energies
Article
Study on Two-Phase Permeation of Oxygen and Electrolyte in
Lithium Air Battery Electrode Based on Digital Twin
Qiang Li 1 , Tanghu Zhang 1 , Tianyu Zhang 1 , Zhichao Xue 2 and Hong Sun 1, *
Citation: Li, Q.; Zhang, T.; Zhang, T.;
Xue, Z.; Sun, H. Study on Two-Phase
Permeation of Oxygen and
Electrolyte in Lithium Air Battery
Electrode Based on Digital Twin.
Energies 2022, 15, 6986. https://
doi.org/10.3390/en15196986
Academic Editors: Alessandro Del
Nevo and Bin Chen
Received: 9 August 2022
Accepted: 19 September 2022
Published: 23 September 2022
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Copyright: © 2022 by the authors.
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This article is an open access article
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conditions of the Creative Commons
Attribution (CC BY) license (https://
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4.0/).
Energies 2022, 15, 6986. https://doi.org/10.3390/en15196986
1 School of Mechanical Engineering, Shenyang Jianzhu University, Shenyang 110168, China
2 School of Science, Shenyang Jianzhu University, Shenyang 110168, China
* Correspondence: sunhongwxh@sina.com
Abstract: In this paper, the saturation of electrolytes on the mass transfer property of porous electrodes
in non-aqueous lithium air batteries has been studied based on digital twin. Herein, we reconstruct
the porous cathode based on X-ray micro-computed tomography (µct) and quantitatively analyze the
pore size distribution, specific surface area, triple-phase interface area, conductivity and diffusion
coefficient of reactants at varying filling degrees of the electrolyte. The results derived from digital
twin provide insight into the gas–liquid two-phase mass transfer performance in the porous cathode
with various degrees of electrolyte saturation and demonstrate that the optimum electrolyte saturation
is 60%.
Keywords: lithium air battery; saturation; X-ray micro-computed tomography; digital twin
1. Introduction
The development of advanced energy storage systems plays a crucial role in electric
vehicles and renewable energy storage systems [1]. Lithium air batteries are energy conversion
devices which show advantages of ultra-high theoretical energy density, low cost, and limited
environmental pollution [2–4]. Hence, the investigation of lithium air batteries has drawn
great attention all over the world in recent years. This novel energy storage device also shows
potential application in related military and communication fields [5]. However, the actual
performance of lithium air batteries is far from its theoretical calculation, resulting from its
fast capacity attenuation during cycling, low cycle numbers, lithium dendrite formation, and
the instability of electrolytes [6–8]. To solve the above problems, great efforts have been made
by researchers to reveal the fundamental mechanism of lithium air batteries.
As the most popular studied lithium air battery, the non-aqueous lithium air battery is
composed of a lithium anode, organic electrolytes, a glass fiber membrane, and a porous
cathode. One of the crucial components in non-aqueous lithium air batteries, the porous
cathode is composed of a gas diffusion layer (GDL) and catalysts loaded on the GDL [9,10].
The porous cathode provides active sites for reaction and space for mass transfer and
products agglomeration. Hence, the rational design of porous cathodes plays a crucial role
in the performance of lithium air batteries, which require high catalytic activity, high specific
area, and reasonable porous structure. As significant parameters of the porous structure,
the pore size distribution and porosity determine the transfer performance of reactants
and products, which is related with the effective oxygen diffusion coefficient [11–13].
Meanwhile, the kinetics of the reaction are also dependent on the specific surface area of the
electrode. An electrode with a high specific area is preferred due to the abundant active sites
provided. In recent research results, Mn-rich cathodes and porous carbon-based electrode
materials for lithium air batteries have been significantly improved [14,15]. Spinel-type
transition metal oxides (Zn, Mn, Ni, Mg, etc.) are good candidates for lithium air batteries
due to their high theoretical capacity, low price, and environmental friendliness [16,17].
For the mass transfer in a porous cathode, reactants transfer to the surface of the triple-
phase interface, where a redox reaction occurs. Therefore, the area of the triple-phase
https://www.mdpi.com/journal/energies
Energies 2022, 15, 6986 2 of 12

interface, which is related with the distribution of oxygen and electrolytes in the porous
electrode, plays a significant role in the performance of lithium air batteries. Hence, it
is essential to obtain the actual structure of porous cathodes to analyze the distribution
of reactants accurately. Many scholars have studied the properties of porous materials
based on µCT. Gao et al. used µCT to scan and reconstruct the GDL and discussed the
optimal pitch of the fiber [18]. Subsequently, Ortega-Ramirez et al. checked the soil layer
with CT to obtain the cross-sections of materials. They reconstructed the soil layer using
GeoDict software and studied the permeability and hydrodynamic coefficient of the soil
layer [19]. Soltani et al. used the same method to analyze the sound absorption performance
of needled nonwovens [20]. Hui et al. also combined µCT and digital twin methods to
study the formation process of the plastic layer in the heating process of coking coal mixture
and analyzed the pore size distribution and porosity of the plastic layer [21].
In addition, the electrolyte saturation in a porous cathode is also related to the area of
the triple-phase interface [22–24]. For electrodes with high saturation, electrolytes drown
the electrode and block the channel for oxygen transfer, leading to a small area of the
triple-phase interface. Meanwhile, at low saturation, the number of electrolytes is limited,
resulting in a small triple-phase interface for reaction. Hence, a reasonable electrolyte
saturation is important and has been widely addressed [25,26]. Furthermore, electrolyte
saturation also influences the mass transfer property of reactants in lithium air batteries.
Esfahanian et al. established a mathematical model to analyze the oxygen transfer in
lithium air batteries. They found that the increase in the oxygen diffusion coefficient had a
positive impact on the discharge performance of the battery [27]. Zhang et al. confirmed
that the filling degree of electrolytes in the positive electrode is related to the oxygen
dissolution rate. When the filling degree of electrolytes is low, the oxygen has a longer
diffusion distance, leading to a decrease in the oxygen dissolution rate [28]. Xia et al. used
carbon materials with high specific surface area as cathode materials and confirmed that the
oxygen diffusion in the air cathode was restricted due to the high saturation of electrolytes,
resulting in the insufficient utilization of the internal space of the cathode [29]. In addition,
the effective conductivity of a cathode is also related to electrolyte saturation. In total,
the filling degree of the electrolytes in a porous electrode has a significant role in the area
of the triple-phase interface, the mass transfer property of the reactant and the effective
conductivity of the porous electrode, resulting in a determining factor of cell performance.
Hence, an optimal electrolyte saturation in lithium air battery should be investigated.
In this paper, the filling degree of electrolyte on the performance of lithium air battery
using MnO2 as catalysts was studied. The digital twin method was used to reconstruct the
porous electrode based on cross-section images obtained from µCT. All simulations were
carried out based on the commercial software of GeoDict. The pore size distribution and
porosity of the porous electrode were analyzed. Furthermore, the effective conductivity,
the area of the three-phase interface, and the effective diffusion coefficient of oxygen in
a porous electrode under varying electrolyte saturations were calculated from the digital
twin model. The optimum filling degree of electrolytes in a porous cathode is obtained
based on the analysis of simulations and verified by experimental results.

2. Numerical Simulation and Experiment

2.1. Reconstruction of Porous Electrode
µCT offers the capability to non-destructively resolve the 3D structure of porous
electrodes. The numerical model of the actual composite electrode comprising of carbon
paper as host and manganese dioxide (MnO2 ) as catalysts was reconstructed by importing
CT images with a voxel of 2 µm. Figure 1 shows the 2D fiber structure obtained from
µCT. According to Figure 1, the white parts, which represent carbon fibers in carbon
paper, are randomly and densely distributed in the central region of the electrode. On
the contrary, the distribution of carbon fibers is loosely distributed at the bottom and
upper region of the electrode. It can be speculated that the densely distributed fiber in
the central part can provide more active sites for reaction than that at upper and bottom
 Energies
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of 13
13

images
images with
with aa voxel
voxel ofof 22 μm.
μm. Figure
Figure 11 shows
shows thethe 2D2D fiber
fiber structure
structure obtained
obtained from from μCT.
μCT.
According
According to to Figure
Figure 1, 1, the
the white
white parts,
parts, which
which represent
represent carbon
carbon fibers
fibers inin carbon
carbon paper,paper, are
Energies 2022, 15, 6986 3 of are
12
randomly and densely distributed in the central region of the electrode.
randomly and densely distributed in the central region of the electrode. On the contrary, On the contrary,
the
the distribution
distribution of of carbon
carbon fibers
fibers is
is loosely
loosely distributed
distributed at at the
the bottom
bottom and and upper
upper regionregion ofof
the
the electrode. It can be speculated that the densely distributed fiber in the central part
electrode. It can be speculated that the densely distributed fiber in the central part can
can
regions
provide since the reaction occurs on the surface of carbon fibers. bottom
The obtained 2Dsince images
provide more
more active
active sites
sites for
for reaction
reaction than than that
that at at upper
upper andand bottom regions regions since the the
were segmented
reaction using a thresholding technique to convert grayscale images to index
reaction occurs
occurs onon the
the surface
surface ofof carbon
carbon fibers.
fibers. The
The obtained
obtained 2D 2D images
images werewere segmented
segmented
images.
using During the reconstruction process, the gray value interval of the pores Duringwas set as
using aa thresholding
thresholding technique
technique to to convert
convert grayscale
grayscale images
images to to index
index images.
images. During the the
0–26.5, and
reconstructionthe gray value intervals of carbon fiber and MnO 2 set as 0–26.5, and the and
were set as 26.5~105.5
reconstruction process,
process, the
the gray
gray value
value interval
interval ofof the
the pores
pores waswas set as 0–26.5, and the gray gray
>105.5,
value respectively.carbon
The reconstructed composite electrode is shown in Figure 2. To save
value intervals
intervals of of carbon fiber
fiber and
and MnO
MnO22 werewere set
set asas 26.5~105.5
26.5~105.5 and and >105.5,
>105.5, respectively.
respectively.
computational
The time, a Representative Elementary Volume (REV) with the dimensions of
The reconstructed
reconstructed composite
composite electrode
electrode is is shown
shown in in Figure
Figure 2. 2. To
To save
save computational
computational time, time,
1000 µm × 1000 µm
aa Representative × 300 µmVolume
Elementary was derived(REV) from
with the
the reconstructed
dimensions electrode,
of 1000 μm as shown
×× 1000 μm in×
Representative
Figure 2. Elementary Volume (REV) with the dimensions of 1000 μm 1000 μm ×
300 μm was derived from the reconstructed electrode,
300 μm was derived from the reconstructed electrode, as shown in Figure 2.as shown in Figure 2.

(a)
(a)

11 mm
mm

(b)
(b)

11 mm
mm

(c)
(c)

11 mm
mm

Figure
Figure1.1.
Figure CT
1.CT tomograms
tomogramsofof
CTtomograms composite
ofcomposite electrode
electrodeinin
compositeelectrode different
indifferent regions:
differentregions: (a)
regions:(a) bottom
(a)bottom region,
bottomregion, (b)
region,(b) central
(b)central
central
region, and
region,and (c)
and(c) upper
(c)upper region.
upperregion.
region.
region,

Air
Air
Carbon
Carbon fiber
fiber Li-O
Li-O2 battery
battery
2
MnO
MnO22

11 mm
mm

Figure
Figure 2.
2. Morphology
Morphology of
of composite
composite electrode.
electrode.
Figure 2. Morphology of composite electrode.

2.2. Construction of Electrode with Different Electrolyte Saturation

The organic electrolyte was introduced to construct an electrolyte filling model based
on the reconstructed composite electrode, as shown in Figure 3. According to the filling
degree of the electrolyte in the composite electrode, the electrolyte filling models can be
Energies
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6986 4 4ofof1313

2.2.
2.2.Construction
ConstructionofofElectrode
Electrodewith
withDifferent
DifferentElectrolyte
ElectrolyteSaturation
Saturation
Energies 2022, 15, 6986
The
The organic electrolyte was introduced to constructan
organic electrolyte was introduced to construct anelectrolyte
electrolytefilling
fillingmodel
modelbased
4based
of 12
on
on the reconstructed composite electrode, as shown in Figure 3. According tothe
the reconstructed composite electrode, as shown in Figure 3. According to thefilling
filling
degree
degreeofofthetheelectrolyte
electrolyteininthe thecomposite
compositeelectrode,
electrode,the
theelectrolyte
electrolytefilling
fillingmodels
modelscan canbebe
classified
classifiedinto
intothree
threetypes,
types,including
includingunfilled,
unfilled,partially
partiallyfilled,
filled,and
andcompletely
completelyfilled
filledmod‐
mod‐
classified into three types, including unfilled, partially filled, and completely filled models.
els.
els.The
Theelectrolyte
electrolytesaturations
saturationsofofthe thedifferent
differentmodels
modelsare are0%,
0%,20%,20%,40%,
40%,60%,60%,80%,
80%,and and
The electrolyte saturations of the different models are 0%, 20%, 40%, 60%, 80%, and 100%, as
100%, as shown in Figure 4. The models with 0% and 100% saturation
100%, as shown in Figure 4. The models with 0% and 100% saturation correspond to the correspond to the
shown in Figure 4. The models with 0% and 100% saturation correspond to the unfilled and
unfilled
unfilled and
andcompletely
completelyfilledfilledtypes,
types,respectively.
respectively.The
Thephysical
physicalparameters
parametersofofthe theelectro‐
electro‐
completely filled types, respectively. The physical parameters of the electrolyte, catalysts,
lyte,
lyte,catalysts,
catalysts, and
and electrodes
electrodes used
used ininsimulation
simulation are
arereported
reported ininother
other literature,
literature,and
and the
the
and electrodes used in simulation are reported in other literature, and the detailed values
detailed
detailed values
values arearelisted
listedininTable
Table 1.1.
are listed in Table 1.

Figure 3.3.Construction
Figure3. Constructionof composite electrode filled with organic electrolytes.
Figure Construction ofofcomposite
compositeelectrode
electrodefilled
filledwith
withorganic
organicelectrolytes.
electrolytes.

Air
Air
Carbon
Carbonfiber
fiberLi-O
Li-O2 battery
2 battery
MnO
MnO2 2
Electrolyte
ElectrolyteininLi-O
Li-O2 battery
2 battery

Figure
Figure Different
4.4.Different
Figure4. electrodes
Differentelectrodes with
electrodeswith electrolyte
withelectrolyte fillingdegrees
electrolytefilling
filling degrees
degrees of
ofof
(a)(a)
0%,
(a) 0%,
(b)
0%, (b) 20%,
20%,
(b) (c)(c)
(c)
20%, 40%,40%,
40%, (d)(d)
(d) 60%,60%,
60%,(e)
(e)
(e)
80%,80%,
80%,andand (f) 100%.
and(f)(f)100%.
100%.

Table 1. Parameters of catalysts, electrolytes, and electrodes used in this model.

Parameters Symbol Value

Conductivity of MnO2 σMnO2 454 S·m− 1
Density of MnO2 ρMnO2 5.03 kg·m3
Conductivity of carbon σcar 30,000 S·m− 1 [30]
Density of carbon ρcar 1800 kg·m3
Conductivity of electrolyte σele 0.225 S·m− 1 [31]
Density of electrolyte ρele 1009 kg·m3 [32]
Diffusivity of oxygen in electrolyte DO2 1.6 × 10− 7 cm− 2 ·s− 1 [33]
Diffusion coefficient of O2 in gas phase Dsel 1.89 × 10− 5 m− 2 ·s− 1
Energies 2022, 15, 6986 5 of 12

2.3. Fundamentals of Simulation

PoroDict module was used to determine the porosity and pore size distribution of
composite electrodes. This module uses two methods to determine pore size, namely,
granulometry and porosimetry [34]. The granulometry method was used in this paper
for the calculation of the pore size distribution. A pore radius is determined by fitting
spheres into the pore volume. To be more accurate, a point belongs to a pore of a radius
larger than r. If a point is inside any sphere of radius r, this point can be fitted into the pore
space. However, the through pores, closed pores, closed pores, and blind pores cannot be
distinguished based on granulometry.
The effective diffusion coefficient is defined as the diffusion rate in porous media,
which is proportional to the diffusion coefficient in open space [35]. The diffusion coefficient
of oxygen in porous media is described by Fick’s first law [36,37], as in Equation (1):

∆c
J = −D (1)
L

where J is the diffusion flux (mol·m−2 ·s−1 ), ∆c is the concentration difference, L is the
diffusion distance, and D is the effective diffusion coefficient. For the diffusion in porous
materials, the effective diffusion coefficient is related to the intrinsic diffusion coefficient of
reactants and the structure of porous electrode. The effective diffusion coefficient follows
Equation (2):
η
D = D0 · (2)
τ
where D0 is the intrinsic diffusion coefficient, η is the porosity of porous electrode, and τ is
the tortuosity of porous electrode.
In a 3D reconstructed porous structure model, the distribution of concentrations can
be solved based on Equation (3) at steady-state conditions:

div( D ( x )∇c)= 0 (3)

where D(x) is the function of local effective diffusion coefficient, ∇c is the concentration
gradient.
For the calculation of O2 effective diffusion coefficient, only the diffusion coefficient
along the Z direction, which is perpendicular to carbon paper, was calculated. To ensure a
constant concentration of O2 at the boundary, a symmetric boundary condition is applied
in this paper. The diffusion of a reactant is driven by the concentration gradient. The inlet
of O2 is located at the upside of the electrode, and the outlet of O2 is set at the bottom of
the electrode. The initial concentrations of O2 at the inlet and outlet are set as 9.69 mol·m−3
and 0 mol·m−3 , respectively. The iterative method was used until the tolerance of effective
diffusion rate is smaller than 0.001.
Electrical conductivity σ is calculated based on Ohm’s Law. Ohm’s Law relates the
electric potential ϕ and the magnitude of current density j:

j = −σ∇φ (4)

where ϕ represents the electric potential between two points. The work conducted by the
electric field force is EL, where E is the strength of the electric field. When the distance
between the two points is small enough, it is approximated by EL = − ϕ. When L tends
to 0, it is denoted as EdL = −dϕ; thus: E = −dφ/dL = −∇φ. The current density can be
obtained by the product of electrical conductivity and electric field strength.
The conductivity of the composite electrode along the Z direction was calculated.
Considering the accuracy and efficiency of computation, periodic boundary condition was
used. To calculate the conductivity of samples, the standard potential of 2.96 V for Li air
battery is applied on the boundary of electrode. The tolerance is also set as 0.001, and the
iterative method is conducted.
Energies 2022, 15, 6986 6 of 12

2.4. Experimental Section

To validate the reliability of the simulation results, the performance of a cell with a
composite electrode was evaluated in this paper. The influence of electrolyte filling degree
on the performance of lithium air batteries was analyzed based on charge–discharge tests.
All reagents used here were analytical grade and used without further purification.
Multi-walled carbon nanotubes (MWCNTs) were purchased from Beijing Deke Daojin
Science and Technology Co., Ltd. (Beijing, China). Manganese dioxide (MnO2 ) as catalyst
was purchased from Aladdin Reagent Co., Ltd. (Shanghai, China). N-methyl-2-pyrrolidone
(NMP) and Polytetrafluoroethylene (PTFE) were bought from Shenzhen Kejing Zhida
Technology Co., Ltd. (Shenzhen, China). Carbon paper (battery level) was purchased
from Shanghai Hesen Electric Co., Ltd. (Shanghai, China). Tetraethylene glycol dimethyl
ether/bis trifluoromethanesulfonimide lithium salt (TEGDME/LITFSI) was purchased
from Shanghai Monils Chemical Co., Ltd. (Shanghai, China). Diaphragm (battery level)
was purchased from Tianjin Yongda Chemical Reagent Co., Ltd. (Tianjin, China).
Firstly, 0.45 g of MnO2 , 0.45 g of MWCNTs, and 0.1 g of PTFE were uniformly mixed,
then an appropriate amount of NMP was dropped into the mixture. Finally, the mixture
was placed in a magnetic stirrer and stirred continuously for 12 h. The obtained mixture
in a sticky paste state was uniformly coated on carbon paper. Then, the obtained sample
with the coating thickness of 300 µm was transferred to a vacuum drying oven and kept at
80 ◦ C for 8 h. Finally, the carbon paper loaded with catalysts was cut into circular slices
with diameters of 16 mm.
Lithium air battery performance tests were carried out based on CR2632 coin cells.
Lithium air batteries were assembled in an argon-filled glove box (O2 < 0.1 ppm and
H2 O < 0.1 ppm). The electrolyte used in this paper was 1 M LiTFSI/TEGDME. To in-
vestigate the filling degrees of electrolyte on lithium air battery performance, batteries
containing different contents of electrolyte were assembled. The battery with 60 µL elec-
trolyte reaches the state of 100% filling degree. Then, 0 µL, 12 µL, 22 µL, 31 µL, 42 µL, and
50 µL of the electrolytes were dropped during the assembling process, corresponding to
the filling degrees of 0%, 20%, 40%, 60%, and 80%, respectively. To evaluate the durability
of the lithium air batteries, charge–discharge tests were performed at a constant current
density of 100 mA·g−1 by LAND test system with cut-off voltage ranging from 2 V to 4.5 V.

3. Results and Discussion

Based on the restructured porous electrode, the porosity and pore size distribution
were calculated. In addition, the influence of electrolyte filling degree on effective oxygen
diffusion coefficient and effective conductivity in the composite electrode were studied.

3.1. Pore size Distribution

The pore size distribution of the composite electrode is shown in Figure 5a. It is obvious
that the inhomogeneous distribution of pore size is found in the composite electrode. The
major pore size is in the range of 10–40 µm, which can provide space for mass transfer
and product deposition. The morphology of the pores in the 3D reconstructed electrode
is shown in Figure 5b. It is qualitatively observed that large pores are distributed on the
upper side and underneath of the composite electrode. The average porosity of the integral
electrode is 0.792. To further analyze the pore structure, the reconstructed electrode was
uniformly divided into five parts along the Z direction. The corresponding porosity of
each part was calculated. The porosity of each part along the direction from the bottom
toward the upper side is 0.959, 0.731, 0.730, 0.724, and 0.816, indicating the nonuniform
distribution of porosity in the electrode along the Z direction. It is clear the largest porosity
is located at the bottom part of the electrode, and the inferior porosity is located on the
upper side. These results imply that relatively large pore sizes and porosities exist in the
underside and upper side of the composite electrode, which may have significant influence
on battery performance.
 rosity of each part was calculated. The porosity of each part along the direction from the
bottom
bottom toward
toward thethe upper
upper side
side is
is 0.959,
0.959, 0.731,
0.731, 0.730,
0.730, 0.724,
0.724, and
and 0.816,
0.816, indicating
indicating the the nonu‐
nonu‐
niform
niform distribution
distribution ofof porosity
porosity inin the
the electrode
electrode along
along the
the ZZ direction.
direction. ItIt is
is clear
clear the
the largest
largest
porosity
porosity is
is located
located at
at the
the bottom
bottom part
part of
of the
the electrode,
electrode, and
and the
the inferior
inferior porosity
porosity is is located
located
on
on the upper side. These results imply that relatively large pore sizes and porosities exist
the upper side. These results imply that relatively large pore sizes and porosities exist
Energies 2022, 15, 6986 in
in the
the underside
underside andand upper
upper side
side ofof the
the composite
composite electrode,
electrode, which
which maymay have have significant
7 of 12
significant
influence
influence on
on battery
battery performance.
performance.

Figure
Figure5.
Figure 5.Pore
5. Poresize
Pore sizedistribution
size distributionofof
distribution MnO
of 2 /MWCNTs
MnO
MnO /MWCNTscomposite
22/MWCNTs compositeelectrode:
composite (a)(a)
electrode:
electrode: 2D2D
(a) pore
2D sizesize
pore
pore distribution;
size distribu‐
distribu‐
(b) 3D(b)
tion;
tion; pore
(b) 3Dsize
3D poredistribution.
pore size
size distribution.
distribution.

3.2.
3.2. Specific Surface
Surface Area and Triple-Phase Interface Area
3.2. Specific
Specific Surface Area Area and
and Triple‐Phase
Triple‐Phase Interface
Interface Area
Area
The average specific surface of the porous electrode is 6.485 ×1010 10210 m2 ·cm−3 . As
The
The average
average specific
specific surface
surface ofof the
the porous
porous electrode
electrode is is 6.485
6.485 ×× 1010 m m2∙cm
∙cm−3−3.. As
As shown
shown
shown in Figure 6a, the calculated specific surfaces of the different parts of the composite
in
in Figure
Figure 6a,6a, the
the calculated
calculated specific
specific surfaces
surfaces ofof the
the different
different parts
parts of
of the
the composite
composite elec‐
elec‐
electrode from, bottom to top, are 1.0791010× 1010 , 7.765 × 1010 , 8.559 × 1010 , 8.751 × 1010 ,
trode from, bottom
trode from, bottom to top, are 1.079 × 10 , 7.765 × 10 10, 8.559 × 10 10 , 8.751 ×
to top, are 1.079 × 10 , 7.765 × 10 , 8.559 × 10 , 8.751 × 10 , and 6.110
10 10 10 10
10, and 6.110
and 106.110 × 1010 m2 ·cm−3 , respectively. It can be seen that the specific areas of the bottom
×× 10
1010 mm22∙cm
∙cm−3−3,, respectively.
respectively. It It can
can be
be seen
seen that
that the
the specific
specific areas
areas of of the
the bottom
bottom partpart and
and
part and upper part are lower than the other parts, which is in accordance with the results
upper
upper part
part are
are lower
lower than
than the
the other
other parts,
parts, which
which is is in
in accordance
accordance with with the
the results
results ofof the
the
of the porosity distribution, as larger porosity results in a lower specific area.
porosity
porosity distribution,
distribution, as as larger
larger porosity
porosity results
results in
in aa lower
lower specific
specific area.
area.

Figure 6.
6. Specific
Figure 6.
Figure Specific surface
Specific area
surface area
surface of
area of different
of different partitions
differentpartitions (a)
partitions(a) and
(a)and triple‐phase
andtriple-phase interface
triple‐phaseinterface (b).
interface(b).
(b).

Since the reaction in the lithium air battery mainly takes place at the triple-phase
interface, the area of the triple-phase interface was calculated for electrodes with different
saturations. According to Figure 6b, the area of the triple-phase interface increases with
the saturation of the electrolyte, increasing until a saturation of 60% is reached. Then, the
triple-phase interface area decreases sharply with an increase in electrolyte saturation. The
highest triple-phase interface area is obtained for the electrode with 60% saturation, while
the electrode with 40% saturation shows a similar value. It can be clarified that the pore
size and porosity are large at the upper side and underneath of the composite electrode,
resulting in the low interface between carbon fiber, oxygen, and electrolyte. However, the
carbon fibers in the central part are compactly interconnected, resulting in low porosity
and a smaller pore size distribution. Hence, the area of the triple-phase interface is high in
the central part of the electrode.

3.3. Oxygen Effective Diffusion Coefficient

Figure 7 shows the distribution of the oxygen concentration distribution in different
electrolyte filling models. It can be seen that the oxygen concentration in gas phase
is significantly higher than that in liquid phase due to the low solubility of oxygen in
 in the central part of the electrode.

3.3. Oxygen Effective Diffusion Coefficient

Figure 7 shows the distribution of the oxygen concentration distribution in diff
Energies 2022, 15, 6986 electrolyte filling models. It can be seen that the oxygen concentration 8inofgas
12 phase i
nificantly higher than that in liquid phase due to the low solubility of oxygen in ele
lytes. Therefore, the concentration of oxygen decreases significantly after passing thr
the interface
electrolytes. Therefore, thebetween the electrolyte
concentration of oxygenand oxygen.significantly
decreases Furthermore,after
the passing
concentration of
gen in abetween
through the interface composite theelectrode decreases
electrolyte with the
and oxygen. increasingthe
Furthermore, saturation of. For the elec
concentration
of oxygen in awith 100% saturation,
composite the insufficient
electrode decreases oxygen
with the supplysaturation
increasing in the electrode
of. Formay
the lead to
electrode withelectrochemical
100% saturation,performance.
the insufficient oxygen supply in the electrode may lead to
poor electrochemical performance.

Figure 7. Oxygen concentration

Figure 7. Oxygen distribution:
concentration(a)distribution:
0% filling degree;
(a) 0% (b) 20%degree;
filling filling (b)
degree;
20% (c) 40%degree; (c
filling
filling degree; (d) 60% filling degree; (e) 80% filling degree; (f) 100% filling degree.
filling degree; (d) 60% filling degree; (e) 80% filling degree; (f) 100% filling degree.

The effective oxygen diffusion

The effective coefficient
oxygen in electrodes
diffusion coefficient with differentwith
in electrodes saturations
differentis saturatio
shown in Figure 8. Compared with the electrode without electrolyte filling, the effective
shown in Figure 8. Compared with the electrode without electrolyte filling, the effe
oxygen diffusion coefficient in the electrode with 20% saturation decreases significantly,
oxygen diffusion coefficient in the electrode with 20% saturation decreases significa
decreasing from 8.1 × 10−6 to 1.7 × 10−6−11 m2 ·s−1 .−11The2is−1owed to the fact that electrolytes
Energies 2022, 15, 6986
decreasing from 8.1 × 10 to 1.7 × 10 m ∙s . The is owed to the9 fact of 13
that electrolytes
have a significantly higher resistance toward oxygen transfer, leading to a lower diffusion
a significantly higher resistance toward oxygen transfer, leading to a lower diffusion
rate in electrolytes than in the gas phase. With a further increase in the electrolyte filling
in electrolytes than in the gas phase. With a further increase in the electrolyte fillin
degree, the effective oxygen diffusion coefficient gradually decreases to 6.7 × 10−12 m2 ·s−1 −12 2 −
gree, the effective oxygen diffusion coefficient gradually decreases to 6.7 × 10 m ∙s
due to the increasing transfer resistance of oxygen with the increased amount of electrolytes.
to the increasing transfer resistance of oxygen with the increased amount of electrol

Figure 8. Oxygen effective diffusion coefficient.

Figure 8.3.4.
Oxygen effective
Effective diffusion
Electrical coefficient.
Conductivity
Effective conductivity is another critical parameter which determines the performance
3.4. Effective Electrical Conductivity
of a composite electrode. Figure 9 shows the potential distribution in models with different
Effective conductivity
electrolyte is another
saturations. It can becritical parameter
seen that whichondetermines
the potential the upsidethe perfor‐
of the electrode is
mance of a composite electrode. Figure 9 shows the potential distribution in models with due to
higher than that at the underside. The nonuniform distribution of potential is found
differentthe
electrolyte saturations.
heterogeneous porousIt structure.
can be seen that the potential on the upside of the elec‐
trode is higher than that at the underside. The nonuniform distribution of potential is
found due to the heterogeneous porous structure.
 3.4. Effective Electrical Conductivity
Effective conductivity is another critical parameter which determines the perfo
mance of a composite electrode. Figure 9 shows the potential distribution in models wi
different electrolyte saturations. It can be seen that the potential on the upside of the ele
trode is higher than that at the underside. The nonuniform distribution of potential
Energies 2022, 15, 6986 9 of 12
found due to the heterogeneous porous structure.

Figure 9. Electric potential distribution: (a) 0% filling degree; (b) 20% filling degree; (c) 40% filling
Figure 9. Electric potential distribution: (a) 0% filling degree; (b) 20% filling degree; (c) 40% filli
degree; (d) 60% filling
degree; (d)degree; (e) 80%
60% filling filling
degree; (e)degree; (f) 100%
80% filling filling
degree; (f) degree.
100% filling degree.

Electrodes with high effective conductivity are conductive to the decrease in ohmic
Electrodes with high effective conductivity are conductive to the decrease in ohm
resistance, resulting in superior lithium air battery performance, especially during operation
resistance, resulting in superior lithium air battery performance, especially during oper
at high current density. Figure 10 shows the effective conductivity of composite electrodes
tion at high current density. Figure 10 shows the effective conductivity of composite ele
with different electrolyte filling degrees. Since oxygen is an insulator, the conductivity
trodes with different electrolyte filling degrees. Since oxygen is an insulator, the condu
is approximate to 0. When the electrolyte filling degree is 0%, it can be inferred that the
tivity is approximate to 0. When the electrolyte filling degree is 0%, it can be inferred th
pores in the composite electrode are filled with oxygen, resulting in the lowest effective
the pores in the composite electrode are filled with oxygen, resulting in the lowest effe
conductivity of 56.0 S·m−1 . With the electrolyte filling degree increasing to 20%, the oxygen
tive conductivity of 56.0 S∙m−1. With the electrolyte filling degree increasing to 20%, t
at the bottom region of the electrode is occupied by electrolytes. Since the conductivity
Energies 2022, 15, 6986
oxygenisathigher
of the electrolyte the bottom
than region
that ofof the electrode
oxygen, is occupied
the overall effectiveby conductivity
electrolytes. Sinceof of
10 thethe condu
13
tivity of the electrolyte is higher than that of oxygen, the
composite electrode increases significantly. The conductivity increases slowly when the overall effective conductivity
electrolyte the composite
filling electrode
degree ranges from increases
20% to 80%.significantly.
The reason Theforconductivity
this is mainly increases
due to the slowly wh
fact thatthatthe
the theelectrolyte
pore sizesize
andfilling degree
porosity ranges
areare from
relatively 20%
low to
ininthe 80%. The reason for this is mainly due
the fact pore and porosity relatively low thecentral
centralpart
partof ofthe
the electrode
electrode
and
and thethe amount
amount of ofelectrolytes
electrolytesfilling
fillingininthethe pore
pore slowly
slowly increases
increases withwith
the the increasing
increasing fill‐
filling degree. It should be noted that the effective conductivity
ing degree. It should be noted that the effective conductivity of an electrode with of an electrode with 100%
100%
saturation significantly increases
saturation significantly increasescompared
comparedtotothat thatwith
with a filling
a filling degree
degree in the
in the rangerange
of 20–of
20–80%. Since the pore size and porosity in the upper side of the electrode
80%. Since the pore size and porosity in the upper side of the electrode is large, this indi‐ is large, this
indicates that a relatively large amount of electrolyte can be reserved. Therefore, the
cates that a relatively large amount of electrolyte can be reserved. Therefore, the effective
effective conductivity reaches 108.1 S·m−1 for an electrode with 100% saturation.
conductivity reaches 108.1 S∙m−1 for an electrode with 100% saturation.

Figure 10.
Figure 10. Effective
Effective electrical
electrical conductivity.
conductivity.

The rational design of a porous cathode requires abundant active sites derived from
high triple‐phase interface area and fast electron and reactant transfer rates coming from
highly effective conductivity and an effective diffusion coefficient. However, the filling
degree of electrolytes has the opposite effect on the effective oxygen diffusion coefficient
and the effective conductivity. In addition, there exists an optimal range of filling degree
Energies 2022, 15, 6986 10 of 12

The rational design of a porous cathode requires abundant active sites derived from
high triple-phase interface area and fast electron and reactant transfer rates coming from
highly effective conductivity and an effective diffusion coefficient. However, the filling
degree of electrolytes has the opposite effect on the effective oxygen diffusion coefficient and
the effective conductivity. In addition, there exists an optimal range of filling degree when
considering the triple-phase interface area. Therefore, it is important to consider the balance
between these parameters related with reaction sites and mass transfer. According to the
simulation results, it can be speculated that the composite electrode with the electrolyte
filling degree in range of 40–60% is preferred.

3.5. Electrochemical Performance Analysis

To verify the speculation that the optimal electrolyte saturation ranges from 40% to
60%, charge–discharge tests were carried out. Figure 11 shows the specific capacity of
the battery under different electrolyte filling degrees. The curves shown in Figure 11 are
based on the experimental data obtained from the actual experiment. As expected, when
the electrolyte filling degree is 0% and 100%, the limited reaction sites and insufficient
oxygen supply result in the low discharge capacity of 1955 mAh·g−1 and 2288 mAh·g−1 ,
respectively. When the electrolyte filling degree increases to 20% and 40%, the specific
capacity was significantly improved to 4320 mAh·g−1 and 4434 mAh·g−1 , respectively.
The reason is the increased area of the triple-phase interface available for reaction and the
enhanced conductivity for charge transfer. Furthermore, the proper pore size and oxygen
diffusion rate also contribute to the improved performance. As the electrolyte filling degree
increases to 60%, a balance between the effective conductivity, diffusion rate of oxygen,
Energies 2022, 15, 6986 11 of 13
and triple-phase interface area is achieved, resulting in the highest discharge capacity of
5034 mAh·g−1 . When the saturation is further increased to 80%, the specific area of triple-
phase interface significantly decreases. Furthermore, the effective diffusion coefficient of
decreases, leading leading
oxygen decreases, to a decrease in the discharge
to a decrease capacitycapacity
in the discharge (3982 mAh∙g ·g−1 ).the
). Hence,
(3982 −1mAh bat‐
Hence,
tery with an electrolyte saturation of 60% shows the best performance due to
the battery with an electrolyte saturation of 60% shows the best performance due to thethe optimal
balance betweenbetween
optimal balance the mass
thetransfer and electrochemical
mass transfer reaction
and electrochemical kinetics,
reaction indicating
kinetics, the
indicating
significance of simulation
the significance prediction
of simulation based
prediction on digital
based twin.
on digital twin.

Figure 11.
Figure Discharge–chargeprofile
11. Discharge–charge profileof of filling
filling degree
degree of of electrolyte
electrolyte at the
at the current
current density
density of
of 100
100
mA∙gmA ·g−1 with
−1 with 2 V discharge
2 V discharge andV4.5
and 4.5 V charge
charge cutoffcutoff voltages.
voltages.

4. Conclusions
In this paper, digital twin technology based on μCT is used to reconstruct the numer‐
ical model of porous cathode in lithium air battery. The results demonstrate that relatively
smaller pore size distribution and lower porosity exist in the center part of the composite
electrode, corresponding to the higher specific area and specific triple‐phase interface
area. The heterogeneous distribution of these intrinsic parameters results in a significant
Energies 2022, 15, 6986 11 of 12

4. Conclusions
In this paper, digital twin technology based on µCT is used to reconstruct the numerical
model of porous cathode in lithium air battery. The results demonstrate that relatively
smaller pore size distribution and lower porosity exist in the center part of the composite
electrode, corresponding to the higher specific area and specific triple-phase interface
area. The heterogeneous distribution of these intrinsic parameters results in a significant
difference in the mass transfer property and cell performance when the electrode is at
different saturations. At the saturation of 60%, the oxygen diffusion coefficient, specific
triple-phase interface area, and effective conductivity are optimized, resulting in the highest
discharge capacity of the lithium air battery. The µCT-based digital twin technology
provides a fast and accurate method to reveal the mass transfer and critical parameters in
composite electrode. Furthermore, this method also provides a valuable forecast for cell
performance and is expected to play an important role in the design of porous electrodes in
energy storage systems.

Author Contributions: Conceptualization and Methodology, Q.L.; software, T.Z. (Tanghu Zhang);
validation, T.Z. (Tianyu Zhang); writing—review and editing, Z.X.; supervision, H.S.; All authors
have read and agreed to the published version of the manuscript.
Funding: This research was funded by the [National Natural Science Foundation of China] grant
number [51902211,51776131,51906166]; the [Liaoning Revitalization Talents Program] grant number
[XLYC1802045]; the [Department of Education of Liaoning Province] grant number [lnzd201902];
and the [Foundation from Liaoning Province of China] grant number [20170540746, LJZ2016013,
lnjc201907].
Acknowledgments: This work is supported by the National Natural Science Foundation of China
[51902211,51776131,51906166]; the Liaoning Revitalization Talents Program [XLYC1802045]; the
Department of Education of Liaoning Province [lnzd201902]; and the Foundation from Liaoning
Province of China [20170540746, LJZ2016013, lnjc201907].
Conflicts of Interest: The authors declare no conflict of interest.

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