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Matlab simulation of lithium ion cell using electrochemical single particle

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Conference Paper · December 2016

DOI: 10.1109/SPEC.2016.7846195

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 Matlab Simulation of Lithium Ion Cell Using
Electrochemical Single Particle Model
Ngoc Tham Tran¹, Mahinda Vilathgamuwa¹, Troy Farrell², San Shing Choi¹
¹School of Electrical Engineering and Computer Science, ²School of Mathematical Sciences
Queensland University of Technology
Brisbane, Queensland, Australia
ngoctham.tran@hdr.qut.edu.au, mahinda.vilathgamuwa@qut.edu.au, t.farrell@qut.edu.au, sanshing.choi@uwa.edu.au
Abstract— Battery modelling is a significant component of
advanced Battery Management Systems (BMSs). The full
electrochemical model of a battery can represent high precision
battery behavior during its operation. However, the high
computational requirement to solve the coupled nonlinear partial
differential equations (PDEs) that define these models limits their
applicability in an online BMS, especially for a battery pack
containing hundreds of cells. Therefore, a reduced SPM-Three
parameter model is proposed in this paper to efficiently model a
lithium ion cell with high accuracy in a specific range of cell
operation. The reduced model is implemented in a Simulink
block for developing an advanced battery modelling tool that can
be applied to a wide variety of battery applications.
Keywords—Lithium ion cell; electrochemical model; Single
Particle Model; Three parameter model
I. INTRODUCTION
Lithium ion batteries are used in many battery storage
systems because of their low self-discharge rates, long life and
high power and energy density [1]. Lithium ion batteries are
used in pure Battery Electric Vehicles (BEVs), Plug-in Electric
Vehicles (PHEVs) and Hybrid Electric Vehicles (HEVs) as a
full or partial replacement of gasoline to achieve more
environmentally friendly, modern transportation [2]. Moreover,
lithium ion batteries are used in large renewable energy storage
systems, such as wind and solar photovoltaics, either as part of
the power grid or in stand-alone installations. In order to
operate batteries optimally with the intention of maintaining
safety and extending battery life, a Battery Management
System (BMS) is essential [3]. An effective BMS should be
able to estimate the state of health and state of charge using
advanced control techniques [4]. Most estimation algorithms
require an accurate battery model that can precisely describe
the voltage response of the battery during the current
charge/discharge process. Therefore, battery modelling has
become an integral part of developing a BMS.
Simple equivalent circuit models are normally applied in
model-based methods. In such models the battery is
represented by an Open Circuit Voltage (OCV) connected in
series with an internal resistance and a parallel circuit that
includes a charge transfer resistance and a double layer
capacitance [5]. This circuit model is very simple and it
requires minimal computation cost to solve. However, batteries
have highly nonlinear electrochemical characteristics that
depend significantly on external and internal conditions.
978-1-5090-1546-7/16/$31.00 ©2016 IEEE
Simple circuit models have only limited capability in
accurately accounting for the dynamic electrochemical
behavior of lithium ion batteries.
The electrochemical model, which accounts for phenomena
such as the transport of charge within the cell, the intercalation
processes that occur within the solid phase electrode materials
and the electrochemical kinetics occurring at the charge
transfer interfaces inside the battery during its operation, is an
alternative model of battery operation [6-8]. With this model
the battery voltage can be accurately predicted, however, the
computational cost associated with solving the coupled, non-
linear partial differential equations that define the model is very
high in comparison with equivalent circuit models. In addition,
depending on the application, the energy capacity of a battery
storage system can vary from kWh to MWh in size [9]. Given
that a single cell has typically only 7.5Wh energy capacity
[10], large capacity systems are usually built using many
battery packs which consist lithium ion cells connected in
series and parallel to achieve the required voltage and capacity
level [11].
A simplified electrochemical model that has low
computational overheads, whilst maintaining its precision in a
specific range of battery operation, would therefore be ideal in
order to facilitate the accurate, real-time resolution and control
of individual cells within a battery storage system. There are
several reduced electrochemical models in the literature [12,
13]. The Single Particle Model (SPM) is one of the practical
solutions that is used to reduce the complexity of the full
electrochemical model from a model of five PDEs and one
algebraic equation into a single PDE and an algebraic equation
[14]. A model reduction using two-parameter and three-
parameter algebraic equations to approximate the PDE
governing the solid-state lithium concentration in the full
electrochemical model has also been developed [13].
This article develops a simple electrochemical model based
on the SPM [14] and in which the governing PDE is
approximated by two differential algebraic equations and one
algebraic equation. This is done in a manner similar to that
given in [13] where the lithium concentration in the single
particle that comprises each electrode can be expressed by a
polynomial function of the particle radius. The model is
implemented in Simulink in such a way that it can be used in
numerous system simulations. The feasibility of the proposed
model is validated by comparing predicted cell voltage from
1
this model with that of the SPM. We find that the proposed The potential in the solid electrodes:
model significantly reduces the computation time for ∂ș s ( x, t ) ie ( x, t ) − I (t )
simulation whilst producing a good approximation to the SPM = (1)
∂x σ
output.
The potential in the electrolyte:
II. ELECTROCHEMICAL MODEL
∂ș e ( x, t ) i ( x, t ) 2 RT § d ln f c / a · ∂c ( x, t )
A schematic diagram of a lithium ion battery is given in Fig. =− e + (1 − tc0 ) ¨1 + ( x, t ) ¸ e (2)
∂x κ F © d ln ce ¹ ∂x
1. The one-dimensional, electrochemical model of this battery
deals with four important domains, namely: the porous The lithium ion concentration in the solid particles:
negative electrode, the porous positive electrode, the separator ∂cs ( x, r , t ) 1 ∂ § ∂c ( x, r , t ) ·
and the electrolyte [12]. During the discharge process, lithium = 2 ¨ Ds r 2 s ¸ (3)
∂t r ∂r © ∂r ¹
ions diffuse from the interior of the solid particles of the
negative electrode to the surface. At the surface they undergo The lithium ion concentration in the electrolyte:
an electrochemical reaction whereby they are transferred into ∂ce ( x, t ) ∂ § ∂ce ( x, t ) · 1 ∂ (ta0ie ( x, t )
the electrolyte phase. Thereafter, the ions travel through the = ¨ De ¸ + (4)
∂x ∂x © ∂x ¹ F ε e ∂x
electrolyte solution to the positive electrode where they again
react at the surface of the solid particles and are intercalated The current in the electrolyte:
into these particles. This processes shown in Fig. 1. The reverse ∂ie ( x, t )
of this occurs in the charge process when the lithium ions flow = aFjn ( x, t ) (5)
∂x
from the solid phase of the positive electrode to the solid phase
of the negative electrode. As the separator form an electrically The molar flux (given by the Butler-Volmer equation):
insulation barrier between the electrodes the flow of electrons i 0 ( x, t ) ª §α F · § −α F ·º
associated with these charge and discharge processes occurs jn ( x, t ) = exp ¨ a ηs ( x, t ) ¸ − exp ¨ c ηs ( x, t ) ¸ » (6)
F «¬ © RT ¹ © RT ¹¼
via an external circuit connecting the two compartments and do
useful work as they do so [15]. Here the over-potential η s ( x, t ) of the intercalation reaction is
The full electrochemical model that describes the above given by:
processes consists of six state variables including the electric η s ( x, t ) = ș s ( x, t ) − ș e ( x, t ) − U (css ( x, t )) − FR f jn ( x, t ) (7)
potential ș s ( x, t ) in the solid electrode, the electric potential
And i 0 ( x, t ) is the exchange current density:
ș e ( x, t ) in the electrolyte, the lithium ion concentration of the
αa αc
active material cs ( x, r , t ) of the positive and negative i 0 ( x, t ) = reff ce ( x, t )α a (cs ,max − css ( x, t )) css ( x, t ) (8)
electrodes, the lithium ion concentration ce ( x, t ) in the
electrolyte, the ionic current ie ( x, t ) in the electrolyte and the III. SPM OF A LITHIUM ION CELL
molar ion fluxes jn ( x, t ) between the active material in the The SPM embodies an approach to reduce the complexity of
the full electrochemical model presented above. It is based on
electrodes and electrolyte. The governing equations of the the assumptions that the applied current to the battery is small
electrochemical model are given by [12]. and the conductivity of the electrolyte is large. Each electrode
compartment is represented by a single particle as depicted in
Fig. 2.

Fig 1. Schematic of one-dimensional electrochemical model of a lithium ion Fig 2. Single Particle Model of a lithium ion cell [12]
cell [4]

2
 The electrolyte concentration is assumed to be constant and Symbol Units
Negative
Separator
Positive
Electrode electrode
that the current in the electrolyte does not vary with space [12].
By applying these assumptions, the lithium ion cell model is Rf mȍ 0 - 0
simplified from one consisting of the PDEs (1), (2), (3), (4), (5) L 10 cm−4
50 25 36.4
and the algebraic equation (6) to the following two PDEs (one De 10−6 cm 2s -1 2.6 2.6 2.6
for each electrode in (9)) and algebraic equation (13) [12].
εs - 0.58 - 0.50
The lithium concentration in the solid particle of electrodes: β − 0% , β + 0% - 0.126 - 0.936
∂cs± ( r , t ) 1 ∂ § ∂cs± (r , t ) · β −100% , β +100% - 0.676 - 0.442
− 2 ¨ Ds ¸=0 (9)
∂t r ∂r © ∂r ¹ εs - 0.58 - 0.50
with initial and boundary conditions given by:
cs ( r ,0) = cs0, ± (r ) (10)
IV. THREE-PARAMETER APPROXIMATION MODEL FOR THE
∂cs± LITHIUM SOLID CONCENTRATION
=0 (11)
∂r r =0 A highly efficient approximation for the SPM can be
± achieved by reducing the PDE (9) of the lithium diffusion in
∂c I (t )
s
= − j ± (t ) = ± (12) particles to differential algebraic equations. Two and three
∂r r = Rp
Fa ± L± parameter models that do this is are presented in [13],
The output voltage of the lithium ion cell: however, the three parameter model was found to be more
accurate at representing the solutions of the PDE. Here we
V (t ) = ș +s0 (t ) − ș −s0 (t ) − I (t ) Rcollector (13) apply the same three parameter model reduction as given in
where: [10] to (9) of the SPM presented in the previous section. A
summary of this model reduction is as follows [10]. The
2 RT § B I (t ) · lithium concentration is assumed to be a polynomial function
ș ±s0 (t ) = sinh −1 ¨ ¸
of the single particle radius and given as,
F ¨ 2a ± L± reff ce0css± (t )(cs±,max (t ) − css± (t )) ¸ (14)
© ¹
R ±f I (t ) cs ( r , t ) = a (t ) + b(t ) ( r / R p ) + d (t ) ( r / R p )
2 4

+ U ± (css± (t )) + ± ± (17)
a L
The Open Circuit Potential of the negative and positive By using this assumption, the first boundary condition
electrodes are functions of stoichiometry and are adapted from ( r = 0 ) in (11) is satisfied and the second boundary condition
[15] as follows: ( r = Rp ) in (12) change into (18):

2 Ds 4 Ds
U − ( β − ) = 8.00229 + 5.0647 β − − 12.578( β − )1/ 2 b(t ) + d (t ) = jn (t ) (18)
− 8.6322 x10−4 ( β − ) −1 + 2.1765 x10−5 ( β − )3/ 2 Rp Rp
(15)
− 0.46016exp[15.0(0.06 − β − )]
− 0.55364exp[( x − 0.92)] The volume-averaged concentration and volume-averaged
concentration flux are expressed in (19) and (20), respectively:
U + ( β + ) = 85.681( β + )6 − 357.7( β + )5 + 613.89( β + ) 4
− 555.65( β + )3 + 281.06( β + ) 2 − 76.648β + (16)
Rp
r2 § r ·
− 0.30987 exp(5.657( β + )115 ) + 13.1983
cs (t ) = ³ 3R 2
cs (r , t )d ¨ ¸
¨R ¸
(19)
r =0 p © p¹
where: β ± = css± (t ) / cs±,max (t ) Rp
§ r ·
r2 d
The PDEs in (9) are solved by using the “pdepe” solver in
qs (t ) = ³ 3R 2
dr
cs ( r , t ) d ¨
¨R
¸
¸
(20)
r =0 p © p ¹
Matlab. The parameters used in the model are those from the
FreedomCar cell and are given in [15] and listed here in Table Substituting (17) into (19) and (20) and evaluating, we have:
1. 3 3
cs (t ) = a (t ) + b(t ) + d (t ) (21)
5 7
TABLE I. FREEDOMCAR CELL MODEL PARAMETERS [15]
3 2
Negative Positive qs (t ) = a (t ) + b(t ) + d (t ) (22)
Symbol Units
Electrode
Separator
electrode
2 Rp Rp
δ 10−4cm 50 25.4 36.4 Evaluating (17) at the surface condition ( r = Rp ), we get:
Rp 10 cm−4
1 - 1
cs ,max
cs (t ) = a (t ) + b(t ) + d (t ) (23)
10−3molcm-3 16.1 - 23.9
ce ,0 10−3molcm-3 1.2 1.2 1.2 The three coefficients a(t ) , b(t ) and d (t ) can be obtained by
i0 manipulating equations (21), (22) and (23) to obtain:
10−3Acm -2 3.6 - 2.6
Rcollector mȍ 1.9 - 1.9 39 35
a (t ) = css (t ) − cs (t ) − 3qs (t ) R p (24)
Ds 10 −12 2 -1
cm s 2.0 - 3.7 4 4

3
 b(t ) = −35css (t ) + 35cs (t ) + 10qs (t ) R p (25) SPM-Three parameter model consist of three differential
algebraic equations, the computation requirement is
105 105 dramatically reduced from that of the SPM and full
d (t ) = css (t ) − cs (t ) − 7 qs (t ) R p (26)
4 4 electrochemical models. Consequently, the cell block can be
connected in series and parallel to achieve the required battery
Substituting (24), (25) and (26) into (17) we obtain: pack voltage and capacity for large battery storage system
39 35 simulation with low computation cost. Fig. 3 shows an
cs ( r , t ) = css (t ) − cs (t ) − 3qs (t ) R p + (−35css (t ) + 35cs (t ) implementation of the cell model in a simple application in
4 4
2
§ r · § 105
4
(27) Simulink. The cell is connected to a Controlled Current Source
105 ·§ r ·
+10qs (t ) R p ) ¨ ¸ + ¨ css (t ) − cs (t ) − 7 qs (t ) R p ¸ ¨ ¸ that represents a constant current load. The lithium ion cell is
¨ ¸ ¹ ©¨ R p ¹¸
© Rp ¹ © 4 4
continuously discharged by different constant current rates
Volume averaging the governing equation (9) we obtain: ranging from 1C to 10C.
Rp
r 2 ª ∂cs (r , t ) 1 ∂ § ∂cs (r , t ) · º § r ·
³ 3R
r =0
2 «
p ¬ ∂t
− 2 ¨ Ds
r ∂r ©
¸ d¨ ¸=0
∂r ¹ ¼» ©¨ R p ¹¸
(28)

Substituting (27) into (28), the volume-averaged

concentration then becomes:
d j (t )
cs (t ) = −3 n (29)
dt Rp

Differentiating equation (9) and volume averaging we have: Fig 3. Simulink model of a lithium ion cell connected to a load with a 1C
discharge current rate
ª ∂cs (r , t ) 1 ∂ § ∂cs (r , t ) · º
− 2 ¨ Ds ¸ Fig. 4 shows the detailed equivalent circuit of a designed
r 2 ¬« ∂t ∂r ¹ ¼» § r ·
Rp
r ∂r ©
³r =0 Rp2
3 ∂
∂r
d¨ ¸ =0
¨ Rp ¸
(30) electrochemical cell named Electro_cell_SPM3. The cell
model consists a SPM-Three parameter model block, a
© ¹
Controlled Voltage Source block, a resistance and a current
Substituting (27) into (30), the volume-averaged sensor. The SPM-Three parameter model block contains
concentration flux is then governed by: Matlab Functions blocks and Integrator blocks used to
d D 45 jn (t ) calculate the cell voltage based on (13), (14), (15), (16), (29),
qs (t ) + 30 2s qs (t ) + =0 (31) (31), and (32). The input of the SPM-Three parameter model
dt Rp 2 R p2
block is the charge/discharge current from the current
The surface concentration of lithium in the particles css (t ) is measurement block. In order to avoid the algebraic loop error,
then obtained by substituting (25) and (26) into (18) to give: an initial condition block (IC block) is added into the SPM-
Three parameter model block to set the initial condition of the
8Rp Rp current input. The output of the SPM-Three parameter model
css (t ) = cs (t ) + qs (t ) − jn (t ) (32) block is then formed an input of the Controlled Voltage Source
35 Ds
block which converts the input signal into an equivalent
Equations (29), (31) and (32) represent the SPM-Three voltage source. The resistor Rcollector represents the cell current
parameter model for the lithium concentration at the surface of collector contact resistance.
the single particle that constitutes each electrode in the SPM
presented above. As stated above, we can see that we have Figs. 5, 6, 7 and 8 depict the comparison between the voltage
reduced a single PDE (9) into an algebraic equation (32) and response of the SPM-Three parameter model, a Two-parameter
two ordinary differential equations ((29) and (31)). The initial version of the SPM (details not given here) and the SPM for
conditions for (29) and (31) are given by the initial state of the five discharge current rates including 1C, 5C, 7C, and 10C. It is
cell. For a single discharge of a new cell these values will be observed that the difference between the SPM-Two parameter
cs ( r ,0) = cs0, ± ( r ) and qs (0) = 0 . To obtain the cell voltage using model and SPM-Three parameter model increases as the
this model, the lithium surface concentration css (t ) from (32) is current rate increases. Furthermore, the SPM-Three parameter
model and the SPM give very similar results.
substituted into (14), (15) and (16) which are then substituted
into (13). The SPM-Three parameter model requires 0.011 second to
simulate the 3600 second discharge profile on a desktop
V. IMPLEMENTATION OF SPM-THREE PARAMETER MODEL FOR computer, which is about 3.06 μsec/sample. On the other hand,
the “pdepe’’ solver in Matlab requires 0.478 second to simulate
LITHIUM ION CELL IN SIMULINK
the same profile on the same desktop computer, which is about
The SPM-Three parameter model that is presented in the 0.133 msec/sample. Thus, the SPM-Three parameter model is
previous section (equations (13), (29), (31) and (32)) is approximately 40 times faster than using the SPM with one
implemented in the Matlab/Simulink environment. In Simulink governing PDE. Consequently, the SPM-Three parameter
it represents a “lithium ion cell block” which can be applied to model is a candidate for real-time control applications since it
various simulation applications in power electronics including requires low computation while maintaining high accuracy
an electrochemical cell within a large battery pack. Since the compared to the SPM.

4
 Fig 4. Equivalent circuit of the SPM-Three parameter model for lithium ion cell

Voltage response 1C discharge rate

4
1C-Two parameter model
1C-Three parameter model
1C-PDE model

3.5
V [V]

2.5
0 500 1000 1500 2000 2500 3000 3500 4000
t [s]
Fig 7. Cell voltage response during 7C discharge rate
Fig 5. Cell voltage response during 1C discharge rate

Fig 6. Cell voltage response during 5C discharge rate Fig 8. Cell voltage response during 10C discharge rate

5
 VI. CONCLUSIONS ACKNOWLEGEMENT
This paper presents a simple electrochemical SPM-Three This work was supported by the Australian Research
parameter battery model for lithium ion cells. We have shown Council Discovery Grant DP160101325.
that the model maintains high accuracy when compared with
the outputs from the SPM whilst achieving an approximately
40 times computational speed increase in our implementation
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