WCIPT 2018 Special Issue

Transactions of the Institute of

Measurement and Control
Evaluation of particle dispersion 1–12
Ó The Author(s) 2019

behaviours in Lithium-ion battery Article reuse guidelines:

sagepub.com/journals-permissions
DOI: 10.1177/0142331219857414
slurry by electrical impedance journals.sagepub.com/home/tim

spectra-tomography method

Zhilong Wang1,2 , Tong Zhao1, Masanori Kanzawa2,

Kai Liu1 and Masahiro Takei2

Abstract
This paper investigated the particle dispersion behaviours of Lithium-ion battery (LIB) slurry by using electrical impedance spectra-tomography (EIST)
method from the perspective of experiment and simulation. In the experiment, an EIST system composed of Field—Programmable Gate Array (FPGA),
multi-plexer, switch circuit and 8-electrode sensor is developed to measure the frequency response of LIB slurry under two different conditions, which
are rotation speed n=0rpm with rotation time t=0min and n=100rpm with t=6min. In the simulation, four different geometry structure models, which
are (a) Carbon Black (CB) linear formation, (b) CB aggregation, (c) CB & LiCoO2 aggregation and (d) network dispersion, are established. Six frequen-
cies, which are f=1 kHz, f=10 kHz, f=50 kHz, f=100 kHz, f=250 kHz and f=500 kHz, are used for the reconstructed conductivity images of LIB slurry in
both the experiment and the simulation. The numerical simulation is used to verify the correctness of the experiment results. After combining the
experiment and the simulation, it is concluded that the agglomeration behaviours of CB and LiCoO2 particles appear within LIB slurry in the case of
n=0rpm with t=0min, while CB path and part LiCoO2 particles coated by CB particles appear in the case of n=100rpm with t=6min. Moreover, high fre-
quencies are suitable to distinguish high conductive CB components from LIB slurry. Furthermore, the developed EIST system has the capability of
monitoring particle dispersion behaviours in LIB slurry, which has the potential to be used for the on-line measurement of LIB slurry in order to
improve the performance of LIB.

Keywords
Particle dispersion behaviours, electrical impedance spectra-tomography (EIST), Lithium-ion battery (LIB) slurry, reconstructed conductivity image

Introduction dispersant on the electrochemical characterizations of LIB

Lithium-ion battery (LIB) as one of the most popular power
sources has been widely used for portable electronics, electric
vehicles (EVs) and plug-in hybrid electric vehicles (PHEVs)
over the past few decades (Zheng et al., 2012). The perfor-
mance of LIB is largely influenced by slurry preparation pro-
cess because particle dispersion behaviours are controlled by
several factors during this process such as rotation speed n,
rotation time t and so on (Kraytsberg and Ein-Eli, 2016).
Especially, a homogenous LIB slurry has the capability of
ensuring the manufactured LIB with high energy density, rel-
atively good safety and good cycling stability (Bai and Song,
2013). Thus, it is necessary to find an on-line approach to
evaluate particle dispersion behaviours in the real-time manu-
facture process of LIB slurry.
Numerous research works have focused on the particle dis-
persion behaviours of LIB slurry. Dominko et al. (2003) pro-
posed a novel coating technology by pre-treating active
materials (AM) with gelatin, which serves as a sort of glue to
catch nano CB. They pointed out that the uniformity of CB
distribution affects significantly LIB cathode kinetics regard-
less of the type of AM particles used. To clarify the effect of
cathode, Zhang et al. (2013) used Triton X-100 as a dispersant
to pre-disperse CB in NMP solvent. Their research results in
that cathodes with pre-dispersed CB exhibit improved rate
behaviour. Zhang et al. (2014) also pre-dispersed CB with
poly acrylic acid (PAA) as dispersant in NMP solvent, they
concluded that pre-dispersed CB is dispersed homogeneously
in the dried composite electrode to form a more uniform con-
ductive network among AM particles. The above-mentioned
investigations are mainly focused on how to successfully dis-
perse particles in LIB slurry by using pre-treating technology;
however, the detailed information of particle dispersion beha-
viours is not clear. As for particle dispersion behaviours, the
1
Faculty of Mechanical and Precision Instrument Engineering, Xi’an
University of Technology, China
2
Division of Artificial Systems Science, Graduate School of Mechanical
Engineering, Chiba University, Japan
Corresponding author:
Tong Zhao, Faculty of Mechanical and Precision Instrument Engineering,
Xi’an University of Technology, Xi’an 710048, China.
Email: tongzhao@xaut.edu.cn
2 Transactions of the Institute of Measurement and Control 00(0)
related research works are also seldom. Bai and Song (2013)
successfully correlated the internal structure that is particle
dispersion behaviours and electrochemical impedance spec-
troscopy of LIB slurry by using an 8-parameter electrical
equivalent circle (EEC); they pointed out that the increment
of the impedance of active material, conductive additive and
binder is caused by the collapse of the network structure
regarding the slurry over time. In addition, Kwon et al. (2015)
investigated the agitation effect on the rheological behaviour
of LIB slurry; the results show that the breakdown of the net-
work structure of LIB slurry is accelerated when applying agi-
tation to the slurry. Thus, research works regarding to
particle dispersion behaviours are considerably superficial by
only mentioning the existence of network structure in LIB
slurry. Meanwhile, lacking on-line measurement of particle
dispersion behaviours in LIB slurry, it is difficult to monitor
rapid variation process of LIB slurry during the manufacture
process of LIB. Therefore, it is very necessary to clarify other
particle dispersion behaviours except network structure, espe-
cially during the slow slurry preparation process in LIB
slurry.
Dielectric analysis is a useful tool for interpreting the
dielectric characteristics of heterogeneous systems and for
obtaining detailed information, especially for suspensions of
spherical colloidal particles (He and Zhao, 2005). Thus,
dielectric characteristics, which are resistance, reactance and
conductivity (Wang et al., 2019), are considered to have an
insight into the internal mechanism of particle dispersion
behaviours in LIB slurry. To understand the dielectric charac-
teristics of LIB slurry, a novel non-invasive electrochemical
impedance spectra-tomography (EIST) method is utilized.
Actually, EIST is a combination of electrochemical impe-
dance spectroscopy (EIS) and electrochemical impedance
tomography (EIT). In EIS, the measurements have been per-
formed within a wide range of frequencies, which allows
frequency-dependent responses to be properly characterized
(Akhavan and Rajabipour, 2013; Baidillah et al., 2017). Thus,
the electrochemical characterizations, which are resistance,
reactance and peak frequencies of LIB slurry, are able to be
obtained from Nyquist plots and Bode plots (Andre et al.,
2011; Vediappan et al., 2014). In EIT, an array of electrodes
attached around the object are used to inject current by
changing adjacent electrode position with measuring the rest
adjacent electrode voltage (Yao and Takei, 2017). Then, the
conductivity distribution images of LIB slurry are able to be
reconstructed by optimizing hyperparameter a and maximum
iterations numbers Imax in Tikhonov algorithm (Baidillah
et al., 2018; Seppänen et al., 2014).
In this paper, EIST method is adopted to perform the
experiment and the simulation with 8-electrode sensors. In
the experiment, LIB slurry is stirred under two different con-
ditions, which are rotation speed n=0rpm with rotation time
t=0min and n=100rpm and t=6min. In the simulation, four
different geometry models, which are (a) CB linear formation,
(b) CB aggregation, (c) CB & LiCoO2 aggregation and (d)
network structure, have been established to change particle
dispersion status in LIB slurry. Six frequencies, which are
f=1 kHz, f=10 kHz, f=50 kHz, f=100 kHz, f=250 kHz
and f=500 kH,z are used for the reconstructed conductivity
images of LIB slurry in the experiment and the simulation.
The dielectric characteristics that reflect particle dispersion
behaviours obtained from the experiment are verified by
those obtained from numerical simulation. Eventually, in
order to clarify how n and t affect particle dispersion beha-
viours during the slow slurry preparation process in LIB
slurry, a comparison based on EIS results between the experi-
ment and the simulation is performed; in order to confirm the
best frequency of the EIST method, a comparison based on
the reconstructed conductivity images between the experiment
and the simulation is performed; in order to obtain high per-
formance LIB, a strategy based on the dielectric characteris-
tics of EIST results is proposed. The final purpose of this
paper is to verify the initial feasibility of EIST method for the
evaluation of particle dispersion behaviours in LIB slurry.
Experiment
Experiment setup
As is shown in Figure 1, the experiment includes two different
setups. Figure 1 (a) shows the experiment setup of LIB slurry
preparation process, which comprises a blade, a beaker, a
motor and a stand. The blade is installed on the stand to mix
LIB slurry under different rotational speed. The beaker is
used to store LIB slurry. Out from the A-A cross section, it is
shown that the diameter of the blade is 45mm, while the
diameter of the beaker is 50mm. Figure 1(b) shows the
experiment setup of 8- EIST system, which is composed
an Arduino board, an 8-electrode sensor, a VCCS, a Field -
Programmable Gate Array (FPGA) board, a PC and a switch
circuit (Xu et al., 2018). The Arduino board is able to sense
and control objects in the physical and digital world by using
a variety of microprocessors and controllers. The 8-electrode
sensor is assigned to surround the boundary of the beaker to
transfer the signal data between the Arduino board and LIB
slurry. The FPGA board installed on Red pitaya is an inte-
grated circuit which is used to generate an AC voltage control
signal and measure the voltage from sensor. The PC is used to
record the measured voltage values. The switch circuit is used
to control the status (ON and OFF) of current injection. The
VCCS, which is called voltage controlled current source, is
used to convert alternating current (AC) voltage control
signal into an AC current control signal. In this EIST sys-
tem, anolog multiplexer which is used to realize the chan-
nel switching, is composed of Arduino board and switch
circuit.
Experimental materials and conditions
Table 1 shows the experimental materials and conditions.
Specifically, two kinds of materials, which are salt solution
and LIB slurry, are used at the present work. The salt solu-
tion is regarded as the reference material with the conductiv-
ity s=3.0 3 10-3 S/m, while LIB slurry, which is composed of
Polyvinylidenefluoride (PVDF) binder, N-methylpyrrolidone
(NMP) solvent, LiCoO2 and CB particles, is stirred under
two different conditions. The diameter of LiCoO2 particles is
dLiCoO2 = 1.0 3 10-5m, the diameter of CB particles is
dCB=5.0 3 10-8m. LiCoO2 particles as active materials has
Wang et al. 3

Figure 1. Experiment setup (a) LIB slurry preparation process, (b) 8-electrode EIST system.

Table 1. Experimental materials and conditions.

Experimental materials and conditions Volume fraction

Reference material Salt solution (O" = 3 x 10-3S/m)

Object 1 LIB slurry (NMP + PVDF + CB + LiCo02)
Rotation speed n: 0 rpm, Time t :0 min
Object 2 LIB slurry (NMP + PVDF + CB + LiCo02)
Rotation speed n: 100 rpm, Time t :6 min

the function of providing Lithium element; CB as conductive
materials is to increase the conductivity of LIB slurry; PVDF
as a binder plays the role of binding LiCoO2 particles and CB
together; NMP as organic solvent can dissolve PVDF.
Besides, the masses of LiCoO2, CB, PVDF and NMP solvent
are 79.8g, 3.52g, 3.4g and 30.6g, respectively. The manufac-
ture process of LIB slurry was shown by the following steps.
Firstly, PVDF and a half of NMP solvent were blended
manually for 5 minutes, and then the remained NMP solvent
was manually mixed for another 5 minutes to make a homo-
geneous PVDF-NMP solution. Subsequently, CB and
LiCoO2 particles are added into the premixed PVDF-NMP
solution, then LIB slurry was obtained by mixing under dif-
ferent conditions. As for object 1, LIB slurry is just as-
prepared one with the rotation speed n=0rpm and rotation
time t=0min; while as for object 2, LIB slurry is stirred under
the conditions of n=100rpm and t=6min. Moreover, in
terms of salt solution, the volume fraction of salt solution is
uS=100%, while, in terms of LIB slurry, the volume fraction
of NMP solution uNMP=60.3%, the volume fraction of
PVDF binder uPVDF=3.9%, the volume fraction of conduc-
tive agent CB particles uCB=3.6 % and the volume fraction
of active material LiCoO2 particles uLiCoO2=32.2 %.
Furthermore, the frequency range of EIST experiment is
changed from 1 kHz to 500 kHz. During this frequency
range, six different frequency points, which are f=1 kHz,
f=10 kHz, f=50 kHz, f=100 kHz, f=250 kHz and f=500
kHz, are used to reconstruct the experimental conductivity
images of LIB slurry. Meanwhile, the amplitude of injected
current is 0.5 mA.
Experiment method
Figure 2 illustrates adjacent current projection based on EIST
method. In EIST method, two adjacent electrodes such as the
electrode-pairs of 1–2 are initially used to inject current, then,
the voltage values of the rest adjacent electrode-pairs such as
(3–4, 4–5, 5–6, 6–7 and 7–8) are measured. Afterwards, except
for the electrode-pairs of 1–2, a circulation among the rest
adjacent electrodes is executed to inject current. Finally,
according to the calculation equation shown in Figure 2, the
total number of measurement voltage ntotal=n 3 (n-
3)=8 3 (8-3)=40. Herein, n is the number of measurement
electrodes. In addition, Electrical Impedance and Diffused
Optical Reconstruction Software (EIDORS) as an open
source software suite is used for the reconstruction conductiv-
ity images based on Newton Raphson algorithm (Sarode
et al., 2012).
The Newton Raphson algorithm is used to calculate the
conductivity of an object by comparing with that of a refer-
ence material. The basic equation is able to be shown as
4 Transactions of the Institute of Measurement and Control 00(0)

complex-valued current. After considering the above-

mentioned equation (6) or equation (7), the conductivity
matrix of LIB slurry can be obtained. In order to obtain the
reconstructed images of conductivity distribution behavior in
LIB slurry, a reference data is needed here. NMP solution is
regarded as the reference data. So, the reconstruction image
of the relative conductivity s
 can be calculated by the follow-
ing equation

sobj  sref
=
s ð9Þ
sref

Figure 2. Adjacent current projection based on EIST method. wherein, sobj is the conductivity of object; while sref is the
conductivity of reference material.

1
f = (Vs  Vo )T (Vs  Vo ) ð1Þ
2 Experiment results
Wherein, u is potential at each measurement point. Vs is the Nyquist plots and Bode plots of LIB slurry
voltage in the case of reference material, Vo is the voltage in
Figure 3 shows the experiment results by using EIST method.
the case of object 1 or object 2. The purpose of EIST method
Specifically, Figure 3(a) illustrates the Nyquist plots of LIB
is to characterize conductivity variation by minimizing the
slurry under two different conditions. One of the condition is
value of u. So, the differentiate u with respect to s is shown
rotation speed n=0rpm with rotation time t=0min, another
as follows
condition is n=100rpm with t= 6min. In addition, Figure
∂f ∂Vs 3(b) illustrates the Bode plots of LIB slurry also under those
= ½ T (Vs  Vo ) = J T (Vs  Vo ) = 0 ð2Þ two different conditions. Obviously, in Figure 3(a), the
∂s ∂s
Nyquist plots in the case of both n=0rpm with t=0min and
Wherein, J is Jacobean matrix. By using Taylor expansion, n=100rpm with t=6min are composed of two semi-circles
the conductivity after kth iteration is able to be evaluated as with a straight line. The diameters of the semi-circles and the
length of the straight line in the case of n=100rpm with
∂f ∂f k ∂2 f t=6min are smaller and shorter than those in the case of
= (s ) + 2 (sk )Dsk ð3Þ
∂s ∂s ∂s n=0rpm with t=0min, respectively. As referred to in our pre-
viously published papers (Wang et al., 2017, 2019), the semi-
Wherein, after using the initial conductivity obtained from
circle in high frequency represents LiCoO2-NMP interface dis-
the solution of forward problem s0, the conductivity is shown
persion, while the semi-circle in low frequency indicates
as
PVDF-NMP solution dispersion. Meanwhile, the length of
 1 the straight line reflects the amount of the conductivity path
Ds = J T J J T (Vs  Vo ) ð4Þ formed by CB in LIB slurry. Thus, the dielectric dispersion
characteristics, which are LiCoO2-NMP interface dispersion
However, because the hessian matrix is always ill posed, then,
and PVDF-NMP solution dispersion, are able to be used to
the Tikhonov regularization method is used to calculate the
explain the particle dispersion behaviours of LIB slurry. In
conductivity, which is expressed by
the case of n=0rpm with t=0min, resistance Z’ and reactance
 1 Z’’ of LIB slurry are relatively large. This means that LiCoO2-
Ds = J T J + lI J T (Vs  Vo ) ð5Þ NMP interface dispersion caused by different permittivity and
conductivity of the LiCoO2 particle and the surrounding
wherein, l is the regularization hyperparameter and I is the
PVDF-NMP solution is also large, which results in the seri-
identity matrix. In addition, the boundary conditions of EIST
ously aggregated LiCoO2 particles; meanwhile, PVDF-NMP
method in terms of 8-electrode sensor includes
solution dispersion caused by the polarization of the counter-
∂f ions in PVDF-NMP solution is also large, which leads to the
f + zl s = Ul ð6Þ seriously aggregated CB particles. In the case of n=100rpm
∂h
ð with t=6min, Z’ and Z’’ of LIB slurry are relatively small.
∂f This means that LiCoO2-NMP interface dispersion is also
s dS = Il ð7Þ
∂h relative small, which results in the slightly dispersion of
el
LiCoO2 particles; meanwhile, PVDF-NMP solution disper-
∂f sion becomes small, which clarified that CB particles are
s =0 ð8Þ slightly dispersed in LIB slurry and part LiCoO2 particles are
∂h
coated by those dispersed CB particles. In Figure 3(b), as
where, zl is effective contact impedance between lth electrode bode plots of LIB slurry have two peak Z’’, two different peak
and medium, h is outward normal to the surface electrodes, el frequencies fpeak,low and fpeak,high are shown. In addition, three
is electrode l, Ul is the complex-valued voltage, Il is the different frequencies, which are f=1 kHz, f=250 kHz and
Wang et al. 5

Figure 3. Experiment results by using EIST method (a) Nyquist plots (b) Bode plots.

f=500 kHz, are also shown in both Figure 3(a) and Figure
3(b), because the experimental reconstructed conductivity
images of LIB slurry will be obtained under those three differ-
ent frequencies. It is obvious that all of those three frequen-
cies, which are f=1 kHz, f=250 kHz and f=500 kHz, are
between fpeak,low and fpeak,high as more detailed information
can be clarified here. However, the above-mentioned dielectric
characteristics are only obtained from the Nyquist plots and
Bode plots in the experiment, which needs to be further
investigated.

Reconstructed conductivity images

Figure 4 shows the experimental reconstructed conductivity
images by using EIST method with Newton Raphson algo-
rithm. In Figure 4, LIB slurries mixed under two different
conditions (n=0rpm with t=0min and n=100rpm with
t=6min) are analysed with six different frequencies, which
are f=1 kHz, f=10 kHz, f=50 kHz, f=100 kHz, f=250 kHz
and f=500 kHz. The color I indicates the aggregation beha-
viours of the clusters of low conductivity LiCoO2 particles,
while the color II represents the aggregation behaviours of
the clusters of high conductivity CB particles. In this regard,
Figure 4 is able to be well explained. In the case of f=1 kHz
and f=10 kHz, the reconstructed conductivity images of LIB
slurries under both n=0rpm with t=0min and n=100rpm
with t=6min conditions have much more color I with a little Figure 4. Experimental reconstructed conductivity images by using
bit of color II, which implies that the centre of the experi- EIST method.
mental reconstructed conductivity images are the clusters of
LiCoO2 particles, while near the boundary of the experimen- slurry under n=0rpm with t=0min condition have both color
tal reconstructed conductivity images are the mixture of I and color II, which are almost the same with that under
NMP solution and very little clusters of LiCoO2 and CB par- n=100rpm with t=6min condition. Specifically, LiCoO2 par-
ticles. This illustrates that lower frequencies, which are f=1 ticles are located at the centre of the reconstructed conductiv-
kHz and f=10 kHz, are not able to visualize the distribution ity images of LIB slurry. Meanwhile, the mixture of NMP
behaviours of high conductivity CB particles regardless the solution and very little clusters of LiCoO2 and CB particles
variation of n and t. Moreover, in the case of f=50 kHz and are located near the boundary of the reconstructed conductiv-
f=100 kHz, the reconstructed conductivity images of LIB ity images of LIB slurry. Thus, medium frequencies, which
6 Transactions of the Institute of Measurement and Control 00(0)
Figure 5. SEM images of LIB slurry under two different conditions (a) rotation speed n=0rpm with rotation time t=0min (b) n=100rpm with t=6min.
are f=50 kHz and f=100 kHz, are also difficult to visualize
particle distribution behaviours in LIB slurry. Furthermore,
in the case of f=250 kHz and f=500 kHz, compared with the
situation where LIB slurry is stirred under n=0rpm with
t=0min condition, it is clear that the color II indicated the
clusters of CB particles is almost homogenous distributed
within LIB slurry under n=100rpm with t=6min condition.
In addition, the reconstructed conductivity images of LIB
slurry in the case of f=500 kHz tend to be much clearer than
those in the case of f=250 kHz. Therefore, higher frequen-
cies, which are f=250 kHz and f=500 kHz, have the capabil-
ity of evaluating particle distribution behaviours in LIB
slurry.
Discussion
In order to verify the correctness of the experiment results,
numerical simulation is also performed to clarify the dielectric
characteristics of LIB slurry by assuming four different geo-
metry models based on particle dispersion behaviours.
According to those two different experiment conditions,
which are rotation speed n=0rpm with rotation time t=0min
and n=100rpm with t=6min, different particle dispersion
behaviours are very necessary to be firstly assumed. As is
shown in the following Figure 5, the realistic scanning elec-
tron microscope (SEM) images of LIB slurry under the condi-
tions of n=0rpm with t=0min (Figure 5(a)) and n=100rpm
with t=6min (Figure 5(b)) are different from each other. In
Figure 5(a), CB particles are seriously aggregated; while in
Figure 5(b), CB particles are slightly aggregated. Thus, con-
sidering the confused particle dispersion behaviours in the
realistic situation shown in Figure 5, it is considerably essen-
tial to simplify particle dispersion behaviours in the simula-
tion. Based on the fact that both of LiCoO2 particles and CB
particles are aggregated in LIB slurry in the case of n=0rpm
with t=0min, part of LiCoO2 particles coated by short CB
particles are slightly dispersed in LIB slurry in the case of
n=100rpm with t=6min, firstly the models of CB & LiCoO2
aggregation and CB aggregation are assumed, respectively.
Furthermore, in order to clarify the full process of particle
dispersion behaviours, the models of CB linear formation and
network dispersion are also assumed. Then, four different
geometry structure models are assumed as follows: (a) CB lin-
ear formation, (b) CB aggregation, (c) CB & LiCoO2 aggre-
gation and (d) network dispersion.
Geometry structure model & meshes of numerical
simulation
Figure 6(a’) as a representative figure only shows the dimen-
sions of the geometry structure models (a) because of the rea-
son that all of those assumed geometry structure models have
the same dimensions. Specifically, the diameter of the outside
circle is 5.0 3 10-2m, the electrode has a square shape with the
size of 2.0 3 10-3m 3 2.0 3 10-3m. Both of the total height and
width of the model are 5.2 3 10-2m. Within the outside circle,
the diameters of those four big circles are 6.0 3 10-3m, the
diameters of 32 small circles are 1.5 3 10-3m. In addition,
those four big circles represent LiCoO2 particles, those 32
small circles indicate CB particles, the rest area indicates
NMP solution. The numbers of LiCoO2 particles and CB
particles are the same for those four different geometry mod-
els. Additionally, although the numbers of LiCoO2 particles
and CB particles in the simulation are much less than those
used in the experiment, however, the effective volume ratio
between LiCoO2 particles and CB particles in the experiment
is almost same with the effective surface ratio between
LiCoO2 particles and CB package in the simulation in order
to unify the conditions between the experiment and the simu-
lation. Herein, CB package represents several single CB parti-
cles, which is used to simplify the simulation.
Figure 6(a) is the geometry structure model same with
Figure 6(a’). In this regard, four different geometry structure
models are assumed from Figure 6(a) to Figure 6(d), which
are (a) CB linear formation, (b) CB aggregation, (c) CB &
LiCoO2 aggregation and (d) network dispersion. Moreover,
instead of using Multiphysics simulation, only electrostatic
Wang et al. 7

Figure 6. Geometry structure models (a’) dimensions of geometry structure model of (a), (a) CB linear formation, (b) CB aggregation, (c) CB &
LiCoO2 aggregation and (d) network dispersion.

field simulation is performed at the present work in order to

simplify the simulation procedure. Furthermore, Figure 7
shows the meshes of those four different models shown in
Figure 6. All of those models are used the type of triangular
meshes. The total mesh numbers of Figure 7(a), Figure 7(b),
Figure 7(c) and Figure 7(d) are 15958, 12986, 13016 and
18986, respectively. Meanwhile, the minimum element size of
the triangular mesh is 1.0 3 10-4m. Three boundary layers are
taken into consideration to improve the accuracy of the simu-
lated results.

Simulation conditions and methods

Table 2 shows the information about EIST simulation condi-
tions based on LIB slurry. Four different components are
included in LIB slurry, which are LiCoO2 as lithium sources,
CB as conductive additives, NMP as solvent, and PVDF as a
binder. Herein, the diameter of LiCoO2 particles is d’LiCoO2
= 6.0 3 10-3m, while the diameter of CB package is
d’CB=1.5 3 10-3m. Besides, the permittivity of LiCoO2, CB,
NMP, and PVDF are 19, 5, 32.2 and 10, respectively. The
conductivities of LiCoO2, CB, NMP, and PVDF are 1.0 3 10-
4
S/m, 6.67 3 104S/m, 1.0 3 10-6S/m and 1.0 3 10-6S/m, respec-
tively. The densities of LiCoO2, CB, NMP, and PVDF are
4.9 3 103 Kg/m3, 1.8 3 103 Kg/m3, 1.89 3 103 Kg/m3 and Figure 7. Simulation meshes of geometry models (a) CB linear
formation, (b) CB aggregation, (c) CB & LiCoO2 aggregation and (d)
1.78 3 103 kg/m3, respectively. In addition, as for the simula-
network dispersion.
tion method, those four different geometry structure models
8 Transactions of the Institute of Measurement and Control 00(0)
Table 2. EIST simulation conditions for LIB slurry
Components LiCoO2
Diameter[m] 6.0310-3
Permittivity [-] 19
Conductivity [S/m] 1.0310-4
Density [kg/m3] 4.93103
Figure 8. EIS results of LIB slurry models (a’) Nyquist plots (b’) Bode plots.
are firstly established in COMSOL Multiphysics. Then, a
constant current with the amplitude of 0.5mA is applied to
inject current for two adjacent electrode pairs. Meanwhile,
the conductivity images of those four different geometry
structure models are reconstructed under six different fre-
quencies, which are f=1 kHz, f=10 kHz, f=50 kHz, f=100
kHz, f=250 kHz and f=500 kHz. As a result, the recon-
structed conductivity images between the experiment and the
simulation have been compared. Eventually, the correctness
of particle dispersion behaviours obtained from the experi-
ment is verified by the experiment.
Comparisons of EIS results between the experiment
and the simulation
Figure 8 shows comparisons of EIS results between the experi-
ment and the simulation. In view of the simplified four differ-
ent geometry structure models, the LiCoO2-NMP interface
dispersion caused by different permittivity and conductivity of
the LiCoO2 particle and the surrounding PVDF-NMP solu-
tion is able to be observed, however, the PVDF-NMP solu-
tion dispersion caused by the polarization of the counterions
in PVDF-NMP solution is not able to be observed because of
the extremely less CB particles. Thus, only the semi-circle in
low frequency range from the experiment is shown here. In
Figure 8 (a’), the diameter of Nyquist plot is largest in the case
of the model of (c) CB & LiCoO2 aggregation. In contrary,
CB NMP (C5H9NO) PVDF
1.5310-3
5 32.2 10
6.673104 1.0310-6 1.0310-6
1.83103 1.893103 1.783103
the smallest diameter of Nyquist plot appears in the case of
the model of (a) CB liner formation. The diameters of
Nyquist plots of the model of (b) CB aggregation model and
the model of (d) network dispersion are slightly larger than
that of the model of (a) CB liner formation. After comparing
EIS results between the experiment and the simulation, it is
clear that Z’ and Z’’ obtained from the simulation are much
more than those obtained from the experiment, which is
caused by the extremely less high conductive CB particles. It
is able to be concluded that the diameter of Nyquist plot of
the model (c) CB & LiCoO2 aggregation obtained from the
numerical simulation results of Figure 8 (a’) has the same ten-
dency with that of LIB slurry experimentally stirred in the
case of n=0rpm.This illustrates that particle agglomeration
behaviours including both CB particles and LiCoO2 particles
appear within LIB slurry in the case of n=0rpm. Moreover,
the diameter of Nyquist plot of the model of (a) CB liner for-
mation obtained from numerical simulation results of Figure
8 (a’) has the same tendency with that of LIB slurry experi-
mentally stirred in the case of n=100rpm. Furthermore, the
resistances Z’ of the model of Figure 6(a) CB liner formation
and Figure 6(d) network dispersion model are smaller than
those of the model of Figure 6(b) CB aggregation and Figure
6(c) CB & LiCoO2 aggregation. This illustrates that CB path
dominated LIB slurry has the minimum Z’ and reactance Z’’;
however, this is only an ideal situation for LIB slurry. In real-
ity, well-mixed LIB slurry is not only composed of CB path
but also CB-coated LiCoO2 particles, which refers to the
Wang et al.
model of (d) network dispersion shown in Figure 8(a’). This
shows that it is the particle aggregation behaviour that results
in the increment of Z’ and Z’’ of LIB slurry. Meanwhile, CB
path together with network structure in LIB slurry can largely
decrease the Z’ and Z’’ of LIB slurry. Therefore, LIB slurry in
the case of n=100rpm with t=6min with small Z’ and Z’’ is
composed of both CB path and CB-coated LiCoO2 particles.
Figure 8 (b’) illustrates the Bode plots of four different geome-
try structure models shown in Figure 6. Nevertheless, as for
those four different geometry structure models, the relaxation
frequencies, which are the frequencies that appear at the peak
of reactance in Bode plots, are almost same with each other.
Meanwhile, those peak frequencies obtained from the simula-
tion are also almost same with those in the low frequency
range obtained from the experiment. This is caused by the fol-
lowing two reasons: on the one hand, the efficient particle sur-
face area under those four different geometry structure
models are the same with each other; on the other hand, parti-
cle numbers in the simulation are much less than those in the
experiment. Considering the above-mentioned reasons, the
correctness of experimental results is then gradually verified
by the current numerical simulation results.
Comparisons of reconstructed conductivity images
between the simulation and the experiment
Figure 9 shows the numerical reconstructed conductivity
images of four different simulated models under six different
frequencies, which are f=1 kHz, f=10 kHz, f=50 kHz,
f=100 kHz, f=250 kHz and f=500 kHz. The number of fre-
quency points between the experiment and the simulation are
the same with each other in order to obtain more detailed
information about particle dispersion behaviours in LIB
slurry. Figure 9(a) illustrates the numerical reconstructed con-
ductivity images of the model of Figure 6(a) CB linear forma-
tion. It is clear that in the case of f=1 kHz, the centre of the
numerical reconstructed conductivity image is color I, which
illustrates the existence of LiCoO2 particles. However, this is
incorrect because the centre is CB particles in terms of the CB
linear formation model. In the case of f=10 kHz, f=50 kHz
and f=100 kHz, color II representing CB particles is in the
centre, and color I indicating LiCoO2 particles is eccentric,
which are almost consistent with Figure 6(b) the CB aggrega-
tion model. In addition, the difference of the reconstructed
images among f=10 kHz, f=50 kHz and f=100 kHz are rel-
atively small. In the case of f=250 kHz and f=500 kHz, it is
obvious that color II is in the centre and color I is eccentric,
which are also consistent with Figure 6(b) the CB aggregation
model. The difference of the numerical reconstructed conduc-
tivity image between f=250 kHz and f=500 kHz is that the
boundary contour in the case of f=500 kHz is much clear
than that in the case of f=250 kHz. Figure 9(b) illustrates the
numerical reconstructed conductivity images of the model of
Figure 6(b) CB aggregation. In the case of f=1 kHz, color II
indicating CB particles appears in the centre of reconstructed
image, which is contradicted by the model of Figure 6(b) CB
aggregation. However, in the case of f=10 kHz, f=50 kHz,
f=100 kHz, f=250 kHz and f=500 kHz, color I representing
9
LiCoO2 particles is in the centre of the CB aggregation
model, while light color II representing CB aggregation is
eccentric. In addition, the numerical reconstructed conduc-
tivity image in the case of f=500 kHz is slightly obvious
than that of any other frequencies. Figure 9(c) illustrates
the numerical reconstructed conductivity images of the
model of Figure 6(c) CB & LiCoO2 aggregation. In the case
of f=1 kHz, light color II representing CB aggregation is in
the centre, which is contradicted by the model of Figure
6(c) CB & LiCoO2 aggregation. However, in the case of
f=10 kHz, f=50 kHz, f=100 kHz, f=250 kHz, color I rep-
resenting LiCoO2 particles is located in the centre position,
light color II indicating the slightly aggregated CB particles
is located in the eccentric position. Furthermore, in the case
of f=500 kHz, the numerical reconstructed conductivity
image is exactly the same with the model of Figure 6(c) CB
& LiCoO2 aggregation. Figure 9(d) shows the numerical
reconstructed conductivity images of the model of Figure
6(d) network dispersion. Similar with the previous three
cases, the numerical reconstructed conductivity image under
f=1 kHz is also opposite to the original model of Figure
6(d) network dispersion. Nevertheless, with the increase of f
from f=50 kHz to f=500 kHz, the numerical reconstructed
conductivity image also reflects the real model of Figure
6(d) network dispersion with little change in the colour var-
iations. This verifies that the CB particles are well dispersed
in LIB slurry. Therefore, after analysing the numerical
reconstructed conductivity images under four different geo-
metry structure models, it shows that the numerical recon-
structed conductivity images are able to be properly
visualized by using high frequencies rather than lower
frequencies.
Compared with the experimental reconstructed conductiv-
ity images shown in Figure 4, the numerical reconstructed
conductivity images shown in Figure 9 also are able to be
classified into two groups. In the case of f=1 kHz, recon-
structed conductivity images in the simulation are opposite to
the established geometry structure models. Meanwhile, in the
case of lower frequencies such as f=10 kHz, f=50 kHz and
f=100 kHz, reconstructed conductivity images in the experi-
ment are considerably ambiguous to distinguish the ingredi-
ent of high conductive CB from LIB slurry. Thus, lower
frequencies are not proper to be used for the reconstructed
conductivity images in terms of both the simulation results
and the experiment results. Moreover, in the case of higher
frequencies such as f=250 kHz and f=500 kHz, the recon-
structed conductivity images are able to reasonably reappear
in the established geometry structure models in the simulation
and to properly reflect particle distribution behaviours in the
experiment. In addition, when compared with SEM images
shown in Figure 5, the reconstructed conductivity images
obtained from the experiment under both the condition of
rotation speed n=0rpm with rotation time t=0min and the
condition of n=100rpm with t=6min show CB aggregation
phenomena in the case of f=250 kHz and f=500 kHz.
Namely, by comparing the reconstructed conductivity images
between the simulation and the experiment, higher frequen-
cies are much more suitable to distinguish high conductivity
10 Transactions of the Institute of Measurement and Control 00(0)

Figure 9. Numerical reconstructed conductivity images of four different geometry structure models ((a) CB linear formation, (b) CB aggregation,
(c) CB & LiCoO2 aggregation and (d) network structure) under six different frequencies (f=1kHz, f=10kHz, f=50kHz, f=100kHz, f=250kHz and
f=500kHz).
Wang et al.
CB from LIB slurry, and then to clarify particle dispersion
behaviours in LIB slurry.
Conclusions
In the present paper, particle dispersion behaviours of LIB
slurry are experimentally investigated by using EIST method.
In the experiment, EIS results, which are resistance, reactance
and peak frequencies of LIB slurry, are firstly obtained within
the frequency range from 4Hz to 5mHz. Meanwhile, eight
electrodes are used to obtain the experimental reconstructed
conductivity images of LIB slurry. Moreover, LIB slurry is
experimentally stirred under two different conditions, which
are rotation speed n=0rpm with rotation time t=0min and
n=100rpm with t=6min, to make a large difference in parti-
cle distribution behaviours. Additionally, in order to verify
the correctness of particle dispersion behaviours of the experi-
ment, a numerical simulation corresponding to the experi-
ment is performed. In the simulation, four different geometry
structure models, which are (a) CB linear formation, (b) CB
aggregation, (c) CB & LiCoO2 aggregation and (d) network
structure, are established. Numerical EIS results are calcu-
lated to compare with those obtained from the experiment.
Meanwhile, numerical reconstructed conductivity images of
four different geometry structure models are compared with
experimental reconstructed conductivity images of LIB slurry
under six different frequencies, which are f=1 kHz, f=10
kHz, f=50 kHz, f=100 kHz, f=250 kHz and f=500 kHz.
Comparisons between the simulation and the experiment are
used to verify the correctness of experimental particle disper-
sion behaviours of LIB slurry. Eventually, the conclusions are
shown as follows:
(1) After comparing the EIS results between the experi-
ment and the simulation, both the agglomeration
behaviours of CB and LiCoO2 particles appear
within LIB slurry in the case of n=0rpm with t =
0min; meanwhile, both CB path and CB-coated
LiCoO2 particles appear in the case of n=100rpm
with t=6min.
(2) It is the higher frequencies (f=250 kHz and f=500
kHz) rather than lower frequencies (f = 1 kHz, f=10
kHz and f = 50 kHz) that can be used to obtain the
proper reconstructed conductivity images for LIB
slurry. This illustrates that high frequencies are suit-
able to distinguish high conductive CB component
from LIB slurry.
(3) LIB slurry composed of both CB path and CB-coated
LiCoO2 particles is regarded as a well dispersed
slurry, the homogeneity of LIB slurry is able to be
evaluated by EIST method because EIST is a power-
ful technique to simultaneously clarify the electroche-
mical characterizations of LIB slurry and to reflect
how particles are distributed in LIB slurry. Based on
those advantages, EIST has the potential to realize
on-line measurement for LIB slurry.
11
Acknowledgement
The authors would like to thank Marlin Ramadhan Baidillah,
who provided technique support in the current work.
Declaration of conflicting interests
The author(s) declared no potential conflict of interests with
respect to the research, authorship and/or publication of this
article.
Funding
The author(s) disclosed receipt of the following financial sup-
port for the research, authorship, and/or publication of this
article: This work was supported in part by the National
Natural Science Foundation of China under Grant 51876175,
in part by the Innovation Capability Support Program of
Shaanxi China under Grant 2018KJXX-067, and in part by
International Research Fellow of Japan Society for the
Promote in of Science (Graduate School of Science &
Engineering, Chiba University).
ORCID iD
Zhilong Wang https://orcid.org/0000-0003-1360-0745
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