Journal of Power Sources 498 (2021) 229884

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Journal of Power Sources

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State of health (SoH) estimation and degradation modes analysis of pouch

NMC532/graphite Li-ion battery
Xiaoxuan Chen a, Yonggang Hu a, Sheng Li a, Yuexing Wang b, Dongjiang Li a, c, d, Chuanjun Luo e,
Xujin Xue f, Fei Xu e, Zhongru Zhang a, Zhengliang Gong g, Yangxing Li h, Yong Yang a, g, *
a
State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen,
361005, China
b
Institute of Electronic Engineering, China Academy of Engineering Physics, Mianyang, 621999, China
c
Forschungszentrum Jülich, Fundamental Electrochemistry (IEK-9), D-52425, Jülich, Germany
d
SVOLT Energy Technology Co., Ltd. No.2199 Chaoyang South Ave. Baoding, Hebei, China
e
Do-Fluoride (Jiaozuo) New Energy Technology Co., Ltd, Jiaozuo, 454150, Henan, China
f
Do-Fluoride Chemicals Co., Ltd, Jiaozuo, 454150, Henan, China
g
College of Energy, Xiamen University, Xiamen, 361005, China
h
54135 Belle Meade Circle, Belmont, NC, USA

H I G H L I G H T S

• The cycling performance and degradation mechanism of NMC532/graphite battery are studied.
• Thermodynamic attributes of capacity loss are simulated by an electrochemical model.
• EVS technique is extended to high C-rate charging scenarios by EMF-extraction method.
• An online SoH estimation model is established by tracking features in IC/DVEMF curves.
• The SoH-estimation model can work well with partial-cycling data.

A R T I C L E I N F O A B S T R A C T

Keywords: Electrochemical voltage spectroscopy (EVS), which includes differential voltage analysis (DVA) and incremental
On-line SoH estimation capacity analysis (ICA), has been used extensively in revealing the aging mechanism and evaluating the oper­
Aging mechanism ating state of Li-ion batteries. The EVS technique is conventionally limited to low-charging-rate scenarios such
Electromotive force
that the polarization effect has a negligible influence on the spectral characteristics. This makes EVS analysis
Incremental capacity
Differential voltage
both time-consuming and unfeasible in real-world scenarios. In this work, for the first time, we have expanded
Electrochemical model the EVS to realistic C-rate operating conditions by combining it with a programmed electromotive-force (EMF)
extraction method to adapt the EVS-based SoH estimation model to any arbitrary charging scenarios. By tracking
the features in the EVS curves, the model can properly estimate cell SoH even with partial (dis)charging data,
with a maximum error of less than 3%. Furthermore, an electrochemical model is established to identify the
thermodynamic attributes on capacity loss. The degradation performance of the NMC532/graphite battery
system under different operating conditions was comprehensively studied based on the comparison analysis
between the modeling and experimental results.

1. Introduction electric vehicles (PHEVs/HEVs/EVs). The ternary nickel-manganese-

cobalt (NMC) layered oxide material system has been promising for
Lithium-ion batteries, as reliable energy sources with high energy positive electrodes of lithium-ion batteries owing to the larger specific
density and high power density, are widely used in plug-in/hybrid/ energy/power densities compared to LiFePO4 and lower cost than

* Corresponding author. State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering,
Xiamen University, Xiamen, 361005, China.
E-mail address: yyang@xmu.edu.cn (Y. Yang).

https://doi.org/10.1016/j.jpowsour.2021.229884
Received 28 December 2020; Received in revised form 29 March 2021; Accepted 1 April 2021
Available online 18 April 2021
0378-7753/© 2021 Elsevier B.V. All rights reserved.
X. Chen et al.
LiCoO2. However, a greater number of complex degradation modes
(DMs) and higher chemical/thermal instability can be introduced into
the system with increasing Ni content, especially in dynamic real-world
scenario [1]. Therefore, estimations of the battery operating state, that
is, the state of health (SoH) and the remaining useful life (RUL), must be
accurate enough for reliable and optimal utilization of a battery before
severe operation failure.
It is well known that the DMs of batteries are highly dependent on
operating conditions, for example, ambient temperature, charge/
discharge rate (C-rate), specified service range (State-of-Charge, SoC),
depth of discharge (DoD), and cumulative charge-throughput. To attain
the optimal service life, it is crucial to determine how each factor affects
the aging behavior of a cell. Loss of lithium inventory (LLI) and loss of
active material (LAM) as two major DMs, are generally considered as the
thermodynamic attributes of irreversible capacity loss [2–5], while the
rate-dependent polarization behavior is the dynamic attribute of
reversible capacity loss. LLI is associated with the solid-electrolyte
interphase (SEI) formation, “dead” Li accumulation caused by
Li-dendrite growth, and transition metal reduction at the anode, etc. The
structural degradation, irreversible phase transition, dissolution and
channel-blockage, etc., are considered the primary causes of LAM.
Post-mortem techniques that unravel the degradation mechanisms at the
material level has been extensively studied [6–8], which can provide
useful insights into the battery failure mechanism, but incapable of
providing temporal solutions for practical battery monitoring or prog­
nosis. Therefore, non-destructive techniques for cell degradation anal­
ysis are gaining increasing interest recently, which further fall roughly
into model-based and data-driven approaches. As for model-based
approach, the degradation behaviors of the cells are simulated by
identifying and adapting the key parameters that reflect the operating
state. Based on the characteristic of the available history data, a suitable
model, i.e. equivalent circuit model (ECM), empirical model or elec­
trochemical model will be chosen for extrapolating the current-status
data towards cell’s future performance. Appropriate optimization al­
gorithm or filtering algorithm, i.e. Genetic algorithm (GA), Kalman filter
(KF), least square method (LSM) and Particle filter (PF) are usually
involved to dynamically update the model parameters [9,10]. Kim et al.
[11]. proposed an on-board SoH estimation model based on dual
extended Kalman filter (EKF) algorithm, where two EKFs were employed
in parallel on an equivalent circuit model. An alternative feedback gain
was additionally applied to measure and minimize the noises. The al­
gorithm was of high complexity and the maximum absolute capacity
estimation error of the model is 5%. Electrochemical model has drawn a
lot of attention due to its explicit simulation of time-domain chemical
processes, where a set of coupled partial differential equations are used
for analyzing mass transport and charge transfer process that evolve
with cell aging. Electrochemical model generally includes
Pseudo-Two-Dimensional (P2D) model and single particle model (SPM).
The real-world implementation of this model is precluded at the stage,
due to the intractable computational burden. Also widespread is
equivalent circuit based models (ECM), where the cell dynamics is
reduced as circuit elements analogs such as resistors, capacitors and
constant phase elements (CPEs). The model can output quick voltage
responses with dynamical input current signal, but the electrochemical
processes and internal states of the cells are often neglected, making it
hard to be coupled with thermal or mechanical properties of a cell. A
monotonic relationship between identified SEI resistance and remaining
capacity was discovered in Ref. [12] with an ECM. The model was
effectively validated by aged and new cells with a SoH estimation error
within 3%. Guo et al. [13] proposed a second order RC ECM, where
transformation function and nonlinear least squares algorithm were
applied on charge curves to iterate the time-based model parameters.
The model was validated by cells of different chemistries and operating
temperatures and the SoH estimation error at all stages of life is under
3% around 500 cycles.
On the other hand, data-driven approach becomes one of the hottest
2
Journal of Power Sources 498 (2021) 229884
research areas nowadays due to their nonlinear matching ability,
enabling the model-free intelligent algorithm, i.e. neural network family
or deep learning, to work well without a priori knowledge of battery
chemistry [14]. Although the data-driven approach has simpler struc­
ture and reduced complexity, it is irrelevant to electrochemical princi­
ples and nonparametric. Consequently, it is unreliable when the test sets
are less than massive. An extreme-learning-machine based SoH esti­
mation algorithm is developed and compared with the classic BP neural
network in Ref. [15], where ohmic internal resistance and polarized
internal resistance are denoted as health indicators. The maximum
estimation error of the proposed strategy is less than 2.5%, demon­
strating a better performance and faster speed than the BP neural
network algorithm, but the condition of impedance measurement is
harsh and time-consuming.
Obviously, no matter what method is taken, it is always challenging
to make a trade-off between model complexity and prediction accuracy.
Notably, the effectiveness of a data-driven approach would be enhanced
significantly if the input features were extracted properly. Among
others, the EVS technique [16,17], consisting of incremental capacity
analysis (ICA) and differential voltage analysis (DVA), has exhibited its
superiority as a simple-implemented and non-intrusive technique
acquiring mechanism-related features to be potentially combined with
data-based approach.
EVS is based on the principle of the Gibbs phase rule. Accordingly,
the enhancement of peaks in the IC and DV curves visually reflects the
emergence of the two-phase region and single-phase region, respectively
[18–21]. Owing to the electrochemical information carried by EVS, this
technique has been used extensively in identifying aging mechanism and
estimating operating states (i.e. SoH and SoC) of the batteries [22–27].
However, this technique is only reliable when the system is under
equilibrium state, which requires a cell being (dis)charged at low and
constant current, in order to obtain a reliable pseudo-OCV curve. This
limitation consequently makes the application of EVS in real-world
scenarios unfeasible. As C-rates increase, features on differential
curves are increasingly obscured due to heterogeneous (de)intercalation
[28] and electrochemical polarization. To solve this dilemma, charging
at a low C-rate (i.e., 0.05C) is commonly adopted as a compromise be­
tween the theoretical electrochemical equilibrium state and a feasible
solution employed in battery management system (BMS). For example,
Li et al. [25] developed a linear regression SoH estimation model based
on tracking evolution of moving-average processed IC curves with cell
ageing, with 5% maximum absolute estimation error until around 88%
SoH. However, the model have limited modeling ability during high
C-rate operating scenarios as the features in IC curves are easily smeared
out by unavoidable data noise. In this work, for the first time, EVS-based
SoH estimation has been extended to high C-rate (dis)charging condi­
tions, by introducing a novel EMF-extraction method into the technique.
The rate-dependent polarization attributes of capacity loss is accord­
ingly mathematically ruled out from the typical discharge curves with
the proposed method. By identifying the feature points (FPs) in the
obtained IC/DVEMF curves and tracking their evolution with cell aging,
the model achieves excellent SoH estimation accuracy with less than ±
1.5% mean absolute error (corresponding to ± 7.5% relative error, as
metrics of 20% useable capacity scale). The model is further validated by
the experimental results of over 15 months life cycle tests on 40 com­
mercial NMC532/graphite cells, where we find it can work well under
various operating conditions, even with partial charging data.
Like the studies reported in the literature, we selected the capacity of
the cell as the health indicator to determine the SoH of a cell in this
work, which is expressed as the ratio of the actual capacity vs. the initial
Q
capacity (SoH = Qinitial
cycle
× 100%.). The equilibrium state is determined by a
novel EMF-extraction method, without interrupting the regular cycling
process, allowing us to rule out the rate-dependent polarization attri­
butes from the thermodynamic ones (i.e., LLI and LAM) of capacity loss
of the cell. The rational design of RPT will be discussed in the experi
 X. Chen et al. Journal of Power Sources 498 (2021) 229884

mental section, and a more detailed description of the EMF-extraction Table 2

algorithm can be found in previous publications [29–33]. With such Cycle life test condition for NMC cells.
refinement of EVS, this technique is feasible for the fast online predic­ Temperature Charging Discharging SOC range Voltage range
tion of battery SoH without compromising precision. rate rate (%) (V)
The contents of the paper are organized into four major sections: 1) 30 ◦ C 0.2 C 0.5 C 0–100 3.0–4.2
Degradation performances of 40 commercial NMC532/graphite cells 1C 0.5 C 0–100 3.0–4.2
under different operating conditions, abuse conditions included, are 2C 0.5 C 0–100 3.0–4.2
qualitatively studied by over-15-month cycle-life test. 2) Typical 0.5C 0.2 C 0–100 3.0–4.2
0.5 C 1C 0–100 3.0–4.2
discharge curves are transformed into the polarization-free VEMF-Q 0.5 C 2C 0–100 3.0–4.2
curves using an EMF-extraction algorithm. Irreversible capacity loss 0.5 C 0.5C 0–30 3.2–3.55
(ΔQir ) is determined and further used as a quantitative indicator to 0.5 C 0.5 C 30–70 3.55–3.75
evaluate the degradation regularities of the battery system. 3) EVS 0.5 C 0.5 C 70–100 3.75–4.2
0.5 C 0.5 C 2.5–3.25
analysis is performed on the VEMF-Q curves to acquire the IC/DVEMF –
0.5 C 0.5 C – 3.6–4.25
curves. A numerical model for SoH estimation is established by tracking 60 ◦ C 0.2 C 0.5 C 0–100 3.0–4.2
the evolution of the feature peaks (FPs) in the differential curves. 4) An 0.5 C 0.5 C 0–100 3.0–4.2
electrochemical model based on porous-electrode theory is established 1C 0.5 C 0–100 3.0–4.2
to determine the individual thermodynamic attribute (LAMNE, LAMPE, 2C 0.5 C 0–100 3.0–4.2
0.5 C 0.2 C 0–100 3.0–4.2
and LLI) of capacity loss. 0.5 C 1C 0–100 3.0–4.2
0.5 C 2C 0–100 3.0–4.2
2. Experimental

2.3. Full-cycle life tests under multivariate stresses

2.1. Chemical system and cycling protocol

The cells used for aging measurements were commercial pouch cells
with a nominal capacity of 10 Ah and the chemistry of LiNi0.5Mn0.3
Co0.2O2 (NMC532)/graphite (DFD Co., Ltd., China). Two identical cells
(same manufacturer and same batch) were aged under the same con­
ditions to verify the efficacy of the test results. The characterization
process was implemented by applying RPT periodically along with
cycling tests. Detailed information about the battery system is listed in
Table 1. The cycling tests were performed with automatic multichannel
5 V-100 A Neware cycling equipment. An environment chamber was
used to control the ambient temperature. To study the impacts of various
operating conditions on the degradation behavior of the cell, factors
including ambient temperature, charge/discharge C-rate, SoC and DoD
range are considered in the testing matrix. Specific test conditions are
detailed in Table 2. Considering that the end-of-life (EoL) of a cell is
commonly defined by 80% SoH, cycling is manually ended once EoL has
been attained in each test.
2.2. Reference performance tests (RPT)
All the tested cells were first subjected to five activated cycles at
room temperature to form a stable SEI. RPT tests were subsequently
performed at regular cycle-number intervals on the cells. Every RPT was
composed of a series of constant-current-constant-voltage (CC-CV)
charge/constant-current (CC) discharge procedures to periodically
derive the EMF curves. The detailed protocol was as follows: A 0.5 C
charging rate was used in the CC-mode, followed by CV charging at 4.2 V
until the charging current dropped below 0.05C. CC discharging at
different C-rates (0.1, 0.2, 0.3, 0.5, 0.75, 1.0, 1.5, and 2 C) continued
until a cut-off voltage of 3.0 V was achieved. The initial maximum
available capacity Q0max was directly obtained from the first RPT, and
Qtmax was acquired by the following EMF with cell aging.
Table 1
Specifications of tested battery system.
Item Specification
Cathode material LiNi0.5Mn0.3Co0.2O2
Anode material Graphite
Nominal Capacity (at 0.3 It rate, 3.0 V–4.2 V) 10 Ah ± 2.5%
Max. charge current 10 C
Max. discharge current 15 C
Charging cut-off voltage 4.2 V ± 1%
Voltage range 2.75–4.2 V
Once the activation process and the initial RPT were completed, the
cycle life tests, set to CC-CV charge/CC discharge mode, began on the
cells according to the protocol shown in Table 2. The charging/dis­
charging cut-off voltages were 4.2 V and 3.0 V, respectively. The
charging stresses included 2 temperatures, each of which corresponded
to 7 different charge/discharge rates; herein, a total of 28 cells are
needed. All the tested cells were regularly re-characterized every 20 d.
2.4. Partial and charge-abuse cycling tests
Degradation performances under partial charging and abuse sce­
narios were studied for 12 cells corresponding to 5 different cycling
conditions, including 3 partitioned SoC intervals and 2 voltage intervals.
A CC-CV charge- CC discharge mode was used to age the cells, and a
current 0.5 C-rate was applied for the CC step; the cut-off voltage
depended on the specific experimental settings. One set of cells was
cycling within a voltage range of [2.5 V, 3.25 V] to reproduce an
excessively low-voltage charging process and another within a voltage
range of [3.6 V, 4.25 V] to reproduce an excessively high-voltage
charging process. The partial charging test was designed by cycling
the cells within three partitioned SoC intervals: [0, 30%], [30%, 70%],
[70%, 100%], corresponding to low, mild and high charge regions
respectively. All the above-mentioned test conditions are also shown in
Table 2.
3. EMF determination and EVS technique implementation
During each RPT test, a set of cell voltage curves versus discharge
capacity at regularly increased C-rates (corresponding to 0.1 C, 0.2 C,
0.3 C and 0.5 C in this work) are plotted, as shown by the solid lines in
Fig. 1 (a). Equilibrium potential of the cell can be mathematically
determined by performing polynomial regression-based extrapolation
on the curves. We tentatively define the discharge curves as “flat po­
tential region” (the part that before the black dotted helper line) and
“steep potential region” (the part after). We notice there is a good linear
relationship between the experimentally determined voltages and the
applied currents at various discharge capacities in the flat potential re­
gion, as shown by Fig. 1 (b). This implies that the equilibrium voltage
can be obtained by linearly extrapolated the V–I function toward the
zero current case at each capacity. Similarly, the linear relationship
exists between discharge capacities and applied currents at different
voltage in the steep potential region, which means that the maximum
capacity can be obtained by linearly extrapolating the curves toward I =

3
­
X. Chen et al. Journal of Power Sources 498 (2021) 229884

Fig. 1. (a) Cell voltage curves at various C-rates during a RPT test (solid lines) and extrapolated EMF curve (the dotted line); (b) Cell voltages at various discharge
capacities as a function of applied current rate in the “flat potential region”; (c) Cell capacities at various discharge voltages as a function of applied current in the
“steep potential region”; (d) Examples of the evolution of discharge curves of different cycling numbers; (e) and the corresponding extrapolated EMF curves; (f)
Evolution of discharge capacity (Qtd ) and maximum cycling capacity (Qtmax ) at the given time (t) as a function of cycle number, where ΔQir and ΔQapp refer to the
irreversible capacity loss and apparent capacity loss, respectively.

0, as shown by Fig. 1 (c). By combining these two parts of the curves

together with moving average [29], a complete EMF curve can be
accordingly determined, as shown by the outermost red dotted line in
Fig. 1 (a). Herein, the effect of polarization is removed theoretically from
the typical discharge curves. The maximum cell capacities (Qmax) at the
cut-off voltage 3.0 V can be derived from the EMF curves under any
operating state, as marked in Fig. 1 (a).
As an example, Fig. 1 (d) and (e) show the discharge voltage curves
and the corresponding extrapolated EMF curves at 120th, 480th and
840th cycles at 1 C, 60 ◦ C, respectively. Although both of the results
indicate the performances of capacity and voltage decrease with cycling,
it is obvious that EMF curves contain more intrinsic and detectable
ageing information. As for aged cells, the voltage plateaus between 3.6 V
and 3.2 V in discharge curves almost coincide with the fresh cell, while
when polarization effect is ruled out from the results, as can be seen from
EMF curves, the discrepancies of the plateaus are distinguishable within
the same voltage range.
As shown by Fig. 1 (f), the capacities extracted from the original
discharge curves and extrapolated EMF curves are defined as discharge
capacity (Qtd ) and maximum cycling capacity (Qtmax ), respectively.
Having the evolution of both Qtd (the blue curve) and Qtmax (the black
curve) with cycles, we observe the certain regularity with state change
of cells only well exists in Qtmax evolution, making it a better indicator of
capacity degradation performance. Therefore, quantitative ageing
analysis is performed upon the evolution of EMF curves by defining the
irreversible capacity loss (ΔQir ) as [30,31]:
ΔQapp = Q0d − Qtd . (2)
The capacity differences between ΔQir and ΔQapp are caused by po­
larization effect, where in most cases, are defined as reversible capacity
loss by established literature, while the amount of ΔQir is totally
depending on thermodynamic failure origins LLI and LAM.
EVS is performed on the obtained EMF curves of all cycling condi­
tions. Fig. 2 exemplarily shows the representative IC/DVEMF-analysis
results at 0.5 C charging rate, 30◦ C and various discharging current
rates. Locally enlarged feature-peaks/valleys shifts are indicated by
black arrows and insets in each figure. After 1000 times cycling, there
are apparent deformations occurred on DVEMF curves. Interestingly, the
level positions of the lowest DVEMF peaks remain rather constant as the
peaks move upwards with cell aging. The other DVEMF peaks of higher
SoC shift towards the higher voltage region. The peaks indicated in the
IC curves regularly shift to lower SoC region as moving upwards with
increasing cycle numbers. According to the above analysis, cell’s
degradation performances under various cycling conditions are regu­
larly reflected by the shift of FPs in IC/DVEMF curves. Owing to the in­
formation of specific electrochemical reaction contained in IC/DVEMF
curves, a functional correlation between curve features and capacity loss
is highly desired.
4. Aging analysis under various operating conditions
4.1. Quantification of degradation state under full-range cycling condition

ΔQir = Q0max − Qtmax . (1) According to equation (1), the irreversible capacity loss at different
Also, the apparent capacity loss is defined as: temperatures as a function of cycle number can be determined from the
EMF results. The left and right columns show the evolution of ΔQir with

4
X. Chen et al.
Fig. 2. The evolution of EMF-derived IC (dQ/dVEMF, (d)–(f)) and DVEMF (dVEMF/dQ, (a)–(c)) results as a function of cycle number at 30 ◦ C, 0.5C charging rate and
various discharging current rates ((a), (d), discharging at 0.2 C-rate; (b),(e), at 0.5 C-rate; (c), (f), at 1 C-rate).
the variation of charging and discharging current rate respectively.
Whatever the C-rate is applied, a linear aging rule is generally observed
from ΔQir at 30◦ C, whereas the cycle life is influenced more by charging
than discharging rate. The linear degradation regularity under room
temperature is mainly attributed to the continuous SEI growth on the
SEI-covered graphite surface, which has been confirmed increasing
linearly with the cycle number [33]. In contrast, an exponential aging
characteristic lies in 60◦ C cycling data. The switch from linear to
non-linear aging regularity under elevated temperature is also in line
with former publications, where the onset of non-linear capacity un­
dershoot was attributed to particle fracture and electronic isolation of
active electrode material [34,35]. Moreover, the high-voltage-driven
side reactions those occur at electrode-electrolyte surface will be
speeded up at higher temperature, according to the Arrhenius law [36].
This can result in increase of cell impedance and further triggering the
potential failure modes such as leakage of electrolyte and/or gas evo­
lution, making a cell reach its EoL earlier [37].
4.2. Quantification of degradation state under partial cycling and charge-
abuse condition
Cell’s aging regularities during partial cycling and abuse conditions
were also studied. Fig. 3 (e) and (f) show ΔQir and maximum capacity
Qt
retention (Qret
max = Q0 .) upon the fragmentary cycle life test as a function
max
max
of cycle number. The discontinuous steps and differences between the
same-condition-tested samples are considered to be related to gas gen­
eration and venting during the long-term electrochemical reaction that
brings inconsistent pressure to the cells. It should also be noted that all
the results discussed in this section are based on the tests terminated
earlier due to Li-plating triggered thermal runaway, which lead to a lack
of long-term cycle life data. As can be seen from Fig. 3 (e), cycling under
an excessive-high voltage range (over 3.7 V) significantly impairs the
available capacity of the cell, and over 70% SoC takes the second place.
5
Journal of Power Sources 498 (2021) 229884
Surprisingly, the cycle life of the cells is almost unaffected in the cases of
cycling under an SoC below 30% or a voltage below 3.25 V, even though
this voltage range is below the rated value. The decline rates of
Qret
max under each partitioned SoC or voltage interval is sorted in
descending order: [3.7 V, 4.25 V] > [70%, 100%] > [30%, 70%] > [0,
30%] ≈ [2.5 V, 3.25 V]. Fig. 3 (f) reveals that for cells cycling in [30%,
70%] SoC, even over 1200 charging cycles, the ΔQir is limited to within
6.09%, whereas for cells cycling in [70%, 100%] SoC, the ΔQir reaches
23.35% for the same cycle number. More strikingly, for cells cycling in
the voltage range of [3.7 V, 4.25 V], ΔQir was 26.80%, even when the
charging times were less than 480.
The above results suggest that cycling conditions notable impact the
cycle life of cells. Cycling within an excessive high-voltage range
dramatically impairs the lifespan of the cell from initial cycling stages,
shortening the cycle life to less than 500 times. Considering that LAM is
rarely detected in the early aging stage [38], LLI is mainly responsible
for capacity loss before the second aging stage. Subsequently, with LAM
being more significant with cell aging, its impact on cell performance
appears in an accelerated manner joining with LLI until the EoL. This
result is an important contribution to the existing literature, where
stress-induced microstructure damage accompanied by repeated Li+
(de)insertion into active material particles is reported as the primary
cause of capacity undershoot under high-voltage cycling [39]. In com­
parison, cycling under a high SoC range, which is also regarded as
considerably damaging the cell, exhibits a completely different degra­
dation regularity. There is almost no obvious increase in ΔQir during the
initial stage, whereas the cell cycle life is still reduced by 50% by its EoL,
indicating that LAM occurring in the later aging stage is the dominant
DM in this case.
5. Model-based approaches for cell aging analysis
In order to identify and quantify capacity loss due to individual DM
and further estimate SoH of the cell, a porous-electrode-theory based
X. Chen et al. Journal of Power Sources 498 (2021) 229884

Fig. 3. Evolution of irreversible capacity loss (ΔQir ) as a function of cycle number at various charging/discharging current rates (0.2, 0.5, 1 and 2 C) and tem­
peratures (30 ◦ C and 60 ◦ C). (a)–(d) complete cycle life test; (e) and (f) partial and abuse cycle test. The numbers before “C” and “D” refer to the charging rate and
discharging rate respectively and the last number refers to the serial number of sample.

electrochemical model and a numerical regression model are estab­
lished. As for each decoupled DM is directly determined by one or a few
parameters of the model’s governing equations, adjustment of the pa­
rameters can influence DMs in proportion and furthermore result in part
of detectable capacity change. By comparing modeling results with test
sets under various charging stresses, the specific DMs occurred as cell
degradation are therefore determined by the electrochemical model,
which was established using COMSOL Multiphysics version 5.2.
Furthermore, given the distinct peaks in the IC/DVEMF curves reveal
particular patterns related to LLI and LAM as cell aging, degradation
diagnostics is conducted by tracking the evolution of FPs over its life­
time. The numerical model is built-up to online estimate SoH at specific
SoCs during the cycling process.
5.1. Mechanisms rationalization by the selection of FPs with kinetic
models
5.1.1. Electrode degradation mode attribution with the electrochemical
model
LLI, LAMNE, and LAMPE, as three major DMs are modeled in the
frame of porous electrode theory, which assumes that the electrode and
electrolyte phases are continuous and the underlying microstructure of
the electrode can be reasonable neglected [40,41]. Previous researches
tend to focus on how LLI and LAM contribute cooperatively to yield
enhanced capacity loss, while often short of quantitative studies on the
individual impact of each DM as cell aging. With investigating key pa­
rameters of the electrochemical model and detecting the resulting ca­
pacity change, it is possible to study LLI or LAM individually. Detailed
theory of the model can be found in Refs. [40,42,43]. A list of param­
eters can be found in the Supporting Information (see Table S1).

6
X. Chen et al.
We notice that electric potential in the solid phase, which can be
determined using Ohm’s law as Eq. (3), is directly limited by LAM:
( )
∇ σ eff ∇ϕs = as Fj. (3)
where
σ eff = σεbrug
s (4)
The effect of tortuosity accompanied with porous media has to be
considered into bulk conductivity of homogeneous solid matrix to obtain
an effective conductivity σeff, as shown in Eq. (4); as, ϕs and j are defined
as specific interfacial surface area, solid-phase potential and exchange
current density respectively. By setting εs with each period decreases to
90% of that as before, meanwhile remaining all the other parameters
unchanged, the model’s output reveals the part of capacity loss induced
only by LAM. The parameters of cathode and anode are adjusted sepa­
rately to distinguish LAMPE from LAMNE. The induced capacity loss and
the accordingly differential results are summarized in Fig. 4 row 2 and
row 3 respectively.
To parameterized LLI, the mass conservation during the electrode
reaction is considered:
ν− M−z− + ν+ M+z+ + ν0 M0 ⇌ne− .
where M-, M+ and M0 are species with specific charge involved in the
reaction. Gibbs free energy of n moles of electrons is expressed by -nFϕ.
The energy balance between the generated electrons and the reactants
follows:
Fig. 4. Representation of the 3 independent DMs. DM1: Loss of lithium inventory (LLI); DM2: Loss of positive-electrode active material (LAMPE); DM3: Loss of
negative-electrode active material (LAMNE). The black curves represent the pristine state and colored curves are corresponding to the indicated aging cycles. From
left to right: (i) EMF curve (voltage v.s. capacity during discharging); (ii) dQ/dVEMF v.s.VEMF (IC curve); (iii) dVEMF/dQ v.s.dQ (DVEMF curve) Three plateaus originated
from the differential curves as indicated as I, II and III. The peaks on DVEMF curve are indicated as β and θ, those on IC curves are indicated as α and γ respectively.
Journal of Power Sources 498 (2021) 229884
c
ν+ ∇μ+ + ν− ∇μ− − ν0 ∇μ = − nF∇ϕ. (6)
c0
where ν refers to the stoichiometric coefficient, determined by the
numbers of Li+ that take part in electrode reaction. To simulate the in­
crease of LLI by this model, ν is decreased by 10% periodically.
Outputting capacity fade during this process, the EMF and IC/DVEMF
curve owing to LLI are respectively obtained, as shown in the first row of
Fig. 4.
As can be seen from row 1 of Fig. 4, when LLI is the only DM during
cycling, there will be no evident change on the shape of EMF curve.
According to Ref. [44], peak β can be defined as the signal of phase
transition process from hexagonally packed phase (customarily named
‘H’ phase) to orthorhombic phase (customarily named ‘M’ phase) of
NMC electrode. We notice that peak β shifts to higher voltage with LLI
during cycling, without variation on the height, which means this pro­
cess is immune to the lack of Li+ within limits. As can be seen from
DVEMF peaks, region II is not shortened until region I totally disappears.
After that, if LLI continues emerging, region II will start to shrink at a
relatively low rate. Interestingly, region III remains fixed no matter how
much LLI is generated, which thereby stabilizes the position of peak α
(5) throughout.
Row 2 of Fig. 4 demonstrates the case that LAMPE, which increases at
10% per cycle, is the only DM that results in capacity fade. Unlike the
result of LLI, the length of region II on DVEMF curve is gravely curtailed
by LAMPE, while region III is completely unaffected. Moreover, it is
worth mentioning that LAMPE is the only factor that can cause “retrac­
tion” on region I, manifesting as tail-end value of DVEMF curve going
7
X. Chen et al.
back and up simultaneously.
Row 3 of Fig. 4 shows the case that LAMNE, which increases at 10%
per cycle, is the only DM that results in capacity fade. Cell’s EMF
manifests completely different tendency comparing to other two situa­
tions. This mechanism is in line with the modeling EMF result shown by
row 3 (i), where we observe the curve is hardly affected by the increase
of LAMNE during the initial period of charging process, but can be
reduced significantly at higher SoC region. As for the IC curve, inter­
estingly, the intensity of β peak decreases with LAMNE while the position
of which does not shift, whereas θ peak shifts to lower potential without
any intensity change during this process. In the case of DVEMF curve of
LAMNE, all of the FPs shift to lower voltage monotonously with the in­
crease of LAMNE, however, the peaks’ shift under LAMNE do not lead to
any shrinkage of region I.
5.1.2. Reveal cell aging mechanism: a comparison of experimental against
modeling results
From the modeling results, it is clear that convolution between LLI/
LAM or LAMPE/LAMNE can lead to totally different variation trends upon
IC/DVEMF curves, therefore the shift of FPs is of great probability being
neutralized when more than one DM exist. However, when each indi­
vidual DM is decouple by the electrochemical mechanism model, FPs
will move drastically with cycling.
Seeing from the experimental results of 30◦ C shown by Fig. 2, α peak
shifts to lower SoC meanwhile the peak height is enhanced; while a
reversed trend is detected on γ peak, for which the position remains
constant and the height is decreased. Moreover, owing to LLI is the only
factor that causes translation on β peak of IC curve, we take this as an
indicator to resolute the effect of LLI. The position of β peak of experi­
mental results is almost unchanged in the process of cycling, indicating
that LLI is not the main DM for NMC532/graphite cells aging under
room-temperature operation. In contrast, as for cycling results at 60◦ C,
as indicated by Fig. S1, α peak and γ peak are observed increasing
simultaneously, and the corresponding SoCs both shift to lower values.
This observation is in accordance with the case of our modeling results
that LAMPE is the rate-determining step under higher temperature
cycling, whereas under the room-temperature situation, LAMPE is
comparable with LAMNE or even less, resulting these two DMs serve as
rate-determining step by turns during each cycle.
In a word, the mechanism model is capable of distinguishing DMs
one from another theoretically and attributing the relevant capacity
fade. It should be noted that a quantification analysis needs to be further
performed on the porous-theory model, if a precise correspondence of
the modeling results to realistic experimental results is required. In order
to further quantify the impacts of the DMs on cell SoH, a numerical
model will be introduced in the next section. The key issue of the model
lies in the selection of proper feature sets which can directly reflect cell
aging.
5.2. On-line SoH estimation with detection of FPs using data-driven model
Nowadays, it is prevalent to use machine learning or deep learning to
estimate cell SoH, where raw current or voltage signals are usually used
as input features without any manipulation. This limits the improvement
in the prediction accuracy because learning highly correlated and
adequate effective features is the only way to ensure high accuracy. In
contrast, this work manipulates the raw discharge data with EMF-
extraction algorithm, and explicitly assigns the shift of PFs in IC/
DVEMF curves to specific electrochemical reaction process. Feature
manipulation is an effective way to get robust correspondences when
data volume is rather limited.
Three FPs in IC and DVEMF curves corresponding to the major DMs
have been determined by the above-mentioned mechanism model.
Based on establishing the mathematical correlation of FPs’ shift with
capacity loss during cycling, a numerical model is obtained to realize
online estimation of cell SoH. This model can work well with not only
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Journal of Power Sources 498 (2021) 229884
full-cycling but also daily segment charging data within a maximum of
3% estimation error for across the entire SoC range during dynamic
cycling process. Nevertheless, the FPs used to train the numerical cor­
relation are conveniently identified and captured by BMSs, which sug­
gests the application prospects of this model.
5.2.1. Feature point acquisition and correlation analysis
From a computational perspective, DVEMF values are simply the re­
ciprocals of IC values at the same point. However, from an 3rd FOI
electrochemical mechanism perspective, IC and DVEMF curve can pro­
vide different insights of cell aging: the peaks or valleys in IC curve
correspond to specific electrochemical reaction, whereas those on
DVEMF curve reflect the phase transformation of active material during
Li+ (de)intercalation [18,45]. In order to integrate structure change and
reaction characteristics into the model, features of both the curves need
to be introduced. Herein, three FPs with monotonic characteristic as
cells degrade are defined, where two of them are extracted from IC curve
while the other one is extracted from DVEMF curve. Again, due to the
differential analysis in this work is based on EMF curve, this model has
the ability to determine thermodynamic capacity fade that independent
from the reversible (polarization induced) part, which can theoretically
yield better SoH estimation accuracy.
These three FPs are supposed to be captured by a BMS according to
the defined SoCs, which are respectively equivalent to 30%, 57% and
89% (Noted that the SoCs here are by the values of the first cycle and
only for denoting the position of FPs), as shown in Fig. 5. The data under
I/2 charging rate are selected as an example to train the SoH estimation
algorithm. Obviously, when the applied (dis)charging rate is changed,
the coefficients of this algorithm accordingly need to be adjusted for
adapting to specific usage scenario. In this model, the cell SoH can be
determined either with complete or segment cycle data: on the one
hand, as long as one of the FPs’ SoC is reached, the current SoH can be
determined at this FP. This makes the model applied for the segment
charging data with flexible initial SoC. On the other hand, if more than
one SoCs of the FPs are reached, the cell SoH can be outputted at the first
SoC positon and further re-corrected at the rest of SoC point(s).
Accordingly, the maximum estimation error of actual SoH can be nar­
rowed down by extracting the overlap.
Relevancy between feature points and cell’s SoH are verified by grey
relational analysis [46,47], in order to rationalize the algorithm that
using shift of FPs to estimate SoH of cells. The compare sequence Xi and
reference sequence Y, which in this case refer to the shift of each FP and
cell’s maximum capacity respectively, are noted as:
xi = {xi (k)|k = 1, 2, …, n}. (7)
y = {y(k)|k = 1, 2, …, n}. (8)
where i is the number of experimental datasets and k is the number of
parameters.
Thus, the correlation coefficient ξi(k) between xi(k) and y(k) can be
calculated by:
minmin|y(k) − xi (k)| + ρmaxmax|y(k) − xi (k)|
(9)
i k i k
ξi (k) = .
|y(k) − xi (k)| + ρmaxmax|y(k) − xi (k)|
i x
where ρ denotes the distinguish coefficient which satisfies ρ∈[0,1]. A
lower ρ value corresponds to a larger distinguished ability. The grey
relational grade ri, which reflects the level of comparative sequences’
relevancy, is therefore calculated by Eq. (10):
1∑ n
ri = ξ (k), ​ k = 1, 2, …n. (10)
n k=1 i
Based on this mathematical expression, the grey relational grade
between each FP and cell’s maximum capacity is calculated as presented
in Table 3. The result suggests that using FPs for correlation analysis is
X. Chen et al. Journal of Power Sources 498 (2021) 229884

Fig. 5. Schematic diagram of the position of three feature points on IC and DV curves and their corresponding SoC value.

Table 3
The grey relational grade between each feature point and cell’s
maximum capacity.
Factor Grey relational grade (%)
1# peak height 76.0
1# peak position – 3rd peak
2# peak height 82.2
2# peak position 80.9
3# peak height 90.8
3# peak position 85.7
statistically significant, which enables a high-confidence estimation for
SoH with tracking of position and intensity change of the FPs as cell
aging.
5.2.2. Establishment of multi-linear regression model for the cell SoH
estimation
In order to associate the cell SoH with the shift of three FPs in IC/
DVEMF curve, a multidimensional linear regressions model is established
based on least squares method (see Methods for details in the supporting
information). One sample cell that was subjected to complete cycle life
test was used to establish a correspondence between FPs and SoH,
dubbed as cell 1. The shift of peak position of the 3 FPs of cell 1 with
cycling number are separately calculated, as summarized in Fig. 7 (a).
Evidently, all three FPs can be identified in the case of cell 1, thus a full-
SoC-range functional relationship can be obtained, as shown by the red
solid line in Fig. 7 (b), (c) and (d). The other cell that underwent the
same duty cycle, dubbed as cell 2, is used for validation of the proposed
model. To further verify the robustness and generalization capability of
the model, 6 more cells, dubbed as cell 3 to cell 8, that with various
initial SoCs are taken to one of the correspondence obtained from cell 1,
limited by the specific applicable range.
To consider the impact of both position and height shift of FPs into
the proposed algorithm, the linear regression model is extended to 3-di­
mensions. Function parameters at each FP are determined, as summa­
rized in Table 4. The resulting distribution surfaces that cover entire SoH
evolution process during cell aging are obtained, as shown in Fig. 6.
Table 4
Algorithm parameters of the linear regression model at each F.
FPs c1 c2 m
1st valley 0.1259 133 0.3723
2nd peak 0.103 − 137.9 0.1186
0.8993 − 1.025 − 2.643
5.2.3. Validation with partial charging and parallel testing result
Fig. 7 (b), (c) and (d) display the results of verification experiments
for the multi-stage SoH estimation model. Cell 2 was subjected to full
life-cycle discharging process following the same duty cycle as cell 1,
whereas the other 6 cells underwent partial discharging within respec­
tive SoC intervals, noted as cell 3, 4 (discharging under the SoC interval
of [30%, 0]), and 5, 6, 7, 8 (discharging under the SoC interval of [100%,
30%]). In the above samples, the data of cell 3 and cell 4 can only be
applied to the numerical relationship derived by the first FP, while the
data of cell 5, 6, 7, 8 are suited to the relationship derived by both the
second and the third FPs. Evidently, cells that are used for practical
applications are hardly subjected to complete SoC cycles, therefore, it is
vital to verify the algorithm can even work well with daily segment
charging data of random SoC range. On the other hand, as for cells
cycling under a wider range, their SoH will be firstly estimated when the
SoC reaches a value corresponding to the first FP (SoC = 89%); as the
(dis)charging proceeds, the SoCs that corresponds to the second and/or
third FPs are reached, the cell’s SoH therefore can be re-assessed and
calibrated, if necessary.
Fig. 7 displays the results of linear regression model corresponding to
each specific SoC’s FPs and the findings of SoH evaluation. The model is
applied to construct the trend lines (red) from cell 1’s fitting algorithm
that are shown with 97% confidence bands (red dotted). The scattered
points represent the testing set of other cells. It is observed that the
deviation among the test sets and the fitted linear curve is within ± 1.5%
error range with respect to the full scale (corresponding to ± 7.5% if
taking 20% useable SoH as metrics), indicating a promising result of the
model. A robust signature exists between cell aging and the shift of FPs
on the de-polarization differential curve (IC and DVEMF).

9
X. Chen et al. Journal of Power Sources 498 (2021) 229884

Fig. 6. Three-dimensional linear regression surface of cell 1’s estimated SoH at three FPs under 0.5C charging- 0.5C discharging.

Fig. 7. (a) Shift of the normalized peak intensity of each feature point in IC/DVEMF curves as a function of cycle numbers of cell 1; (b)–(d) Correlation between cell
SoH and peak intensity of the first, second and third FP respectively. Solid lines in the diagram correspond to the fitting results of the specific FP from cell 1 and
dashed lines correspond to ± 1.5% error bounds.

5.3. Integration of aging mechanism with data-based SoH evaluation
model
Based on the two modeling methods discussed above, we not only
established an online SoH estimation algorithm, but also revealed the
aging mechanism by an electrochemical model. It should be noted that
the lower limit for the initial discharging SoC of tested cells must fall
upper 30%, as otherwise, the cells need to be charged in prior to be
suited to the algorithm. The block diagram of the proposed integrated
analysis process flow is presented in Fig. 8, which can be summarized in
the order of these steps as follows:
● Dataset generation: a testing protocol covering various charging
stresses is designed for studying cell aging regularity under different
(dis)charging rate, temperature and SoC/voltage intervals. Based on
the testing results, with a mathematical extrapolation algorithm,
EMF curves that correspond to different charging scenarios are
determined. Therefore, the polarization disturbance can be ruled out
from the dataset and the capacity loss obtained from EMF curve is
introduced solely by the thermodynamic origins LLI and LAM.
● EVS analysis: EMF curves are differentiated to obtain IC/DVEMF
curve respectively as a function of cycle number.
● Establishment of data-based model: If-else statements are firstly
implemented on the differential curves: if a cell’s current SoC is over
30%, its FP is supposed to be extracted at one of the three specific
SoC values during discharging process, and further taken into Eq.
(S1) to obtain the estimated capacity. The SoH distribution plane can
be re-adjusted and calibrated once the SoC of a cell falls at other
lower specific value as the cell discharging. Else, the cell is supposed
to be subjected to charging process to assure that the data falls in the
algorithm’s scope of application.
● Establishment of kinetic mechanism model: by adjusting single
simulation parameter in porous-electrode theory model framework,
the major DMs, including LLI, LAMPE and LAMNE are decoupled.
Nevertheless, each DM’s contribution on cell’s capacity fade is
individually determined by this model.
● Aging analysis: quantifying irreversible capacity loss and maximum
capacity retention with the cell cycle-life-test data.

10
X. Chen et al.
Fig. 8. The flowchart of the analysis process of the mechanism-numerical model.
6. Conclusion
In this work, the aging behaviors under various charging stresses of
NMC532/graphite battery system are comprehensively investigated
through an over-15-month life cycle test, including abuse and partial
charging scenarios. EVS technique is combined with a novel EMF-
extraction method, which makes IC/DV analysis no longer restricted
to low C-rate (dis)charging conditions for maintaining the quasi-
equilibrium state, instead, it can be applicable for any dynamic oper­
ating conditions. A vital degradation indicatorsΔQir is obtained from
EMF analysis, are defined for quantitatively evaluating cell degradation
performance under different operating conditions. Nevertheless, the FPs
in IC/DV curves are proved related to major thermodynamic DMs (LLI,
LAMNE and LAMPE) by an electrochemical model. The complex aging
mechanism is revealed based on comparison of tested dataset with the
electrochemical model, which can be summarized as the following
points:
(1) Battery degradation under room-temperature exhibits a linear
dependency on the charge throughput, while under elevated
temperature, a transition from linear to non-linear characteristic
is observed in the later aging stage. The earlier appearance of the
turning point with lower charging rate is a strong signal for LLI to
be the most dominant degradation mode.
11
Journal of Power Sources 498 (2021) 229884
(2) Li plating plays the main role in performance degradation under
room-temperature cycle-life aging, while LAM (structure break­
down) and LLI (Li plating) are both of primordial importance
under elevated temperature cycle-life aging. Advanced and
effective post-mortem techniques are highly desired to distin­
guish DMs from microscope insights.
(3) Cycling under high SoC interval has less adverse effect on the
lifespan of cells comparing to under a high voltage interval.
Cycling under bottom SoC interval or low voltage interval both
have rather small impacts on battery performance. High charging
currents has more significant influence on capacity degradation
than high discharging currents.
Furthermore, a numerical model for online estimating the cell SoH is
proposed, based on tracking the shift of three FPs corresponding to
different SoCs in EMF-derived IC/DVEMF curves. Grey relational analysis
is carried out to reveal a clear correspondence between the shift of FPs
and cell’s SoH at three specific SoCs. Accordingly, the model is estab­
lished with multiple linear regression algorithm, which is capable of
online estimating cell SoH within 3% absolute error bounds, demon­
strating considerable potential being applied on BMS.
CRediT authorship contribution statement
Xiaoxuan Chen: Conceptualization, Data curation, Software,
X. Chen et al. Journal of Power Sources 498 (2021) 229884

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R&D Program of China (grant no. 2018YFB0905400), Collaborative [28] K.A. Severson, P.M. Attia, N. Jin, N. Perkins, B. Jiang, Z. Yang, M.H. Chen,
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