Proceedings of the International Symposium on

Sustainable Systems and Technologies, v4 (2016)

Physical and Chemical Degradation of Lithium Ion Batteries under
Landfill Disposal Conditions
Kayla Collins Clemson University, mkc@clemson.edu
Macey Bosley Winthrop University, bosleym2@mailbox.winthrop.edu
Annick Anctil Michigan State University, anctilan@egr.msu.edu
Marian Kennedy Clemson University, mskenne@clemson.edu
Brian Powell Clemson University, bpowell@clemson.edu
Abstract. The quantity of Li-ion batteries is growing due to their increased use in consumer
products and electric vehicles, and at the end of their useful life, this large quantity of batteries
could end up in solid waste landfills. Within the United States only New York and California
currently ban their disposal, which means Li-ion batteries could become a long-term source for
metals leaching in landfills. To address this potential concern, this study characterizes the
degradation of Li-ion battery electrodes and leaching of metals in simulated landfill conditions.
Several types of Li-ion battery brands and cathode types (Li3NiMnCoO6, LiFePO4, and LiMn2O4)
were tested by exposing them to two simulated landfill leachates (pH 4.9 and 7.5) for two weeks.
EPA Method 1311 was conducted for comparison with the leaching results. Battery electrodes
were digested to determine the total amounts of metals. The physical properties of pristine and
post-leaching battery electrodes were examined using scanning electron microscopy. Results
after two weeks in the simulated leachates showed concentrations leaching of nickel (0.002 0.48 mg/g), cobalt (9.9x10-7 - 0.055 mg/g), copper (6.5x10-5 - 0.40 mg/g), manganese (4.0x10 5-0.03 mg/g), and iron (0.007 - 4.63 mg/g). The concentrations of metals leached over two
weeks were below regulatory limits for the United States, however copper and nickel
concentrations exceeded regulatory limits set by California, which is in line with current disposal
regulations. Unlike the two-week leaching tests, results from the T.C.L.P. showed mercury
concentrations exceeding the regulatory limits for the Li3NiMnCoO6 battery, but the other two
cathode types did not exceed any regulatory limits. Current work is focusing on intermediatescale testing which includes more realistic landfill conditions with solid waste and leachate over
a longer time frame. The results are useful for comparing with intermediate-scale testing in more
realistic landfill conditions, as well as in policy decisions for recycling at end of life, and for
updating current life cycle assessments to include disposal during the end-of-life phase. This
work was supported by the National Science Foundations REU program under grant number
1460863 and the Clemson University Department of Materials Science and Engineering.

Proceedings of the International Symposium on Sustainable Systems and Technologies (ISSN 2329-9169) is
published annually by the Sustainable Conoscente Network. Jun-Ki Choi and Annick Anctil, co-editors 2016.
ISSSTNetwork@gmail.com.
Copyright 2016 by Kayla Collins, Macey Bosley, Annick Anctil, Marian Kennedy, Brian Powell Licensed under CCBY 3.0.
Cite as:
Physical and Chemical Degradation of Lithium Ion Batteries under Landfill Disposal Conditions Proc. ISSST, Kayla
Collins, Macey Bosley, Annick Anctil, Marian Kennedy, Brian Powell. Doi information v4 (2016)

Physical and Chemical Degradation of Lithium Ion Batteries under Landfill Disposal Conditions

Introduction. One of the greatest challenges of modern society entails meeting the growing
energy demands while minimizing long-term environmental effects from both the production and
storage of that energy. Electrical energy is often stored within batteries which act as portable
power supplies for electronic devices such as cell phones and, more recently, electric vehicles.
To improve battery capacity and power density lifetimes at lower costs to consumers, the
materials within batteries are being altered, resulting in a shift from nickel-metal hydride
batteries to Li-ion batteries. Li-ion batteries are now supplanting nickel-metal hydrides in electric
vehicles (Catenacci et al., 2013; USEPA, 2013) and in portable devices, with the increased
probability that these batteries will end up in landfills (Marom et al., 2011). While Li-ion batteries
are not generally considered environmentally hazardous compared to metal hydride batteries
containing lead, mercury and cadmium, disposal of Li-ion batteries in landfills present
environmental risks from the leaching of organic electrolytes, toxic metals, lithium salts, and
carbonaceous material (Richa et al., 2014). Therefore, the disposal of Li-ion batteries can have
a direct adverse environmental effect through the release of battery components which needs to
be studied to develop appropriate end of life strategies.
Limitations to Current Regulatory Methods. U.S. Environmental Protection Agency (EPA)
regulations and some individual state standards are used to determine the toxicity of potentially
hazardous e-waste. EPA Method 1311 (USEPA, 1992), which outlines the Toxicity
Characteristic Leaching Procedure (TCLP) is widely used to categorize the toxicity of lightemitting diodes (Lim et al., 2011), personal computer components (Li et al., 2009; Komilis et al.,
2013) and other household e-waste (Musson et al., 2006). However, the use of these current
regulatory leaching methods to assess the toxicity of different e-wastes may be less than
accurate (Poon and Lio, 1997; Kosson et al., 2002; Ghosh et al., 2004; Karamalidis and
Voudrias, 2007). Specifically, the TCLP may be inadequate due to evaluating and regulating
wastes using a single, worst-case test condition leading to both over-regulation and inadequate
protection of the environment (Kosson et al., 2002). The TCLP does not account for a range of
pH values, which is known to affect the leaching of metals and anions (Karamalidis and
Voudrias, 2007). The regulatory limits were set to account for the likely dilution and attenuation
that will occur in subsurface transport by multiplying the drinking water standards of 1986,
authorized by the Safe Drinking Water Act, by a factor of 100 (USEPA, 1995). Although the
drinking water standards have changed since 1986 (USEPA, 2014), the regulatory limits for the
TCLP have not. Thus, there is a need to compare TCLP results for Li-ion batteries with results
from laboratory scale landfill leachate experiments and intermediate-scale landfill experiments.
Through such experiments, the ability of these methods to properly characterize disposal of Liion batteries can be assessed.
Research Question. The degradation of Li-ion batteries followed by metal ion release is
facilitated by acidic leachate in the early lifetime of a municipal solid waste landfill. The metal
ions released could be transported in landfill leachate at concentrations of concern. Without a
ban on landfill disposal, Li-ion batteries could become a long-term source of metals leaching in
landfills and potentially to the surrounding environment if improper management occurs. To
address this potential concern, this study characterizes the degradation of Li-ion battery
electrodes and leaching of metals in simulated landfill conditions.
Investigative Method. The methods in this study have been employed to characterize the
degradation of Li-ion battery electrodes and subsequent metal leaching under simulated landfill
conditions. Several types of Li-ion battery brands and cathode types (Li3NiMnCoO6, LiFePO4,
and LiMn2O4) were tested. These batteries were selected based on manufacturer marketing as
Li-ion batteries. However, the specific chemistry of the cathodes, anodes, and electrodes was
not provided with the battery packaging.

Collins et al.

Landfill Leachate Simulants. After discharging four batteries of each type using resistors
followed by copper wire, the outer plastic labels were removed. Two of each battery type were
mangled by cutting half of the top edge of the positive terminal. Batteries were placed in 60 mL
bottles with the simulated landfill leachates (Table 1) in a 3-to-1 fluid-to-sample ratio, which was
sufficient to completely submerge the batteries. Samples were left undisturbed at room
temperature. After 24 hours and 2 weeks, 5 mL aliquots were taken from each sample and
analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES, Perkin Elmer
Optima 3100) to determine the concentrations of metals leached from each battery. The pH was
also recorded of each aliquot to track fluctuations as leaching occurred.
Table 1. Simulated Landfill Leachate Components and Concentrations
Simulated Leachate 1 (pH 7.5)
Simulated Leachate 2 (TCLP leachate, pH 4.9)
Component
Concentration
Component
Concentration
Calcium carbonate
1100 mg/L
Glacial Acetic Acid
5.7 mL/L
1 N NaOH
64.3 mL/L
Sodium carbonate
11500 mg/L
DI Water
930 mL/L
Ammonium chloride
650 mg/L
Acetic acid
548 microliter/L
Propionic acid
192 microliter/L
Butyric acid
422 microliter/L
Pentanoic acid
163 microliter/L
Hexanoic acid
232 microliter/L
Sodium citrate
46,400 mg/L
Hydroxylamine hydrochloride
31.7 mg/L
EPA Method 1311: Toxicity Characteristic Leaching Procedure (TCLP). EPA Method 1311
(TCLP), which is used to determine if an unlisted waste should be classified as hazardous
waste based on toxicity, was conducted for comparison with the two week simulated landfill
leaching tests. For this study, samples consisted of 2 grams of each battery types jellyroll. The
TCLP sample preparation steps involve crushing a sample to a particle size of less than 9.5 mm,
adding an extraction fluid at a 20:1 fluid-to-sample ratio, and rotating the sample in extraction
fluid for 18 hours. A preliminary evaluation determines which of two extraction fluids to use. One
liter of TCLP extraction fluid consists of either 5.7 mL glacial acetic acid, 64.3 mL 1 N sodium
hydroxide, and 930 mL of reagent water resulting in a solution pH of 4.93 0.05, or 5.7 mL
glacial acetic acid and 994.3 mL reagent water resulting in a solution pH of 2.88 0.05 (USEPA,
1992). After rotating, the samples are filtered through 100 nm pore diameter nylon filters. The
filtrate is then acidified with nitric acid and analyzed by ICP-OES to determine the
concentrations of metals present.
Digestion of Battery Jellyrolls. Battery electrodes were digested to determine the total amounts
of metals for each type of battery tested, which could be compared with the concentrations
leaching in the simulated leachates. The aluminum housing of each battery was removed using
hand tools, as to gain access to the jellyroll (rolled anode and cathode). Two uniform samples
(~500 mg each) were taken from each battery type. Each 500 mg sample was placed in a
separate digestion tube and acidified using 10 mL of concentrated nitric acid. The samples were
digested for 15 minutes at 175C in a MARS microwave digester. Samples were filtered with 0.2
micron filters, diluted to 0.2 % and 10%, and analyzed by inductively coupled plasma optical
emission spectroscopy (ICP-OES, Perkin Elmer Optima 3100RL) to determine the
concentrations of metals in each battery jellyroll.

Physical and Chemical Degradation of Lithium Ion Batteries under Landfill Disposal Conditions

Physical Characteristics of Battery Jellyrolls. The physical properties of pristine and postleaching battery electrodes were determined using scanning electron microscopy (SEM, Hitachi
SU6600) in combination with metal mapping (Aztec software program). SEM images were taken
of pristine battery anodes and cathodes, leached battery anodes and cathodes, and suspended
particles from the leachate solutions.
Results. After two weeks submerged in the landfill leachate simulants, results showed
concentrations leaching of nickel (0.002-0.48 mg/g), cobalt (9.9x10-7-0.055 mg/g), copper
(6.5x10-5-0.40 mg/g), manganese (4.0x10-5-0.03 mg/g), and iron (0.007-4.63 mg/g). The
concentrations of metals leached over two weeks were below regulatory limits for the United
States, however copper and nickel concentrations exceeded regulatory limits set by California,
which is in line with currently disposal regulations. Unlike the two-week leaching tests, results
from the T.C.L.P. showed mercury concentrations exceeding the regulatory limits for the
Li3NiMnCoO6 battery, but the other two cathode types did not exceed any regulatory limits
(Table 2). From the digestion of the Li3NiMnCoO6 battery jellyroll, between 0.16 and 1.23
percent of the total amounts of Al, Co, Cu, Hg, In, Mn, Ni, and Pb in the battery leached during
the two week period, indicating a potential long-term source of metals entering the leachate in a
landfill (Figure 1). SEM with metal mapping showed changes that occurred from pristine to
leached batteries, such as cobalt which was not detected on a pristine battery graphite on
copper foil layer but is present after submersion in TCLP extraction fluid (Figure 2).
Table 2. TCLP Results shown with TCLP and Safe Drinking Water Act (SDWA) Regulatory Limits.
LiMn2O4
LiMn2O4
Li3NiMnCoO6
LiFePO4
TCLP Limits SDWA Limits
(Brand 1)
(Brand 2)
[mg/L]
[mg/L]
[mg/L]
[mg/L]
[mg/L]
Element
[mg/L]
Pb
0.11
ND
ND
ND
5.0
0.015
ND
ND
ND
0.002
Hg
4.26
0.2
CA only
Co
260.7
1.04
0.01
ND
80
74.7
ND
ND
1.3
Cu
134.5
25
1.14
ND
ND
Ni
39.6
20

Figure 1: Percentage of Metals Leached during TCLP. Percentages of the total digested amount of each metal
leached using the TCLP regulatory method per Li3NiMnCoO6 battery jellyroll. Cobalt, copper, mercury, and nickel
exceeded the threshold values for toxicity.

Collins et al.

Figure 2a: SEM and Metal Mapping. SEM secondary electron images and metal mapping of a Li3NiMnCoO6 anode
(graphite on copper foil) in pristine condition (prior to leaching).

Figure 2b: SEM and Metal Mapping. SEM secondary electron images and metal mapping of a Li3NiMnCoO6 anode
(graphite on copper foil) after 17 days of leaching in TCLP extraction fluid.
Discussion. The quantity of Li-ion batteries is growing due to their increased use in consumer
products and electric vehicles, and at the end of their useful life, this large quantity of batteries
could end up in solid waste landfills where their disposal is not well studied. Li-ion batteries
could become a long-term source for metals leaching in landfills from the degradation of battery
electrodes. Using a worst-case, complete submersion in leachate simulants, the concentrations
of metals leached from the three Li-ion battery types tested over two weeks were below
regulatory limits for the United States, however copper and nickel concentrations exceeded
regulatory limits set by California, which is in line with currently disposal regulations. Unlike the
two-week leaching tests, results from the T.C.L.P. showed mercury concentrations exceeding
the regulatory limits for the Li3NiMnCoO6 battery, but the other two cathode types did not
exceed any regulatory limits. From the total digestion of the Li3NiMnCoO6 battery, between 0.16
and 1.23 percent of the total amounts of Al, Co, Cu, Hg, In, Mn, Ni, and Pb in the battery
leached during the two week period, indicating a potential long-term source of metals entering

Physical and Chemical Degradation of Lithium Ion Batteries under Landfill Disposal Conditions

the leachate in a landfill. Current work is focusing on intermediate-scale testing which includes
more realistic landfill conditions with solid waste and leachate over a longer time frame, which
will be useful for comparison with the data in this study. Implementing recycling policies should
consider environmental aspects in addition to economic aspects, and this work can help to fill
knowledge gaps about Li-ion battery landfill disposal. The results are also useful for updating
current life cycle assessments to include disposal during the end-of-life phase which can
provide a more realistic model of current practices.
Acknowledgements. This work was supported by the National Science Foundations REU
program under grant number 1460863 and the Clemson University Department of Materials
Science and Engineering and Department of Environmental Engineering and Earth Sciences.
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