Journal of Energy Chemistry 92 (2024) 738–758

Contents lists available at ScienceDirect

Journal of Energy Chemistry

journal homepage: www.elsevier.com/locate/jechem

Characterization and identification towards dynamic-based electrical

modeling of lithium-ion batteries
Chuanxin Fan a, Kailong Liu b, Yaxing Ren c, Qiao Peng d,⇑
a
School of Automation, Nanjing Institute of Technology, Nanjing 211167, Jiangsu, China
b
School of Control Science and Engineering, Shandong University, Jinan 250100, Shandong, China
c
School of Engineering, University of Lincoln, Lincoln LN6 7TS, UK
d
Information Technology, Analytics & Operations Group, Queen’s University Belfast, Belfast BT9 5EE, UK

a r t i c l e i n f o a b s t r a c t

Article history: Lithium-ion batteries are widely recognized as a crucial enabling technology for the advancement of elec-
Received 10 December 2023 tric vehicles and energy storage systems in the grid. The design of battery state estimation and control
Revised 5 January 2024 algorithms in battery management systems is usually based on battery models, which interpret crucial
Accepted 5 January 2024
battery dynamics through the utilization of mathematical functions. Therefore, the investigation of bat-
Available online 1 February 2024
tery dynamics with the purpose of battery system identification has garnered considerable attention in
the realm of battery research. Characterization methods in terms of linear and nonlinear response of
Keywords:
lithium-ion batteries have emerged as a prominent area of study in this field. This review has undertaken
Lithium-ion battery
Battery dynamics
an analysis and discussion of characterization methods, with a particular focus on the motivation of bat-
Nonlinear characterization tery system identification. Specifically, this work encompasses the incorporation of frequency domain
Nonlinear battery model nonlinear characterization methods and dynamics-based battery electrical models. The aim of this study
is to establish a connection between the characterization and identification of battery systems for
researchers and engineers specialized in the field of batteries, with the intention of promoting the
advancement of efficient battery technology for real-world applications.
Ó 2024 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by ELSEVIER B.V. and Science Press. All rights reserved.

Chuanxin Fan received the Ph.D. degree in engineering
from University of Warwick, United Kingdom, in 2022.
He is currently a lecturer in the School of Automation,
Nanjing Institute of Technology, China. His research
interests include system identification, advanced char-
acterization, states estimation and their applications in
energy storage such as lithium-ion batteries.
Kailong Liu received the Ph.D. degree in electrical
engineering from Queen’s University Belfast, United
Kingdom, in 2018. He is a full professor in the School of
Control Science and Engineering, Shandong University,
China. His research interests include modeling, opti-
mization and control with applications to electrical/
hybrid vehicles, energy storage, battery manufacture
and management.

⇑ Corresponding author.
E-mail addresses: Kailong.Liu@email.sdu.edu.cn, kliu02@qub.ac.uk (K. Liu), Qiao.Peng@qub.ac.uk (Q. Peng).

https://doi.org/10.1016/j.jechem.2024.01.040
2095-4956/Ó 2024 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.
C. Fan, K. Liu, Y. Ren et al.
Yaxing Ren received the Ph.D. degree in electrical
engineering and automation from the University of
Liverpool, United Kingdom, in 2017. He is currently a
lecturer with the School of Engineering, University of
Lincoln, United Kingdom. His current research interests
include control engineering, mechatronics, batteries,
electric vehicles, and renewable power generation.
1. Introduction
The transition from vehicles powered by fossil fuels to those
powered by electricity is a significant global revolution that will
impact society, commerce, and politics in the twenty-first century
[1]. The United Kingdom has recently unveiled its ambitious initia-
tive, called the ‘‘Future of mobility,” which aims to position the UK
as a frontrunner in the development and production of zero-
emission vehicles. As part of this mission, the UK has set a chal-
lenging objective for all new cars and vans to achieve effective zero
emission capabilities by 2040. In addition, as part of its extensive
array of new climate regulations known as ‘‘Fit-for-5500 package,
the EU Commission has released a proposal which will essentially
prohibit the sale of gasoline vehicles in the EU starting in 2035. In
2019, New Zealand became a part of the Electric Vehicles (EVs) Ini-
tiative with the goal of turning into a carbon-free economy by
2050. Additionally, China has announced its intention to reach
peak emissions by 2030 and achieve carbon neutrality by 2060,
which is a crucial measure in addressing climate change.
The lithium-ion battery (LIB) is widely regarded as the most
auspicious energy storage system for EVs in order to achieve this
objective, owing to its superior cycle performance, high energy
density, and high power density [2–4]. Currently, there has been
a significant amount of research interest in the development of
battery management technologies in order to maximize the effi-
ciency of lithium-ion batteries. Irrespective of the battery’s chem-
ical composition, EV applications require an efficient battery
management system (BMS) to guarantee the reliable functioning
of batteries through the prevention of physical harm, temperature
fluctuations control, mitigation of capacity loss, and prevention of
cell unbalancing [5–7]. BMS ensures the battery safety by regulat-
ing its operating conditions and provides accurate estimations of
state of charge (SOC) and state of health (SOH) for EV battery packs
[8–10]. Furthermore, the BMS has a crucial function in regulating
and updating data, identifying malfunctions, and attaining maxi-
mum battery efficiency [11]. Through the implementation of
sophisticated battery management technologies, the energy can
be efficiently and intelligently pulled from batteries, which can
result in an increased driving range, a significant extension of bat-
tery lifespan, and reduced maintenance costs.
Characterization tests encompass the comprehensive and sys-
tematic procedures used to investigate LIB dynamics and proper-
ties. The characterization tests have been utilized to analyze the
LIB performance and to determine the extent of battery degrada-
tion. These tests also help in identifying and quantifying the degra-
dation, which in turn helps to develop new electrode materials,
electrolytes, and cell designs. In addition to LIB properties and
dynamic responses determined through specific characterization
tests, researchers can accurately simulate the relationship between
current and voltage by developing dynamics-based mathematical
models and extracting key parameters [12]. Hence, it is crucial to
739
Journal of Energy Chemistry 92 (2024) 738–758
Qiao Peng received the Ph.D. degree in management
school from Queen’s University Belfast, United Kingdom,
in 2022. She is a lecturer in the Information Technology,
Analytics, and Operations Group, Queen’s University
Belfast, United Kingdom. Her research interests include
the applications of machine learning, data analysis,
modelling and prediction technologies in many fields
including battery management, and energy data
analysis.
devise effective characterization tests during the development of
battery models for BMS applications.
Mathematical models, which replicates the relationship
between LIB inputs and outputs, are identified based on battery
dynamics, which acts as the first foundation for the development
of sophisticated battery management technologies [13,14]. Accu-
rate battery models, which interprets battery dynamic processes,
can be implemented to guarantee secure and efficient LIB opera-
tions in real-time applications [15,16]. Furthermore, the utilization
of a comprehensive battery model can also aid in the prediction of
novel battery material performance in terms of their current-
voltage properties, characteristics, and aging. This, in turn, con-
tributes to the advancement of next-generation battery technol-
ogy. Thus, it is imperative to develop an advanced dynamics-
based battery model that precisely depicts the battery features in
order to improve EV applications and develop novel battery
technologies.
In this work, the focus is on establishing a bridge between the
characterization and identification of battery systems, in terms of
battery dynamics, for researchers and engineers in this field. This
comprehensive analysis focuses exclusively on the characteriza-
tion methods employed in conjunction with dynamic-based bat-
tery electrical models. Specifically, this work encompasses the
incorporation of recently developed nonlinear characterization
methods and nonlinear battery models. Researchers interested in
post-mortem tests can refer to the review by Lu et al. [17] and
for non-invasive tests by Barai et al. [18]. As for the review of
parameterization for physical-based battery models, readers can
refer to the study by Andersson et al. [19].
The paper’s main contents are structured as follows: Section 2
outlines the key dynamic processes that occur within a LIB and
their connection to the voltage losses that affect the observed volt-
age at the battery terminals. From a system identification (also
known as battery modeling) perspective, the dynamic response
of electrochemical processes can be categorized as either linear
or nonlinear dynamics based on their mathematical interpreta-
tions. The process of identifying the specific battery models
involves examining the specific characterization tests that provide
information about the dynamic response of terminal voltage. In
particular, Section 3 provides an overview of research areas where
nonlinear characterization tests are applied to study the dynamic
response. Section 4 reviews the predominant battery mathematical
models used in practical applications. These models are either
based on mathematical representations of fundamental electro-
chemical processes or on a phenomenological description of the
dynamic behaviors of lithium-ion batteries. Section 5 outlines the
primary conclusions of this study.
2. Key dynamic processes of lithium-ion batteries
The LIB is a complex electrochemical system that is difficult to
fully comprehend using mathematical functions. However, for
C. Fan, K. Liu, Y. Ren et al.
battery modeling, a highly accurate model can be achieved by
accurately interpreting the key dynamic processes. Irrespective of
the electrode materials employed, every electrochemical and phys-
ical activity occurring results in a distinct decrease in voltage,
which is contingent upon the excitation current [20]. From the per-
spective of modeling, the dynamic response can be classified as
nonlinear and linear dynamics, respectively. The common electro-
chemical and physical processes in lithium-ion batteries include
electrical potential, charge transfer reactions, diffusion processes,
and thermodynamics. These processes will be briefly discussed in
the following sections.
2.1. Linear dynamics
2.1.1. Electrical potentials
The LIB electrical potentials are determined by the voltage drop
across the resistance, which arises from the movement of electrons
in the electrodes and the transport of ions through the electrolyte
and membrane. The phenomena are dictated by the electronic con-
ductivity of the electrodes and current collectors (often made of
copper and aluminum) as well as the ionic conductivity of the elec-
trolyte and membrane [21]. The relationship is summarized by
Ohm’s Law for electromagnetics:
J ¼ rE
where E represents the electric field intensity in volts per meter
(V m1), J represents the volume current density, which is a vector
defining the flow of current in amperes per square meter (A m2),
and r represents the conductivity in inverse meters (r1m1).
The potentials in the physical model class are established
according to the boundary conditions of solid phase charge conser-
vation, which are delineated as follows:
rs;n es;n @/@xs;n jx¼0 ¼ rs;p es;p @/@xs;p jx¼L ¼ Aiapp
surf
rs;n es;n @/@xs;n jx¼Ln ¼ rs;p es;p @/@xs;p jx¼LLp ¼ 0
where @/
iapp
@x
is electric field intensity and Asurf
is current density. There-
fore, when the parameters are assumed to remain constant, the
electrical potential yields a linear dynamic.
2.1.2. Non-linear dynamics
Charge transfer reactions occurring at the electrodes, specifi-
cally oxidation and reduction, are non-linear Faradaic processes.
These processes are distinguished by a non-linear correlation
between the density of electric current and theover-potential. This
relationship is mathematically represented using the Butler-
Volmer equation as shown in Eq. (3).




i0;k aa F aF
j¼ exp g  exp  c g ; k 2 fn; pg
F RT RT
The variables in the equation are defined as follows: j repre-
sents the volume rate of lithium-ion generation, i0;k represents
the exchange current density, k represents the electrodes (with n
representing the anode and p representing the cathode), g repre-
sents the over-potential, aa represents the anodic transfer coeffi-
cient, ac represents the cathodic transfer coefficient, F is the
Faraday’s constant, R is the gas constant, and T is the temperature,
respectively.
Eq. (3) demonstrates the relationship between the current flow-
ing and the potential difference between the electrode and the bulk
electrolyte. This relationship applies to a basic, single-molecule
redox reaction where cathodic/anodic reactions take place on the
electrode. It is assumed that the concentration at the electrode is
almost identical to that in the bulk electrolyte, which enables the
current to be described solely in terms of potential. The exponen-
Journal of Energy Chemistry 92 (2024) 738–758
tial correlation between the volume rate of lithium-ion generation
and g in Eq. (3) is anticipated to lead to nonlinearity that con-
tributes to the voltage at the battery terminals.
2.1.3. Diffusion processes
Diffusion processes take place in both solid and electrolyte
phases of a LIB, resulting from disparities in Li-ion concentration.
The diffusion process of the solid phase in electrode particles can
be mathematically described by Fick’s second law in spherical
dimensions.


@cs;k Ds;k @ @cs;k
¼ 2 r2 ; k 2 fn; pg ð4Þ
@t r @r @r
Here Cs,k is the Li-ion concentration in particles, the diffusion
coefficient of lithium is Ds,k, time t and the spatial coordinate r.
The nonlinearity of Li-ion distribution in particles arises from its
relationship with nonlinearity through the Butler-Volmer reaction
in the boundary conditions.
 
@cs;k  @cs;k 
¼ 0; Ds;k ¼ jk ð5Þ
@r r¼0 @r r¼Rs
where jk represents the rate that lithium ions move away from the
surface of particles. At the center of the spherical particle (r = 0),
ð1Þ there exist zero flux, however, on the particle surface (r = Rs), the
flux equals to the rate that Li-ions are being consumed or produced
as a result of the electrochemical reaction taking place at the solid
electrolyte interface. Eq. (4) presupposes that the electrode consists
of isotropic, homogeneous, and uniformly sized spherical particles
[22]. The consistent depiction of electrode micro-structure leads
to a smooth and uniform process of Li- ion intercalation and de-
intercalation within the electrode. This approach is effective in ana-
lyzing discharge and charge behaviors, especially at low to moder-
ate rates [23]. LIB electrodes exhibit significant heterogeneity in
ð2Þ their architectures, as demonstrated by Shearing et al. [24]. Further-
more, the assumption of spherical results in the micro-structure of
the electrode being situated in a 1-dimensional domain character-
ized by spherical symmetry. The mathematical representation is
simplified to a level that makes it computationally feasible, while
still preserving enough of the underlying physics to properly fore-
cast the behavior of the batteries and record their internal states
[25].
Within the electrolyte, ionic transport is achieved through the
simultaneous occurrence of two dynamic processes. One phe-
nomenon takes place as a result of migration propelled by a local-
ized electric field, while the other phenomenon occurs due to ion
diffusion generated due to concentration gradients [26]. The
preservation of species in the electrolyte phase can be mathemat-
ically represented by Eq. (6). This Equation assumes that the elec-
ð3Þ trolyte consists of a binary salt dissolved in a single solvent.
However, it is possible to treat mixtures of multiple non-aqueous
liquids or polymers with different molecular weights as a single
solvent without compromising the accuracy of the analysis [22].


@ce;k @ @ce;k 3es;k ð1  tþ Þ
ee;k ¼ De ebe;k þ jk ð6Þ
@t @x @x Rk
where ce,k represents lithium ion concentration, es,k represents
active particles volume fraction, Li+ transference number is t +, Li-
ion diffusion coefficient in electrolyte is De, radius of active material
particles is Rk, net molar flux of lithium ions exiting the particle
kinetic is jk, Bruggeman porosity exponent b, electrolyte volume
fraction is ee,k, and time is t.
According to the findings presented in [27], the influence of the
ionic transport mechanism in the electrolyte on the LIB nonlinear-
ity is anticipated to be negligible. Therefore, when examining the
effect of diffusion processes on LIB nonlinearity, it can be
740
C. Fan, K. Liu, Y. Ren et al.
concluded that solid diffusion processes occurring in spherical par-
ticles are the dominant contributing factor [28].
2.1.4. Thermodynamic
Thermodynamics is a field of physics that deals with the funda-
mental principles governing the physical and chemical properties
of matter in a state of equilibrium [29]. In the LIB study, thermody-
namics are typically demonstrated by examining the electrode
open circuit potential (OCP) in relation to the stoichiometry. While
considering battery modeling, a commonly used option is to utilize
observed OCP vs. SOC curves, as depicted in Fig. 1(a). In the context
of the complete cell setup, the OCP is referred to the open circuit
voltage (OCV). The OCV, denoted as UOCV, is defined as the disparity
between the cathode potential Up and the anode potential Un when
the individual electrodes are in equilibrium state, such as when
there is no current flowing. The schematic illustrating three poten-
tial options is depicted in Fig. 1(b). It is important to understand
that the term ‘‘RE” refers to a reference electrode that is placed
within a LIB to directly measure the potentials of the negative
and positive electrodes. This allows for a precise assessment of dif-
ferent electrochemical features of the battery’s internal processes
[30].
The relationship between the potential of individual electrodes
and the full cell OCV is defined by Eq. (7).
U OCV ¼ U p  U n
The measurement of the electrode potential Uk are conducted
by employing a half cell configuration or a reference electrode
within a potentiostat [12]. The electrode potential encompasses
the data of electrode thermodynamic, including the quantity of
phase transitions that occur in the electrode during charging and
discharging (most battery electrodes experience multiple phase
transformations), as well as the Li-ion quantity intercalated in each
phase [32]. The chemical potential can be employed to mathemat-
ically quantify the electrode potential during a phase transforma-
tion. The potential measures the variance in internal energy
resulting from the ionic fluctuation. The Nernst equation as defined
by Eq. (8), is frequently employed to establish the connection
between the equilibrium electrode potential Uk and the species
concentration involved in the electrode process depicted in Eq. (9):
RT C O
U k ¼ U 0k þ ln ; k 2 fn; pg
nF CR
O þ ne R ð9Þ
Fig. 1. The diagram of battery thermodynamic: (a) Measured OCP vs. SOC curves of full cell, cathode, and anode potential [31]. (b) The schematic illustrating the relationship
among the three potentials of a LIB.
Journal of Energy Chemistry 92 (2024) 738–758
The given information includes the equilibrium potential U 0k ,
the number of electrons exchanged in the redox reaction n(where
n = 1 for Li-ion systems), the concentration of the oxidant Co, and
the concentration of the reductant CR [33]. The value of U 0k in inter-
calation reactions represents the energy of ions that are inserted
into particular positions within the host material lattice [34].
2.2. Summary
The key dynamic processes of LIBs have been briefly described
in relation to both linear and nonlinear dynamics. It should be
noted that the dynamic processes of batteries are inherently com-
plex and interconnected, making it difficult to provide a compre-
hensive description and individual modeling of all battery
processes. This review focuses solely on the primary dynamics
associated to the battery voltage response, which are related to
battery system identification. In order to investigate the dynamic
processes and collect essential data for identifying battery models,
existing characterization tests are reviewed in terms of time
domain and frequency domain characterization tests, respectively.
3. Characterization tests of lithium-ion batteries
Battery characterization tests can be categorized into invasive
ð7Þ [17] and non-invasive [18] tests. Typically, invasive tests are con-
ducted on disassembled cells to analyze physical and chemical
properties of the materials. The X-ray diffraction (XRD) is a tech-
nique that is applied to ascertain the elemental composition, crys-
tal structure, and theoretical density of materials, based on their
chemical and material properties. Consequently, invasive testing
allows for the LIB examination and the establishment of electro-
chemical models, as elaborated in [12]. Nevertheless, these tests
are detrimental since they hinder the possibility of conducting
repeated characterization tests on the same LIB, hence impeding
the ability to monitor the changes in LIB features over time. More-
over, battery engineers lacking the necessary training in handling
dangerous substances face difficulties in carrying out the intricate
procedures involved in cell deconstruction. Hence, the utilization
of intrusive characterization falls outside the purview of this work.
Unlike invasive testing, non-invasive tests are designed using
ð8Þ the battery’s electrical input–output relationship, which allow for
the non-destructive measurement of LIB properties. This accessi-
bility is beneficial for both industrial and academical researchers.
By performing non-invasive tests, it is possible to compare the per-
formance of LIBs and monitor how their performance changes over
741
C. Fan, K. Liu, Y. Ren et al.
their lifespan. This allows for the measurement of the deterioration
of LIBs, such as energy capacity fade and impedance rise [35]. In
addition, when it comes to battery modeling, the non-invasive
tests can be used to analyze the linear and nonlinear dynamic pro-
cesses of lithium-ion batteries.
This section reviews the characterization tests, which are sepa-
rated into time domain tests and frequency domain tests based on
the specific analysis approach. In addition, the applications on bat-
tery modeling are in-depth introduced to provide the connection
between battery dynamic processes and system identification.
3.1. Time domain characterization tests
The voltage/current load signals and battery current/voltage
response are documented as digital dataset in the time domain
by employing specialized experimental apparatuses. These data
points can be subjected to direct analysis in the time domain. Since
no supplementary techniques, such as Fourier transforms, are nec-
essary, the time domain tests are simple to conduct and integrate
into practical applications. In the battery modeling, the capacity is
intricately linked to battery SOC, which influences the values of
parameters in the battery models. Additionally, the OCV curve
serves as the foundation of the battery models, dictating about
90% voltage loss. This section provides an overview of time domain
characterization tests used for battery modeling. These tests
include constant current tests, which are used to determine battery
cell capacity, and OCV tests, which establish the link between OCV
and SOC based on thermodynamics.
3.1.1. Constant current capacity test
Capacity refers to the quantification of the overall electric
charge that can be stored in a battery. The quantification of this
measurement relies on the quantity of active material present in
the electrodes during the intercalation process [36]. The cell capac-
ity, which is determined by the lithium inventory and/or active
material, serves as a reliable indicator for assessing battery health.
A commonly employed method to measure the capacity of a LIB
is to charge the cell until it reaches its maximum capacity and then
discharge it until it reaches the minimum voltage limit, as depicted
in Fig. 2. The constant-current constant-voltage (CC-CV) approach
is frequently used as a practical test to charge battery cells. The
procedure involves applying a consistent flow of electric current
to the cell until the voltage reaches to the upper cut-off voltage.
Fig. 2. An example of the CC-CV charging and CC discharging pattern is provided,
employing a charge rate of 0.3 C and a discharge rate of 1 C. It is important to be
aware that the battery cell used in this test has a discharge rate of 11.5 mA per hour
(1 C-rate).
742
Journal of Energy Chemistry 92 (2024) 738–758
It is followed by a constant voltage charge until a low current
approaches the cut-off [37]. The discharge step employs a constant
current (CC) profile to generate discharge curves. The capacity
value of the battery cell is obtained by integrating the current in
ampere-hours (Ah) over time using Coulomb counting. The utiliza-
tion of this measurement technique has various benefits, including
the ease of interpreting the outcomes, the ability to repeat the pro-
cess, and the high level of precision in measuring current (particu-
larly in scenarios with constant power profiles) [18].
The battery capacity is determined by the charge–discharge
current rates and temperature during operation. As stated in Sec-
tion 2, the Butler-Volmer framework governs the reaction in the
electrodes. When a high C-rate current is fed to a LIB, the overpo-
tential increases. In conjunction with an increase in the battery
internal resistance, the equilibrium potential decreases as the
SOC falls. At a low SOC level, there is a slow increase in overpoten-
tial, resulting in the cell’s voltage reaching the low cut-off thresh-
old before all its capacity is exhausted. Therefore, the available
storage capacity of a cell decreases when a high C-rate of current
is applied [38]. This effect is commonly observed when various
constant current profiles are employed for LIB discharging. Fur-
thermore, the rate at which lithium ions intercalate is dependent
upon the temperature. Higher temperatures lead to increased ion
mobility and solid phase diffusion, resulting in reduced internal
resistance and overpotential. Consequently, a LIB can provide
greater capacity prior to reaching the lower voltage threshold,
while the converse holds true for colder temperatures. Given that
cell capacity relies upon testing conditions, it is imperative to
maintain consistent test parameters over the duration of the
testing.
Regarding battery modeling, the CC tests are frequently
employed to estimate parameters by fitting discharge curve for
the electrochemical models [39]. Although the presence of numer-
ous unknown parameters in electrochemical models may make
uncertainties about the capacity to uniquely determine model
parameters, CC tests can effectively achieve a relative error of less
than 2% while validating the parameterized model under driving
cycles [40]. However, this method is rarely used to parameterize
battery models that utilize electrical components, such as resistors
and capacitors, to create a circuit network that accurately repre-
sents the behavior of a battery. When modeling batteries, the
behavior of these elements is affected by the duration of the mea-
surements and is only appropriate for simulating dynamics with
short time constants. Nevertheless, the customary duration for
CC capacity tests is approximately 3600 s (for a 1 C load scenario),
which proves to be excessive for the resistor and capacitor combi-
nations found in battery mathematical models. The authors sug-
gest that the CC tests can be used to parameterize mathematical
models that related to appropriate dynamic representations with
large time constants, which allows the expansion of battery models
for practical applications.
3.1.2. Open circuit voltage tests
The OCV is a vital factor for battery models, which represents
the battery’s thermodynamic equilibrium potential when it is dis-
connected to a current load. Typically, it is represented as a func-
tion of battery SOC. It serves as a theoretical voltage source that
is both ideal and adjustable in the model, to which over-
potential is introduced. As mentioned in Section 2, the OCV versus
SOC curve of a LIB is determined by the OCP of both positive and
negative electrodes. When it comes to battery modeling, the
electrode OCP curves are incorporated into both electrodes of
electrochemical models. Additionally, the battery OCV curve is
included in battery mathematical models to account for thermody-
namics at the full-cell level. The OCV hysteresis is a unique feature
of a LIB that is attributed to the route dependency of OCV. From a
C. Fan, K. Liu, Y. Ren et al.
thermodynamics standpoint, the causes of OCV hysteresis can be
described: the main cause of hysteresis is the multi-particle effect,
as described in [41], which is characterized by the non– monotonic
potential of individual particles. The active electrode material
undergoes a two-phase transition due to mechanical stress and
microscopic deformation during Li-ion insertion/extraction pro-
cesses. Furthermore, the Shrink- core model demonstrates that
the arrangement of phases at each SOC is influenced by the battery
material’s charging and discharging history [42]. The OCV hystere-
sis causes the cell’s OCV to vary between charge and discharge,
even when the SOC levels are same. The significance of hysteresis
in ensuring the accuracy of SOC estimation has been demonstrated
in [43]. The literature reported the highest hysteresis value in an
LFP cell (38 mV), whereas the lowest value was observed in the
LTO cell (16 mV) [44].
The galvanostatic intermittent titration technique (GITT) and
the pseudo-OCV (pOCV) test in the time domain are the most used
method to measure OCV curves. The OCV hysteresis level, which is
observed in OCV curves, can also be assessed by OCV tests. The
subsequent discussion provides an overview of the tests used to
measure OCV and the accompanying hysteresis.
Popularized in the late 1970 s, the GITT is a technique that can
provide information on the kinetics and thermodynamics of an
electrochemical system under investigation [45–47]. GITT applies
a transient current to modify the battery SOC, followed by an
extended period of relaxation while no current passes through
the battery cell. The relaxation period is a set interval of time until
a state of equilibrium is reached, indicated by the condition when
the rate of change of energy (dE/dt) approaches zero [12]. This
method is repeated until the terminal voltage has been achieved
to a desired level. The voltages measured at the end of the relax-
ation periods are selected and graphed to determine the OCV of
the LIB, referred to as GITT-OCV in this context. The duration and
intensity of the discharge/charge phase, as well as the duration
of the relaxation period, are governed by the temperature and
the desired level of precision [18]. Barai et al. suggested that the
best balance between accuracy and testing duration is achieved
by measuring OCV for 1% increase in terms of SOC level, with a
relaxation time of 4 h [44]. This study proposes that a duration
of 4 h is adequate for a LIB to attain a pseudo-equilibrium state.
Beyond this level, any additional changes in voltage, generally
below 1 mV, cannot be accurately measured by employing stan-
dard cell characterization equipment.
The use of GITT has been extensively employed in battery mod-
eling, ranging from the extraction of parameters for battery math-
ematical models to the direct utilization of OCV data in state
estimations. Birkl et al. devised an OCV estimate model that incor-
porates temperature dependency and voltage hysteresis. This
model is intended to be integrated into a complete cell model
within a BMS. The model is calibrated using OCV obtained from
an NMC battery under different temperature settings, resulting
that the error is less than 5 mV [34]. Nevertheless, the short inter-
vals of relaxation period (about one hour) are concise and might
potentially lead to a greater margin of error in the model. It is
worth noting that the literature suggests a one-hour relaxation
period is deemed appropriate for LFP batteries [48]. However, it
may be improbable that the duration will be sufficient for other
battery chemistry to attain electrochemical equilibrium
[49,44,50]. Mao et al. conducted an enhanced GITT test, utilizing
different pulse current loads and relaxation time, to quantify the
OCV for the advancement of the electrochemical model. The find-
ings indicate that the model is universally applicable and particu-
larly accurate when dealing with scenarios with a lower discharge
rate of current pulses and an extended relaxation period [51]. The
GITT was performed by Delacourt et al. to verify the accuracy of
battery models and investigate diffusion coefficients of a LiyFe-
743
Journal of Energy Chemistry 92 (2024) 738–758
SO4F electrode [52]. In addition, GITT is utilized to estimate the
transport and diffusion related parameters of Li + ions. This data
is then used to assist in the modeling of a positive electrode made
of a layer transition metal-oxide [53]. Chen et al. utilized GITT to
get OCV curves in order to parameterize multi-scale battery mod-
els [12]. The electrochemical dynamics of lithium ions are modeled
using GITT [54]. GITT is acknowledged as a potent methodology in
the scientific world, capable of offering crucial insights to greatly
enhance model performance. An inherent limitation of this
approach is the potentially protracted duration required for test-
ing, which may extend up to a fortnight (specifically, 17 days for
a GITT test as reported in [44]). Therefore, further investigation is
necessary to decrease the time of the GITT test.
Since a GITT experiment takes several weeks to complete, a
pseudo-OCV (pOCV) is created by performing low rate galvanos-
tatic cycling, which is a shorter testing period. In low-rate cycling
testing, it is common to use a C/25 or lower constant charge/dis-
charge rate. This can limit the impact of kinetic factors, decrease
electrode polarization, and reduce the formation of ohmic heat.
During low-rate cycle testing, the contribution of ohmic loss to
battery terminal voltage is minimal [55], and no generation of
ohmic heat is assumed. In addition, a unified voltage profile may
be created by calculating the average of the voltage profiles for
both charging and discharging at a low rate [56]. The OCV refers
to the voltage measured without any loads. Therefore, the aver-
aged voltage profile derived from low-rate cycling should be accu-
rately referred to as pseudo-OCV. Fig. 3 displays the LFP cell pOCV
(red curve) at a temperature of 20 °C.
The pOCV has been extensively utilized for battery modeling
due to its simplicity and straightforward implementa- tion of
low-rate cycling experiments [56]. Xing et al. derived pOCV pro-
files by calculating the averaged C/20 charging and discharging
voltage curves at various temperatures. They then formulated a
SOC prediction method based on this pOCV, which demonstrates
exceptional accuracy in relation to temperature [57]. Less et al.
empirically ascertained the OCV by subjecting the cell to a charging
and discharging process at a C/50 C-rate in order to parameterize a
micro-scale model [58]. Barai et al. proposed that the pOCV
appears to an optimal trade-off in terms of time and accuracy, as
stated in their study [18]. Nevertheless, Chen et al. contended that
the OCV derived by GITT and pOCV exhibit noticeable differences
[12]. When using a slow galvanostatic cycle to record pOCV, the
polarization resulting from the resistance of the cell will be notice-
able, even at low current rates. Furthermore, pOCV tests demon-
Fig. 3. The LFP cell pOCV (average OCV) at 20 °C, which presents a flat pOCV curve
from 25% to 80% SOC in the small plot [57].
C. Fan, K. Liu, Y. Ren et al.
strate the phase transition voltage instead of the pure thermody-
namic. This means that the OCV hysteresis is intertwined with
the battery overpotential, resulting in a greater hysteresis voltage
compared to the GITT tests [59]. Thus, in [12], the authors
acknowledged the significance of the GITT test in generating pre-
cise OCV curves, which serve as a valuable tool for investigating
the thermodynamics of cells.
By far, the analysis has examined the utilization of time domain
characterization tests to get capacity and OCV data for the purpose
of identifying battery systems. The subsequent section presents the
frequency domain approach used to examine the LIB impedance
and the nonlinear dynamics of charge transfer.
3.2. Frequency domain characterization tests
Recently, frequency domain characterization tests have also
been developed as the increase of LIB applications. In contrast to
the tests conducted in the time domain, the voltage data obtained
from the LIB measurements and the designed excitation current
data are converted into the frequency domain for subsequent anal-
ysis. Due to inherent distinctness of the characteristic frequency
range of each electrochemical dynamic, it is possible to gain fur-
ther understanding of the LIBs dynamics that cannot be accessed
in the time domain. Furthermore, researchers have expanded their
focus from linear dynamics to non-linear dynamics in order to gain
a thorough knowledge and in-depth analysis of lithium-ion
batteries.
3.2.1. Electrochemical impedance spectroscopy
The electrochemical impedance spectroscopy (EIS) is a widely
used method in the frequency domain to study the underlying
electrochemical dynamics of a LIB. The working principle of EIS is
depicted in Fig. 4. The detailed guidance and theoretical framework
can be referred to [60]. The EIS technique allows for the analysis of
the battery’s linear response throughout a broad frequency spec-
trum ranging from mHz to MHz. The battery system is subjected
to a sinusoidal signal, which is an alternating current (AC), gener-
ated using galvanostatic equipment. The response is then evalu-
ated by monitoring the alternating voltage (galvanostatic
measurement). Alternatively, the system can be stimulated with
a sinusoidal voltage and the resulting sinusoidal current can be
measured (potentiostatic measurement).
Under optimal circumstances, both situations should yield
equal outcomes. By employing a fast Fourier transformation
(FFT), the excitation signal and response data undergo a transfor-
mation from the time domain to the frequency domain. Before con-
ducting additional analysis, it is necessary to evaluate the EIS
Fig. 4. Working principle of electrochemical impedance spectroscopy [28].
744
Journal of Energy Chemistry 92 (2024) 738–758
result’s quality. Referring to [61], the validity of the conclusions
of EIS is contingent upon the fulfillment of the constraints of stabil-
ity, causality, linearity, and time-invariance. The Kramers-Kronig
relation is used to assess the EIS quality. Nevertheless, as depicted
in Fig. 5, the LIB, functioning as an electrochemical system, exhibits
a quasi-linear correlation between current and voltage under cer-
tain circumstances, such as when operating at a stable state with
a low-intensity input current. Therefore, when conducting gal-
vanostatic measurements, a modest amplitude excitation current
IAC of roughly C/20 is employed to ensure accurate EIS tests [62].
Within a linear or pseudo-linear system, when a sinusoidal cur-
rent is applied, the resulting voltage response is also sinusoidal,
with the same frequency (x). However, the amplitude of the volt-
age is scaled and there is a phase shift (u), as shown in Fig. 4. The
sinusoidal excitation current with a small amplitude can be
obtained in the frequency domain as follows:
IAC ðxÞ ¼ I0 ðxÞ expðju1 ðxÞÞ ð10Þ
where I0 is the current amplitude. The angular frequency x is
defined as
x ¼ 2pf ð11Þ
The expression for the sinusoidal voltage response (x) of the
system, with a phase shift of U, at an angular frequency of x, is
VðxÞ ¼ V 0 ðxÞ  expðj  u2 ðxÞÞ ð12Þ
u2 ¼ u1 þ U ð13Þ
The complex impedance Z(x) of a LIB is determined according
on the definition of impedance, which is analogous to Ohm’s law.
VðxÞ V 0 ðxÞ  expðj  u2 ðxÞÞ
ZðxÞ ¼ ¼ ¼ jZ 0 j  expðj  UðxÞÞ
IAC ðxÞ I0 ðxÞ  expðj  u1 ðxÞÞ
¼ jZ 0 jðcos U þ j  sin UÞ ð14Þ
The impedance of a LIB can be represented graphically using a
Nyquist plot, which consists of the real part Rm(Z(x)) and the
imaginary part Im(Z(x)), as expressed in the following Equation
RefZðxÞg ¼ jZ 0 j  cos U ð15Þ
ImfZðxÞg ¼ jZ 0 j  sin U ð16Þ
The standard Nyquist plot in Fig. 6 represents the impedance of
a LIB across a wide range of frequencies. The LIB dynamic processes
can be divided and associated with specific frequency ranges that
Fig. 5. Example of the current–voltage relationship in a pseudo-linear LIB.
Reproduced with permission from Ref. [63]. Copyright 2015, The Royal Society of
Chemistry.
C. Fan, K. Liu, Y. Ren et al. Journal of Energy Chemistry 92 (2024) 738–758

battery must be studied assuming linearity. However, nonlinear

battery dynamics, specifically the charge-transfer reactions at the
electrodes described by Butler-Volmer kinetics, cannot be ade-
quately stimulated when a small amplitude sinusoidal excitation
current is applied, as discussed in Section 2. Consequently, the cru-
cial data regarding battery nonlinearity is not accessible and is typ-
ically disregarded when it comes to characterization and modeling.
In order to address this deficiency, nonlinear characterization
methods have been devised on lithium-ion batteries in recent
times. The forthcoming section will provide an explanation of the
nonlinear characterization tests.
Fig. 6. A standard Nyquist plot illustrating the impedance spectrum of an LIB. The
LIB dynamic behavior is defined by several characteristic points [64].
3.2.2. Total harmonic distortion analysis
In order to further investigate LIB dynamics, an extension to EIS
involves subjecting the battery to moderate or high amplitude cur-
possess distinct characteristics [65]. The impedance spectrum in
rent signal. This causes the LIB to exhibit a weak or strong nonlin-
Fig. 6 displays several commonly utilized reference points for char-
ear relationship between current and voltage, which can be
acterizing a LIB. The point at which Im(Z(x) = 0 represents the
represented as a nonlinear transfer function. Fig. 7 demonstrates
intersection between capacitive and inductive behavior, and only
the response of a generic nonlinear transfer function to a sinusoidal
a nearly pure ohmic resistance is detected at this point. Above this
signal. Due to the nonlinear transfer function, applying a symmet-
frequency threshold, the battery’s inductive reactance resulting
rical excitation signal with equal amplitudes on both sides results
from current collectors and cable connections can be detected
in an output response in the time domain that exhibits different
[66]. Two partial circle plots, which are interpreted as double layer
amplitudes for positive and negative values. However, the funda-
and charge transfer process of electrodes, can be observed in high
mental frequency of the excitation signal remains unchanged.
frequency and mid- high frequency range. These processes often
The output response to a single-frequency sinusoidal excitation
exhibit as a combination of capacitive and resistive behavior. The
current generates higher harmonics of the fundamental frequency
range termed as low frequency range corresponds to diffusion pro-
in the output Fourier spectrum. Typically, any signal that repeats
cesses occurring in the electrode active material. Thus, main LIB
over time may be expressed as a combination of several sinusoidal
dynamics can be distinguished by employing the EIS test. Noted
oscillations with frequencies that are multiples of the original fre-
that, due to the dependence on two electrode measurements for
quency. These additional oscillations, known as ‘‘harmonics,” can
EIS of LIBs, abnormal impedance spectra may be observed. For
be identified via Fourier transformation [71].
example, if the time constants of the interfacial electrochemical
Prior to the emergence of the nonlinear analysis concept in LIB
processes at the two electrodes are similar, the Nyquist plot will
area, harmonics in the voltage response were regarded as inciden-
show merged mid frequency arcs [67]. This merging makes it chal-
tal outcomes that resulted in inaccuracies in impedance measure-
lenging to differentiate between the processes. The mid frequency
ment and even rendered the EIS results invalid [72,73].
semi-circle appears from the combined charge transfer resistances
Nevertheless, researchers have observed in recent years that har-
of the two electrodes and the resistance caused by ion movement
monics can offer valuable information about the internal state of
through the SEI layers at the cathode and anode. The literature
a system, provided that an appropriate framework for interpreta-
reports that the diameter of the semicircle increases as the poten-
tion is employed [74].
tial increases during charging and decreases as the potential
Initial research focused on analyzing the nonlinearity of electro-
decreases during discharging [68]. Furthermore, the distinct
chemical systems by examining variance in impedance response
Nyquist behaviors can be noticed while the anode material and
with increasing amplitude of perturbation signal [75]. The specific
the SOC of LIB are different [69].
subjects are the measurement of corrosion current and charge-
In terms of battery modeling, the typical approach with EIS is to
transfer coefficients by assessing the alteration of the impedance
develop fractional order models and determine model parameters
spectrum’s fundamental frequency [76,77]. In recent times, the
by fitting the Nyquist plot [70], which will be introduced in Sec-
analysis of total harmonic distortion (THD), a technique typically
tion 4. While EIS has been extensively used in the battery field, it
employed in acoustics research to identify noise [78], has been
is important to note that successful EIS requires certain require-
applied to characterize electrochemical systems like fuel cells
ments to be met, such as linearity of the system. This means that
[79]. Fig. 8 illustrates the voltage response of a fuel cell to a sinu-
the analysis is limited to the linear frequency response, while the
soidal input current. The THD of fuel cell systems is the ratio of

Fig. 7. The source of harmonic oscillations in a nonlinear transfer function when subjected to a sinusoidal signal [72].

745
C. Fan, K. Liu, Y. Ren et al. Journal of Energy Chemistry 92 (2024) 738–758

Fig. 8. The schematic diagram illustrates the THD voltage response of a direct methanol fuel cell, represented in both time domain and frequency domain [80].

the combined amplitude of voltage responses at all higher har-

monic frequencies (k  2) to that of the fundamental frequency
(k = 1).
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P1
jY k j2
k¼2
THD ¼ ð17Þ
Y1
The identification of distinct electrochemical processes can be
achieved by analyzing the THD variation across the frequency
range. Mao et al. found that the THD outperforms the EIS in accu-
rately determining the kinetics of methanol oxidation in direct
methanol fuel cells [81,80]. The THD was utilized to investigate
the oxygen reduction reaction processes in proton exchange mem-
brane fuel cells and determine which one closely resembles reality
[79]. However, throughout that period, the examination of nonlin-
ear response by THD was restricted inside the field of fuel cells.
Currently, three novel methods for characterizing LIBs nonlin-
Fig. 9. Working principle of nonlinear frequency response analysis [28].
ear dynamic response are proposed based on the selection of per-
turbation signal amplitude. These methods include nonlinear
electrochemical impedance spectroscopy (NLEIS) which uses a teries. Furthermore, the NFRA technique is utilized on both newly
moderate-amplitude sinusoidal current, nonlinear frequency formed and deteriorated cells to examine the harmonic spectra.
response analysis (NFRA) which uses a large-amplitude sinusoidal This analysis is conducted to identify lithium plating and estimate
current, and a multisine-based method which involves superim- SOH of the cells [85–87]. In order to validate the experimental find-
posing a broadband sinusoidal current. ings, the NFRA technique was employed using both the P2D model
and the SPM model [27,88]. Wolff et al. conducted a model-based
3.2.3. Nonlinear electrochemical impedance spectroscopy analysis to investigate the origin of higher harmonics and the influ-
Murbach et al. introduced an analytical–numerical method ence of parameter fluctuations on nonlinearities. The findings
using the P2D model to assess the impedance spectra of EIS and show that the nonlineary caused by charge transfer reactions and
NLEIS [82]. The NLEIS results obtained from commercial LIBs indi- solid diffusion processes overlap in specific frequency ranges [89].
cate that the NLEIS spectra’s second harmonics are responsive to Both NLEIS and NFRA exhibit encouraging efficacy in delivering
degradation in charge transfer symmetry, while the conventional thorough examination of nonlinear processes and can be regarded
EIS primarily detects alterations in charge transfer rates [83]. An as significant supplementary techniques for dynamic analysis of
open-source software platform called Impedance Analyzer was LIBs in terms of state estimation and health determination. Never-
built in Murbach’s study to include physics-based analysis into theless, while these nonlinear characterization methods have pro-
NLEIS analysis. ven the efficacy in estimating parameters and identifying aging
mechanisms, there is a lack of data in current literature about their
3.2.4. Nonlinear frequency response analysis use in battery modeling. Furthermore, doing a comprehensive
NFRA, which involves applying large-amplitude perturbations, assessment of the nonlinear response across the entire range of fre-
has been used to characterize higher harmonics in lithium-ion bat- quencies necessitates an exceedingly long experimental duration,
teries. Fig. 9 depicts the operational concept of NFRA. Like NLEIS, lasting up to several hours. Consequently, these techniques are
NFRA examines higher harmonics, such as Y2, Y 3, . . ., Y n, to assess confined to laboratory environment.
a battery’s properties and study nonlinear phenomena. Harting
et al. utilized NFRA on LIBs and established a correlation between 3.2.5. Multisine-based nonlinear characterization tests
nonlinear frequency response and EIS impedance spectrum, and a In terms of signal design, the nonlinear characterization meth-
systematic depiction of the LIB dynamics is acquired [84]. The pur- ods aforementioned involve the use of a successive single sweep
pose was to examine the impact of nonlinear processes on the bat- sinusoidal signal that covers a wide range of frequencies. However,
746
C. Fan, K. Liu, Y. Ren et al.
this approach results in time- consuming testing for low frequency
trials. In the recent time, researchers have conducted initial inves-
tigations to capture the linear and nonlinear dynamics of batteries
using different multisine excitation signals. These studies draw
inspiration from the theory of frequency domain system identifica-
tion. The use of such signals has the potential to greatly reduce
testing time and enable on-board BMS applications.
In order to carry out the nonlinear characterization approach
using multisine, the initial stage involves designing the multisine
excitation signal. The multisine signal is a periodic broadband signal
and created by overlaying sinusoids, allowing for flexibility in
designing its harmonic content and spectrum amplitude [90]. An
equation representing a general multisine signal is given by Eq. (18).
X
K
uðnÞ ¼ Ak sin ð2pnkf s =N þ uk Þ n ¼ 0; :::; N  1 ð18Þ
k¼1
The variables in the equation are defined as follows: N repre-
sents the number of samples taken per period, K represents the
highest harmonic number of the signal, fs represents the sampling
frequency, k represents the amplitude of th k th harmonic, and uk
represents the phase of the k th harmonic. The value of N for a mul-
tisine can be adjusted to provide flexibility, and the frequency res-
olution is defined as f0 = fs / N Hz.
Referring to Shannon theorem, the maximum value for the har-
monic K must be less than or equal to N /2. Therefore, the maxi-
mum frequency is achieved by multiplying f0 by K, and it should
cover the whole frequency range of the battery characterization.
In order to achieve a stable and balanced condition for the duration
of the characterization process, the direct current frequency,
namely the n = 0 harmonic, is eliminated to obtain a current signal
with an average value of zero. Fig. 10 illustrates an instance of a
multisine signal that has eliminated both odd and even harmonics
in both the time domain and frequency domain.
The working principle of the multisine-based technique is illus-
trated in Fig. 11. When the multisine test is performed on a nonlin-
ear system, such as a LIB, the energy introduced at the excited
harmonics is transmitted and detected at various harmonic loca-
tions in the output spectrum. This observation is an indicator of
the nonlinearity of the system [91]. In the signal design technique,
it is crucial to determine the harmonic content fk, amplitude spec-
trum Ak, and harmonic phases uk in order to accurately character-
ize the battery nonlinearity. The signal harmonic content fk can be
selectively chosen within the considered bandwidth to achieve
certain objectives, resulting in both stimulated and suppressed
harmonics. The collection of stimulated harmonics is represented
as Hexc, while the collections of inhibited harmonics are marked
as Hsupp,odd and Hsupp,even in relation to the odd and even harmon-
ics, respectively. The rationale behind the suppression of harmon-
Fig. 10. An example of the multisine signal design, which is designed in frequency domain and then converted into time domain for experiments by the inverse DFT method.
747
Journal of Energy Chemistry 92 (2024) 738–758
ics is to utilize the obscured odd and even harmonics for the
identification of odd and even order nonlinearities, respectively.
These nonlinearities are represented by the green and red squares
shown in Fig. 11.
In theory, the amplitude Ak can be freely chosen to induce a sys-
tem to transition into a nonlinear state. Different amplitudes result
in varying degrees of system nonlinearity [92]. However, in order
to keep simplicity of signal design step, a flat spectrum is com-
monly used in the signal design. This means that the amplitude
of all the stimulated harmonics is set to the same value. Subse-
quently, the root-mean square magnitude of the devised multisine
signal can be adjusted in the time domain to a particular
amplitude.
To achieve various amplitude distributions, the phases of the
excited harmonics uk can be adjusted flexibly [93,94]. In order to
meet the technical limitations set by the rig thresholds and address
safety considerations, it is important to minimize large peaks in the
designed signal. This can be achieved by optimizing the multisine
signal and reducing a phase-related measure called the crest factor
[95].
The battery voltage response to a time-domain multisine cur-
rent signal is recorded for analysis under predetermined condi-
tions, including temperature and SOC. The input current i[p](t)
and output voltage v[p](t) values are subsequently recorded in the
time domain as follows:
½p
i ðnÞ; t½p ðnÞ p ¼ 1; 2; :::; P n ¼ 0; :::; N  1 ð19Þ
The variable p represents the specific period of the input signal i
(n) and the output voltage response v(n). The P represents the
number of periods under each condition. The discrete fourier trans-
form (DFT) allows for the transformation of time domain data into
the frequency domain, resulting in input and output spectra.
X
N1 X
N1
I½p ðkÞ ¼ i ðnÞe2jpkn=N ; V ½p ðkÞ ¼
½p
v fpg ðnÞe2jpkn=N ; k ¼ 0; :::; N  1
n¼0 n¼0
ð20Þ
where I (k), V (k) in Eq. (20) denote the spectrum of i (n), v (n)
[p] [p] [p] [p]
at the k th harmonic. The voltage output data in the frequency
domain can be decomposed into distinct sets of harmonics:
the excited harmonics (Hexc), the suppressed odd harmonics
(Hsupp,odd), and even harmonics (Hsupp,even):
½p ½p ½p
V ½p ðkÞ ¼ V 0 ðkÞ þ V S ðkÞ þ NV ðkÞ k 2 Hexc ð21aÞ
½p ½p
V ½p ðkÞ ¼ V S ðkÞ þ NV ðkÞ k 2 Hsupp;odd [ Hsupp;even ð21bÞ
½P
where V 0 ðkÞ is the linear voltage response of a battery that
½P
only appears on the excited harmonics, V S ðkÞ indicates the battery
C. Fan, K. Liu, Y. Ren et al.
Fig. 11. Working principle of multisine-based nonlinear characterization method.
½P
nonlinearity, and N V ðkÞ indicates the noise distortion from practical
environment and measurement hardware in the voltage output
½P
spectrum [94]. The variable V 0 ðkÞ represents the linear voltage
½P
response, specifically on the excited harmonics. V S ðkÞ shows the
½P
presence of battery nonlinearity, whereas N V ðkÞ represents the
noise distortion caused by the practical environment and measure-
ment hardware in the voltage output spectrum [94].

The mean spectrum V ðkÞ can be determined by averaging the
voltage output spectra V ½P ðkÞ over P periods, in order to minimize
½P
the impact of noise (N V ðkÞ), as seen in Eq. (22a). It is important to
observe that the variable P in this context represents the measured
time intervals when the battery achieves a stable condition. More-
over, as per Eq. (22b), it is possible to compute the variance r ^ 2
 a sophisticated battery model.
that represents the level of uncertainty associated with V ðkÞ . Statis-
tically, uncertainty is influenced by environmental noise and hard-
ware equipment, thus the fewer variances suggest the greater
confidence in characterization outcomes.
 1X P
V ðkÞ ¼ V ½p ðkÞ
P p¼1
 2
 ½p 
P V ðkÞ  VðkÞ
X
r
^ 2V  ;k ðkÞ ¼ ð22bÞ
p¼1
PðP  1Þ
In theory, the linear system output response will maintain the
same harmonics as the input signal, while the amplitude and phase
vary. Nevertheless, in the case of a non-linear system, the inter-
modulation results in the emergence of extra harmonic compo-
nents at non-excited harmonic places in the output spectrum.
Therefore, the presence and magnitude of odd and even order non-

linearities, denoted as V (k), can be detected and measured by ana-
lyzing the energy exhibited at the suppressed harmonics k 2 Hsupp,
odd and k 2 Hsupp,even in the voltage response spectrum.
There is a scarcity of literature discussing the capture of battery
dynamics utilizing multisine signals. Zappen et al. employed the
multisine signal as a rapid characterization method for collecting
impedance data [95]. Nevertheless, the research exclusively exam-
ines the LIB linear dynamics. Widanage et al. utilized pulse-
multisine signals for battery characterization to represent battery
linear and nonlinear dynamic behaviors [96]. The pulse-multisine
approach involves stimulating the battery at a higher frequency,
so harnessing the benefits of a signal with ample power. Regret-
tably, the study failed to examine the nonlinearity of the battery
system specifically in relation to both odd and even non-linear
distortions. Furthermore, the typical frequency range was deliber-
Journal of Energy Chemistry 92 (2024) 738–758
ately chosen to be below 1 Hz, resulting in the exclusion of electro-
chemical activities occurring at higher frequencies. Relan et al.
utilized a multisine to analyze the battery’s response in order to
construct a polynomial state-space battery model [97]. Firouz
et al. employed random phase multisine signals with various real-
izations to distinguish the variance of LIB nonlinear distortion and
noise [92]. Compared to standard single sine sweep measurements,
multisine excitation signals necessitate a shorter testing duration.
Using several signal realizations to characterize nonlinear distor-
tion will result in longer testing duration and increased computa-
tion cost for the signal design. Currently, the multisine signal is
being used to record battery dynamics as a specialized nonlinear
characterization method. Fan et al. utilized the random phase
odd multisine signal to examine the nonlinear characteristics of
the cathode and anode subsystems in experimental three-
electrode NMC/silicon-graphite cells [31]. This study examines
the impact of different SOC levels and input excitations on the non-
linear behavior of both the full cell and individual electrodes. The
findings indicate that the dominant source of nonlinearity in the
experimental lithium-ion batteries is the even nonlinearity origi-
nating from the cathode. Fan et al. performed a sensitivity analysis
on battery nonlinearities using a multisine signal on an electro-
chemical battery mathematical model [98]. This analysis supports
the idea of asymmetry in charge transfer kinetics as reported by
NLEIS [83].
As previously stated, multisine signals are used as perturbation
signals for identifying nonlinear systems [94]. The battery models
that represent LIB linear and nonlinear behaviors can be deter-
mined by the frequency domain identification approach with uti-
lizing the multisine-based method [99,100]. Thus, the multisine-
based nonlinear characterization method is regarded as a potential
V ðkÞ
tool for both studying battery nonlinear dynamics and developing
3.3. Discussion and future direction
Characterization tests, which employ specialized excitation sig-
nals and analytic theories, are utilized in the investigation of bat-
ð22aÞ tery dynamic processes by measuring voltage and current data of
lithium-ion batteries. This section reviews the characterization
tests which can be utilized to investigate the key dynamic pro-
cesses discussed in Section 2, such as capacity tests for diffusion
processes, OCV tests for thermodynamics, EIS for electrical
potential- related impedance, and nonlinear response analysis
methods for charge-transfer reactions. The spectrum of these char-
acterization methods is provided and tabulated in Table 1.
3.3.1. Applications of characterization tests
The aforementioned characterization tests have been utilized in
actual engineering applications, in addition to the previously
described application of battery modeling.
The constant-current capacity tests are reported to be
employed in characterizing degradation. The aging of LIBs involves
various electrochemical processes, which leading to variations of
battery dynamics processes. The characterization methods quan-
tify LIB degradation by characterizing the aging-related indicators,
such as the loss of cell capacity (capacity fade) and the increase in
cell resistance (power fade). Specifically, constant-current capacity
tests are employed to determine capacity fade. For example, Wang
et al. used various constant-current capacity tests with different C-
rates to investigate the effect of LIB aging [101], and Gao et al. con-
ducted experiments using low C-rate constant-current testing to
examine the aging mechanisms and develop a life model for the
LIBs under different charging loads [102].
The OCV results can offer valuable insights regarding LIB degra-
dation, when used in conjunction with other characterization tests
748
C. Fan, K. Liu, Y. Ren et al.
Table 1
Summary of test method, data extracted, test duration, modeling applicability, and nonlinearity analysis of modeling- oriented characterization methods in the literature.
Test method Data extracted
CC Capacity test Cell capacity
GITT Actual OCV vs. SOC
Pseudo-OCV test pOCV vs. SOC
EIS Cell Impedance
THD Nonlinear distortion
NLEIS Cell nonlinearity
NFRA Cell nonlinearity
Multisine test Cell impedance and nonlinearity
and post-mortem tests. For instance, a OCV model-based diagnos-
tic method is developed by Pan et al. to quantify the loss of active
materials and lithium inventory [103]. The degradation mecha-
nisms of LIBs can be diagnosed based on the reconstruction and
translating transformations of OCV curves [104]. Furthermore,
the OCV is also employed for SOH estimation. A model based on
OCV, with a simplified thermal model, is suggested to accurately
estimate the SOH of batteries [105]. The findings demonstrate that
the OCV model is capable of accurately estimating the SOH of a
LiFePO4 cell subjected to temperature fluctuations.
The EIS test is extensively utilized in literature for dynamic
evaluation of LIBs, including crucial aspects such as SOC estima-
tion, temperature estimation, and aging determination [106].
Wang et al. demonstrated that the EIS can be utilized to accurately
forecast the SOC of a LIB [107]. In addition, the LIB temperature can
be correlated with the frequency where the Nyquist plot intersects
with the real axis [108]. The results indicate that the frequency
fluctuates in accordance with the temperature variation. The
research of EIS has been expanded to include the estimation of
interior temperature in real-time, as demonstrated in a more
recent investigation [109]. Furthermore, since the LIB impedance
varies when it undergoes age deterioration, scientists utilize EIS
to precisely measure the aging of LIBs and estimate SOH. Liu
et al. reviewed EIS measurement methods based on different prin-
ciples and proposed the relationship between EIS and the aging
effect mechanism of LIBs [110].
The nonlinear response analysis method is employed for identi-
fying aging mechanisms and characterizing degradation recently.
The NFRA has been shown to identify the safety–critical aging
mechanism of Lithium plating [85]. Additionally, the NFRA has
been utilized as a reliable and data-driven method for identifying
the SOH of batteries. A degradation model is developed using sup-
port vector regression, utilizing highly informative NFRA data sets
[86]. The NFRA also demonstrates the capability to estimate the
deterioration of capacity in lithium-ion batteries caused by the
depletion of active material [87]. The decrease in capacity is
directly related to the ratio of the RMS values of the second and
third harmonic responses, when subjected to various excitation
amplitudes within the frequency range that is responsive to elec-
trochemical processes, specifically around 1 Hz. The multisine-
based method has also been employed to investigate LIB degrada-
tion [111]. The results indicate that when the LIB degrades, the rise
in impedance-related linear approximation, as obtained by the
multisine-based method, aligns well with the findings of the tradi-
tional EIS. The change of nonlinearities is illustrated in relation to
the impact of degradation modes.
3.3.2. Limitations and future directions
From the standpoint of battery system identification, the cell
capacity and OCV curve serve as fundamental components in all
mathematical models pertaining to batteries. These parameters
are typically assessed using time domain methods. Various capac-
ity tests that utilize a broad range of C-rates and temperatures are
demonstrated in the literature. In order to effectively characterize
Journal of Energy Chemistry 92 (2024) 738–758
Test duration (h) Modeling application Nonlinearity analysis
3–20 U Not considered
>100 U Not considered
25–100 U Not considered
2–4 U 
2–4  U
2–4  U
2–4  U
<1 U U
cell capacity data for certain usage profiles, it is imperative to take
into account both the temperature and the C-rates. For OCV curve
measurement, both GITT and pOCV tests are widely employed in
the battery modeling studies. The lengthy duration of the GITT test
and the involvement of potential OCV hysteresis in the p OCV
method are significant obstacles for both approaches. In future
research, it is crucial to focus on reducing the test length of GITT
and minimizing the OCV hysteresis of the p OCV method. These
kinds of improvement have the potential to enhance the applica-
bility of these two approaches in the field of characterization.
Frequency domain characterization methods are developed
rapidly in recent years. The use of EIS has been regarded as a highly
promising approach for the estimation of various cell properties.
Nevertheless, the practical uses of this method in automotive sce-
narios are limited due to the necessity of a sophisticated test
equipment to guarantee accuracy and reproducibility. With the
further deepening of the study of battery dynamics, battery charac-
terization tests have begun to gradually develop from linear
dynamic to the field of nonlinear dynamic response. However,
the measuring time of the single-sine sweep methods, such as
EIS, NLEIS, and NFRA, restricts this type of method within the lab-
oratory environment, which is an obstacle to BMS applications.
In contrary, the multisine-based method can be utilized to cap-
ture battery nonlinearity and can also function as a specialized tool
for nonlinear characterization. The time of multisine-based tests is
considerably shorter compared to single-sine sweep methods for
the same frequency range. This makes multisine-based tests the
ideal choice for on-board applications. However, despite the lim-
ited amount of literature dedicated to investigating battery nonlin-
earity using the multisine-based method, there exists a knowledge
gap regarding the relationship between the origin of the nonlinear-
ity and the key electrochemical process that contributes to it.
The future trajectory of nonlinear characterization methods,
specifically in the context of newborn battery testing techniques,
revolves around the objectives of standardization. Test plans are
determined by the availability of equipment and time, as well as
the requirements for data and the downsides associated with
them. At present, there is a lack of a universally applicable test plan
for measuring battery nonlinearity. Consequently, the outcomes
obtained through various approaches cannot be directly linked
and examined. Among the various methods considered, it is only
possible to compare the trend of nonlinearity variation rather the
value of nonlinearity. This presents a challenge for the advance-
ment of nonlinear response analysis. In forthcoming times, it will
be imperative to establish the amplitude, frequency range, or
specific character frequency of the standard excited signal in the
context of the single-sine based approach. The multisine-based
method necessitates an investigation of the inter-modulation of
signals, which should be examined in relation to the magnitude
of the signal as well as the selection of excited harmonics. The min-
imization of inter-modulation effects on characterized nonlinearity
can be achieved by regulating the aforementioned parameters
during the signal design step. This ensures that the outcomes of
multisine-based methods may be comparable to those of existing
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C. Fan, K. Liu, Y. Ren et al. Journal of Energy Chemistry 92 (2024) 738–758

single-sine methods, such that the multisine-based methods can
be employed for estimating battery health state and identifying
lithium-ion plating, similar to single-sine methods. In addition,
due to their fast characterization feature, the development of a
multisine-based operando nonlinear characterization method and
multisine-based charging protocol may be considered for the pur-
pose of maximizing the efficiency of lithium-ion batteries.
4. Mathematical models of lithium-ion batteries
Battery mathematical models are developed to replicate the LIB
current–voltage relationship using the previously described bat-
tery dynamic reactions. Characterization tests provide experimen-
tal data on dynamic processes that can be used to identify battery
systems from a modeling perspective. Interpreting the fundamen-
tal dynamics in battery models can lead to an improvement in
model accuracy. There are two main groups of existing battery
mathematical models: electrochemical models, which are based
on fundamental electrochemical theory, and ECMs, which employ
a combination of analogies with electrical systems. Noted that this
review does not cover Machine Learning models, as they involve
the use of statistical algorithms to learn directly from data, which
requires a significant amount of data for modeling.
4.1. Electrochemical models
In recent years, researchers have put forth electrochemical
models that aim to characterize the LIB behaviors by utilizing the
physical geometries and electrochemical mechanisms in the elec-
trodes and electrolyte.
4.1.1. Pseudo-two-dimensional model
Doyle et al. introduced the porous electrode theory as a basis for
characterizing lithium-ion cells. They delineated the pseudo-two-
dimensional (P2D) model, a widely employed physics-based elec-
trochemical framework [112,113]. The schematic representation
of the P2D model is illustrated in Fig. 12, as well as the governing
equations and boundary conditions of P2D model are listed in
Table 2. The battery is partitioned into three distinct regions in
the x-direction, which correspond to the negative electrode, the
separator, and the positive electrode, respectively. In contrast to
the electrodes, where Li-ions are present in both solid and liquid
states, the separator contains only liquid lithium ions. Li ions inter-
calate into and deintercalate from the solid-phase material in the
solid phase. Li-ions are presented in the electrolyte as dissolved
particles in the liquid phase. LIBs undergo charge and discharging
processes determined by the Li-ions intercalation and deintercala-
tion between solid particles in the negative and positive electrodes.
The readers can refer to [112] for more details of the P2D model.
It is noteworthy to remark that the electrochemical model
incorporates the nonlinear dynamic processes described in Sec-
tion 2. This incorporation allows the P2D model to generate precise
voltage predictions. In addition to forecasting the battery’s macro-
scopic current–voltage relationship, the model can simulate in
real-time the battery’s internal microscopic data, including the dis-
tribution of particle concentration. In addition, by simulating
dynamic processes at the microscopic level in electrodes, the P2D
model permits coupling with parasitic reactions to simulate aging
mechanisms including SEI formation and lithium plating [114].
While the P2D model exhibit excellent precision, the intricate
descriptions require complex model structures that are costly to
develop and have to operate at a slow pace. The depiction of ion
diffusion processes, mass and charge conservation, and ion distri-
bution necessitates a set of partial differential equations (PDEs),
resulting in the complexity of these models. There are no analytical
solutions available for these models, and identifying the parame-
ters is extremely difficult with this sort of approach. Therefore,
the P2D model is unfeasible for implementation in on-board BMS
applications [115].

4.1.2. Single particle models

Fig. 12. The schematic diagram of the pseudo-two-dimensional model. Reproduced
with permission from Ref. [98]. Copyright 2021, SAGE Publications Ltd.
In recent years, researchers have suggested simplifications of
the P2D model to make it less difficult for control- oriented appli-
cations. The proposed methodology involves replicating the move-
ment of ions between the electrodes by utilizing multiple spherical

Table 2
Governing equations of the P2D model.

Description Equations Boundary conditions

   
Mass conservation @cs;k Ds;k @@c @cs;k  @cs;k 
@t ¼ r 2 @rs;k
r 2 @r @r r¼0 ¼ 0; Ds;k @r r¼R ¼ jk
   s

Charge conservation @/s;k
@x rs;k es;k @x
@ 3e F
¼ Rs;kk jk rs;n es;n @/@xs;n  ¼ rs;n es;n @/@xs;p  ¼ Aiapp
 x¼0  x¼L surf

rs;n es;n @/@xs;n  @/ 

¼ rs;n es;n @xs;p  ¼0
x¼Ln x¼LLp
   
@ce;n  @ce;p 
ee;k @c@te;k ¼ @x@ De ebe;k @c@xe;k þ 3es;k ð1t
þ
Mass conservation Þ
@x x¼0 ¼ @x x¼L ¼ 0
Rk jk
 
@/e;n  @/ 
@x  ¼ @xe;p  ¼0
x¼0 x¼L
b @/e;k
þ
b 2RTð1t Þ @ ln ce;k 3es;k F
Charge conservation @
e
@x ðK e;k @x  K e;k e
F @x Þ ¼  Rk jk
i
Butler-Volmer a F
g a F
g
k ¼ fn; pg
F ðexpð RT Þ  expð RT ÞÞ;
0;k a c
j¼
0 k¼s
 aa  ac
Exchange current
i0;k ¼ kk cae a  cs;k;max  cs;k jr¼Rk  cs;k jr¼Rk
Overpotential g ¼ /s;k  /e;k  U k ðcs;k jr¼Rk Þ; k 2 fn; pg
Terminal Voltage Rk
UðtÞ ¼ /s;p ðL; tÞ  /s;n ð0; tÞ  Asurf
f
iapp ðtÞ

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C. Fan, K. Liu, Y. Ren et al. Journal of Energy Chemistry 92 (2024) 738–758

particles. This concept was initially introduced and has since been with boundary conditions in Eq. (25),
expanded to include lithium-ion batteries [116]. The single particle
@cs @cs  1
model (SPM) is one of the widely applied simplified electrochemi- ð0; tÞ ¼ 0; ðR ; tÞ ¼    IðtÞ ð25Þ
cal battery model [117]. The SPM provides a comprehensive @t @t s Ds Fa L
account of the thermodynamics of LIBs, the diffusion of Li- ions The evolution of lithium concentration in the electrolyte phase
within the active material of separate electrodes, and the charge- follows Eqs. (26), (27) and (28),
transfer kinetics at which Li-ions are transferred during the inter-
calation/deintercalation reaction at the interface between the @ce @ 
 @c e 1  t0c
ee ðx; tÞ ¼ Deff
e ðce Þ ðx; tÞ þ IðtÞ ð26Þ
solid/liquid interface. @t @x @x FL
In contrast with the P2D model, the SPM assumes that the flow
of molecules from the solid phase to the electrolyte is consistent @csep @ sep
sep @c e
throughout both electrodes. It simplifies individual electrode as a esep e
ðx; tÞ ¼ Deff
e ðc e Þ ðx; tÞ ð27Þ
e
@t @x @x
single spherical particle and completely disregards the movement
of the electrolyte. The findings indicate that the computing time is @cþe @ þ
þ @c e 1  t 0c
considerably lower compared to the P2D model. Nevertheless, þe ðx; tÞ ¼ Deff
e ðc e Þ ðx; tÞ  IðtÞ ð28Þ
@t @x @x FLþ
when the electric current exceeds 1 C, maintaining the accuracy
of the model becomes challenging due to the absence of a well- with boundary conditions in Eq. (29),
defined distribution of Li + concentration and potential in the elec-
@ce @cþe þ
trolyte phase [118]. Therefore, an extended version of the SPM, ð0 ; tÞ ¼ ð0 ; tÞ ¼ 0 ð29aÞ
known as the single particle model with electrolyte dynamics
@t @t
(SPMe), was developed, which incorporates both the dynamics of
@ce  @csep
Deff ðce ðL ÞÞ
e
the solid phase and the electrolyte phase [119]. ðL ; tÞ ¼ Dsep;eff ðce ð0sep ÞÞ ð0sep ; tÞ ð29bÞ
e
@x e
@x
4.1.3. Single particle model with electrolyte dynamics
@csep @cþ
ðLsep ; tÞ ¼ Dþ:eff ðce ðLþ ÞÞ e ðLþ ; tÞ
e
The SPMe has gained significant popularity in practical applica- Dsep;eff ðce ðLsep ÞÞ ð29cÞ
tions owing to its exceptional model accuracy. In the SPMe, the Li-
e
@x e
@x
ion concentration in electrodes is assumed fixed in the spatial
ce ðL ; tÞ ¼ ce ð0sep ; tÞ ð29dÞ
coordinate x and uniformly in time t. The exchange current density
is estimated by its average value, which is independents of x. More-
over, it is assumed that the total Li-ion quantity in both the solid ce ðLsep ; tÞ ¼ ce ðLþ ; tÞ ð29eÞ
and electrolyte phase remains constant, enabling the flux to be Finally, the terminal voltage output is a nonlinear function of
proportional to the excitation current. The inclusion of the factors the PE and NE surface lithium concentrations (cþ 
ss ðtÞ and css ðtÞ),
for ohmic potential drop resulting from the conductivity of elec- the electrolyte lithium concentrations at the positive and negative
trolyte. For the governing equations, the assumption of the SPMe current collectors (ce (0+, t) and ce (0-, t), respectively), and the
model leads to a linear relationship between molar ion flux j and input current I (t), as in Eq. (30):
the input current I as Eq. (23),
VðtÞ ¼ U þ ðcþss ðtÞ=cþs;max Þ  U  ðcss ðtÞ=cs;max Þ
 IðtÞ þ IðtÞ 
jn ðtÞ ¼  ; jn ðtÞ ¼ þ þ ð23Þ þkconc ln ce ð0þ ; tÞ  ln ðce ð0 ; tÞÞ
Fa L Fa L 
þkconc ln ce ð0þ ; tÞ  ln ðce ð0 ; tÞÞ
Subsequently, the PDEs in the P2D model become decoupled, as
þ  ð30Þ
shown in Fig. 13. The behavior of lithium concentration in both the þ sep  R R
þ L þ2L2j þL  aþfLþ þ afL IðtÞ
solid and electrolyte phases are described as follows. It should be
h    i
noted that {+, sep, } represent the positive electrode (PE), separa- þ RT sinh
1
 2aþ LIðtÞ  sinh
1 IðtÞ
aF þ þ
i ðtÞ 2a L i ðtÞ
tor, and negative electrode (NE) domain, respectively. 0 0


@cs 1 @ @c where i0 represents the exchange current density, and
ðr; tÞ ¼ ½Ds r 2 s ðr; tÞ ð24Þ h iaa
@t r 2 @r @t   a
i0 ðtÞ ¼ k css ðtÞ c  ce ð0 ; tÞðcs;max  css ðtÞÞ ð31Þ

The readers can refer to [119] for more details of the derivation
of the SPMe equations. Compared to the conventional SPM, the
overpotential, which is caused by the electrolyte concentration in
the voltage expression, enhances accuracy of SPMe voltage output
for high C-rate loads. It is worth mentioning that despite the wide-
spread use and relatively high accuracy of electrochemical models
in the scientific community, these models still have limitations and
simplifications in their mathematical representations. For instance,
Fick’s law of diffusion assumes a uniform current density and
transforms the LIB active material of the battery spherical particles
[120]. One key benefit of SPMs is their ability to decouple and solve
concatenation dynamics and potentials independently, requiring
minimal computational effort in contrast to the P2D model. This
is made possible by the assumption of uniform molar flux. As a
result, SPMs have been implemented for various purposes, includ-
ing online estimation and battery life modeling. As an illustration,
Fig. 13. The block diagram of the SPMe. Reproduced with permission from Ref. Han et al. simplified a physics-based electrochemical model in
[119]. Copyright 2017, IEEE. order to calculate battery SOC [121]. Li et al. introduced an SPM
751
C. Fan, K. Liu, Y. Ren et al.
integrated with a chemical/mechanical degradation model for esti-
mating battery SOH [122]. The behavior of various degradation
mechanism models implemented within an SPM framework was
evaluated and analyzed [123]. In the last few years, model order
reduction algorithms have been implemented to facilitate wide-
spread applications. These algorithms include balanced truncation
[124], Padé approximation [125], and residue grouping [126]. By
implementing these algorithms, the complexity of electrochemical
models has been diminished without compromising their accu-
racy. While these approaches do lead to a certain degree of infor-
mation loss in the reduced-order models, they are more
favorable for practical BMS applications [127].
Nevertheless, one obstacle associated with the physics-based
electrochemical models mentioned earlier is the parameterization
of the diverse dynamics in both the electrode and electrolyte. The
electrochemical models necessitate plenty of parameters, thereby
augmenting the complexity of the parameterization procedure
[12]. Thus, it is practically difficult to employ the electrochemical
models in real-time applications. The purpose of conducting char-
acterization experiments, as mentioned in Section 3, is to clarify
the thermodynamic and kinetic characteristics of a LIB. This data
is crucial for the development of electrochemical models. As an
illustration, the OCV of the LIB and the diffusion coefficient at var-
ious SOC were determined utilizing GITT [47]. The exchange current
density and activation energy for individual electrodes can be cal-
culated by the EIS test and mathematically represented by using
the Arrhenius equation. Subsequently, the reaction rate may be
computed [128]. In addition to the requisite characterization meth-
ods, in order to acquire a comprehensive parameter set for electro-
chemical models, plenty of chemical/physical experiments must be
employed to gather vital physical property values. The tests include
scanning electron microscopy (SEM) to analyze the morphology of
electrodes, inductively coupled plasma optical emission spec-
Table 3
Schematic diagram of various time-domain equivalent circuit models.
Models Model structure
Rint model
Thevenin model
DP model
RCH model
Journal of Energy Chemistry 92 (2024) 738–758
troscopy (ICP-OES) and energy-dispersive X-ray spectroscopy
(EDS) to determine elemental composition, XRD to analyze the
crystal structure of materials, and theoretical density [12]. The exe-
cution of these assessments and evaluations poses obstacles in the
integration of EV functionalities and could prove problematic for
scientists and engineers lacking experimental proficiency.
4.2. Equivalent circuit model
The ECMs have attracted significant attention due to their lower
computing burden and fewer parameters compared to electro-
chemical models. The ECMs employ various basic electrical circuit
elements, including a voltage source (representing OCV), resistors
(representing electron and ion movement resistance), and parallel
branches consisting of resistor–capacitor (RC) combinations (rep-
resenting battery polarization), to simulate the current–voltage
characteristics and transient response of a LIB [120]. The classifica-
tion of established ECMs in the literature typically falls into two
categories: time-domain ECMs (a time-domain ECM is a mathe-
matical representation that relies on measurements of current
and voltage in the time domain), which are referred to as
integer-order models, and frequency-domain ECMs (a frequency-
domain ECM is a model that is established utilizing data obtained
by means of frequency-domain characterization methods), which
comprise fractional order models (FOMs) and nonlinear equivalent
circuit models (NLECMs).
4.2.1. Time-domain equivalent circuit models
The time-domain ECMs consist of a voltage source, resistor,
capacitor, inductance, and other electrical components. These com-
ponents are employed to simulate the voltage and current charac-
teristics of a battery terminal. The fundamental time-domain ECMs
are depicted in Table 3. A basic time-domain ECM is developed by a
Model equtions and features
Ubatt = Uocv  I  R0
where Ubatt is the terminal voltage,
Uocv represents the OCV,
I is the input current,
and R0 is the battery Ohmic resistance.
Ubatt = Uocv  Up  I  R0
where Rp is the polarisation resistance,
Cp is the polarisation capacitance, and Up is the voltage of RC branch.
Ubatt = Uocv  Up1  Up2  I  R0
where Rp1, Rp2 are the polarisation resistance,
Cp1, Cp2 are the polarisation capacitance, and Up1, Up2 are the voltage of RC branches.
Ubatt = Uocv  Up1      Upn  I  R0 + hk
where Rp1, Rpn are the polarisation resistance,
Cp1, Cpn are the polarisation capacitance,
Up1, Upn are the voltage of RC branches, and hk is the hysteresis voltage
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C. Fan, K. Liu, Y. Ren et al.
resistor coupled in series with a voltage source. The purpose is to
explain the battery OCV, which is referred to the Rint model
[129]. The model can be readily identified and used for battery
modeling. However, there is no electrochemical process dynamics
considered in this model, leading to a low level of accuracy when
dealing with slow dynamic profiles [130]. In order to enhance
the model precision and incorporate LIB dynamic behaviors, a par-
allel RC branch is introduced into the circuit of the Rint model. This
new configuration is known as the Thevenin ECM [131]. This
model represents the polarization between the electrode and elec-
trolyte, providing a more precise description of the LIB dynamic
behavior. To account for the polarization caused by the concentra-
tion and electrochemical separately, He et al. introduced an addi-
tional RC branch to the Thevenin model, also known as the DP
model [132]. Enhanced accuracy can be achieved in ECMs by incor-
porating many RC branches. However, as the amount of RC
branches rises, the model representation becomes more intricate,
rendering the identification of model parameters more challenging
and impractical for real- world applications. Therefore, it is advised
to restrict the number of RC branches in an ECM to less than four,
as suggested in the literature [133].
Furthermore, the RC ECMs can be combined with specialized
components that illustrate the battery’s hysteresis behavior,
referred to the RCH model. Hysteresis is a fundamental thermody-
namic property of a LIB that causes the OCV to vary between the
charging and discharging operations [134]. The hysteresis varies
depending on the cell chemistry. Nejad et al. conducted a compar-
ison of the hysteresis levels between LiPO4 and NMC cell chemistry
after a one-hour rest period. The findings indicate that the hystere-
sis levels for LiPO4 are significantly greater than those for NMC
chemistry. Furthermore, within the medium SOC range of approx-
imately 20% to 80%, the OCV curve for the LiPO4 cell remains rela-
tively constant. This suggests, while estimating the SOC, a minor
error in measurement within this range may lead to a significant
deviation from the true SOC level [135]. Thus, it is crucial for devel-
oping a model that incorporates the hysteresis behavior for LiPO4
cell, as opposed to NMC chemistry. Hu et al. conducted a compre-
hensive comparison of twelve frequently used ECMs to assess their
practicality based on model complexity and precision. They deter-
mined that the first-order RC branch ECM is the most suitable for
NMC batteries, while the first-order RC ECM with hysteresis is
the optimal selection for LiPO4 batteries [136].
ECMs have the benefit of a straightforward model structure and
effortless identification. As a result, these models are extensively
used in BMS applications, including the estimation of different states
[137]. The SOC estimation involves the integration of ECMs with var-
ious algorithms such as the extend kalman filter (EKF) [138], a Luen-
berger observer [139], a least squares technique [140], a fuzzy-logic
system [141], and a sliding mode observer [142]. The SOH estima-
tion is also examined utilizing the electrochemical models in BMS.
Due to the impracticality of directly measuring SOH, sophisticated
algorithms are employed to estimate the changes in deterioration
markers to determine the aging condition, such as battery internal
resistance and capacity. Tong et al. enhanced the estimation of states
of charge and health by employing the EKF and recursive least
squares [143]. Furthermore, Kim et al. developed an EKF to deter-
mine the internal resistance for SOH estimation [144]. Similarly,
the genetic resampling particle filter is utilized to determine the
internal resistance of the battery pack for the purpose of estimating
SOH [145]. Pei et al. utilized the double EKF to concurrently estimate
the state of power and model parameters in real-time applications
[146]. The ECMs and the Kalman Filter family algorithm have been
extensively employed in the literature for estimating battery states
in EV applications [147].
Nevertheless, a drawback of a time-domain ECM is its inability
to directly correlate an electrical circuit component with a specific
753
Journal of Energy Chemistry 92 (2024) 738–758
battery physical phenomenon. This limitation restricts the in-
depth understanding of LIB behaviors and hinders the interpreta-
tion of physical processes like battery aging [148]. Furthermore,
the LIB nonlinearity is not well represented by the electrical circuit
components used in conventional ECMs. As a result, these ECMs,
which have constant parameters, can only accurately model the
battery’s behavior in the middle-to-high SOC (greater than 20%)
and at low current loads. For example, consider the reference
[149]. The DP model yields precise outcomes ranging from 20%
to 100% SOC, with an error of less than ± 10 mV, during a 0.5 C
constant-current discharge pause load. When the SOC is less than
19.5%, the estimated voltage significantly deviates from the actual
value, with a maximum 60 mV error. This suggests that the accu-
racy of the model decreases in the low SOC region. Furthermore,
as the current load increases, the root mean square error (RMSE)
of ECM shows a rise from 3 mV at 75.9% SOC and 25 mV at
11.5% SOC in the 0.5 C case to 24 mV at 75.9% SOC and 42 mV at
11.5% SOC in the 2 C case. These findings suggest that the ECM
accuracy declines significantly as the current load rises. Further-
more, Xiong et al. showed that RMSE of the Thevenin model
increases significantly from 5 mV at 80% SOC to 17 mV at 10%
SOC under the DST test (the DST test is a commonly employed
dynamic driving profile that assesses the vehicle’s performance
and is also utilized to verify the reliability of models or the effec-
tiveness of algorithms [150]) [151]. Therefore, it may be inferred
that linear ECM models are inadequate for maintaining a high
degree of precision when working at low SOC levels.
4.2.2. Frequency-domain equivalent circuit models
In contrast to the previously described time-domain ECMs,
frequency-domain ECMs have gained increasing interest in recent
years for modeling electrochemical power sources. These models
are examined and constructed using data collected from frequency
domain characterization tests. The LIB frequency response exhibits
specific features, such as the impedance measured by EIS tests.
Frequency-domain ECMs provide a notable benefit in representing
the non-local and heterogeneous phenomena commonly found in
electrochemical systems, like the non-uniform potential distribu-
tion [152]. Hence, this model is regarded as a highly suitable option
in various areas of battery management. These areas encompass
frequency domain modeling for battery health diagnosis and heat-
ing, as well as state estimation and fault diagnosis [148]. Regarding
identification approaches, frequency-domain ECMs can be divided
into two distinct categories: the FOM and the NLECM.
The FOM was initially introduced for NiMH cells in [153], where
the parameters were determined using impedance data [154]. How-
ever, because there were no suitable numerical methods available at
that time to convert the frequency- domain model into the time
domain for implementation. The development of the FOM has been
driven by the utilization of fractional-order calculus and the incor-
poration of additional elements that demonstrate memory effects,
as proposed by the circuit analysis theory [155]. An intrinsic charac-
teristic of electrochemical battery systems is the simultaneous
occurrence of several dynamic processes, as indicated in Section 2,
which exhibit distinct time scales [148]. In EIS, faster dynamic pro-
cesses have smaller time constants compared to slower dynamic
processes. These processes can be distinguished by analyzing the
impedance across a wide range of frequencies. The literature exten-
sively documents the presence of fractional-order behavior in bat-
tery impedance spectra, which has consequently led to the
development of the constant phase element (CPE).
The modeling concepts of the FOMs involve creating an equiva-
lent circuit that accurately represents the exper- imentally
observed impedance data collected from EIS. This is achieved by
incorporating circuit parts, as shown in Fig. 14.
C. Fan, K. Liu, Y. Ren et al. Journal of Energy Chemistry 92 (2024) 738–758

In order to utilize FOM in BMS applications, it is necessary to

implement the CPE element in the time domain. The fractional-
order operator for a CPE in Eq. (32) is mathematically defined as
a
Dat ðÞ ¼ ddtðÞ a
a . The equation using the operator Dt ðÞ characterizes

dynamic processes that possess an infinite number of dimensions.

For the purpose of analysis and numerical implementation, three
distinct definitions have been suggested to describe fractional
order derivatives: Riemann-Liouville (RL), Caputo, and Grunwald-
Letnikov (GL) [159]. The GL offers a straightforward method of dis-
cretization, and its formulation can be easily applied in numerical
computations [160]. The GL fractional derivative is precisely
defined as


1 X a
t=T
Dat f ðtÞ ¼ lim a ð1Þk f ðt  kTÞ; ð36Þ
T!0 T k¼0 k

where T denotes the sampling time interval, t / T represents the lar-


Fig. 14. Example of fractional order based EIS fitting. Reproduced with permission
gest integer less than or equal to t / T, and
a denotes the Newton
from Ref. [148]. Copyright 2020, Springer Ltd. k
binomial term defined as


In addition to the circuit components found in traditional ECMs a Cða þ 1Þ
¼ ; ð37Þ
as discussed in Section 4.2.1, a CPE introduced in [156] is incorpo- k Cðk þ 1Þ  Cða  k þ 1Þ
rated into the circuit to represent the phenomenon of LIB capaci-
tance dispersion. The frequency- dependent electrical impedance where the gamma function, denoted as C(), is a mathematical func-
of the CPE, denoted as ZCPE, is defined as tion that serves as a generalization of factorial functions in both real
and complex fields. It is often referred to as Euler’s second integral.
1 1  ap ap
Z CPE ðxÞ ¼ for a 2 ð1; 1Þ; The function is defined as follows:
a ¼ a cos  j sin ;
C CPE ðjxÞ C CPE ðx Þ 2 2 Z 1
ð32Þ CðaÞ ¼ na1 en dn: ð38Þ
0
the exponent a represents a fractional-order that is associated with
A detailed exposition of these definitions, together with their
capacitance dispersion. CCPE denotes the capacity coefficient, j rep-
distinctive characteristics, has been provided in [161]. When mod-
resents the imaginary unit, and x represents the angular fre-
eling batteries, the parameter a typically falls within the range of
quency. The CPE element can be seen as an electrical element
[0, 1]. A fractional value of a can represent a memory effect in
that has a constant-phase angle of ap∕2. Furthermore, different
terms of (t). The memory effects observed in lithium-ion batteries
conventional components can be symbolized by assigning equiva-
are caused by dynamic processes, including charge transfer reac-
lent phase shifts, such as resistance (a = 0), capacitance (a = 1), and
tions and diffusion processes. These operations involve voltage
inductance (a =  1). The CPE can represented by a linear function
information in the time domain and can be represented using frac-
with a slope of  tan(ap∕2) in the Nyquist plot. This allows for the
tional derivatives. By applying CPEs, it is possible to relief the plate
emulation of a straight line in the low frequency band, which is not
hypothesis that is the basis for the real electrodes. This allows for
possible with an ideal resistance or capacitance. In this instance,
the description of non-uniform border and scattered intercalation/
the CPE is generally referred to as the Warburg element, as
deintercalation processes within individual electrodes [70].
described in the graphical representation [152]:
Recently, researchers have been investigating numerous FOMs
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi for modeling lithium-ion batteries by utilizing the principles of
tanh jx=xD
Z W ð xÞ ¼ Z D pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ; ð33Þ fractional calculus. Fig. 15 displays the typical FOMs for LIBs. They
jx=xD
achieved this by replacing the CPE to ideal capacitance in the RC
where xD represents characteristic frequency and ZD denotes branch, as illustrated in Fig. 15(a). Nonetheless, in order to perform
diffusion resistance, respectively. numerical calculations, the fractional equations must be converted
The Zarc element, which is represented as a semi-circle within into ordinary difference equations using a sophisticated approxi-
the mid-frequency range, is typically modeled by a parallel connec- mation algorithm called Oustaloup recursive approximation
tion of a CPE and an ideal resistance, written as R//CPE: [162]. However, this conversion process may impact the accuracy
of the model due to the determination of frequency bounds. For
R enhancing model precision, the inclusion of a Warburg element
Z arc ðxÞ ¼ a ð34Þ
1 þ RC CPE ðjxÞ (W) in conjunction with the charge-transfer resistor (R1) of a
fractional-order model is depicted in Fig. 15(b) [154]. The FOM
By eliminating x, one obtains
demonstrates a significant level of precision in predicting voltage

2

 in relation to experimental data, which is achieved by implement-
R R ap 2 R ap 2
Z 0arc ðxÞ  þ Z 00arc ðxÞ  cot ¼ csc ð35Þ ing the GL fractional derivative. Additionally, the FOM is employed
2 2 2 2 2
to analyze the impedance spectra of an LFP cell, as described in
The circle is centered at (R∕2, R cot (ap/2)/2) and has a radius of [163]. The Warburg element is connected in series with the R//
R csc(ap/2)/2, as depicted in Fig. 14. By utilizing fractional-order CPE branch to model the LIB dynamics as presented in Fig. 15(c)
calculus, the CPE can greatly enhance the practicality of FOMs for [164]. The Fig. 15(d) shows the FOM with two R//CPE branches
EIS fitting. The FOM can be utilized to build a correlation between connected in series. This configuration has been utilized and is
changes in impedance and the condition of the battery in applica- anticipated to exhibit greater robust to uncertainties, as stated in
tions, such as health diagnosis [157] and AC heating [158]. the reference [165].
754
C. Fan, K. Liu, Y. Ren et al.
Fig. 15. The conventional fractional order models employed to represent a Lithium-
ion battery.
The FOM has proven to be advantageous due to its high preci-
sion and ability to accurately represent physical events. However,
due to its status as a relatively new type model, the identification
of the model has limitations in terms of practical applications. Fur-
ther investigation is necessary to address these limitations. The
identification methods used for the FOMs can be classified into
two primary categories: offline identification and online identifica-
tion. In the frequency-domain offline identification, researchers
utilize the FOM modeling method to directly extract the parame-
ters of FOMs by fitting EIS test data. This approach eliminates the
need for difficult calculations caused by CPE elements [148]. Andre
et al. developed a mathematical model to analyze the NMC battery
impedance spectra and to estimate the terminal voltage [166]. The
results indicate that the FOM has superior estimation fidelity com-
pared to a third-order ECM. However, it is necessary to execute the
time-consuming EIS measurements to parameterize the FOMs in
the frequency domain, which prevents the FOM from practical
applications [167]. Furthermore, the validity of an EIS test depends
on restricting the amplitude of the excitation current signal to a
relatively low level. As a result, this offline method can only be
employed to develop a model using the LIB impedance when it is
in a nearly linear state. Unfortunately, this means that the LIB non-
linearity, when subjected to high loads, is overlooked. In addition,
the evolutionary algorithms such as the genetic algorithm [168]
and particle swarm optimization [169] are utilized to determine
the FOM parameters by analyzing the current and voltage
response. Nevertheless, the primary challenge in mode identifica-
tion lies in determining the order of FOMs. The CPE differential
order can be determined by fitting the impedance curve obtained
from EIS in the frequency domain. However, no evidence can be
utilized to determine the model order in the time-domain algo-
rithm before the parameterization step. As a result, the identifica-
tion becomes a nonlinear optimization challenge and cannot be
easily solved using gradient-based evolutionary algorithms. An
example of a Warburg-type element does not have a fixed differen-
tiation order in the FOMs [170]. Moreover, the significant compu-
tational expense associated with these evolutionary techniques for
CPEs should not be underestimated.
Online identification is preferable over offline identification for
existing BMSs in order to accurately capture the variations of bat-
tery states. However, the heavy computational cost needs to be
considered. Many online identification approaches, particularly
evolutionary algorithms, are not compatible with a BMS due to
the significant processing resources needed for online identifica-
tion to adjust to changing profiles. However, the efficient online
identification approaches, such as recursive least squares and vari-
ations of the Kalman filters, are mentioned as potential candidates
for additional investigations and applications in the future research
755
Journal of Energy Chemistry 92 (2024) 738–758
[148]. Regarding the practical use of FOMs in EVs or grid systems,
they are currently not viable due to the lack of identification meth-
ods that are both low in computing cost and adequately addressed.
In contrast to FOMs, the NLECM, which is a subset of nonlinear
models developed using frequency domain identification methods,
considers the aforementioned constraints. The methodology uti-
lizes system identification methodologies, which are based on
experimental design and the identification of non-linear dynamics.
The flexibility and innate nonlinearity of actual systems have made
nonlinear system identification a subject of interest for scientists
and engineers. Previously, nonlinear models were frequently cre-
ated to represent intricate mechanical systems that exhibit hys-
teresis distortions, such as the switched reluctance motor [171],
the hysteresis system [172], and the wet- clutch [173]. NLECMs
have been recently introduced into the LIB realm. It is important
to mention that the nonlinear models herein represent the LIB non-
linearity using explicit mathematical functions, rather than the lin-
ear parameter varying type nonlinear models described in [174].
In order to establish a nonlinear model, it is essential to quan-
tify the degree of nonlinearity with particular tests designed for
nonlinear characterization. The concept of best linear approxima-
tion (BLA) is introduced by Schoukens et al. in frequency domain
system identification. Its purpose is to identify, assess, and mea-
sure nonlinearities in the frequency domain by utilizing periodic
multisine perturbation signals [175]. The study conducted by Fir-
ouz et al. involved doing a BLA analysis on NMC pouch cells of
lithium-ion batteries to accurately measure both the linear impe-
dance and nonlinearities [92]. However, these studies only devel-
oped non-parametric models in the frequency domain. For model
parameterization, the structure of nonlinear models can be found
in the literature, such as block- oriented nonlinear models [176],
nonlinear state space models [177], and nonlinear auto-
regressive exogenous models [178]. The block-oriented nonlinear
model is favored among these systems due to its simplicity. The
system divides the nonlinear dynamic behavior into two compo-
nents: a linear time-invariant dynamical block and a static nonlin-
earity block [179]. Moreover, the notable benefit of this structure is
the capability to establish a connection with the tangible occur-
rences of the system, which has particular significance in the mod-
eling of electrochemical systems [99]. The standard block-oriented
architectures commonly shown in the literature are illustrated in
Fig. 16. This model consists of linear blocks (highlighted in red with
capital letters) and nonlinear blocks (highlighted in blue with low-
ercase letters), which can be arranged in various configurations,
such as parallel, series, feed-forward, and feedback. Hammerstein
and Wiener configuration systems are commonly employed for
nonlinear system identification due to their practical applicability,
simplicity, and efficiency [180,181].
A limited number of articles have explored the use of block-
oriented nonlinear models for battery system modeling. Widanage
et al. introduced a Wiener configuration NLECM for a NCA battery.
The model was developed based on experimental data gathered
using a pulse-multisine identification excitation technique [99].
In this model, the linear ECM represents the electrical behavior
of the internal ohmic resistance and short time constant polariza-
Fig. 16. Diagram of block-oriented nonlinear models in form of (a) Hammerstein,
(b) Wiener, (c) Hammerstein-Wiener and (d) Wiener-Hammerstein system [179].
C. Fan, K. Liu, Y. Ren et al.
tion. The nonlinear over-voltage block interprets the nonlinear
relationship between voltage and current caused by transport lim-
itations. The OCV with hysteresis block represents the battery OCV,
incorporating thermodynamic information. The LIB physical phe-
nomena can be associated with both linear and nonlinear compo-
nents, offering useful insights that cannot be captured by a
conventional linear ECM. The validation results indicate that the
NLECM demonstrates a lower RMSE and maximum error compared
to a second-order ECM at various SOC levels. However, the exam-
ination of the NLECM accuracy across an entire SOC range load pro-
files is not included, and the LIB employed in this work only
demonstrates mild nonlinearity. Allafi et al. developed an online
parameter estimation method for the NLECM and concluded that
it is a promising option for real BMS applications due to its ability
to minimize calculation load and reduce parameter identification
cost [182]. Firouz et al. devised a Hammerstein-Wiener nonlinear
model to address the scenarios with higher levels of nonlinearity
in an all-solid-state battery. Nevertheless, the multiple nonlinear
blocks lead to the significant computational expense and identifi-
cation challenge [180]. Recently, Fan et al. developed a battery
model called NLECM with diffusion dynamics (NLECM-diff) using
a physical-based data-driven approach [100,183]. The model struc-
ture is illustrated in Fig. 17. The NLECM-diff model has the capabil-
ity to analyze the electrochemical processes of batteries, including
electrical potentials, charge-transfer reactions, and diffusion pro-
cesses. And the model has been proven to possess comparable pre-
cision as the commonly employed electrochemical model across
different current loads.
Despite the NLECM exhibits a reasonably high level of accuracy
in the whole SOC range by interpreting nonlinear dynamic pro-
cesses, its nonlinear structure causes challenges for online param-
eter identification. Furthermore, the nonlinear block also leads to
Fig. 17. The Li-ion battery data-driven NLECM-diff model’s structure. The overall
model comprises a linear ECM followed by a non-linear function that accounts for
over-voltage, a parallel OCV and hysteresis model block, and a dynamic block that
represents diffusion [100].
Table 4
Overview of battery mathematical models.
Model Number of parameters Number of equations
DFN 35 (including electrode OCVs) 8*
SPM 24 4*
SPMe 30 6*
ECM 4 (assuming 1st order) 7 (including interpolation functions)
FOM 5 (assuming 1st order) 7 (increases once implemented)
NLECM 8 (assuming 2nd order) 9 Multisine test, OCV
NLECM-diff 10 (assuming 2nd order) 10
*
Noted that the number of equations increases up to hundreds when the governing equations are discretized for solving.
**
Noted that physical parameters of electrochemical models can be shared.
756
Journal of Energy Chemistry 92 (2024) 738–758
difficulties for traditional state estimation method, which requires
further investigation.
4.3. Discussion and future direction
In summary, Table 4 lists the important characteristics of the
battery models reviewed in previous research, including the num-
ber of parameters and equations, the necessary tests for character-
ization, and the interpretation of nonlinearity.
Mathematical models of batteries have been developed for esti-
mating the current-voltage relationship of lithium- ion cells. These
models are based on either fundamental physical principles or
empirical dynamic response. The computational cost of electro-
chemical models is significant due to the complex nature of the
governing equations, which involve high-order PDEs that requires
to be solved using mathematical methods such as finite-difference
or finite-volume approaches. Furthermore, the characterization
experiments pose a challenge in obtaining 35 parameters [12].
For example, the particle size for the active materials needs to be
measured using SEM, which requires a substantial amount of rele-
vant knowledge and significant financial resources [17]. On the
contrary, ECMs have the advantages of low computational cost
and requiring minimal characterization tests for parameterization,
making ECMs preferable for practical applications. The number of
parameters that need to be estimated in the structure of ECMs typ-
ically less than 10 s.
Additionally, system identification typically involves the use of
approximately three characterization approaches that are uncom-
plicated to perform. Therefore, the selection of battery model types
should be dependent on factors such as calculating cost and users’
knowledge background.
The future direction of battery mathematical models is centered
on the goal of interpretation, especially for ECMs. The majority of
existing ECMs are currently restricted to replicating input–output
relationships through the employment of electrical components,
without the capacity of interpreting the LIB dynamic processes.
Nevertheless, the lack of comprehensive physical dynamics inter-
pretation remains a limitation of ECMs, which results the response
of ECMs cannot be interpreted physically. It is crucial to establish
connections between the key dynamic processes and the corre-
sponding modules in order to obtain depth essential data for
degradation study and battery design. For example, the depletion
of active lithium ions due to cycle aging may affect diffusion pro-
cesses, such that the diffusion-related module could be coupled
with a charge–discharge model grounded on first principles to pre-
dict the LIB capacity degradation [185]. In addition, the charge-
transfer block can be employed for the purpose of identifying
lithium plating, due to the fact that the LIB nonlinearity, which is
primarily affected by the charge-transfer reaction, has been shown
to be associated with the process of lithium plating [85]. Thus, it is
Characterization tests Nonlinearity interpretion Ref.
FIB-SEM, GITT, EIS, ICP-OES, EDS, OCV, Yes [12]
Capacity test
Same as DFN** Yes [184]
Same as DFN** Yes [119]
HPPC, OCV No [136]
EIS, OCV No [70]
Yes [99]
Multisine test, OCV, CC-discharge Yes [100]
C. Fan, K. Liu, Y. Ren et al.
necessary for advanced battery models to interpret LIB dynamics in
the context of on-board BMS applications.
5. Conclusions
The rapid development of battery technology has led to great
interest and attention in the fields of characterization and identifi-
cation. Both specialized areas of study are distinct but intricately
interconnected. The contribution of this paper is to establish the
relationship between these two disciplines in terms of battery
dynamic processes, with the aim of providing comprehensive
review and support for researchers and engineers lacking relevant
background knowledge. Firstly, the key dynamic processes of
lithium-ion batteries were reviewed from the perspectives of lin-
ear and nonlinear dynamics, which are related to battery system
identification. Subsequently, a review was conducted on character-
ization tests used to obtain precise dynamic data for battery mod-
eling. Finally, an examination was conducted on battery models,
particularly physical-based electrochemical models and
application-oriented ECMs, with the aim of interpreting various
battery dynamics. For practical applications, the corresponding
characterization methods can be determined in accordance with
the preferred battery model types required for specific scenarios.
In addition, this review built up a connection between advanced
nonlinear characterization techniques and nonlinear equivalent
circuit models, providing valuable insights for readers who aim
to develop the optimal range of battery applications.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The project was supported by the National Natural Science
Foundation of China (Grant No. 62373224), the Scientific Research
Foundation of Nanjing Institute of Technology (Grant No.
YKJ202212), the Nanjing Overseas Educated Personnel Science
and Technology Innovation Project, and the Open Research Fund
of Jiangsu Collaborative Innovation Center for Smart Distribution
Network, Nanjing Institute of Technology (Grant No. XTCX202307).
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