Journal of The Electrochemical

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Degradation Behavior of Graphite–Nickel Cobalt Aluminum Oxide

Lithium Ion Cells with Series Connections Including an Overcharged Cell
To cite this article: Norihiro Togasaki et al 2022 J. Electrochem. Soc. 169 030547

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 Journal of The Electrochemical Society, 2022 169 030547
1945-7111/2022/169(3)/030547/10/$40.00 © 2022 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited

Degradation Behavior of Graphite–Nickel Cobalt Aluminum Oxide

Lithium Ion Cells with Series Connections Including an
Overcharged Cell
Norihiro Togasaki,z Tokihiko Yokoshima,* and Tetsuya Osaka**,z
Research Organization for Nano and Life Innovation, Waseda University, Shinjuku-ku, Tokyo 162-0041, Japan

Cycle life of series-connected lithium-ion battery (LIB) modules in the presence or absence of an overcharged cell is reported, and
degradation behavior is characterized by electrochemical impedance spectroscopy (EIS) and differential voltage analysis (DVA).
Three-stage capacity decay is solely observed in modules in the presence of an overcharged cell, which is exposed to a state of
charge (SoC) of ⩾105% during cycling. The module without overcharged cells or with an overcharged cell at an SoC of <103%
exhibits capacity decay as a function of the square root of cycle numbers. EIS and DVA analyses confirmed that the overcharged
cell with an SoC of ⩾105% in the module deteriorates more harshly than the other cells and that deterioration occurs especially at
the cathode. Cycle dependence of the charge/discharge cutoff voltage of LIBs revealed that the cell capacity of the overcharged cell
shrinks with the end point on charge as a fulcrum, thereby decreasing the lower cutoff voltage as cycling progresses. Such a voltage
change of an overcharged cell directly affects module capacity, leading to three-stage capacity decay. This study reveals a potential
risk in series-connected cells using a wide SoC range and provides critical insights for safe operation without balance circuits.
© 2022 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited. [DOI: 10.1149/1945-7111/
ac5d92]

Manuscript submitted January 14, 2022; revised manuscript received February 28, 2022. Published March 25, 2022.
Supplementary material for this article is available online

Lithium-ion batteries (LIBs) have been widely used in electric
vehicles (EVs), on-site storage for solar or wind power, and
application of power leveling from power plants. As years progress,
their demand will continuously increase because of the current
environmental concerns. Recent improvements in battery materials
have increased the energy density to satisfy the requirements for a
long driving range and high energy storage.1,2 From the perspective
of battery operation, the utilization of an extended state of charge
(SoC) range in battery cells is a potential option to increase output
energy. However, the utilization of SoC beyond a thermodynami-
cally stable range in LIBs, which is referred to as overcharge or
over-discharge, leads to the serious deterioration of battery cells.3–5
Overcharge causes detrimental problems in LIBs, including the
deformation of cathode-active materials,6 oxidation of electrolytes,7
dissolution of transition metal,3,8 and deposition of lithium metal on
the anode,9 leading to serious capacity deterioration. Over-discharge
leads to the breakdown of the solid electrolyte interphase (SEI) on
the anode,10 dissolution of the copper current collector,10,11 destruc-
tion of the cathode crystal structure,12 and cracking of the cathode
due to over-lithiation,13–15 also leading to serious capacity deteriora-
tion. For high-energy 18650-type cylindrical cells of graphite/nickel
cobalt aluminum oxide (NCA) systems, cycling operations at over-
charge (SoC ⩾ 107%) and over-discharge (SoC ⩽ −3.9%) lead to
serious capacity decay of the battery cell, and capacity decay can be
predicted in advance by electrochemical impedance spectroscopy
(EIS) measurements.3,4
For practical applications, battery cells are generally connected in
series and/or parallel to form a battery module to satisfy require-
ments of high power and high-capacity density. To extract as much
electrochemical energy as possible from the battery module, in
addition to the utilization of a wide SoC range, the SoC of each
battery cell in the module should be similar to prevent the battery
cells from being exposed to an overcharge or over-discharge during
charge–discharge operation. However, the SoC of each cell in the
module can vary during charge–discharge operations because of
variations in manufacturing tolerance or an inhomogeneous oper-
ating temperature gradient.16 Although a battery management
system (BMS), which approximates the cells in the module as one
equivalent cell, has been widely adopted to estimate either capacity
*Electrochemical Society Member.
**Electrochemical Society Fellow.
z
E-mail: n-togasaki@ruri.waseda.jp; osakatets@waseda.jp
fade or resistance increase to understand the degree of deterioration
for the module, BMS cannot determine capacity and power fading at
the cell level. BMS only approximates the capacity and power fading
as an equivalent single value for the whole battery stack.17
In parallel connections, there is no risk for overcharge or over-
discharge in constituent cells during cycling as the voltage of each
cell is regulated by BMS; despite this fact, an unbalanced SoC or
uneven deterioration among cells possibly occurs because of loading
current distribution caused by the difference in cell impedance,18,19
cell capacity,19 and temperature gradient.18 Pastor-Fernandez et al.
have reported that the initial difference of the state-of-health for
resistance and capacity converges to a low value with the progress of
cycling in the module with parallel connections.17
LIBs with series connections are most likely to exhibit over-
charge and over-discharge because balancing of energy, such as a
uniform SoC and a uniform cell capacity, is strongly required for
constituent cells in series-connected LIBs; hence, series connections
are widely used in active or passive balance circuits to moderate the
voltage distribution of each cell.20 However, it is difficult to apply
such balance circuits for bipolar-structured batteries because of
limited areas of their extremely thin electrodes. The additional
installation of balance circuits also could lead to other disadvan-
tages, i.e., increased manufacturing costs and limited freedom of
battery design. Therefore, understanding the deterioration behavior
of series-connected LIB modules and constituent cells in the
presence of overcharge or over-discharge cells is one of the most
critical issues to be addressed for the development of next-genera-
tion batteries. For over-discharge in series-connected cells, one
numerical simulation study has reported that a distinctly low-
capacity cell connected in series achieves the fully discharged state
sooner than the other cells during discharge, leading to the increase
in the internal resistance and irreversible capacity of the cell.21
Currently, a similar phenomenon has been experimentally confirmed
by Langner et al.; at least two cells are connected in series, and the
cell with a low capacity is exposed to over-discharge, which lead to
the dissolution of copper at the anode current collector to deposit on
the nickel manganese cobalt oxide (NMC) cathode.22 Guo et al. have
reported that in the four connected in-series cells, the extremely
over-discharged cell corresponds to SoC ⩽ −13%. This revealed
copper deposits on the NMC cathode at the interface between the
separator and the NMC cathode, which subsequently resulted in
local short circuits.23 However, thus far, less experimental data and
 Journal of The Electrochemical Society, 2022 169 030547
marginal discussion are available to explain the degradation me-
chanism of series-connected cells in the presence of overcharge.
In this study, charge–discharge cycling tests with four config-
urations of battery modules with five series-connected LIB cells in
the presence or absence of an overcharged cell were performed, and
the degradation behavior of each cell was meticulously characterized
by electrochemical impedance spectroscopy (EIS) and differential
voltage analysis (DVA). Furthermore, we revealed the reason for
steep capacity decay of the battery module during charge–discharge
cycling by tracking the cycle dependence of the charge/discharge
cutoff voltage. The results obtained herein provide insights into
inherent problems occurring in series-connected cells with high
energy density, which are operated without a balancing circuit.
Experimental
Commercial 18650-type cylindrical cells with a capacity of 2.9
Ah were used throughout. The anodes and cathodes in the cells,
which were graphite and nickel cobalt aluminum oxide (NCA),
respectively, were destructively investigated in our previous study.3
We focused on a NCA cathode because of its better energy density
and cycle life with low cost than other cathode materials (e.g.,
lithium cobalt oxide and lithium iron phosphate). LIBs of graphite/
NCA systems have been widely used in EVs such as Tesla Model S
and Model X, ended up realizing longer driving range to date.1
According to product specifications, 3.00 V as SoC0% and 4.20 V as
SoC100% were defined. Fig. S1 (available online at stacks.iop.org/
JES/169/030547/mmedia) shows the curve of the open-circuit
voltage (OCV) of a pristine graphite/NCA lithium-ion cell as a
function of SoC. In this study, four configurations of modules
(Modules A − D) incorporating five in-series-connected LIBs were
prepared. To perform charge–discharge cycling in the presence or
absence of an overcharged cell in the module, SoC-balanced and
-unbalanced modules were prepared. Module A was an SoC-
balanced module, while Modules B, C, and D were SoC-unbalanced
modules. Before charge–discharge cycling, the voltage of each cell
in Module A was set to be identical to 3.47 V (SoC20%). To prepare
SoC-unbalanced modules, the voltage of one cell in Modules B, C,
and D was varied against 3.47 V (SoC20%); the voltage of four cells
were set to be 3.47 V (SoC20%), while the voltage of another cell
was set to 3.52 V (SoC25%) for Module B, 3.55 V (SoC30%) for
Module C, and 3.58 V (SoC35%) for Module D. Charge–discharge
cycling tests were conducted using a battery-testing instrument
Figure 1. (a) Charge capacity fading and (b) capacity retention of series-connected graphite–NCA cells of Module A, Module B, Module C, and Module D.
Each module was subjected to charge–discharge cycling in the voltage range of 17.35 V–21.00 V with the CC-CV sequence (constant current for charging =
1.45 A, constant current for discharging = 2.90 A, cutoff current for charging or discharging = 0.1 A).
(HJB3060SD, Hokuto Denko), which was operated in the total
voltage range of 17.35 V − 21.00 V, using a constant-current or
constant-voltage (CC–CV) protocol, with charging and discharging
load currents of 1.45 A (0.5 C-rate) and 2.90 A (1.0 C-rate),
respectively. The termination current was set to 0.1 A. Fig. S2
shows the voltage profile of constituent individual cells at the first
cycle in Modules A − D. None of the cells in Module A exhibited
overcharge, and charge–discharge cycling at each cell was operated
at 3.47–4.20 V (SoC20%–SoC100%). For the lower cutoff voltage,
SoC 20% was adopted during cycling by following a typical
specification for EVs.24–26 For the upper cutoff voltage, SoC100%
was adopted to investigate the cycling performance in the extended
SoC range, while the upper cutoff voltage was generally set to be
SoC80%–SoC90% for EVs.25,27 Instead, each of Modules B, C, and
D exhibited one overcharged cell, and the upper cutoff voltage
corresponded to SoC102.5% for Module B, SoC105.0% for Module
C, and 108.0% for Module D.
After charge–discharge cycling at 0, 178, 404, 835, 1000, and
1200 cycles, Modules A − D were dissembled to measure the
capacity of individual cells. Capacity was measured in the voltage
range of 3.00 − 4.20 V using a CC–CV sequence (constant current
= 0.29 A, cutoff current = 0.029 A). The degree of capacity
degradation at each cycle was quantified by capacity retention,
which can be calculated by the following equation:
QCycled
Capacity retention [%] = × 100
QInitial
where QCycled is the charge capacity after cycling, and QInitial is the
charge capacity of a pristine cell. In addition, the capacity retention
of each module was calculated; QCycled is the charge capacity after
the cycle, and QInitial is the charge capacity at the first cycle.
In addition to capacity measurement, electrochemical measure-
ments, i.e., EIS and DVA, were performed to understand deteriora-
tion in the presence or absence of overcharge during cycling.
Impedance spectra of the battery cells were measured using a
potentiostat (CellTest System 1470E, Solartron) and a frequency
analyzer (CellTest System 1400, Solartron) at the OCV, with a
10 mV (zero to peak) AC signal in the frequency range of 10 kHz to
10 mHz. The cell voltage for impedance measurements was set to
4.20 V (SoC100%). Data fitting was performed using the Microsoft
Excel Solver package in order to understand the calculation process
clearly instead of using commercially available software. The fitted
 Journal of The Electrochemical Society, 2022 169 030547
data were obtained by minimizing the sum of all differences between
the experimental and calculated data from the equivalent circuit at
each frequency, similar to the procedure detailed in our previous
studies28,29 and in the literature by other researchers.30 For DVA, a
small charging current of 0.1 A (ca. 0.034 C-rate) was applied to the
battery cell in the voltage range of 2.50–4.20 V to obtain a quasi-
open-circuit potential profile. The obtained potential profile was
converted to dV/dQ to estimate the degree of deterioration of the
anode and cathode as well as electrode balancing between the anode
and cathode. Fig. S5a shows the dV/dQ peaks derived from the
anode or cathode from a pristine cell, which were identified with
either anode or cathode with reference to the results reported in our
previous study.3 The analytical sequences in detail are mentioned
elsewhere.3,4,31
Results and Discussion
Figures 1a and 1b show capacity fading during cycling in the
SoC-balanced module (Module A) and—unbalanced modules
(Modules B, C, and D). Charge–discharge cycling in the constituent
single cells of Module A is operated in SoC20%–SoC100%; as a
result, none of the cells are exposed to overcharge during cycling.
Instead, each of the Modules B, C, and D contains one overcharged
cell during cycling. Fig. S2 shows the voltage profile at the first
cycle of the constituent cells in the module. With the progress of
cycling, the capacity in Module A gradually decreases, affording a
linear curve as a function of the square root of cycle numbers
(Fig. 1b). The deterioration rate is calculated to be ca. −11 mAh/
Cycle Number ), corresponding to the result where charge–-
discharge cycling using an identical type of a single cell is operated
in SoC20%−SoC100%,3 that is, capacity retention is not affected by
cell configuration (single cell or module) when an identical SoC
range per cell is used. Similar fading is apparent in Module B,
suggesting that the incorporation of an overcharged cell that is
exposed to SoC102.5% during cycling does not affect the cycling
performance of the module. Compared with those observed in
Module A and Module B, capacity fading in Module C and
Module D exhibits different behaviors; both these modules exhibit
three-stage capacity fading. In the first stage, the capacity gradually
decreases with the progress of cycling in a manner similar to that
observed for Module A and Module B until 830 cycles for Module C
and until 300 cycles for Module D (≈−11 mAh/ Cycle Number ). In
the second stage, capacity deterioration occurs more rapidly until
1000 cycles for Module C and until 480 cycles for Module D,
leading to a final steep capacity drop in the third stage. Such three-
stage capacity fading is not observed in a single cell when cell
cycling is performed under overcharge; in the single cell, two-stage
capacity fading is observed under overcharge cycling.3 Therefore,
these multiple deterioration steps must be related to cell configura-
tions with series connections. Compared with that observed for
Module C, the steep capacity deterioration at the second and third
stages for Module D is apparent in the earlier cycles, suggesting that
the SoC variation of the module affects the module capacity
retention, and that the incorporation of a high overcharged cell
promotes severe deterioration.
To identify the deterioration of cycled cells in the module, the
capacities of each of the constituent cells were measured after 0,
1000, and 1200 cycles for Module A and Module B, and after 0, 178,
404, 835, and 1000 cycles for Module C. Figure 2a–2c show the
capacity retention of the constituent cells in Module A, Module B,
and Module C. Each of five series-connected cells in the module is
A1–A5 for Module A, B1–B5 for Module B, and C1–C5 for Module
C. During charge–discharge cycling, the cells operating under
overcharge (SoC > 100%) are denoted as “o.c.” in the cell number.
The capacity retention of the cells (A1–A5) in Module A is identical
to each other at 0, 1000, and 1200 cycles, and the capacity retention
decreases similarly as the square root of cycle numbers because there
is no difference in the SoC variation. The capacity retention of
Module A similarly decreases, as is observed for the capacity
retention of the constituent cells (A1 − A5), suggesting that gradual
capacity decrease of the constituent cells affects the overall capacity
of the module. The capacity retention of constituent cells (B1 − B4,
and B5_o.c.) in Module B and that of Module B exhibits cycle
dependence similar to that observed for Module A. A significant
difference in the capacity retention between Module A and Module
B is not observed because the overcharged cell (B5_o.c.) in Module
B, which is exposed to SoC102.5% during cycling, deteriorates in a
manner similar to that observed for the other cells (B1–B4).
A significant difference is observed in Module C, which
comprises one overcharged cell that is exposed to SoC105.0%
during cycling. The cycle dependence of the capacity retention of
constituent cells (C1–C5) in the module decreases linearly until 835
cycles, while the capacity retention of the overcharged cell (C5_o.c.)
only drops afterward. A capacity retention of 87.1%–87.6% is
observed for non-overcharged cells (C1–C4) at 1000 cycles; this
value is almost the same as that obtained from the constituent cells in
Module A (A1–A5: 87.7%–88.5%) and in Module B (B1–B4:
87.8%–88.8%). Therefore, the overcharged cell of C5_o.c., which
is exposed to SoC105.0% during cycling, in the module selectively
deteriorates. In the same manner, the capacity retention of Module C
decreases steeply after 835 cycles. Since the capacity retention of
non-overcharged cells (C1–C4) in Module C is similar to that of the
cells (A1–A5) in Module A and the cells (B1–B4) in Module B, such
steep capacity retention drop is attributed to the deterioration of the
overcharged cell (C5_o.c.). Notably, the capacity retention of the
overcharged cell of C5_o.c. at 1000 cycles is less than that of
Module C, implying that module capacity retention does not actually
reflect the severity of degradation of a certain cell in the module. The
deterioration mechanism accounting for this phenomenon is dis-
cussed in the following section.
The steep capacity decay of the module is confirmed to be caused
by the capacity reduction of the overcharged cell that is exposed to
⩾SoC105.0% during charge–discharge cycling. To investigate the
deterioration based on overcharge, EIS measurement for the cells in
Module A, Module B, and Module C was performed. Each of the
constituent cells in the module was extracted from the module after
charge–discharge cycling and was subjected to EIS measurement.
Figure 3a shows the equivalent circuit used to analyze the impedance
spectra in this study. The equivalent circuit comprises three RC
parallel connections, corresponding to the SEI film, anode, and
cathode with a parallel connection of an inductor (L) and resistor
(RI), respectively. These four components are connected in series
with a solution resistance (RS). The CPED at the end of the
equivalent circuit is added to express the impedance in the diffusion
area. To fit the squashed semicircles in the Nyquist plot, a constant-
phase element (CPE) is utilized to express interfacial capacitance.
The capacitance of the SEI, anode, or cathode is calculated using the
following equation:
C = T1 / pR (1 − p ) / p ,
where T and p are the CPE constant and CPE exponent, respectively;
R corresponds to resistance (RF for SEI film, RCT-A for anode, and
RCT-C for cathode), which are connected in parallel to CPE (CPEF
for the SEI film, CPEA for anode, and CPEC for cathode). The
detailed description of this circuit is reported in our previous paper.4
Typical fitting results and their fitting errors plotted as a function of
the input frequency signals are shown in Fig. S3.
In EIS analysis, time constant is one of the most effective
indicators for understanding the deterioration degree of elementary
reactions occurring in the cell. The time constant can be calculated
from the interfacial capacitance multiplied by the resistance in each
reaction component. Generally, the time constant exhibits a strong
temperature dependence. For instance, the time constants for the
SEI, anode, and cathode are known to increase with the decrease in
the temperature because of sluggish electrochemical reactions.3,32
This phenomenon is mainly caused by the temperature dependence
 Journal of The Electrochemical Society, 2022 169 030547

Figure 2. Capacity retention of graphite–NCA cells extracted from (a) Module A, (b) Module B, and (c) Module C after charge–discharge cycling at 0, 1000,
and 1200 cycles for Module A and Module B and after charge–discharge cycling at 0, 178, 404, 835, and 1000 cycles for Module C. In this figure, graphite–NCA
cells in the presence of overcharge during cycling are denoted as “o.c..” The capacity retention of each module is also shown in this figure.

of reaction resistances, which increase as a function of the decrease
in the temperature, while interfacial capacitance is basically in-
dependent of temperature. Under constant-temperature conditions,
the time constant varies in response to the deterioration degree of the
reaction component in LIBs; the greater is the deterioration, the
higher is the time constant, which is related to the sluggishness in
electrochemical reactions. In graphite/NCA lithium-ion cells, the
time constants of the SEI, anode, and cathode moderately change
when charge–discharge cycling is performed within the SoC range
according to the battery specification (Figs. S4a–S4c). For instance,
when a minor change in electrode materials occurs such as small
cracks in active materials, the time constant does not change
considerably because the enlarged surface area by small cracks in
electrode materials reduces charge-transfer resistance and increases
interfacial capacitance simultaneously. On the contrary, when
charge–discharge is performed beyond a thermodynamically stable
voltage range for electrode materials, the time constant considerably
changes as shown in Fig. S4d for overcharge and in Fig. S4e for
over-discharge. According to our previous study3 where the gra-
phite/NCA single cells are cycled in overcharge, i.e.,
SoC20%–SoC107%, the time constant of the cathode exhibits a
strong dependence on cycle numbers and increases rapidly with the
progress of cycling, while those of the anode and SEI decrease (Fig.
S4d). The increase in the time constant of the cathode may be caused
by the surface deposition of the resistive layer via electrolyte
oxidation33 and/or structural defects, such as cation mixing that
impedes Li+ diffusion,34 leading to the increase in RCT-C. The
decrease in the time constant of the SEI and anode is mainly caused
by the deposition of the metal on the anode surface due to the
overcharge-induced dissolution of the NCA cathode active materials,
which leads to the reduction in the interfacial capacitance of the SEI
and anode.3
Figures 3b–3d shows the time constant of the SEI, anode, and
cathode reactions in the constituent cells in Module A, Module B,
and Module C as a function of the square root of cycling numbers. In
all cases, the elementary processes of the SEI, anode, and cathode
are successfully distinguished. Before cycling (at 0 cycle), the
logarithm values of the time constant for the SEI, anode, and
cathode are roughly −3.5, −2.6, and −0.7, which corresponds to our
previous results.3,4
In Module A, the time constant of the cathode moderately
increases with the progress of cycling, while the other two elemental
components of the SEI and anode are almost constant throughout
cycling, which are similar to the results when charge−discharge is
performed using a single cell in SoC20%−SoC100% during cycling
(Fig. S4c) because each of the five cells (A1–A5) exhibits an
identical voltage profile during cycling where charge–discharge is
performed in SoC20%–SoC100% (Fig. S2a). Hang et al. also
reported that the capacity decay is mainly caused by the deterioration
of transition metal oxide cathode rather than anode materials when
the charge-discharge cycling is performed in the voltage range
within the battery specification.35 A similar tendency regarding the
time constant is observed for Module B. Module B incorporates one
overcharged cell during cycling, which is denoted as B5_o.c. in
Fig. 3c. However, the time constants of the SEI, anode, and cathode
in the overcharged cell (B5_o.c.) are almost identical to those in the
 Journal of The Electrochemical Society, 2022 169 030547

Figure 3. (a) Equivalent circuit used to analyze the impedance spectra of graphite–NCA cells. Notations: L and RI, inductance and resistance of the battery leads
and connected cable, respectively; RS and RF, resistances of the electrolyte and SEI, respectively; CPEF, constant-phase element of the SEI; RCT-A and RCT-C,
charge-transfer resistances of the anode and cathode, respectively; and CPEA and CPEC, constant-phase elements of the anode and cathode electrode surfaces,
respectively. Cycle dependence of the time constants of SEI, anode, and cathode of single cells in (a) Module A (A1 − A5), (b) Module B (B1 − B5), and (c)
Module C (C1 − C5), which was calculated from fitting results. The single cells were extracted from the module after charge−discharge cycling at 0, 1000, and
1200 cycles for Module A and Module B and after charge–discharge cycling at 0, 178, 404, 835, and 1000 cycles for Module C, which were subjected to EIS
measurements at 4.20 V (SOC100%). In this figure, graphite–NCA cells in the presence of overcharge during cycling are denoted as “o.c..”

other cells (B1–B4), suggesting that a slight overcharge at
SoC102.5% during cycling does not promote specific deterioration
of the cell.
In the presence or absence of overcharged cells, a remarkable
difference in the time constants is observed in cathode reactions in
Module C; the time constant of the overcharged cell (C5_o.c.) is
clearly greater than those of other cells (C1–C4) in Module C. As
mentioned before, an increase in the time constant is indicative of
sluggish electrochemical reactions via the surface deposition of a
resistive layer and/or structural defects, both of which impede the
Li+ reaction on the cathode. Typically, the time constant increases
with the progress of cycling under a harsh cycling condition of
overcharge (Fig. S4d)3 or over-discharge (Fig. S4e).4
To understand the cycle dependence of elementary electroche-
mical reactions of the cathode, the charge-transfer resistance (RCT-C)
and interfacial capacitance (CC) in Module A, Module B, and
Module C were analyzed. Figures 4a–4f shows the fitting results.
Regardless of the presence or absence of overcharge, the RCT-C and
CC of constituent cells in Module A (A1–A5) and in Module B
(B1–B5) are almost identical to each other at 0, 1000, and 1200
cycles, which subsequently increase in a gradual manner with the
progress of cycling. From this result, the gradual increase in the time
constant of cathode reactions in Module A and Module B shown in
Figs. 3b and 3c is attributed to the increase in RCT-C and CC.
For Module C, the RCT-C of an overcharged cell (C5_o.c.)
increases more considerably than that of other cells (C1–C4); the
RCT-C of the overcharged cell (C5_o.c.) gradually increases twice as
that of non-overcharged cells (C1–C4) at each cycle until 835 cycles,
followed by a steep increase afterward. This phenomenon is similar
to that reported in our previous study3 and is possibly related to the
overcharge-induced surface deposition of the resistive layer by
electrolyte oxidation33 and/or structural defects such as cation
mixing that impedes Li+ diffusion.34 Meanwhile, in the presence
or absence of overcharge until 835 cycles, a significant difference in
CC is not observed; the CC of the five cells (C1–C5) increases
similarly until 835 cycles. This phenomenon is in agreement with
that reported in our previous study,3 indicating that the deterioration
of the NCA cathode does not considerably affect interfacial
capacitance because conductive additives, which are generally added
to the cathode, exhibit a considerably higher areal capacity than that
of NCA-active materials.36 On the other hand, the CC of the
overcharged cell (C5_o.c.) slightly decreases after 835 cycles, and
it is almost identical to that of the pristine cell at 1200 cycles. The
reduction of CC after 835 cycles may be caused by the isolation of
conductive additives in the cathode on account of serious cracking
 Journal of The Electrochemical Society, 2022 169 030547
Figure 4. Fitting results for the charge-transfer resistance of the NCA cathode (RCT-C) in constituent cells in (a) Module A, (b) Module B, and (c) Module C, and
the interfacial capacitance of the NCA cathode (CC) in constituent cells in (d) Module A, (e) Module B, and (f) Module C. In this figure, graphite–NCA cells in
the presence or absence of overcharge during cycling are denoted as “o.c..”
under a long period of charge–discharge cycling under overcharge.
Hence, EIS analysis of the cathode confirmed that the higher value
for the time constant of the overcharged cell (C5_o.c.) than those for
the non-overcharged cells (C1–C4) is mainly caused by the increase
in the charge–discharge resistance of RCT-C. Fitting results of the
solution resistance (RS), SEI film resistance (RF), the interfacial
capacitance of the SEI (CF), the charge-transfer resistance of anode
(RCT-A), the interfacial capacitance of the anode (CA) in Module A,
Module B, and Module C are described in Fig. S6.
The serious deterioration of the cathode induced by overcharge is
also confirmed by DVA. Figures 5a–5e shows the capacity retention
of the total capacity (QT) and degradation indicators of the graphite
anode (QA), NCA cathode (QC), and capacity balancing (QB) in the
graphite–NCA cells in Module C. The incorporated cells in Module
C (C1–C5) were extracted from the module after charge–discharge
cycling at 0, 178, 404, and 835 cycles and were subjected to DVA.
In each cell, the capacity retention of the total capacity QT at 0, 178,
404, and 835 cycles is almost the same, suggesting that significant
cell capacity deterioration does not appear until 835 cycles regard-
less of the presence or absence of overcharge, which corresponds to
the result shown in Fig. 2c. The anode capacity (QA) of each cell in
Module C exhibits a similar behavior; in the presence or absence of
overcharge cycling, the anode capacity does not exhibit a significant
difference. On the other hand, a remarkable difference in the
capacity retention of the cathode is observed (QC), while the
capacity retention in the cells C1–C4 gradually decreases in a
similar manner with the progress of cycling, reaching 75%–84% at
835 cycles; on the other hand, the capacity retention of the
overcharged cell C5_o.c. deteriorates more rapidly to ca. 69% at
835 cycles, suggesting that charge–discharge cycling under over-
charge at SoC105% leads to the deterioration of the cathode capacity
more severely than in the other cells.
The capacity retentions of QT in the constituent cells in Module C
are identical to each other because of the electrode balancing
between the anode and cathode (QB), although the capacity retention
of QC in the overcharged cell is less than that of the others. For the
most part, the capacity of QB in C5_o.c. is greater than that of the
other cells (C1–C4) at each cycle number. Keil et al. have reported
that when side reactions occur on the cathode surface such as
electrolyte oxidation and transition-metal dissolution, the OCV
curve of the cathode shifts toward the increase in QB,37 thereby
increasing cell capacity. A similar discussion has been conducted by
Dahn et al.38 The cell C5_o.c. is solely exposed to overcharge in
Module C, that is, the cathode is exposed to a thermodynamically
unstable voltage range, possibly promoting side reactions at the
cathode and subsequently leading to the increase in QB; hence, QT is
similar although the QC of C5_o.c. is less than that of the others
(C1–C4). The DVA and voltage profiles of C5_o.c. at 1000 cycles
are quite different from those at 0, 178, 404, and 835 cycles (Figs.
S5b and S5c) and are possibly related to the further deterioration of
the cathode. A significantly different DVA profile is no longer
appropriate for DVA; hence, no further DVA after 835 cycles is
performed in this study.
EIS and DVA confirmed that an overcharged cell with an SOC of
⩾105% in the module deteriorates more harshly than the other cells
and that deterioration especially occurs at the cathode. To
 Journal of The Electrochemical Society, 2022 169 030547

Figure 5. The total capacity (QT) and degradation indicators of the graphite anode (QA), NCA cathode (QC), and capacity balancing (QB) in the graphite–NCA
cells of (a) C1, (b) C2, (c) C3, (d) C4, and (e) C5_o.c., which were extracted from Module C after charge–discharge cycling at 0, 178, 404, and 835 cycles.

understand the effect of such peculiar deterioration of the over-
charged cell in the module on the unique three-stage capacity fading
observed in Fig. 1, the cycle dependence of the charge/discharge
cutoff voltage of LIB cells in the module is investigated. Figure 6a
shows the cycle dependence of the charge/discharge cutoff voltage
of the cells D1 and D5_o.c. in Module D. The cell D5_o.c., which is
exposed to SoC108.0% during cycling, is shown in order to discuss
the behavior as an overcharged cell, while cell D1 is shown as a
representative for a non-overcharged cell during cycling among
D1–D4 cells because D1–D4 cells exhibit an identical charge–-
discharge profile during cycling. Figures 6b–6g shows presumable
OCV curves of D5_o.c. and D1 from the result in Fig. 6a. The
yellow dotted square areas in the Figs. 6b–6g represent the voltage
range during the charge–discharge cycling of the cell D5_o.c. and
D1 in the module. Notably, the horizontal axis of SoC0%
−SoC100% corresponds to the capacity of 0 − 2900 mAh of a
pristine cell of graphite–NCA LIBs. Before cycling, the SoCs of D1
− D4 and D5 are set to SoC20% and SoC35%, respectively.
Figure 6b shows the OCV curves before cycling: The OCV curve
of D5_o.c. is shifted toward the left for ΔSoC15% against that of D1
− D4. The charge cutoff voltage of B3 gradually decreases in the
first 20 cycles, while that of A14 slightly increases (Fig. 6a).
Because the discharge cutoff voltage of D5_o.c. and D1 does not
change considerably in the first 20 cycles, the SoC difference
between D5_o.c. and D1 is suggested to be slightly reduced in the
first 20 cycles. Figure 6c shows the OCV curves of D5_o.c. and D1:
the OCV curves of D5_o.c. slightly shifts toward the right to reduce
the charge cutoff voltage, while that of D1 slightly shifts toward the
left to increase the charge cutoff voltage. The increase in the charge
cutoff voltage of D1 is related to the compensation of the reduced
voltage of D5_o.c. because the charge cutoff voltage of the module
during cycling is set to a constant value of 21.00 V. A slight shift in
the OCV curve of D5_o.c. toward the right may be related to the side
reactions on the cathode surface.37
 Journal of The Electrochemical Society, 2022 169 030547

Figure 6. (a) Charge and discharge cutoff voltages of D1 and D5_o.c. in Module D as a function of cycle numbers. The constituent cells of D1 and D5_o.c. in
the module are a non-overcharged cell and an overcharged cell in the module, respectively. The cell D1 is a representative result of non-overcharged cells of D1
− D4. Presumable OCV curves of cell D5_o.c. and cell D1 at (b) 0 cycle, (c) 20 cycles, (d) 300 cycles, (e) 320 cycles, (f) 480 cycles, and (g) 530 cycles from the
data of Fig. 6(a). Degradation stage I, stage II, and stage III correspond to (b)–(d), (e)–(f), and (g), respectively. Notations: the horizontal axis of SoC [%] is
calculated by the rated capacity of a pristine cell, the voltage range of which is 3.00–4.20 V according to battery specifications. The calculated module SoHs are
also described in the figure.

After 20 cycles, the charge cutoff voltage of D5_o.c. and D1 does
not significantly change until 300 cycles except for a slight decrease
in the discharge cutoff voltage in D5_o.c. and an increase in the
discharge cutoff voltage in D1 between 260 and 300 cycles. At 300
cycles, the discharge cutoff voltage of D5_o.c. and D1 becomes
almost identical. As the charge cutoff voltages of D5_o.c. and D1 are
almost constant at 20–300 cycles, the cell capacity of D5_o.c. must
drop considerably more than that of D1 (Fig. 6d). Therefore, the
OCV curves of the overcharged cell (D5_o.c.) and non-overcharged
cell (D1) in Module D change from Figs. 6b to 6d in the first stage of
capacity retention.
The second stage of capacity deterioration occurs between 320
and 480 cycles. From 300 cycles to 320 cycles, the charge cutoff
voltage of D5_o.c significantly decreases. At the same time, the
 Journal of The Electrochemical Society, 2022 169 030547
charge cutoff voltage of D1 increases to compensate for the total
voltage of the module. The discharge cutoff voltage of D5_o.c.
becomes slightly less than that of D1 at 320 cycles. Therefore, the
OCV curves of D5_o.c. and D1 at 320 cycles can be plotted in
Fig. 6e: The OCV curve of D5_o.c. shifts toward the right to reduce
the charge cutoff voltage with a large drop in the cell capacity, while
the OCV curve of D1 shifts toward the left to increase the charge
cutoff voltage with a small drop in the cell capacity. A small increase
in the module capacity after 300–310 cycles, which is observed in
Fig. 1, is attributed to such a shift in the OCV curves of constituent
cells in the module. The shift in the OCV curve in D5_o.c may be
related to the side reaction on the cathode surface as the cathode is
exposed to the potential for a long period of time, where the cathode
is thermodynamically unstable. At 320 − 480 cycles, the charge
cutoff voltages of D5_o.c. and D1 are almost constant; the former is
ca. 4.31 V, and the latter is ca. 4.15 V. On the other hand, the
discharge cutoff voltage of D5_o.c. decreases steeply, while that of
D1 increases moderately. According to the charge/discharge cutoff
voltage, the OCV profiles of D5_o.c. and D1 at 480 cycles can be
plotted in Fig. 6f. Hence, in the second stage of capacity deteriora-
tion, the OCV curves of the overcharged cell (D5_o.c.) and non-
overcharged cells (D1 − D4) change (Figs. 6e and 6f).
In the third stage of capacity deterioration (>480 cycles), the
discharge cutoff voltage of B3 is observed to decrease more steeply
than that in the second stage, while the discharge cutoff voltage of
D1 increases. Because charge cutoff voltages of D5_o.c. and D1 do
not change with respect to the change in the second stage of capacity
deterioration, the OCV curves of D5_o.c. and D1 at 530 cycles in the
third stage of capacity deterioration can be expressed as shown in
Fig. 6g.
From the cycle dependence of the charge/discharge cutoff
voltage, the OCV profiles of the cells in the presence or absence
of overcharge are presumably described. In the first stage of capacity
deterioration, the capacity retention in the presence or absence of an
overcharged cell in Modules A–D (≈−11 mAh/ Cycle Number )
does not exhibit a significant difference. However, the capacity of
the overcharged cell decreases more harshly than that of the other
non-overcharged cells (Figs. 6b–6d). Interestingly, the capacity
decay of the overcharged cell occurs with the end point on charge
as a fulcrum. Before cycling, the discharge cutoff voltage of the
overcharged cell is 3.58 V (SoC35%), where it is in the middle of the
voltage plateau in the OCV curve; hence, the degree of capacity
fading of the overcharged cell does not directly affect module
capacity, leading to a similar capacity retention in Modules A − D in
the first stage of capacity decay. In the second stage, the discharge
cutoff voltage of the overcharged cell decreases steeply and achieves
a voltage drop from 3.47 V to 3.30 V (from SoC20% to SoC5%),
which is attributed to the phase transition of the graphite anode
(Stage3 → Stage1L).39 Such a voltage drop predominantly affects
the module capacity, leading to the steep decay of capacity in the
second stage. In the third stage, the discharge cutoff voltage of the
overcharged cell is in the region for the solid solution of the graphite
anode,40 where changes in voltage are more steep than those
observed in the second stage, thereby inducing a more steep capacity
decay of the module.
Hence, the capacity of the overcharged cell in the module shrinks
with the end point on charge as a fulcrum, and the reduction in the
discharge cutoff voltage of the overcharged cell predominantly
affects the total module capacity. In this study, an SoC-unbalanced
module was prepared to examine charge–discharge cycling with
overcharge. This situation is likely to occur in series-connected cells
under capacity variation in LIB cells due to manufacturing tolerance.
For advanced battery designs, bipolar-structured LIBs incorporating
solid electrolytes or polymer gel electrolytes have been widely
researched thus far to realize extremely large energy storage.41,42
Single-frequency EIS to detect uneven SOC variations in the series-
connected cell module before cycling has been reported.43 For
securing battery safety of the module during or after cycling, the
detection of excessively deteriorated cells in the module prior to the
serious capacity decay could be the next target to be addressed. From
the EIS analysis in this study, the RCT-C of the overcharged cell is
greater than those of the other cells in the module at the very start of
charge–discharge cycles (Fig. 4c) even though the module capacity
with an overcharged cell is almost the same as that without an
overcharged cell. Further analysis is underway in our laboratory.
Conclusions
Degradation mechanisms of series-connected cells in the pre-
sence or absence of an overcharged cell are investigated. For
commercially available graphite-NCA LIBs, three-stage capacity
fading is observed in the presence of an overcharged cell, the charge
cutoff voltage of which is ⩾SoC105.0% during cycling. Unlike
parallel connections, EIS and DVA confirmed that the overcharged
cell solely deteriorates more severely than other constituent cells in
series connections and that the deteriorated cell capacity appears to
affect the module capacity in the later stage of capacity fading (in the
second and third stages). At the first stage, the capacity fading of the
overcharged cell occurs more severely than that of other non-
overcharged cells with the end point of charge as a fulcrum, which
does not considerably affect module capacity because the voltage
range utilized in the overcharged cell is still similar to that of the
other non-overcharged cells. At the second stage, the capacity in the
overcharged cell starts to affect the module capacity, and more rapid
capacity fading is observed in the module because the lower cutoff
voltage of the overcharged cell decreases due to the shrinkage in the
capacity, the voltage change of which corresponds to the potential
transition in graphite between stages 2 L and 3. The capacity fading
mechanism of the module in the third stage is similar to that in the
second stage, but module capacity fading occurs more steeply, which
is related to the fact that by shrinking the cell capacity of the
overcharged cell, the lower cutoff voltage of the overcharged cell
steeply decreases because of the solid solution region in graphite.
Thus, the overcharged cell incorporated in the module deteriorates
more severely after the second stage, and its capacity retention is less
than that from the total battery module, suggesting that it is difficult
to assess module safety by using the total capacity of the module.
Without disassembling the module, it is difficult to evaluate the
capacity of constituent cells in the module. This problem is thought
to be apparent in bipolar-structured all-solid-state battery cells when
charge–discharge operation is performed under the control of the
total module voltage without any balance circuits. This study
exposes potential risks in the design of such next-generation
batteries and provides critical aspects for safety in the development
of large-scale energy storage.
Acknowledgments
This study was supported by the JST-OPERA Program (grant
number: JPMJOP1612), Japan.
Author contributions
N. T. designed, performed, and analyzed all experiments reported
in this manuscript. N. T. drafted the paper. All authors contributed to
the discussion and interpretation of the results. This study was
supervised by T. O.
ORCID
Norihiro Togasaki https://orcid.org/0000-0003-4817-7166
Tokihiko Yokoshima https://orcid.org/0000-0003-0645-070X
Tetsuya Osaka https://orcid.org/0000-0001-8307-132X
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