very
small sample of test data and, in the cases of the lithium-carbon monofluoride
and lithium-copper oxide, represent the results of one series of abuse tests of
one manufacturer's batteries. However, continuing mishaps involving lithium-
thionyl chloride and lithium-sulfur dioxide batteries make it difficult to ig-
nore their previous accident histories. The occurrence of at least two acci-
dents (New York and Massachusetts) during the first quarter of 1983 indicates
that problems with lithium batteries have not fully been eradicated.
Although verbal accounts were common, little documented evidence exists for
accidents occurring in the battery manufacturing and disposal industries. Battery
manufacturers either do not keep such records or consider them proprietary In-
formation. The only disposal-related accident which could be documented during
this survey involved a series of lithium battery fires and explosions occurring
at a landfill near Ossining, New York in April 1981. Three dozen drums filled
with lithium batteries (not specifically identified but inferred to be thionyl
Information via personal communications
35
-------
chloride) caught fire and exploded. These drums had been transported to the
landfill for burial. According to the newspaper account , the drums had been
left uncovered and in the open for several days prior to the accident. No
precipitating cause or explanation was given.
Nondisposal-related accidents involving lithium batteries have been docu-
mented for years. Bowers and Spencer have documented numerous cases of
mishaps involving lithium batteries. These studies give indication that lithium-
thionyl chloride and lithium-sulfur dioxide batteries are a matter of concern
and should be handled with care.
The Citizen Register, Gannett Newspaper Service, Westchester County, New York,
April 21, 1981 edition
36
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REFERENCES
1. Mallory Bulletin 279-1. Procedure for Using and Handling the Lithium/
Organic Electrolyte/Sulfur Dioxide Battery. Mallory Battery Company,
Tarrytown, New York, 1979.
2. Abraham, K.M. et al. Investigations of the Safety of Li/SOCl2 Batteries.
R&D Technical Report DELET-TR-78-0564-1, U.S. Army Electronics Research
and Development Command, May 1979.
3. American Institute of Chemical Engineers. Fire & Explosion Index Hazard
Classification Guide, 5th Edition Appendix A, Dow Chemical Company, 1981.
4. Sax, N.I., Editor. Dangerous Properties of Industrial Materials,
5th Edition, Van Nostrand Reinhold Company, New York, 1979.
5. International Technical Information Institute (ITI). Toxic and Hazardous
Industrial Chemicals Safety Manual, 5th Edition, ITI, Japan, 1979.
6. Hawley, G.G. The Condensed Chemical Dictionary, 10th Edition,
Van Nostrand Reinhold Company, New York, 1981.
7. Merck and Company. The Merck Index, 9th Edition, Merck and Company,
New Jersey, 1976.
8. Toxic Substance List. H.E. Christensen and T.T. Luginbyhl, Editors,
1974 Edition, National Institute for Occupational Safety and Health,
Maryland, 1974.
9. Wilson, David G. Health Hazards of Solid-Waste Treatment.
Dangerous Properties of Industrial Materials, 5th Edition,
Van Nostrand Reinhold Company, New York, 1979.
10. Dey, A.N. and Holmes, R.W. Analysis of Pressure Producing Reactions in
Lithium-Sulfur Dioxide Cells. Prepared for the U.S. Army Electronics
Research and Development Command, Report No. DELET-TR-77-0472-F,
November 1979.
11. Duracell. Lithium/Sulfur Dioxide Primary Battery System.
Product Bulletin No. 479, November 1982.
12. Taylor, H., Bowden, W. and Barrella, J. Li/S02 Cells of Improved Stability.
28th Power Sources Symposium, June 1978.
13. DiMasi, G.J. and Christopulos, J.A. The Effect of the Electrochemical
Design Upon the Safety and Performance of the Lithium-Sulfur Dioxide Cells.
Proceedings of 28th Power Sources Symposium, June 1978.
14. Dey, A.N. et al. Lithium-Thionyl Chloride Battery. Prepared for
U.S. Army Electronics Technology and Devices Laboratory, ERADCOM,
Report No. DELET-TR-78-0563-5, June 1980.
37
-------
15. Schlaikjer, C.R. and Young, C. Lithium Corrosion and Voltage Delay
in Li,BinCl.n/SOCl9 and LiAlCl,. Proceedings of 29th Power Sources
Conference.June 1980.
16. Abraham, K.M. et al. Investigations of the Safety of Li/SOCl2 Batteries.
Prepared for the U.S. Army Electronics Research and Development Command,
Report No. DELET-TR-78-0564-2, July 1979.
17 Kim, K.Y. et al. Studies on Thermochemical and Electrochemical Reactions
and Heat Distribution in Li/SOCl2 Battery System. Proceedings of the
29th Power Sources Conference, June 1980.
18. Johnson, L.J. and Willis, A.H. User Considerations in Lithium Thionyl
Chloride Batteries. Proceedings of 29th Power Sources Conference,
June 1980.
19. Higgins, R.L. and Erisman, L.R. Applications of the Lithium/Carbon
Mono-Fluoride Battery. Proceedings of 28th Power Sources Symposium,
June 1978.
20. Bowers, F.M. Safe, Useful Lithium Batteries for the Navy. Naval Surface
Weapons Center, Research and Technology Department, Report No.
NSWC/WOL TR-77-140, December 1977.
21. Ikeda, H. et al. Characteristics of Cylindrical and Rectangular Li/Mn02
Batteries. Proceedings of 29th Power Sources Conference, June 1980.
22. Moses, P.R. et al. Dimensional Stability of Li/Mn02 Cells.
Duracell International Inc.
23. Holmes, C.F. et al. The Use of Microcalorimetry in Characterization of
Lithium Pacemaker Batteries. Proceedings of 28th Power Sources Symposium,
June 1978.
24. Eveready Miniature Lithium Batteries. Union Carbide Product Bulletin,
September 1980.
25. Uetani, Y. et al. FeS/Li Organic Electrolyte Cell. Proceedings of
28th Power Sources Symposium, June 1978.
26. Solar, R.J. and Kafesjian, R. Comparison of Accelerated Test Methods
to Determine Capacity of Lithium Silver Chromate Pacemaker Batteries.
American Edwards Laboratories Division, American Hospital Supply Corporation,
27. Liang, C.C. and Holmes, C.F. Lithium Pacemaker Batteries-An Overview.
Presentation at Electrochemical Society, Inc., October 1979.
28. Eppley, W.J. et al. Reserve Low Temperature Lithium-Organic Electrolyte
Cell. IECEC '75 Record, pp. 418-421.
29. Levy, S.C. Electrical and Environmental Testing of Lithium V205 Cells.
Proceedings of 27th Power Sources Symposium, June 1976.
38
-------
30. Horning, R.J. and Viswanathan, S. High Rate Lithium Cell for Medical
Application. Proceedings of 28th Power Sources Conference, June 1980.
31. Walk, C.R. and Merz, W.C. Constant Potential Testing As A Method of Cell
Characterization and Evaluation. Proceedings of 26th Power Sources
Conference, May 1974.
32. Tadiran Israel Electronic Industry Limited. TADIRAN High Energy Lithium
Batteries. Technical Report LBR 1505, October 1980.
33. Brooks, E.S. Evaluation of Designs for Safe Operation of Lithium
Batteries. 26th Power Sources Symposium, 1974.
34. Federal Aviation Administration. FAA Standard, Lithium S02 Batteries.
Technical Standard Order Authorization Amdt. 37-44.
35. U.S. MIL STD - 810C, MIL-B-180.
36. U.S. Environmental Protection Agency. Structural Integrity for Hazardous
Wastes. USEPA Proposed Rules for Identification and Listing.
Federal Register, PART IV, December 18, 1978.
37. Shah, P.K. Analysis of Li/SO, Safety. 28th Power Source Symposium,
June 1978.
38. Bauman, H. Multifunctional Explosive Battery. U.S.A.F. Armament
Laboratory, Report No. AFATL-TR-73-4, January 1973.
39. Bajpai, S.N. and Zalosh, R.G. Survey of Lithium Battery Hazards,
Standards, and Safety Test Development. Factory Mutual Research Corporation
Technical Report J.I. OG1E6.RK, March 1982.
40. McCartney, J.E. et al. Development of Lithium Inorganic Electrolyte
Batteries for Naval Applications. NTIS Report No. AD-A020 144,
October 1975.
41. Merely, D. and Solar, R.J. The Li/SOCl. Cell As An Effective Power Source
for Heart Pacer Application. 28th Power Sources Symposium, June 1978.
42. Higgins, R.L. Development of the Calcium Thionyl Chloride System.
29th Power Sources Conference, June 1980.
43. Babai, M. and Zak, U. Safety Aspects of Low-Rate Li/SOCl2 Batteries.
29th Power Sources Conference, June 1980.
44. Dey, A.N. Primary Li/SOCl- Cells II. Thermal Runaways and Their
Prevention in Hermetic D Cells. 26th Power Sources Symposium,
June 1974.
39
-------
45. Dey, A.N. Sealed Primary Lithium-Inorganic Electrolyte Cell.
U.S. Army Electronics Research and Development Command,
DELET-TR-74-0109-F, July 1978.
46. Taylor, H. and McDonald, 6. Abuse Testing of Li/SO- Cells and Batteries.
27th Power Sources Symposium, June 1976.
47. Zupancie, R.L. et al. Performance and Safety of Small Cylindrical
Li/SOCl2 Cells. 29th Power Sources Conference, June 1980, p. 157.
48. Rosansky, M.G. and Watson, T. Manufacture of High Reliability Lithium
Sulfur Dioxide Batteries. 29th Power Sources Conference, June 1980,
p. 98.
49. Taylor, H. and McDonald, B. Abuse Testing of Li/S02 Cells and Batteries.
27th Power Sources Symposium, June 1976, p. 66.
50. Jumel, Y. and Broussely, M. Properties of the Li-CuO Couple.
28th Power Sources Symposium, June 1978, p. 222.
51. Crumrine, K. et al. Investigation of the Environmental Consequences of
Disposal of the Lithium Organic-Electrolyte S0_ Battery. ADA050512,
U.S. Army Electronics Command, 1978.
52. Spencer, E.W. Lithium Batteries: New Technology and New Problems.
Professional Safety. January 1981, pp. 27-30.
53. Turner, A.E. et al. Further Studies on the High Energy Li/CuO Organic
Electrolyte System. 29th Power Sources Conference, June 1980.
40
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APPENDIX A
GENERALIZED ABUSE TESTS
41
-------
TABLE A-l
MECHANICAL SHOCK TEST (DROP TEST)
Reference(s); 32-38
Cells Tested; Fully charged; partially discharged; overdischarged
Test Temperature; +25°C
Test Description! Free fall of test cell from a height of 5 meters onto
concrete test pad
Suggested Evaluation Criteria
Rating
High hazard
Moderate hazard
Low hazard
Observation
1. Fire/explosion
1. Heating of cell (cell wall temperature to 150°C
or greater)
2. Venting of toxic, flammable or corrosive gas
3. Leakage of electrolyte
1. Cell breach w/o leakage
2. Change in open circuit voltage
3. Change in weight
4. Venting of nontoxic, nonflammable, noncorrosive gas
5. No change in physical appearance or characteristics
other than impact deformation
42
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TABLE A-2
SHORT CIRCUIT
References; 32,39
Cells Tested; Fully charged; partially discharged; overdischarged
Test Temperature; +25°C
Test Description: 1. Connect terminals of cell through resistance
of 0.005 ohms or less
2. Short circuit for 24 hr
Suggested Evaluation Criteria
Rating
High hazard
Moderate hazard
Observation
1. Fire/explosion
1. Heating (cell wall temperature to 1508C or greater)
2. Venting of toxic, flammable or corrosive gas
3. Leakage of electrolyte
Low hazard
1. Swelling of cell
2. Change in weight
3. Venting of nontoxic, nonflammable noncorrosive gas
4. No change in physical appearance of cell
43
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TABLE A-3
IMMERSION TEST
References; 33,40
Cells Tested; Fully charged; partially discharged; overdischarged
Test Temperature; +25°C
Test Description; Completely immerse cell for 24 hr in:
a. Fresh water
b. Salt water
Suggested Evaluation Criteria
Rating Observation
High hazard 1. Fire/explosion
Moderate hazard 1. Heating (cell wall temperature to 150°C or greater)
2. Evolution of toxic, flammable or corrosive gas
Low hazard 1. Evolution of nontoxic, nonflammable, noncorrosive gas
2. No reaction
-------
TABLE A-4
CELL DEFORMATION TEST (CRUSH TEST)
References; 33,52,53
Cells Tested: Fully charged; partially discharged; overdischarged
Test Temperature: +25°C
Test Description; 1. Monitor open circuit voltage of cell and cell wall
temperature
2. Crush lower half of cell until internal short circuit
develops (noted by a reduction in cell voltage)
3. Maintain compression force for 24 hr
Suggested Evaluation Criteria
Rating
High hazard
Observation
1. Fire/explosion
Moderate hazard
1. Heating of cell (cell wall temperature to 150°C
or greater)
2. Venting of toxic, flammable or corrosive gas
3. Leakage of electrolyte
Low hazard
1. Venting of nontoxlc, nonflammable, noncorrosive gas
2. No leakage or physical change other than impact
deformation
-------
TABLE A-5
ELEVATED TEMPERATURE TEST
References: 32,43,48
Cells Tested; Fully charged; partially discharged; overdischarged
Test Temperature; 150°C
Test Description; Placed cell or battery in 150°C over for minimum of 24 hr
Suggested Evaluation Criteria
Rating Observation
High hazard 1. Fire/explosion
Moderate hazard 1. Venting of toxic, flammable or corrosive gas
2. Leakage of electrolyte
Low hazard 1. Venting of nontoxic, nonflammable, noncorrosive gas
2. Swelling of case
3. No change in physical dimensions or weight
-------
TABLE A-6
INCINERATION TEST
Reference: 49
Cells Tested; Fully charged; partially discharged; overdischarged
Test Temperature: Flame temperatures or furnace heated to at least 540°C
Test Description: Cell or battery exposed to flame environment and incinerated
Suggested Evaluation Criteria
Rating Observation
High hazard 1. Explosion
*
Moderate hazard 1. Production of toxic or corrosive gas
2. Increase in flame temperature or observed
exothermic reaction
Low hazard 1. Production of toxic or corrosive residue
2. No toxic or corrosive residue after burning
Other than those normally associated with the combustion of cellulose products
47
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TABLE A-7
FOREIGN OBJECT PENETRATION TEST
References; 32,33,43,50
Cells Tested: Fully charged; partially discharged; overdischarged
Test Temperature: +25°C
Test Description; 1. Monitor open circuit voltage and cell wall temperature
2. Penetrate cell with electrically conductive nail,
spike or rod - leave in place
3. Monitor open circuit voltage and cell wall temperature
for 24 hr
Suggested Evaluation Criteria
Rating
High hazard
Observation
1. Fire/explosion
Moderate hazard
Low hazard
1. Heating of cell (cell wall temperature to 150°C
or greater)
2. Venting of toxic, flammable or corrosive gas
3. Leakage of electrolyte
1. Venting of nontoxic, nonflammable, noncorrosive gas
2. No leakages or physical change other than
impact damage
48
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TECHNICAL REPORT DATA
(Please tad Instrucnora on the reverse before completing)
REPORT NO.
3. RECIPIENT'S ACCESSIOWNO.
4. TITLE AND SUBTITLE
HAZARD ASSESSMENT OF MANAGEMENT OF WASTE LITHIUM BATTERIES
3. REPORT DATE
June 1983
a. PERFORMING ORGANIZATION CODE
7. AUTHOFKS)
B.C. Vincent
8. PERFORMING ORGANIZATION REPORT NO.
OH1N6.RG
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Factory Mutual Research Corporation
1151 Boston-Providence Turnpike
Norwood, MA 02062
10. PROGRAM ELEMENT NO. '
11. CONTRACT/GRANT NO.
68-01-6698
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Solid Waste
U.S. Environmental Protection Agency
401 M St SW
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final fOct.. 1982 - Apr. . 1983
14. SPONSORING AGENCY CODE
S. SUPPLEMENTARY NOTES
as a
The purpose of the study was to assess the hazards associated with the dis-
enl St^ 1ithllM ba"erleS USlng exlStln* lithlum ta«^ safety test and
accident data. A survey was conducted to determine 1) basic cell constituents
2? D±CtrChriCal TaCt.i0n by-P"du"s of ^e various lithium batteries?^
2 products of reactions between cell constituents and water or heat. An ad-
Mf^, S^ud WaSte dlsp°sal technies was conducted. This involved
i fi"tion of both lithium battery management practices and conventional
hHe P0f \ tfchnlques- Uslr* the ^formation from these surveys, the
hazards assorted with the collection, processing, and disposal of waste lithium
batteries were quantified. The following conclusions were reached:
1) Litnium-thlonyl chloride and lithium-sulfur dioxide batteries should b*
'ent±al "-entLnal wastf dis-
thionvJ rhnr^a iJS^ ba"ery Byste*3 » ("thiui^aulfur dioxide , lithium-
J«i Jj ^loride, lithium-manganese dioxide and lithium vanadium pentoxide) con
tain highly toxic compounds which may contaminate the environment i? released
0 "thi* batteries,
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Croup
Lithium Batteries
'rimary Batteries
Lithium Battery Safety
Waste Management
Municipal Solid Waste
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. Of PAGES
53
20. SECURITY CLASS (This page)
UNCLASSIFIED
22. PRICE
EPA Porm 2230-1 (9-73)
49
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