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Copper Dissolution in Overdischarged Lithium-ion Cells: X-ray

Photoelectron Spectroscopy and X-ray Absorption Fine Structure
Analysis
To cite this article: Christopher E. Hendricks et al 2020 J. Electrochem. Soc. 167 090501

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 Journal of The Electrochemical Society, 2020 167 090501

Copper Dissolution in Overdischarged Lithium-ion Cells: X-ray

Photoelectron Spectroscopy and X-ray Absorption Fine Structure
Analysis
Christopher E. Hendricks,1,2,z Azzam N. Mansour,1,* Daphne A. Fuentevilla,1 Gordon
H. Waller,1 Jonathan K. Ko,1 and Michael G. Pecht2
1
Naval Surface Warfare Center Carderock Division, United States of America
2
Center for Advanced Life Cycle Engineering, College Park, Maryland, United States of America

In some applications, such as military or back-up energy applications, lithium-ion batteries can undergo storage for multiple years
without use. If the batteries are not properly maintained, the pack voltage can decrease over time due to cell self-discharge, battery
management system power requirements, and parasitic loads. However, lithium-ion batteries have a recommended discharge
voltage limit corresponding to a nominal 0% state of charge, and if discharged below this limit, they will experience an
overdischarge condition which can lead to dissolution of the copper current collector and introduce potential safety and
performance issues. This paper investigates the nature of copper dissolution in overdischarged lithium-ion batteries including the
relative concentration and chemical state of the copper found in overdischarged batteries through characterization by X-ray
photoelectron spectroscopy and X-ray absorption fine structure spectroscopy.
© 2020 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. This is an open access
article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/
by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/
1945-7111/ab697a]

Manuscript submitted November 21, 2019; revised manuscript received January 3, 2020. Published February 4, 2020. This paper is
part of the JES Focus Issue on Battery Safety, Reliability and Mitigation.

Lithium-ion batteries are increasingly being employed in appli-
cations ranging from consumer electronics to military and aerospace
applications. Compared to other rechargeable battery technologies,
lithium-ion batteries have a high cell potential, energy density, and
cycle life that make them attractive as an energy source. To prevent
excessive degradation and potential safety hazards, lithium-ion
batteries need to be operated within stable voltage, current,
temperature, and pressure limits, which is often accomplished
through a battery management system. Well-designed battery
management systems can prevent batteries from overcharging to
voltages above the stable voltage limit, however, a battery manage-
ment system itself cannot prevent a battery from overdischarging
below the stable voltage limit without an external source of power. If
a battery is not maintained and regularly charged, the battery’s
voltage may slowly decrease due to parasitic loads and internal
losses, eventually causing an overdischarge condition. Alternatively,
imbalances in cells connected in series can lead to inadvertent
overdischarge of one or more cells during use, potentially resulting
in the negative electrode reaching a greater potential than the
positive electrode. This phenomenon is known as voltage reversal
and is considered a more aggressive form of overdischarge.
Overdischarge has been studied through electrochemical mea-
surements of negative electrode half-cells, three-electrode cells, and
full cells. In experiments carried out in half-cells, bare copper foils
and graphite coated copper foils1–4 were placed in electrolyte
solutions, and researchers found that copper dissolution occurs at a
voltage of approximately 3.5 V vs Li/Li+, and that a graphite coating
limited the amount of copper dissolved when compared to the bare
copper foil. A half-cell voltage of 3.5 V corresponds to roughly a
full-cell voltage of 0.5 V for cells containing a layered-type
transition metal oxide cathode (i.e. having the generic composition
LiMO2 where M = Co, Mn, Ni, Al). Copper in the electrolyte was
measured through inductively coupled plasma (ICP) analysis.
In three-electrode and full cell studies, cells can either be
overdischarged into reversal,5–9 which requires a power supply to
force the cell voltage into a negative regime, or overdischarged to
voltages as low as 0 V.10–16 Depending on the severity of the
overdischarge condition, the cell can be rendered useless or may be
*Electrochemical Society Member.
z
E-mail: Christopher.hendricks@navy.mil
recovered. The failure mechanism of overdischarge into reversal is
fairly well understood, as the negative electrode’s copper current
collector is oxidized to Cu2+ and eventually plates on the positive
electrode where it is reduced to Cu. Eventually an internal short
circuit is formed; however, the state of charge (SOC) is low enough
that it typically does not result in a thermal runaway event.5–9 More
interesting is whether a cell that is overdischarged and is recoverable
(i.e. can be recharged and cycled) poses a safety risk. At high SOC,
cells are more likely to undergo thermal runaway if an internal short
circuit develops.17
Maleki and Howard10 repeatedly overdischarged small prismatic
cells to voltages between 2.0 and 0 V to induce copper dissolution.
Performance was degraded for cells cycled to 1.0 V or below, and
cells behaved most erratically when overdischarged to 0 V. The
presence of copper was confirmed on both sides of the separator for
one of the 0 V samples using energy dispersive spectroscopy (EDS),
but was not found in the other 2 cells overdischarged to 0 V. The
authors do not provide an additional explanation of this discrepancy
other than the fact that the behavior of the cell was unpredictable
when overdischarged to 0.0 V.
Crompton and Landi11 investigated copper dissolution thresholds
in 3-electrode pouch cells and explored pre-lithiation strategies for
zero-volt storage of lithium-ion batteries. Direct measurement of the
dissolved copper was not conducted in the study, but the authors
found that a negative electrode potential of 3.1 V vs Li/Li+ resulted
in a small oxidative current, with higher voltages leading to
increased currents. While this value is lower than the 3.4–3.6 V vs
Li/Li+ reported elsewhere,1,2 the authors attributed this to ambient
conditions, electrolyte composition, and non-faradaic processes.
Fuentevilla et al.12 and Hendricks et al.13 presented X-ray
photoelectron spectroscopy and X-ray absorption fine structure
spectroscopy results from large-format (>30 Ah) nickel cobalt
aluminum (NCA) oxide cylindrical cells experiencing overdischarge
to voltages as low as 0 V. Copper was detected on both electrodes
from cells that were stored at less than 0.5 V, whereas no copper was
observed on electrodes from cells stored at 0.5 V and above.
Li at al.14 overdischarged LiCoO2 cells to voltages between 0 and
3 V and studied copper deposition on the positive electrode using
inductively coupled plasma (ICP) analysis. Furthermore, the thick-
ness of the cells and the gas composition were studied.
Overdischarge to 0 V led to the generation of gases, most notably
CO2, and the performance was significantly affected. ICP analysis
 Journal of The Electrochemical Society, 2020 167 090501
showed that approximately 200 μg of copper per g of positive
electrode material was detected at voltages of 3.0, 1.0, and 0.4 V. In
contrast, cells overdischarged to 0 V contained a copper content of
approximately 900 μg g−1 of positive electrode material.
Kumai et al.15 repeatedly overdischarged LiCoO2 cells to –10%
SOC with no voltage limits implemented, with the cell reaching 0 V
by the 50th cycle. While copper dissolution was not measured, gas
evolution was attributed to accelerated electrolyte decomposition as
a result of copper plating that inhibits lithium intercalation.
Love and Gaskins16 overdischarged pouch cells with a LiCoO2
positive electrode and graphite negative electrode. Their report
primarily focuses on swelling due to gas generation and reduction
in charge/discharge cycles. When a cell was repeatedly over-
discharged to 1.2 V, the thickness increased by over 3.5 mm after
200 cycles. Furthermore, the cells reached 20% capacity loss within
57 cycles, which is at least 4 times fewer cycles than the same cells
operated in their normal cycling range. Copper analysis was not
performed, and may not have occurred based on the voltage ranges
tested. Instead, solid electrolyte interphase (SEI) layer decomposi-
tion, reformation, and gas generation may have consumed lithium,
resulting in a reduced cell capacity.
Overdischarge of lithium-ion batteries has the potential to lead to
a number of side reactions within a lithium-ion battery including
dissolution of the copper current collector, degradation of the SEI
layer on the negative electrode, and gas generation. Depending on
the severity of the overdischarge condition, the battery could
experience more rapid capacity fade or develop internal short
circuits. Typically, the internal short circuits do not cause a
catastrophic failure, due to the low SOC of the cell at the time the
short initiates; however, it is not clear from the literature whether
cells experiencing a single overdischarge can be recharged and
reused. This paper seeks to utilize both surface- sensitive (X-ray
photoelectron spectroscopy, XPS) and bulk (X-ray absorption fine
structure, XAFS) analytical techniques to learn about the chemical
state, amount, and location of copper in cells that were over-
discharged for more than 9 months to identify the risk for short
circuiting.
Experimental
Cells for this study were selected from battery packs containing
series-connected 52 Ah cells. The cells are cylindrical (54 mm
diameter × 208 mm length) and the positive and negative electrodes
contain nickel cobalt aluminum (NCA) oxide and graphite, respec-
tive, as the active material. A population of 15 cells was over-
discharged to 0.5 V, 0.25 V, or 0 V for over 9 months at room
temperature of 25 ± 3 °C. The cells were then split into groups to
either undergo disassembly without recharge, recharged once at a
C/5 C-rate (10.4 A) and then discharged at the same rate to 0% SOC
prior to disassembly, or set aside to cycle between 2.5 V and 4.1 V at
a C/2 C-rate (26 A). A sample of cells above 2.5 V were not
overdischarged and simply stored at open circuit to be used as
control samples. All cells were disassembled in a discharged state
inside of an argon-filled glovebox with oxygen content less than
1 ppm. As the electrode sheets were unwound, the negative and
positive electrodes were separated, and wound individually around
separate mandrels. Samples were removed corresponding to dif-
ferent locations within the electrode winding, including areas close
to the cell casing (exterior), after unwinding approximately 2 m of
electrode material (middle) and after unwinding approximately 4 m
of electrode material (interior). Roughly 50 mm × 50 mm square
samples were cut from each section of the electrode for XAFS, and
two 11-mm-diameter samples were punched out of the electrode for
XPS. All samples were stored in the glovebox and either transferred
to the XPS in an airtight transfer vessel or spent up to 5 days in
sealed plastic sample holders outside of the glovebox during XAFS.
XAFS sample preparation.—Reference powders were collected
for a number of relevant copper, nickel, and cobalt compounds
including: Cu(OH)2, Cu2O, CuO, CuF2, LiNiO2, NiO, LiCoO2, and
LiNi0.8Co0.15Al0.05O2. The choice of compounds was based on
potential copper compounds that could be formed in a lithium-ion
battery under overdischarge conditions as well as the primary
lithium-ion battery active positive electrode material of interest for
this study. Reference samples were prepared by manually grinding
powders with a mortar and pestle. An ultrasonic sifter was then used
to collect particles less than 20 μm in diameter. The amount
of powder used for each sample was calculated to coincide with a
K-edge step of approximately 1. The powder was then combined
with boron nitride and mixed with a magnetic stir rod until a uniform
mixture was attained. Approximately 80 mg of each mixture was
then placed into a pellet mold and compressed using a force of 1.5
metric tons. The mold was disassembled to remove the 12-mm-long
by 5-mm-wide rectangular sample pellet. The pellet was then
mounted on Scotch-brand tape to avoid contamination.
Samples of lithium-ion battery electrodes were transferred to the
beamline in sealed plastic sample holders and Scotch-brand tape was
used to mount samples for analysis. The tape was used to peel one
side of the electrode off of the current collector. In the case of the
overdischarged negative electrodes, the graphite was collected as
large flakes that delaminated from the electrode.
XAFS analysis.—X-ray absorption fine structure (XAFS) ana-
lysis was performed at the Advanced Photon Source (APS) at
Argonne National Laboratory on beamline 5-BM-D. Experiments
were run under a general user proposal submitted to the APS.
Beamline 5-BM-D uses bending magnets to direct X-rays at the
samples located within the beam’s path. A Cambera passivated
implanted planar silicon (PIPS) fluorescence detector was used to
measure copper on the negative electrode of the battery. Ion chamber
detectors were used to measure the intensities of the incident X-rays,
the transmitted X-rays through the sample, and the transmitted
X-rays through the reference foil. Nickel and cobalt in the positive
electrode were measured in transmission mode, and copper in the
negative electrode could also be measured in transmission mode
simultaneously with the fluorescence signal.
The monochromator was tuned based on the reference foil
selected. The reference foil was chosen as copper when investigating
the negative electrode (without current collector) for evidence of
copper dissolution. The reference foil was chosen as nickel and
cobalt when investigating the positive electrode for potential
changes in the oxidation state of the positive electrode
(LiNi0.8Co0.15Al0.05O2) as a result of overdischarge. This required
2 sets of scans for each sample, once at the nickel K-edge, and again
at the cobalt K-edge.
The X-ray cross-section was approximately 1 mm × 7 mm, and
samples were cut in excess of this cross section. It was possible to
locate the center of the sample by performing vertical and horizontal
scans while monitoring the transmitted and fluoresced signal and
selecting the location that provided either the maximum (fluores-
cence) or minimum (transmission) signal. Scans for the copper
K-edge were performed between 8.779 keV and 10.079 keV with
5 eV step in the pre-edge region, 0.5 eV step in the XANES region,
and 0.05 Å–1 step in the EXAFS region. Scans were performed with
the same pre-edge, XANES, and EXAFS step settings for the nickel
K-edge between 8.133 keV and 9.433 keV, and scans for the cobalt
K-edge were performed between 7.509 keV and 8.809 keV.
XPS sample preparation.—The same reference powders studied
under XAFS were examined by XPS. Electrode samples were
attached to the sample holder with double-sided tape inside of the
argon-filled glovebox and transferred to the XPS intro chamber in an
inert sample transfer vessel. The sample transfer vessel was
connected directly to the XPS and placed under vacuum before
opening the vessel. At no point was the sample exposed to air.
XPS analysis.—XPS analysis was performed at Naval Surface
Warfare Center Carderock Division using a Physical Electronics
 Journal of The Electrochemical Society, 2020 167 090501
Figure 1. Cu K-edge XANES of some copper reference compound, namely,
Cu, Cu2O, CuO, Cu(OH)2, CuF2.
VersaProbe II scanning X-ray photoelectron spectroscopy microp-
robe. The VersaProbe features a monochromatic Al-Kα X-ray source
that can precisely perform analysis on an identified sample region.
Samples are transferred into the XPS ultrahigh vacuum chamber
through an intro chamber that is pumped down to 4 × 10–4 Pa. The
XPS data collection commenced when the ultrahigh vacuum analysis
chamber reached ∼2 × 10–8 Pa. The sample height is adjusted to
maximize the signal intensity and survey and multiplex scans were
performed on all of the samples. Multiplex scans of the negative
electrodes focused on Li1s, C1s, O1s, F1s, P2p, and Cu2p3/2
photoelectron lines, and the positive electrode scans additionally
included Co2p and Ni2p orbitals. Scans were taken over a 200 μm ×
1000 μm area with an electron take-off angle of 45°. The 200-μm X-
ray beam was electronically rastered to minimize X-ray damage of
the samples. The analyzer pass energy was set to 117.4 eV for
survey spectra and 23.5 eV for multiplex spectra, which enabled
resolutions of 1.76 eV and 0.35 eV, respectively. Argon ion
sputtering was conducted using an ion gun set to a power of 3 kV,
which has been calibrated to mill at a rate of approximately
8 nm min−1 of SiO2.
Results and Discussion
XAFS.—XAFS data were analyzed using the Demeter software
suite for calibration, pre-edge background subtraction, normalization
and extraction of the EXAFS spectra (Athena package), and model
fitting (Artemis package). All of the spectra were calibrated and
aligned using the measured reference foil (Cu for the negative
electrode and Ni/Co for the positive electrode). The X-ray absorp-
tion near edge structure (XANES) for various reference copper
compounds is shown in Fig. 1, and those for cells held at 0 V and
0.25 V are shown in Fig. 2. Measurements of negative electrodes
from the 0.5 V and 2.5 V conditions demonstrated negligible copper
K-edges, indicating that copper dissolution only occurs under 0.5 V
for this cell design. The spectra in Fig. 1 clearly display the
sensitivity of the XANES region to composition, changes in
oxidation state, and changes in local coordination geometry. The
spectra in Fig. 2 have differences in the intensity of the pre-edge
shoulder at 8981 eV as well as at and above the K-edge. The changes
in intensity as a function of energy are unique for each compound as
seen in Fig. 1, and samples containing multiple compounds can be
represented as a linear combination of the two, with the intensity
depending on the mole fraction of each compound.
Comparisons between the overdischarged negative electrodes and
the reference compounds are made in Fig. 3 by looking at the raw
XANES data as well as the first derivative of the XANES data. Data
from all 0 V and 0.25 V cells most closely matched the Cu2O and
Figure 2. Cu K-edge XANES of different negative electrodes collected
from cells overdischarged to 0 or 0.25 V as well as after being recharged and
discharged to 0% state of charge.
Cu(OH)2 reference compounds as seen in Fig. 3a. The pre-edge
feature illustrated with the dashed vertical line labeled A corre-
sponds with the pre-edge shoulder observed in Cu2O, whereas the
dashed vertical lines B and C match those observed for Cu(OH)2.
Figure 4 illustrates this further by looking at the Fourier transforms
of the extended X-ray absorption fine structure (EXAFS) oscillations
that are associated with interactions and collisions between ejected
electrons and the surrounding atoms. There is close agreement with
the Cu2O and Cu(OH)2 spectra; however, the reduced amplitude of
the peaks above 2 Å illustrates the amorphous nature of the Cu(OH)2
found in the negative electrode.
To explore the differences between the different storage condi-
tions, data from both fluorescence and transmission mode measure-
ments were evaluated. Table I contains the copper K-edge step
magnitude for the different storage conditions as measured in
transmission mode and the calculated copper loading in each of
the samples. Values range from 0.37 mg cm−2 for a 0 V cell to
0.070 mg cm−2 for a 0.25 V cell. The K-edge step for 0.5 V and
2.5 V cells is sufficiently low that copper can be assumed to be
absent from these samples. The concentrations were calculated using
the absorption cross section at 30 eV above and below the Cu edge
energy edge of 8979 as calculated by the software code
Hephaestus.18 The magnitude of the K-edge step relates to the
relative concentration of copper in each of the samples, and clearly
shows a trend toward higher copper species concentrations in more
severely overdischarged cells (0 V and 0.25 V) compared to healthy
(2.5 V) or mildly overdischarged (0.5 V) cells. To determine the
contribution of different copper species to the overall copper signal,
the EXAFS spectra for each of the cells is fitted to a linear
combination of contributions from the first coordination sphere of
copper in Cu2O and Cu(OH)2. This assumes that all samples contain
the same two copper compounds in varying concentrations. This
model is supported by the observation made on the basis of the
XANES spectra. The first shell scattering paths for Cu(OH)2 and
Cu2O were calculated using Feff within the Artemis software
package. Crystal structure data for Cu(OH)2 and Cu2O were obtained
from literature.19,20 The Cu2O contribution was limited to the first
shell which consists of 2 oxygen atoms at a distance of 1.83 Å. On the
other hand, the Cu(OH)2 contribution was limited to four oxygen
atoms at 1.96 Å and one oxygen atom at 2.36 Å. The many-body
amplitude reduction factor was constrained to the value derived from
fitting the Cu reference data. After fitting the entire data set to the
model, the model agreed quite well with the experimental data as
seen in Fig. 5. The model parameters are summarized in Table II
and Table III. Table II provides the refined parameters for the
 Journal of The Electrochemical Society, 2020 167 090501

Figure 3. Cu K-edge XANES (left) and its derivative (right) of 0 V cell compared to reference compounds, a.) Cu2O and Cu(OH)2, and b.) CuF2, Cu, and CuO.
The pre-edge feature for the 0 V cell aligns more closely with that of Cu2O (a) than that of Cu (b) as seen by the dashed line labeled A. Examination of the 1st
derivative of XANES data demonstrates that the post-edge features for the 0 V cell align with those of Cu(OH)2 (a) and not those of Cu, CuO or CuF2 (b) as seen
by the dashed lines B and C.

coordination distance and the disorder for the various contributions
from Cu2O and Cu(OH)2 as seen for copper in the negative electrode
samples. Table III demonstrates how the concentration of Cu2O and
Cu(OH)2 vary with respect to electrochemical test conditions. The
concentration of Cu2O is higher for the 0 V cells compared to the
0.25 V cells. Furthermore, recharging the cell results in higher
concentrations of Cu2O as well. In addition, the XANES data
for dissolved Cu were also analyzed in terms of a linear combination
of XANES data for Cu2O and Cu(OH)2, and the results were
qualitatively similar to the XAFS curve fit analysis results.
The positive electrodes were scanned at the copper, nickel, and
cobalt K-edges. The copper fluorescence signal could not be
resolved due to interference from the other metals contained in the
positive electrode. Both the nickel and cobalt K-edges did not show
any differences between different storage conditions and the control
samples. The absence of a change in oxidation state in the positive
electrode indicates that overdischarge does not lead to degradation of
the positive electrode active material as seen in Fig. 6.
XPS.—The XPS data were analyzed using the Multipak software
from Physical Electronics. Copper reference compounds were
measured and the Cu2p3/2 region is shown in Fig. 7. CuF2 was
consistent with literature and exhibited a high binding energy
(935.8 eV) compared to all of the measured samples.21 The binding
energy scales for the negative electrode and positive electrode samples
were calibrated based on the hydrocarbon C1s peak occurring at
284.8 eV. Once calibrated, the spectra were deconvoluted using a
Gauss-Lorentz function with an iterative Shirley background correc-
tion and fit to symmetric Gauss-Lorentz curves. For the positive
electrode C1s fit, an asymmetric curve was fit for the carbon black
signal. Each of the multiplex scans for the different electrode samples
was fit and a summary of the negative electrodes Cu2p3/2 fit is
summarized in Table IV.
XPS measurements of the negative electrode samples harvested
from 2.5 V cells did not reveal any copper, consistent with
expectations. Only one 0.5 V sample exhibited a well-defined copper
peak, with about 0.1 atomic percent of copper detected. Samples from
0.25 V and 0 V cells contained copper of 1–3 atomic percent. The
samples are summarized in Table V. It is apparent that 0.5 V is close
to the copper dissolution point and even at this voltage, some limited
dissolution is possible; however, as no copper is found on the positive
electrode side, extensive copper dissolution is likely not occurring.
The 3 samples (exterior, middle, and interior) from each cell did not
demonstrate significant differences in the atomic percentage of
measured elements and the multiplex spectra were consistent as well.
Table V provides values for the scanned elements.
The negative electrode multiplex data are shown in Fig. 8, with
the C1s spectra used for energy scale calibration on the top and the
 Journal of The Electrochemical Society, 2020 167 090501

Figure 4. Fourier transform of EXAFS data for overdischarged cell and Figure 5. Comparison of Fourier transforms of experimentally measured
reference compounds Cu2O and Cu(OH)2. The Fourier transforms were k3-weighted EXAFS data (solid curve) and fitted model (dash curve) for the
performed from k3-weighted EXAFS spectra over the k-range of 3-12.0 Å−1 0 V negative electrode.
and a Hanning window of 1.0 Å−1.

Table I. Copper K-edge step measured in transmission mode. Cu2p3/2 spectra on the bottom. The C1s spectra contains 3 primary
contributions to the signal including an overlapping region con-
Transmission Cu loading sisting of hydrocarbon contamination and carbon singly bonded to
Storage Condition Cu K-Edge Step (mg cm−2) carbon. The other two peaks are representative of SEI layer
components including lithium alkyl-carbonates (carbon singly
0V 0.0722 0.304 bonded to oxygen) and lithium carbonate or carbon in the carboxylic
0.25 V 0.0165 0.070 group (carbon singly bonded to two oxygen atoms and doubly
0V, recharged 0.0873 0.368 bonded to one oxygen). The Cu2p3/2 spectra highlights contributions
0.25 V, recharged 0.0169 0.071 from both Cu2O and Cu(OH)2 with primary peaks occurring at
0.5 V, recharged 0.0002 0.000 approximately 933 eV and 935 eV, respectively. The satellite peaks
2.5 V 0.00002 0.000 between 939 and 947 eV are only seen in compounds with Cu2+
oxidation state, and can be associated with Cu(OH)2. In the 0.25 V
recharged cell, a low intensity C1s peak around 282.5 eV is observed
and can be attributed to intercalated graphite. The same cell also has
Cu2p3/2 spectra that are shifted to lower binding energies, with the
Table II. Model parameters.
first peak occurring closer to 932.5 eV. This binding energy is more
representative of Cu2O found in literature.22 While the binding
E0
energies of metallic copper and Cu2O are close together, as seen in
S 02 N R (Å) σ2 (Å2) (eV) Fig. 7, metallic copper has a Cu2p3/2 peak with a narrower FWHM
(0.96 for metallic copper vs 1.35 for Cu2O) based on our own
Cu(OH)2 4 1.939 0.0031 measurements. Furthermore, the presence of metallic copper was not
(0.004) (0.0010) detected during the XAFS analysis. Even though the XAFS analysis
0.86 1 2.335 0.036(0.018) 0.5 was performed in open air, metallic copper would have still been
(0.004) (0.4) detected even if the surface was oxidized. The positive electrode C1s
Cu2O 2 1.805 0.0028 and Cu2p3/2 spectra can be found in Fig. 9. The copper signal is
(0.004) (0.0014) weaker on the positive electrode, resulting in a noisy Cu2p3/2 signal.

Table III. Mole fraction of copper compounds in cells held at different storage conditions.

Storage Condition Mole Fraction (Cu(OH)2) Mole Fraction (Cu2O) R-Factor

0V 0.87(0.04) 0.13(0.04) 0.0018

0.25 V 0.93(0.05) 0.07(0.05) 0.014
0 V, recharged 0.78(0.04) 0.22(0.04) 0.0020
0.25 V, recharged 0.84(0.05) 0.16(0.05) 0.032
 Journal of The Electrochemical Society, 2020 167 090501

Figure 7. Cu2p XPS spectra for some copper reference compounds, namely,
Cu, Cu2O, CuO, Cu(OH)2 and CuF2.

surface film on the cell cycled 40 times following an overdischarge

Figure 6. Cobalt and nickel K-edges for NCA reference material, and
positive electrodes extracted from 2.5 V and 0 V cells.
Similarly to the negative electrode, the Cu2p3/2 signal from the
positive electrode can be deconvoluted into peaks representing
contributions from Cu2O and Cu(OH)2, albeit shifted to a slightly
higher binding energy. The presence of a satellite structure further
supports the presence of Cu(OH)2. The resolution of the peaks is
difficult due to the weak copper signal which can explain some of
the uncertainty in the peak location and full width at half maximum
(FWHM).
One of the 0.25 V cells cycled 40 times between 2.5 V and 4.1 V
following overdischarge was disassembled and the negative elec-
trode was examined using XPS. Initially, very little copper was
detected on the surface of the electrode, and argon ion sputtering was
employed to remove surface layers to determine if decomposition
products on the surface of the electrode obscured the copper signal.
Figure 10 shows the C1s and Cu2p3/2 spectra before and after 5 min
of Argon ion sputtering. Sputtering was performed to remove the
event. The presence of copper reemerges following the sputtering
and the location and FWHM of the peak are consistent with Cu2O.
Argon sputtering below 5 keV can reduce CuO to Cu2O23; however,
the presence of CuO was not observed during XAFS experiments.
Therefore, the Cu2O observed is not attributed to reduction of CuO.
Cu(OH)2 has been shown to reduce to Cu2O after exposure to X-rays
as well as with Argon ion sputtering,24 which may explain why
Cu(OH)2 is not detected in the cell cycled 40 times.
Taken together with the XAFS data, it is clear that Cu2O and
Cu(OH)2 are present within the battery. During overdischarge, the
copper current collector is oxidized to both Cu+ and Cu2+. The
copper ions are carried through the separator by the electrolyte,
which is supported by the presence of copper species on both the
negative and positive electrodes. The exact mechanism by which the
Cu2O and Cu(OH)2 are formed was not the focus of this study,
however, a number of mechanisms are possible. While trace
amounts of H2O can lead to the formation of Cu(OH)2, there is
not sufficient water in the electrolyte to support this as the primary
mechanism. Instead, it is hypothesized that a reaction with the
electrolyte solvents is responsible for the formation of Cu2O and
Cu(OH)2. Upon recharge, the formation of additional Cu2O can
be the result of reduction of copper species at the surface. This
explains the XAFS observation that the samples primarily contain
Cu(OH)2 with increased Cu2O upon recharge. The XPS data shows
the opposite, with Cu2O dominating the Cu 2p3/2 spectra. While
the bulk of the sample may contain more Cu(OH)2, Cu2O on the
surface will primarily show up in the XPS measurements. A
qualitative assessment of Cu(OH)2 and Cu2O solubility was con-
ducted by suspending reference species in vials of electrolyte. The
powders were found to settle out of suspension quickly with no
obvious changes in the volume of powder or color of the solution
indicating solubility.

Table IV. Binding energy and full-width at half maximum (FWHM) values for negative and positive electrode Cu2p3/2 fits.

Storage Condition Cu2p3/2 Negative Electrode Binding Energy (FWHM) Cu2p3/2 Positive Electrode Binding Energy (FWHM)

0V 933.0 eV (1.66) – Cu2O 935.0 eV (2.24) – Cu(OH)2 933.3 eV (1.97) – Cu2O 935.2 eV (3.06) – Cu(OH)2
0.25 V 933.0 eV (1.87) – Cu2O 935.1 eV (1.62) – Cu(OH)2 933.6 eV (1.72) – Cu2O 935.3 eV (1.94) – Cu(OH)2
0 V, recharged 933.0 eV (1.49) – Cu2O 934.8 eV (2.91) – Cu(OH)2 932.0 eV (1.62) – Cu2O 934.5 eV (3.71) – Cu(OH)2
0.25 V, recharged 932.7 eV (1.88) – Cu2O 935.6 eV (0.62) – Cu(OH)2 933.6 eV (2.07) – Cu2O 935.2 eV (2.97)– Cu(OH)2
 Journal of The Electrochemical Society, 2020 167 090501

Table V. Atomic percentage for different storage conditions and locations within each cell.

Atomic Percentage, % (Exterior, Middle, Interior)

Storage condition Location Li 1 s C 1s O 1s F 1s P 2p Cu 2p3/2

0V Exterior 7.7 35.3 35.4 13.6 4.1 3.8

Middle 8.8 46.0 25.3 14.5 3.1 2.3
Interior 10.1 40.1 27.4 15.7 3.5 3.2
0.25 V Exterior 12.4 40.3 26.1 16.4 3.9 1.0
Middle 17.4 39.1 17.9 21.9 3.0 0.6
Interior 11.7 41.3 26.1 15.7 4.1 1.3
0 V, recharged Exterior 20.3 34.9 21.9 19.3 3.3 0.3
Middle 25.1 28.8 16.7 26.9 2.3 0.3
Interior 12.6 40.1 26.2 16.1 3.7 1.4
0.25 V, recharged Exterior 16.1 34.5 22.0 22.9 3.0 1.4
Middle 15.2 38.7 22.2 20.3 2.7 1.0
Interior 18.0 36.5 20.3 22.4 2.0 0.8
0.5 V Exterior 16.7 40.8 17.2 21.8 3.6 0
Middle 17.4 38.2 17.5 23.4 3.5 0
Interior 14.3 40.7 22.8 17.9 4.2 0.1
2.5 V Exterior 17.4 40.1 23.8 16.1 2.7 0
Middle 18.2 38.2 23.8 17.1 2.8 0
Interior 18.4 40.5 24.6 13.9 2.6 0

Figure 8. C1s (top) and Cu2p3/2 (bottom) XPS multiplex spectra of negative Figure 9. C1s (top) and Cu2p3/2 (bottom) XPS multiplex spectra of positive
electrodes extracted from cells overdischarged to 0 or 0.25 V as well as after electrodes extracted from cells overdischarged to 0 or 0.25 V as well as after
being recharged and discharged to 0% state of charge. The spectra were being recharged and discharged to 0% state of charge. The spectra were
calibrated to hydrocarbon at 284.8 eV. calibrated to hydrocarbon at 284.8 eV.
 Journal of The Electrochemical Society, 2020 167 090501
Figure 10. C1s (top) and Cu2p3/2 (bottom) XPS multiplex spectra of the
negative electrode extracted from a cell overdischarged to 0.25 V and
subjected to 40 cycles of charge and discharge between 2.5 V and 4.1 V. The
spectra were collected before and after 5 min of sputtering.
While the presence of Cu2O and Cu(OH)2 on the surface of the
electrodes will certainly lead to performance loss, the formation of a
hard short circuit is unlikely due to the non-conductive nature of the
copper species; however, the existence of copper ions in the
electrolyte solution does not completely preclude the formation of
metallic copper. Metallic copper and other copper compounds such
as CuO and CuF2 are not detected during both XPS and XAFS
analysis. This is evident when comparing the XAFS reference
spectra in Fig. 1 and the XPS reference spectra in Fig. 7.
Performance degradation is observed in the capacity fade plots
obtained by cycling the cells repeatedly within their nominal range
(2.5 V to 4.1 V) following the single overdischarge event as seen in
Fig. 11. Overdischarged cells demonstrate as much as 10% capacity
fade within 40 cycles, compared to the control sample which showed
no degradation in capacity. In general, the lower the overdischarge
voltage, the greater the capacity fade. Capacity loss can be attributed
to a number of failure mechanisms, while several possibilities can be
eliminated. All of the cells experienced only a single overdischarge
event prior to cycling within their nominal voltage range, therefore,
repeated degradation of the SEI layer and significant copper
dissolution are unlikely to contribute to the longer-term loss of
capacity. The initial loss of capacity can be attributed to the
reformation of the SEI layer, which can undergo dissolution when
the battery was overdischarged.10,11 Further capacity fade is likely
due to other failure mechanisms, as the cells were not over-
discharged repeatedly. One potential contribution to the continued
capacity fade is that the presence of copper species on the electrodes
can inhibit lithium intercalation, resulting in accelerated electrolyte
decomposition and a reduced discharge capacity.6,15 This is further
Figure 11. Following overdischarge to 0, 0.25, or 0.5 V, cells were cycled
and their capacity fade behaviors were compared to that of a control/healthy
cell. The average of capacity from 3 cells at each overdischarge condition is
plotted with error bars representing 1 standard deviation.
supported through the XPS analysis showing the presence of copper
on the surface of the electrodes. The capacity fade can also be
attributed to loss of adhesion between the negative electrode and the
copper current collector.6 Although the electrode jelly roll is under
compression, cyclic stresses due to intercalation can lead to localized
separation of the electrode from the current collector. Once parts of
the electrode are removed from the conductive network, the battery
loses some of its charge storage capabilities. This is further
supported through destructive physical analyses in which the cell
was disassembled and the electrode sheets unwound. In over-
discharged cells, the negative electrode either adhered to the
separator or delaminated in large flakes from the copper current
collector. This is in contrast to the cells operated at 0.5 V and above,
in which the electrode had to be peeled off of the current collector
for XAFS measurements. It is likely that a combination of these
failure mechanisms is responsible for the capacity fade observed by
the overdischarged cells.
Failure due to internal short circuit was not observed, unlike
some previous studies.6,7,9,10 First and foremost, the cell never
entered into voltage reversal, which has been shown to deposit
copper on the electrodes and form an internal short circuit.9 In these
instances, it is assumed that the copper is metallic in nature.
Secondly, the cell only experienced a single overdischarge event,
limiting the amount of copper that could be dissolved. Finally, long-
term storage of the batteries at the overdischarge condition in this
study provided opportunities for the copper ions to react with the
electrolyte rather than form metallic copper on the anode by
immediately recharging an over-discharged cell. Under the condi-
tions tested, no metallic copper was found; however, this does not
preclude metallic copper formation under different conditions.
Further investigation into copper dissolution is warranted because
it suggests that the formation of metallic copper is not guaranteed
following an overdischarge event even when eventually recharged.
This opens the possibility of continuing to use batteries that
experience a single overdischarge event with the knowledge that
capacity fade will increase and some residual risk may remain.
Conclusions
The occurrence and chemical state of copper dissolution in large
format lithium-ion batteries subjected to over-discharge voltages of
0 V, 0.25 V, and 0.5 V, were studied using surface- (XPS) and bulk-
sensitive (XAFS) analytical techniques, and compared to cells that
did not experience overdischarge. The presence of copper was
evident in all samples held below 0.5 V using both XPS and XAFS
 Journal of The Electrochemical Society, 2020 167 090501
measurements. This is consistent with values reported in literature
and indicates that at voltages below 0.5 V, the copper current
collector began dissolving from both the exposed foil and along the
current collector/electrode interface and enters the electrolyte solu-
tion phase.
In all cases where the cell was overdischarged beyond 0.5 V,
adhesion between the negative electrode and the copper current
collector was reduced, contributing in part to a capacity fade as
much as 10% in 40 cycles compared to control samples with no
capacity fade during the same timeframe. Loss of adhesion was
observed while disassembling the cell, in which large flakes of
graphite adhered to the separator leaving bare copper current
collector behind. This only occurred in overdischarged cells.
Furthermore, copper species deposition on the electrode surfaces
contributes to a reduction of capacity due to blocking of intercalation
sites. Taken together, the primary failure mechanism in cells held at
low voltages, recovered, and subsequently cycled is a combination
of degradation of electrode connectivity and reduction in intercala-
tion sites. The magnitude of this effect is directly tied to the amount
of copper dissolved and redeposited on the electrode surfaces, which
is a function of storage voltage.
The copper species that were observed are non-conductive in
nature. This reduces the risk of an internal short circuit when a
battery is overdischarged a single time such that the potential of the
negative electrode reaches the copper dissolution limit but is not
pushed further into reversal. For this particular cell, this corre-
sponded to full cell voltages below 0.5 V. Formation of metallic
copper is still possible under different abuse scenarios, such as
overdischarge into reversal; however, during repeated cycling over
40 cycles following a single overdischarge event, no indication of an
internal short circuit or metallic copper formation was identified.
Accelerated capacity fade was the primary failure mode observed as
a result of copper dissolution when cells were overdischarged to
voltages as low as 0 V.
Lithium batteries can sit in storage for extended periods of time.
Through a combination of self-discharge and parasitic loads such as
the battery management system, the voltage of the battery can fall
below the manufacturers’ recommended lower voltage cutoff. If this
voltage is sufficiently low, copper dissolution can occur. Previously
it was thought that dissolved copper will form metallic copper and
pose a risk for internal short circuit, effectively rendering the battery
useless. This paper demonstrates that under some usage conditions,
recovery is possible without the formation of metallic copper, albeit
with accelerated performance degradation. This may not be accep-
table for all applications, and ultimately the tradeoffs need to be
weighed against the operational requirements.
Acknowledgments
The authors acknowledge support under the Naval Innovative
Science and Engineering (NISE) program at the Naval Surface
Warfare Center Carderock Division. The XAS experiments were
performed at the DuPont-Northwestern-Dow Collaborative Access
Team (DND-CAT) located at Sector 5 of the Advanced Photon
Source (APS). DND-CAT is supported by Northwestern University,
E.I. DuPont de Nemours & Co., and the Dow Chemical Company.
This research used resources of the Advanced Photon Source, a U.S.
Department of Energy (DOE) Office of Science User Facility
operated for the DOE Office of Science by Argonne National
Laboratory under Contract No. DE-AC02–06CH11357. Christopher
E Hendricks and Michael G Pecht would like to thank the more than
150 companies and organizations that support research activities at
the Center for Advanced Life Cycle Engineering (CALCE) at the
University of Maryland annually.
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