Case Studies in Thermal Engineering 13 (2019) 100387

Contents lists available at ScienceDirect

Case Studies in Thermal Engineering

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

Characteristic investigation of an electrochemical-thermal coupled

T
model for a LiFePO4/Graphene hybrid cathode lithium-ion battery
⁎
Yuan Lia, Fei Qib, Hao Guoc, Zhiping Guod, , Meiying Lid, Wenliang Wud
a
College of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
b
School of Mechanical and Electric Engineering & Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University,
Suzhou 215021, China
c
Jiangsu Provincial Key Laboratory of Advanced Robotics & Robotics and Microsystems Center, Soochow University, Suzhou 215021, China
d
College of Mechanical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China

A R T IC LE I N F O ABS TRA CT

Keywords: It is a promising development strategy to use LiFePO4/Graphene (LFP/G) hybrid cathode lithium-
LiFePO4/Graphene ion batteries for electric vehicles (EVs), which can simultaneously solve issues of the lengthy
Lithium-ion battery charging time and the battery pack heat. To capture the characteristic regulation of the tem-
FLUENT perature distribution, the working voltage, the current density, and the total heat generation of
Electrochemical-thermal coupled model
the LFP/G battery, an electrochemical-thermal coupled model for the LFP/G battery was de-
veloped through a new modeling method in ANSYS FLUENT. The experimental results showed
that tendencies of the temperature distribution and the working voltage were not only agreed
well with simulations, but also accurately verified the hottest area of the LFP/G battery. Further
studies used the comparative analyses of the maximal temperature between the LFP/G battery
and the conventional LFP battery at different discharged C-rates, the results indicated that the
LFP/G battery could restrain the increase of temperature through reduced contact resistances.
Our results suggested that the electrochemical-thermal coupled model could be used for electric
vehicles battery management system applications.

1. Introduction

In recent years, as the decline of global petroleum resources and the deterioration of environmental pollution, therefore, seeking
for efficient methods to solve the above-mentioned crisis has become the focus of many research institutions in most countries. As
electric vehicles (EVs) are considered as the most promising transportation with zero-emission for the future, which rely on the
battery to drive. LiFePO4(LFP) owned orthonormal olivine structure is determined to be an outstanding cathode material for the
Lithium-ion battery, which has a stable working voltage (3.2 V), a high theoretical capacity (170 mA h/g), and a strong structure (O
and P are tightly bind with a strong covalent bond as well as the thermal stability of the material is superior during the charge).
Moreover, the electrochemical property of the LFP battery at normal temperature is also very excellent [1,2]. However, there are
some disadvantages in commercial application of LFP batteries, which contain the weak electronic conductivity and the restricted li-
ion diffusion coefficient as well as the high heat generation [3–5]. Thus, it is pressing to find a method to enhance the electrochemical
properties of the LFP battery.
Up to data, the modified electrode material is an effective measure to improve the electrochemical performance of the lithium-ion

⁎
Corresponding author.
E-mail address: [email protected] (Z. Guo).

https://doi.org/10.1016/j.csite.2018.100387
Received 16 November 2018; Received in revised form 20 December 2018; Accepted 30 December 2018
Available online 08 January 2019
2214-157X/ © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

Nomenclature x100%,y100% stoichiometry at 100% SOC

Ce average electrolyte concentration
δ thickness ki0 exchange current density coefficient
Rs particle radius αa, αc charge-transfer coefficient
εs active material volume fraction Ds solid phase Li diffusion coefficient
εp polymer phase volume fraction σ solid phase conductivity
εf conductive filler volume fraction De Electrolyte phase Li+ diffusion coefficient
εe porosity p Bruggeman porosity exponent
cs,max maximum solid phase concentration k electrolyte phase ionic conductivity
x0%,y0% stoichiometry at 0% SOC t+0 Li+ transference number

battery. The currently modified method is surface coating, which can decrease the ionic resistance and the electronic resistance of
active materials [6–8]. The reaction between active materials and electrolytes can be reduced by surface coating. At the meantime,
surface coating can reduce oxygen release in the overcharge process and stabilize the phase transition of matrix materials, thus, the
improvement of the electrochemical performance of the lithium-ion battery owes to surface coating [9–13]. At present, there are
many kinds of materials used for surface coating, one of the most effective way is carbon-coating which can establish a mixed
conducting network to provide pathway for electron transfer and li-ion diffusion, resulting in the improvement of electrochemical
properties.
Graphene is a single atom thickness of the carbon with a 2D (two-dimensional) crystalline layer. It has many advantages, in-
cluding the ultrahigh theoretical specific surface area, the outstanding electronic, and mechanical properties [14,15]. For the con-
ventional electrode structure, the current collector is directly coated by the active material, thus, the additional contact resistance
occurs at the interface among them to result the issue of the high heat generation in the conventional LFP battery. However, one of
the most important applications of the graphene is that to form the LPF/Graphene composite cathode which has 3D (three dimen-
sional) porous structure to reduce the contact resistance, as shown in Fig. 1(c). The cathode is modified by graphene for the lithium-
ion battery application in EVs, which are the trend of future developments about new energy vehicles, because of it has the ex-
ceptional electrical function, the mechanical character, and the thermal property. Therefore, electrode materials are modified by the
graphene for lithium-ion batteries that require relevant research to explore the electrochemical and the thermal behavior.
Mathematical modeling and simulation have always been an essential part of the research and development in the battery field.
The battery model is not only can be used to describe and predict the electrochemical and thermal performances of the battery, but
also significantly reduces the cost of the experiment. In principle, the battery model consists of one or more mathematical equations,
such as empirical models [16], equivalent circuit models [17,18], and 3D lumped thermal models as well as electrochemical models
[19–23]. All of these battery models can predict the heat generation within the battery, the charging and discharging profiles, and the
electrochemical process. The empirical model [16], which is the simplest and the earliest battery model with only one equation, it
describes an intuitive relationship without considering any physical properties (electrochemical process) of the battery. The
equivalent circuit model [17,18] is modeled by using the circuit relationship to describe the current and voltage characteristics of the
battery. However, it also has little physical properties within the battery. The 3D lumped thermal model [19–23], which assumes
materials of the battery have same electrical and thermal properties, the heat generation, and the temperature distribution. The
electrochemical model [19–23], which is made up of two different solid electrodes that immersed in the electrolyte. Moreover, the
charge transfer reaction occurs on the surface of each electrode which acts as the charge transfer medium from the electron (on
electrode) to ion (in electrolyte). The characteristics of the electron flow conform to Ohm's law, but the characteristics of the ion flow
are limited to the diffusion. As long as the battery has the active reducing substance and the oxidizing substance, the battery can
produce the current when the external load is connected. The separator in the battery is used to prevent the short circuit among
electrodes. Electrochemical-thermal coupled model is not only can carry out electrochemical reactions, but also can simulate the
thermal character of the lithium-ion battery. The porous electrode and the concentrated solution theory establish the model [24].

Fig. 1. (a) Electrode and particle domains in the electrochemical-thermal model; (b) Exfoliation process from graphite to graphene nanosheet; (c)
Structure of mixed conducting LFP/G composites.

2
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

The electrochemical-thermal model is the basis of other thermal models, which can better reflect the inconsistency of temperature
distribution in a single battery. Faray et al. [25] present a model coupled with an electrochemical model, heat generation model, and
thermal model, which shows accurate terminal voltage and core temperature prediction at various operating conditions. A 3D
electrochemical-thermal model was proposed by Xu et al. [26], which consisted of 3D current collectors and 1D local cell units to
predict the electrochemical process of the battery. Although Faray and Xu's models show good agreement with experimental values,
they will cost a lot of time consumption. Li et al. [27] develop a simplified electrochemical-thermal model with a lower computation
cost, which coupled with lumped thermal analysis and the calculation of heat generation. Bahiraei et al. [28] also present a simplified
electrochemical-thermal model, which firstly solved in 1D to keep the coupled model correct enough, and then the electrochemical
heat source by using UDF are carried out in 3D to research the non-uniform temperature distribution. Basu et al. [29] develop a
coupled 3D electrochemical thermal model which used computational fluid dynamics (CFD) package Starccm+ to predict the
thermal performance. Above peers’ models are based on the porous electrode theory combined with energy conservation equation,
which are resolved by using Matlab or CFD (such as Starccm+ or Comsol multiphysics solver). However, fewer studies have focused
on the coupled electrochemical-thermal model by using ANSYS FLUENT.
For this work, an improved ANSYS FLUENT MSMD (Multi-Scale Multi-Domain) electrochemical-thermal model coupled with
mass, charge, and energy conservation as well as electrochemical kinetics was proposed. The improved electrochemical-thermal
model was based on the porous electrode theory coupled with a 3D hierarchical porous structure of LFP/G hybrid cathode to
accurately predict the heat generation rate, heat dissipation rates and temperature distribution of the LFP/G hybrid cathode lithium-
ion battery.

2. Electrochemical-thermal model description

2.1. Pseudo two-dimensional electrochemical-thermal model

The P2D (Pseudo two-dimensional) model was used in this paper, which was based on Newman's group proposed a physics model
by using porous electrode, concentrated solution theories and the equations of the mass, charge, and energy conservation as well as
the electrochemical kinetics [30]. Li-ion migration can be accurately captured in this model. Fig. 1(a) showed the basic structure of
the Lithium-ion battery. The composite electrode consisted of active materials and electrolyte solution. The electrolyte phase con-
tinuously flowed the negative electrode, the separator and the positive electrode, while solid phase only existed in the negative and
positive electrode. The solid active material was modeled as a matrix of mono-sized spherical particles. The active material particles
of positive and negative electrodes were iron phosphate (LiFePO4) and amorphous carbon (LiC6), respectively. The separator, a
porous polymer membrane, which can form a physical barrier to block the movement of active material particle between the two
electrodes. During discharging, Li-ion stored in the anode was de-inserted and then released as ions in the electrolyte. Driven by
diffusion (concentration gradient) and migration (potential gradient), Li-ions travelled through the separator to the cathode where
they inserted in the lattice of the cathode active material. This process was reversed during the battery charging.
The electrochemical reactions occurred at the interface of the electrode and electrolyte among the negative and positive during
discharge and charge. A 3D porous LFP/G hybrid cathodes could increase the conducting interface of the electrode and electrolyte.
Graphene is a single atomic monolayer of graphite, which has three types of methods to prepare graphene, respectively are chemical
vapor deposition (CVD), Wurtz type reaction (by using CCl4, and substitution chlorine with conductive-C˭C-layers), and chemical
exfoliation [31]. Fig. 1(b) illustrates the chemical exfoliation to prepare graphene nanosheets, and the thickness of the graphene
nanosheet is only 0.81 nm [32]. Graphene has two dimensional nanostructures with outstanding electronic and mechanical prop-
erties as well as high surface area [33]. It is worth mentioning that the graphene can reduce the internal resistance of the battery and
hence enhances the output power [34–38].
Herein, we developed a novel 3D LFP/G hybrid cathode with a porous structure in ANSYS FLUENT. Fig. 1(c) represented the
structure of mixed conducting LFP/G composites, in which the bridging graphene nanosheets can form an effective conducting
network. At the same time, a porous structure between LiFePO4 and graphene nanosheets was formed by the random hybrid com-
posite, which can facilitate the penetration of the electrolyte to the surface of active materials, resulting in superior rate capability
and higher reversible capacities in comparison with the conventional LiFePO4. Graphene nanosheets integrated with porous LiFePO4
can create an effective electronically conducting network.

2.2. Electrochemical kinetics at the interface

Butler-Volmer equation [39] explained the local charge transfer current density as showed in Eq. (1):

α F α F
jn = j0 ⎧exp ⎛ a ⋅η ⎞ − exp ⎛− c ⋅η ⎞ ⎫
⎨
⎩ ⎝ RT ⎠ ⎝ RT ⎠ ⎬ ⎭ (1)

where j0 is the current density of exchange,αa and αc are charge transfer coefficients of the anodic and cathodic, respectively,F is the
Faraday constant and η is the local over potential.
The current density of exchange is found from Eq. (2) [40]:

j0 = Fk 0 c1αa (cs, max − cs, surf )αa csα, surf

c
(2)

3
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

where k0 is the constant of reaction rate, cs,max is the maximum value of lithium concentration both in the two electrodes and cs,surf is
the lithium concentration located at the surface of the active particles. The subscripts s define the solid phase and l represent the
electrolyte phase. The over potential is expressed as Eq. (3) [41]:
η = ϕs − ϕl − Ueq (3)
where φs is the potential of solid phase, and φl is the potential of electrolyte phase. Ueq represents the electrode's open circuit
potential.

2.3. Charge conservation, ions transport, and mass balance

The charge produced by oxidation processes is equal to the charge consumed by reduction process. This relationship can define as
a function of current and potential gradients by using Ohm's law. The transfer of ions in electrolyte complies with the Nernst-Planck
equation, which take into account the migration and diffusion terms, as shown in the following Eq. (4):
∂ ⎛ eff ∂ ⎞ ∂ ⎛ eff ∂
ke ⋅ ⋅ϕe + kD, e⋅ (lnce ) ⎞ + j Li = 0
∂x ⎝ ∂x ⎠ ∂x ⎝ ∂x ⎠ (4)
where j is the current density in the electrolyte or solid phase, φe is the potential of electrolyte, ce is the electrolyte concentration, k eff
Li

is the effective conductivity of electrolyte, while kDeff, e is the diffusion conductivity driven by concentration.
Since the charge transport in solid is restricted by Ohm's law, there is no need for the diffusion term to drive electron transport in
solid.
∂ ⎛ eff ∂ ⎞
σ ⋅ ⋅ϕs = j Li
∂x ⎝ ∂x ⎠ (5)
where σ eff
is the electronic conductivity of solid phase.

2.4. Heat generation sources in electrochemical-thermal model

ANSYS FLUENT did not have the ability to simulate the heat generation during reaction processes, so the heat generation sources
related to electrochemical term of the LFP/G hybrid cathodes lithium battery were proposed in this paper. In order to solve this
problem, a UDF (User Defined Function) was developed to calculate the heat generation during electrochemical reactions. The heat
generation sources related to electrochemical term in lithium-ion battery could conclude three main heat sources, respectively were
electronic ohmic heat sources (Se ) caused by internal contact resistances, heat from the reaction current and overpotentials (Sr ) , and
ion ohmic heat sources (Si ) caused by the motion of Li-ions cross the solid and electrolyte phases. Heat sources have an effect on the
performance and degradation of the battery materials during operating processes, which can be described in following heat sources.
Rc
Se = I 2
A (6)
where I is electronic current, A is plane area of electrode parallel to current collector, R c is internal contact resistances.
The reaction heat source is defined as in Eq. (7), which is usually treated as calculation value of the temperature [42].

Table 1
Model parameters for a 10Ah LiFePO4/Graphene hybrid cathode lithium-ion battery.
Parameter Negative electrode Separator Positive electrode unit

Design specification (geometry δ 50 * 10−4 25.4 *10−4 36.4 *10−4 cm

and volume fractions) Rs 1 * 10−4 1 * 10−4 cm
εs 0.58 0.5
εp 0.048 0.5 0.11
εf 0.04 0.06
εe 0.332 0.5 0.33
Solid and electrolyte phase Li+ cs,max 42.2 * 10−3 74.9 * 10−3 mol cm−3
concentration x0%,y0% 0.123 0.939
x100%,y100% 0.685 0.434
ce 1.2 * 10−3 1.2 * 10−3 1.2 * 10−3 mol cm−3
Kinetic and transport properties ki0 13.2 6.79 A cm−2
α a, α c 0.5,0.5 0.5,0.5
Ds 1.0 * 10–11 1.85 * 10–11 cm2 s−1
σ 1 0.1 S cm−1
De 2.6 * 10−6 2.6 * 10−6 2.6 * 10−6 cm2 s−1
p 1.5 1.5 1.5
k 7.9ce * 7.9ce *
exp(−13472 Ce1.4 ) exp(−13472Ce1.4 ) S cm−1
t+0 0.363 0.363 0.363

4
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

x + dx
Sr = A ∫ j Li (∅s − ∅e − U ) dx
x (7)
The ion ohmic heat source is defined as in Eq. (8),
x + dx 2 2
⎡σ eff ⎛ ∂∅s ⎞ + k eff ⎛ ∂∅e ⎞ + k eff ⎛ ∂lnce ⎞ ⎛ ∂∅e ⎞ ⎤ dx
Si = A ∫ ⎢ ⎝ ∂x ⎠ ⎝ ∂x ⎠
D
⎝ ∂x ⎠ ⎝ ∂x ⎠ ⎥
x ⎣ ⎦ (8)
Heat sources in Eq. (6), Eq. (7), and Eq. (8) have been implemented in the UDF and linked to the governing equations in ANSYS
FLUENT. Due to the 3D LFP/G hybrid cathode with a porous structure, the R c and A have been defined by the UDF that can reduce
internal contact resistances and increase the conducting interface of the electrode and electrolyte, respectively. Furthermore, the
detailed LFP/G hybrid cathode lithium-ion battery parameters can be seen in Table 1. Table 1 refers to the geometrical and design
parameters used in modeling process, including kinetic and transport properties as well as thermal properties.

3. Numerical simulation and experimental setup

3.1. Numerical simulation

In this study, the computational fluid dynamic (CFD) analysis was performed by using ANSYS FLUENT software which used the
finite-volume technique to untangle the physics equations. The mathematical formulations were resolved in the model combined heat
transmission moot points which containing all mechanisms of heat transfer such as conduction and convection and radiation.
In order to prognosticate the behavior of chemical, thermal and electrical processes in a battery, we used MSMD (Multi-Scale
Multi-Dimensional) battery model solver in ANSYS FLUENT, otherwise, the heat generation sources related to electrochemical term
of the LFP/G hybrid cathodes lithium battery were developed in this paper. The changed rules of the battery working voltage, the
current density distribution, and the total heat generation field are discussed by solving established model.

3.2. Experimental setup

A 3.2 V 10Ah prismatic LFP/G battery was put as an object for the experiment. Fig. 2(a) presented dimensions of the battery and
eight locations of thermocouples. Fig. 2(b) described the test equipment for the experiment. The charge or discharge of the battery at
different rates were completed by using a Neware battery test system. In order to collect the real-time data of temperature variations
of the battery during test, 8 K-type thermocouples with an accuracy of ± 0.1 °C were pasted at eight positions on the surface of the
battery. The sampling period of the temperature at eight positions were 10 s, which record by the control computer. A constant
temperature chamber ensured a stable ambient temperature for the battery test, which had a control range from 0 °C to 100 °C and a
control accuracy of ± 0.1 °C.
In this study, the discharged test at 0.5C, 1C, 2C and 4C were researched under the ambient temperature of 20 °C, respectively.
The variation of the battery temperature was continuously collected until SoC = 0 (State of Charge), which mean that the battery
arrived at the end of discharge. The discharged test at different rates were carried out three times, and the result of temperature
deviation collected at the same location of the battery surface was lower than 1 °C. Hence, the averaged temperature of three times
per location was applied in this paper.

4. Results and discussion

The averaged temperature of the LFP/G battery surface was obtained via simulation and experiment, which showed in Fig. 3(a).

Fig. 2. (a) The dimension of the battery and eight locations of thermocouples; (b) Demonstration of the test equipment.

5
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

Fig. 3. (a) Thermal validation; (b) Electrochemical validation; (c) Temperature and working voltage error analysis.

0.5 C, 1C, 2C, and 4C discharged tests were done at the ambient temperature of 20 °C. The temperature was the average of the battery
surface temperatures measured by eight thermocouples. As shown in Fig. 3(a), the average of the battery surface temperature
respectively increased by about 5 °C, 10 °C, 20 °C, and 25 °C on the basis of the ambient temperature under different discharged rates
(0.5C, 1C, 2C and 4C). It could be found that the surface temperature was lower than Xu et al. [26] (conventional LiFePO4 battery)
experimental measurement result, this was due to 3D porous LFP/G hybrid cathode used in this paper to model, which could reduce
the contact resistance and restrain temperature arise.
Fig. 3(b) compared the numerical simulation and the experimental measurement about the working voltage under 0.5C, 1C and
2C discharged rates. The simulation results agreed well with the experimental data, however, there were still some differences
between the simulation and the experiment. The difference among the results can be explained as: for one hand, the battery model
parameters came from literature, which may have little difference compared with this experimental battery. For the other hand, there
are not have the uniform electrochemical reaction on the active material surface. Last but not least, the internal equilibrium as-
sumption may not completely response during discharge. The thermal validation (in Fig. 3(a)) and the electrochemical validation (in
Fig. 3(b)) could illustrate that the electrochemical-thermal coupled model for the LFP/G battery was developed accurately.
Based on the above analysis, both the thermal validation and the electrochemical validation were carried out by the simulated
values and experimental datasets. One criterion, i.e. the root mean square error (RMSE), was used to evaluate the error performance
about the averaged temperature and the working voltage, as shown in Fig. 3(c). The max temperature RMSE and the working voltage
are 0.2202 °C and 0.09966 V, respectively. The RMSE is defined as follows:

k
∑i = 1 |AE − AS |2
RMSE =
k (9)

where k is sampled points, AE and AS represents the experimental data and simulated values, respectively.
The distribution of the current density of the LFP/G battery was presented at 1C discharged process as shown in Fig. 4. The color
of arrows indicated the magnitude level of the current density. As shown in Fig. 4, the direction of current flow could form a

Fig. 4. The distribution of the current density of the battery at 1C discharged process.

6
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

circulation, which mean that the current input through the negative current collecting tab and then output through the positive
current collecting tab. The magnitude of current density decreased gradually with the increase of distance of two tabs. Closed to the
edge of the battery, the magnitude of current density was almost small. This is due to part of the current changes the direction of
motion when it is near to the edge, resulting in the current goes vertically into sandwich structure of adjacent local cell units. Since
the battery is overlapping by some cell units, the current perpendicularly flowed through the cell unit is named the local working
current which function is participating in the electrochemical reaction both the negative electrode and the positive electrode. In the
battery cell unit, the electric conductivity of current collectors (Cu and Al) is much higher than other component layers (pe, ne and
sp). In the battery, cell units are paralleled via current collectors to connect. The positive and negative tabs serve as the “bridge” to
connect external load.

(a) 2min (b)30min

(c)50min (d) 2min

Fig. 5. The potential distribution of the positive and negative current collectors at the 1 C discharged rate. Discharge time is (a, d) 2 min, (b) 30 min,
(c) 50 min.

7
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

The potential distribution of the positive and negative current collectors at the 1 C discharged rate were presented in Fig. 5. It
could be seen in Fig. 5(a-c), when the discharged time were 2 min, 30 min, and 50 min, the value of the potential of positive current
collector were about 3.27 V, 3.05 V, and 2.86 V, respectively. The potential distribution of the negative current collector was shown
in Fig. 5(d). When the discharged time was 2 min, the value of the potential of negative current collector is almost 0 V. This is because
the boundary condition of the negative tab of the model was defined as 0 V. According to Ohmic law, the direction of current and
potential gradient is opposite. Therefore, it could be known in Fig. 4, the current flowed into the negative tab and then spread to the
entire region, at last flowed out the positive tab. The magnitude of current density decreases gradually with increase of distance of
two tabs. However, the magnitude variation trend of potential is completely opposite to that of the current density, as shown in Fig. 5.
The distribution of the LFP/G battery working voltage under 1 C discharge rate at time of 2 min, 30 min and 50 min were showed
in Fig. 6. It could be found out that the working voltage of the entire battery was uneven during the discharged process. However, the
working voltage of the entire battery dropped slightly from discharged time 2–50min, this was because the LFP/G battery had a stable
discharged voltage. It could be observed that there was a large potential gradient closed to the positive tab (left tab), because the
positive current collector and tab were consisted of Al foil, while the negative current collector and tab (right tab) were composed by
Cu foil. The electric conductivity of Al foil was lower than Cu foil, which resulted in generating potential gradient closed to the
positive tab. Further, the unevenness of local working voltage was owing to the heterogeneous electrochemical reaction rate of the
battery. The local working voltage was difference between positive and negative current collector potential.
The simulation of total heat generation source at different discharged C-rate (1C, 2C, and 4C) with constant ambient temperature
(20 °C) were presented in Fig. 7(a), (c) and (e), meanwhile the experimental measurement of total heat generation source at same
operation condition were showed in Fig. 7(b), (d) and (f). The data of experiment obtained from 8 thermocouples, as shown in
Fig. 2(a). To compare the experiment and the simulation, which we could find out that the simulation results agree well with the
experimental data. For Fig. 7(b), (d) and (f), each color block coded as green represented the coldest zone and dark read represented
the hottest zone. In Fig. 7(b), 10, 20, 30, 40 and 50 were the time to indicate the start of the test, respectively, the unit was minute.
Each column of the block collected temperature was the interval of two minutes. Similarly, for Fig. 7(d), each column of the block
collected temperature was the interval of one minute, which began at 5 min; for Fig. 7(f), each column of the block collected
temperature was the interval of twenty seconds, which began at 1 min.
Fig. 7 showed the top of the cell closed to tabs (thermocouple 1 and 2) were the hottest location (dark red) at different C-rates and
the middle of the cell (thermocouple 3, 4 and 5) were the hotter location (light yellow) at different C-rates. Both simulations and
experiments verified that the total heat generation source was gradually shifted from the bottom of the cell (thermocouple 6, 7 and 8)
towards to the top (thermocouple 1 and 2) of the cell. This phenomenon was similar to the trend of current density, which can be
explained by internal architecture of the LFP/G battery. LFP/G batteries were main composed of multiple layers of sandwiched
electrodes, current collectors and separator. Between each layer of the positive and negative electrodes nipped current collectors
which welded together with the cell tabs to maintain the external connection. Therefore, in order to provide power for external
connection, all current flowed towards to the top of the battery and current density increases towards to the top of the battery. Thus,
the total heat generation source rises largely at the top of the battery.
The total heat generation of the #mark of the battery at different discharged C-rate was monitored, as shown in Fig. 8. During 1C
discharge, the initial phase (before 500 s) of total heat generation slowly increased, and then maintained steadily trend in the middle
period, the trend curve of total heat generation suddenly increased occurred at last period (after 3000 s). During 2C discharged
process, the heat generation linearly increased (before 400 s) and then the heat generation in the plot frequently fluctuated until the
end of the discharged process. During 4C discharged process, the heat generation rapidly increased (before 200 s) and then waved a
little period at the middle of the discharge until the end of the discharged process. The exothermic process of the battery during
discharged were own to the larger current density, the fluctuation of total heat generation source curves monitored in # mark of the
LFP/G battery was caused by three main heat sources, respectively were electronic ohmic heat sources (Se ) , heat from the reaction
current and overpotentials (Sr ) , and ion ohmic heat sources (Si ) .

2min 30min 50min

Fig. 6. The distribution of the battery working voltage under 1C discharged rate at time of 2 min, 30 min and 50 min.

8
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

(a)1C-rate Simulation (b) 1C-rate Experiment

(c) 2C-rate Simulation (d) 2C-rate Experiment

(e) 4C-rate Simulation (f) 4C-rate Experiment

Fig. 7. Total heat generation source for simulation (a), (c), (e) and surface temperature obtained from 8 thermocouples for experiment (b), (d), (f).

9
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

Fig. 8. The total heat generation of the #mark of the battery at different discharged C-rate (1C, 2C, 4C).

5. Conclusion

A simplified pseudo electrochemical-thermal coupled model for the LFP/G hybrid cathode Lithium-ion battery was developed in
this study. The accuracy of the pseudo electrochemical-thermal coupled model was further validated by monitoring electrochemical
performance and thermal behavior of the LFP/G battery. Both the experiment and the simulation proved that the LFP/G battery could
restrain the increase of temperature during the discharged process. The distribution of the working voltage, the current density and
total heat generation source of the battery during discharged process could be presented by solving electrochemical-thermal coupled
model. During the discharged process, the non-uniform distribution of the voltage and the current density were due to the internal
structure of the LFP/G battery. The total heat generation distribution was presented, which agrees well with the experimental results.
Furthermore, it was verified that closed to two tabs were the hottest area of the battery.

Acknowledgments

This work was supported by the Major Program of Natural Science Foundation of Inner Mongolia Autonomous Region, China
[Grant no. 2017ZD02]; Natural Science Foundation of Jiangsu Province, China [Grant no. BK20140301]; National Natural Science
Foundation of China, China [Grant nos. 11402156 and 61503269]; and Research and Innovation Project of Postgraduate of Inner
Mongolia Autonomous Region, China [Grant no. B20171012803Z].

Conflict of interest

No conflict of interest exits in the submission of this manuscript, and manuscript is approved by all authors for publication. I
would like to declare on behalf of my co-authors that the work described was original research that has not been published pre-
viously, and not under consideration for publication elsewhere, in whole or in part. All the authors listed have approved the
manuscript that is enclosed.

References

[1] J. Kang, F. Yan, P. Zhang, C. Du, Comparison of comprehensive properties of NiMH (nickel-metal hydride) and Li-ion (lithium-ion) batteries in terms of energy
efficiency, Energy 70 (2014) 618–625.
[2] E.M. Krieger, J. Cannarella, C.B. Arnold, A comparison of lead-acid and lithium-based battery behavior and capacity fade in off-grid renewable charging
application, Energy 60 (2013) 492–500.
[3] S.Y. Chung, J.T. Bloking, Y.M. Chiang, Electronically conductive phospho-olivines as lithium storage electrodes, Nat. Mater. 1 (2002) 123–128.
[4] C.C. Li, Y.H. Wang, T.Y. Yang, Effects of surface-coated carbon on the chemical selectivity water-soluble dispersants of LiFePO4, J. Electrochem. Soc. 158 (2011)
828–834.
[5] X.W. Zhang, X. Kong, G. Li, J. Li, Thermodynamic assessment of active cooling/heating methods for lithium-ion batteries of electric vehicles in extreme
conditions, Energy 64 (2014) 1092–1101.
[6] C.D.L. Casas, W. Li, J. A review of application of carbon nanotubes for lithium ion battery anode material, J. Power Sources 208 (2012) 74–85.
[7] B. Scrosati, J. Hassoun, Y.K. Sun, Lithium-ion batteries. A look into the future, Energy & Environ. Sci. 4 (2011) 3287–3295.
[8] N. Nitta, F. Wu, J.T. Lee, G. Yushin, Li-ion battery materials: present and future, Mater. Today 18 (2015) 252–264.
[9] V. Palomares, A. Goni, I.G. Muro, I. Meatza, M. Bengoechea, I. Cantero, T. Rojo, Conductive additive content balance in Li-ion battery cathodes: commercial
carbon blacks vs. in situ carbon from LiFePO4/C composites, J. Power Sources 195 (2010) 7661–7668.
[10] X. Yang, Y. Xu, H. Zhang, Y. Huang, Q. Jiang, C. Zhao, Enhanced high rate and low-temperature performances of mesoporous LiFePO4/ketjen black nano-
composite cathode material, Electrochim. Acta 114 (2013) 259–264.
[11] G. Qin, Q. Wu, J. Zhao, Q. Ma, C. Wang, C/LiFePO4/multi-Walled carbon nanotube cathode material with enhanced electrochemical performance for lithium-ion
batteries, J. Power Sources 248 (2014) 588–595.
[12] A. Varzi, C. Ramirez-Castro, A. Balducci, S. Passerini, Performance and kinetics of LiFePO4-carbon bi-material electrodes for hybrid devices: a comparative study
between activated carbon and multi-walled carbon nanotubes, J. Power Sources 273 (2015) 1016–1022.

10
Y. Li et al. Case Studies in Thermal Engineering 13 (2019) 100387

[13] H. Zhang, Y. Chen, C. Zheng, D. Zhang, C. He, Enhancement of the electrochemical performance of LiFePO4/carbon nanotubes composite electrode for Li-ion
batteries, Ionics 21 (2015) 1813–1818.
[14] M.D. Stoller, S. Park, Y. Zhu, J. An, R.S. Ruoff, Graphene-based ultracapacitors, Nano Lett. 8 (2008) 3498–3502.
[15] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
Science 306 (2004) 666–669.
[16] R.S. Patil, V.A. Juvekar, Analysis of multiparticle bipolar electrolysis using single particle cell model, Chem. Eng. Sci. 110 (2014) 72–82.
[17] X. Hu, S. Li, H. Peng, A comparative study of equivalent circuit models for Li-ion batteries, J. Power Sources 198 (2012) 359–367.
[18] L.H. Saw, Y. Ye, A.A.O. Tay, Electro-thermal characterization of lithium iron phosphate cell with equivalent circuit modeling, Energy Convers. Manag. 87 (2014)
367–377.
[19] V. Ramadesigan, P.W.C. Northrop, S. De, S. Santhanagopalan, R.D. Braatz, V.R. Subramanian, Modeling and simulation of lithium-ion batteries from a systems
engineering perspective, J. Electrochem. Soc. 159 (2012) 31–45.
[20] J. Jaguemont, L. Boulon, Y. Dubé, A comprehensive review of lithium-ion batteries used in hybrid and electric vehicles at cold temperatures, Appl. Energy 164
(2016) 99–114.
[21] A. Fotouhi, D.J. Auger, K. Propp, S. Longo, M. Wild, A review on electric vehicle battery modelling: from lithium-ion toward lithium-sulphur, Renew. Sustain.
Energy Rev. 56 (2016) 1008–1021.
[22] Q. Wang, B. Jiang, B. Li, Y. Yan, A critical review of thermal management models and solutions of lithium-ion batteries for the development of pure electric
vehicles, Renew. Sustain. Energy Rev. 64 (2016) 106–128.
[23] R. Zhao, S. Zhang, J. Liu, J. Gu, A review of thermal performance improving methods of lithium ion battery: electrode modification and thermal management
system, J. Power Sources 299 (2015) 557–577.
[24] C.R. Pals, J. Newman, Thermal modeling of the lithium/polymer battery, J. Electrochem. Soc. (1995) 142.
[25] F. Mohammed, S. Haitham, F. Matthias, H. Saeid, Combined electrochemical, heat generation, and thermal model for large prismatic lithium-ion batteries in
real-time applications, J. Power Sources 360 (2017) 618–633.
[26] M. Xu, Z. Zhang, X. Wang, L. Jia, L. Yang, A pseudo three-dimensional electrochemical–thermal model of a prismatic LiFePO4 battery during discharge process,
Energy 80 (2015) 303–317.
[27] L. Junfu, W. Lixin, L. Chao, W. Han, L. Xuan, New method for parameter estimation of an electrochemical-thermal coupling model for LiCoO2battery, J. Power
Sources 307 (2016) 220–230.
[28] B. Farid, G. Maryam, F. Amir, Z. Gholam-A, A pseudo 3D electrochemical-thermal modeling and analysis of a lithium-ion battery for electric vehicle thermal
management applications, Appl. Therm. Eng. 125 (2017) 904–918.
[29] B. Suman, S.H. Krishnan, M.K. Subramanya, S. Taewon, K.S. Dong, Coupled electrochemical thermal modelling of a novel Li-ion battery pack thermal man-
agement system, Appl. Energy 181 (2016) 1–13.
[30] M. Doyle, T.F. Fuller, J. Newman, Modeling of galvanostatic charge and discharge of the lithium/polymer/insertion cell, J. Electrochem. Soc. 140 (1993)
1526–1533.
[31] H. Bi, F. Huang, Y. Tang, Z. Liu, T. Lin, J. Chen, W. Zhao, Study of LiFePO4 cathode modified by graphene sheets for high-performance lithium ion batteries,
Electrochim. Acta 88 (2013) 414–420.
[32] Y. Zhou, Q.L. Bao, L.A.L. Tang, Y.L. Zhong, K.P. Loh, Hydrothermal dehydration for the “Green” reduction of exfoliated graphene oxide to graphene and
demonstration of tunable optical limiting properties, Chem. Mater. 21 (2009) 2950–2956.
[33] I.W. Frank, D.M. Tanenbaum, A.M. Van, der Zande, P.L. McEuen, Mechanical properties of suspended graphene sheets, J. Vac. Sci. Technol. 25 (6) (2007)
2558–2561.
[34] C. Su, X. Bu, L. Xu, J. Liu, C. Zhang, A novel LiFePO4/graphene/carbon composite as a performance-improved cathode material for lithium-ion batteries,
Electrochem. Acta 64 (2012) 190–195.
[35] Y. Shi, S.-L. Chou, J.-Z. Wang, D. Wexler, H.-J. Li, H.-K. Liu, Y. Wu, Graphene wrapped LiFePO4/C composites as cathode materials for Li-ion batteries with
enhanced rate capability, J. Mater. Chem. 22 (32) (2012) 16465–16470.
[36] O. Toprakci, H.A.K. Toprakci, L. Ji, Z. Lin, R. Gu, X. Zhang, LiFePO4 nanoparticles encapsulated in graphene-containing carbon nanofibers for use as energy
storage materials, J. Renew. Sustain. Energy 4 (2012) 110–121.
[37] S.W. Oh, Z.-D. Huang, B. Zhang, Y. Yu, Y.-B. He, J.-K. Kim, Low temperature synthesis of graphene-wrapped LiFePO4 nanorod cathodes by the polyol method, J.
Mater. Chem. 22 (33) (2012) 17215–17221.
[38] Y. Zhang, W. Wang, P. Li, Y. Fu, X. Ma, A simple solvothermal route to synthesize graphene-modified LiFePO4 cathode for high power lithium ion batteries, J.
Power Sources 210 (2012) 47–53.
[39] V. Ramadesigan, P.W.C. Northrop, S. De, S. Santhanagopalan, R.D. Braatz, V.R. Subramanian, Modeling and simulation of lithium-ion batteries from a systems
engineering perspective, J. Electrochem. Soc. 159 (2012) 31–45.
[40] M. Doyle, Comparison of modeling predictions with experimental data from plastic lithium ion cells, J. Electrochem. Soc. 143 (1996) 1890.
[41] W. Fang, O.J. Kwon, C. Wang, Electrochemical–thermal modeling of automotive Li-ion batteries and experimental validation using a three-electrode cell, Int. J.
Energy Res. (2010) 107–115.
[42] V. Srinivasan, C.Y. Wang, Mathematical modeling of current-interrupt and pulse operation of valve-regulated lead acid cells, J. Electrochem. Soc. 150 (2003)
98–106.

11