Particuology 61 (2022) 18–29

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Particuology
journal homepage: www.elsevier.com/locate/partic

Invited review

Balancing particle properties for practical lithium-ion batteries

Jing Zhang, Jinshuo Qiao, Kening Sun, Zhenhua Wang ∗
Beijing Key Laboratory for Chemical Power Source and Green Catalysis, School of Chemistry and Chemical Engineering, Beijing Institute of Technology,
Beijing 100081, China

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

Article history: As a state-of-the-art secondary battery, lithium-ion batteries (LIBs) have dominated the consumer elec-
Received 4 February 2021 tronics market since Sony unveiled the commercial secondary battery with LiCoO2 as the negative
Received in revised form 6 May 2021 electrode material in the early 1990s. The key to the efficient operation of LIBs lies in the effective contact
Accepted 15 May 2021
between the Li-ion-rich electrolyte and the active material particles in the electrode. The particle prop-
Available online 6 June 2021
erties of the electrode materials affect the lithium ion diffusion path, diffusion resistance, contact area
with the active material, the electrochemical performance and the energy density of batteries. To achieve
Keywords:
satisfied comprehensive performance and of LIBs, it is not only necessary to focus on the modification of
Lithium-ion battery
Particle properties
materials, but also to balance the properties of electrode material particles. Therefore, in this review, we
Particle size analyze the influence of particle properties on the battery performance from three perspectives: particle
Particle size distribution size, particle size distribution, and particle shape. A deep understanding of the effect and mechanism of
Particle shape particles on electrodes and batteries will help develop and manufacture practical LIBs.
© 2021 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of
Sciences. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Introduction Lithium ion battery is essentially a repeated cycle “flow” of

A worldwide energy crisis broke out in the 1970s, and there was
a severe shortage of oil supply. Since then, governments around the
world have focused on promoting the development of renewable
energy, and launched numerous initiatives on advanced energy
conversion and storage technologies (Li & Lu, 2020; Li, Lu, Chen,
& Amine, 2018; Obama, 2017). Meanwhile, many scientists and
automotive engineers had devoted themselves to the research of
batteries and electric vehicles. At present, as the state-of-the-art
secondary batteries, lithium-ion batteries (LIBs) have been widely
used as a major power source for portable electronic devices, elec-
tric vehicles and energy storage systems (Goodenough & Park,
2013; Tarascon & Armand, 2001). In 2019, the Royal Swedish
Academy of Sciences announced that the Nobel Prize in Chem-
istry 2019 was awarded to three pioneers, Professor M. Stanley
Whittingham of the State University of New York at Bingham-
ton, Professor John B. Goodenough of the University of Texas at
Austin, and Akira Yoshino, a chemist from Asahi Kasei Corpora-
tion in Japan, to honor their outstanding contributions in battery
technology research and development.
∗ Corresponding author.
E-mail address: wangzh@bit.edu.cn (Z. Wang).
lithium ions between two electrodes and lithium ions will be
constantly extracted and inserted in the positive and negative
materials (Zubi, Dufo-López, Carvalho, & Pasaoglu, 2018), which is
the contacting and reaction process between the electrode mate-
rial particles and the electrolyte (Goodenough & Park, 2013; Kweon
et al., 2004). Therefore, the lithiation and delithiation process influ-
enced by the particle properties of electrode materials. Due to the
high specific surface area of the active material particles in the elec-
trodes, and the diversity of multi-level structure in the transmission
and chemical transformation, balancing the properties of particles
has become the key to technological breakthroughs in practical
LIBs (as shown in Fig. 1). The morphology and size of the parti-
cles affect the lithium ion diffusion path, diffusion resistance and
the contact area between active material and electrolyte, thereby
influencing the electrochemical performance of LIBs (Shirazi, Azadi,
& Rabczuk, 2016; Xiao et al., 2013; Xu, Chen, Zhou, Sui, & Zhou,
2020). Smaller particles normally have a shorter length of the elec-
tron path from the inside to the surface of the particle, and the
spherical particles can offer larger contact area and raise the active
material content in the electrode. In the meanwhile, the particle
size distribution has a direct impact on the accumulation of the
electrode material particles, and this spatial effect will affect the
deintercalation of lithium ions, thus affecting the battery perfor-
mance (Taleghani, Marcos, Zaghib, & Lantagne, 2017; Wang, Ke,
Huang, & Liu, 2018).

https://doi.org/10.1016/j.partic.2021.05.006
1674-2001/© 2021 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
J. Zhang et al.
Fig. 1. Balancing the properties of particles has become the key to breakthroughs
in practical LIBs.
With respect to the critical elements (cathode, anode, electrolyte
and separator) of LIBs, the cost of cathode and anode materials
accounts for half of the entire battery cost, the development of
electrode materials, especially cathode active materials, is impor-
tant to satisfy requirements such as energy density, cost, and in
particular, safety of LIBs. Reducing the particle size of the cath-
ode materials and using spherical particles are the simple ways to
increase the volumetric energy storage capacity (Liu et al., 2020).
The modification of the cathode material surface is considered to
be the easiest route to improve the electrochemical performance
of cathodes, such as doping (Gao, Xu, & Zhang, 2018; Wang, Cheng,
Yu, Lyu, & Guo, 2020), surface coating (Chen et al., 2017; Kumar,
Nazzario, Torres-Castro, Pena-Duarte, & Tomar, 2015; Li, Wang,
Zhao, Zhang, & He, 2019; Li, Xiang et al., 2019), and nanocrystalliza-
tion (Eftekhari, 2017; Ellingsen et al., 2016). A deep understanding
of the effect and mechanism of particles on electrodes and batteries
will help develop and manufacture high-performance LIBs, since
the battery performance is determined by a combination of dif-
ferent particle properties of electrode materials. Therefore, in this
review, we mainly analyze the influence of cathode material parti-
cle properties on the battery performance from three perspectives:
particle size, particle size distribution, and particle shape. In addi-
tion, the impacts of electrode processing (mixing, coating, drying
and calendering) on the electrode particles and properties are also
discussed in this review. The future perspectives about the field are
discussed at the end of the review.
Particle size and distribution
Majdabadi et al. proved that in the electrode, the particle
size, uneven distribution of the particle size, surface resistance,
and equilibrium potential of the active materials will all have a
huge impact on the electrochemical performance of the battery
(Majdabadi, Farhad, Farkhondeh, Fraser, & Fowler, 2015). Under-
standing the structural properties of batteries is of considerable
significance to battery designers in order to improve battery sys-
tems, and many works had been done over the years (Palacin, 2009;
Taleghani et al., 2017). The main methods of particle size testing
are sedimentation method, laser method, screening method, image
method and resistance method (Hu, Lu, & Liang, 2015; Niu, 2018).
In the laboratory environment, scanning electron microscopy is
commonly used to test particle size and distribution. In the bat-
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Particuology 61 (2022) 18–29
tery industry, the laser method is generally used to test the particle
size, such as the Zetasizer Nano ZS90 particle sizer.
Particle size
At the particle scale, electrochemical kinetics involve the liquid
phase diffusion of Li-ions within the electrolyte to each individual
cathode particle, the charge-transfer reaction at the cathode-
electrolyte interface, and transport of Li-ions and electrons within
particles (Chung, Bloking, & Chiang, 2002; Dudney & Li, 2015).
Tsai et al. revealed the limiting factors of rate performance by
studying the charge-transfer reaction and bulk ion diffusion at the
particle scale (Tsai et al., 2018), and the results showed that the
commercially-relevant NMC particle sizes of 5–10 ␮m exhibited
mixed-control kinetics. In addition, the potentiostatic intermittent
titration tests analysis yielded the electrochemical Biot number
(B), which characterized the relative rates of interfacial reaction
and bulk diffusion. And the equation calculation showed that as
the electrode particle radius decreased, the value of B increased,
i.e., the rates of interfacial reaction and bulk diffusion increased.
Therefore, there have been many attempts to reduce the particle
size of the cathode material as a method to increase the reaction
area and to reduce the Li-ion diffusion distance in the particles.
Reducing particle size contributes to enhancing the electrochemi-
cal performance (especially improving rate capability) on almost all
of cathode materials (Fey, Chen, & Kao, 2009; Kang & Ceder, 2009;
Zhang, 2011).
Size reduction
The layered LiCoO2 has been found as cathode material in 1980
(Mizushima, Jones, Wiseman, & Goodenough, 1980) and exten-
sively studied because of its excellent electrochemical properties,
high volume energy density and the ease of synthesizing a hexago-
nal ␣-NaFeO2 structure (Thackeray et al., 2007). Hasan et al. (Hasan
et al., 2020) studied the effect of particle size on the electrochem-
ical characteristics of LiCoO2 cathodes (LCO) by synthesizing LCO
of different average particle sizes. The average particle sizes (i.e.,
diameter, d) of LCO cathode materials were approximately 1.5
and 3.8 ␮m, labeled as S-LCO and L-LCO, respectively. The cycle
test at 0.1 C in the range of 3.0–4.5 V vs Li/Li+ yielded a higher
capacity retention of 94.2% for S-LCO compared to 91.1% for L-LCO
after 25 cycles, and S-LCO sample exhibited better rate capabil-
ity compared to L-LCO. Smaller particle size enables a decrease in
the pathway for Li-ion diffusion (L), thus reducing the time con-
stant for ionic diffusion according the relationship t = L2 /D, where
L is the diffusion length and D is the solid-state chemical diffu-
sion constant (Aricò, Bruce, Scrosati, Tarascon, & Schalkwijk, 2005).
Accordingly, the reduced time constant signifies a faster diffusion
in the cathode materials, which would enable a higher rate capa-
bility. Moreover, a faster transport of ions in smaller particle size
results in a smaller concentration gradient (dC/dR), where C denotes
the Li+ concentration as a function of the radial distance (R) from
the center of a particle. As the concentration gradient might result
in a mechanical stress, a smaller particle size could minimize the
mechanical stress and provide a better cycle performance (Hasan
et al., 2020). On the other hand, the S-LCO with the smaller particle
size exhibited higher average voltage and specific capacity than that
of L-LCO, which indicated that the smaller particle size contributed
to reducing the overpotential. And the mechanism might be that the
increase of specific surface area reduced the current density and
thus the charge transfer overpotential, while the decrease in the
solid-state Li-ion diffusion length also reduced the concentration
overpotential (Hasan et al., 2020).
For LiFePO4 material with olivine structure, particle size reduc-
tion has been employed in a number of studies as an effective
method to improve the high-rate capacity and cycling stability
J. Zhang et al.
Fig. 2. (a) Discharge curves of lithium-ion batteries with LiFePO4 of different particle
sizes at different discharge rates. Lithium ion concentration (b) and local current
density (c) at interface of cathode and separator in battery with different LiFePO4
particle sizes at different discharge rates (Xu, Chen, Zhou, Sui, & Zhou, 2020).
(Fey et al., 2009; Kang & Ceder, 2009; Zhang, 2011), since the
transport distance for electrons and Li-ions can be shortened by
reducing the particle size. Satyavani et al. (Satyavani, Ramya Kiran,
Rajesh Kumar, Srinivas Kumar, & Naidu, 2016) found that when
the LiFePO4 particle size was reduced from micron to nanome-
ter, the conductivity and diffusion coefficient of LiFePO4 particles
increased by an order of magnitude and the rate performance was
greatly improved. Xu et al. established a quasi-2D model of LIB
to simulate the discharge process, and studied the influence of
LiFePO4 particle size on rate performance (Xu, Chen, Zhou, Sui, &
Zhou, 2020). As shown in Fig. 2, the differences between discharge
curves at different rates were relatively small when the particle
size of the cathode material was small (0.5 ␮m). However, the out-
put voltage and maximum capacity at high rates were significantly
reduced when the particle size increased, especially when the par-
ticle size exceeds 3.5 ␮m. Indeed, much the kinetic limitation in
LIBs that causes slow charging comes from the slow solid-state dif-
fusion of Li-ions through the micron length scale powders making
up the electrodes. Thus, if the electrodes were made out of nano-
rather than micron-scale powders, diffusion path lengths would be
shorter and charging times could be faster (Lesel, Cook, Yan, Lin, &
Tolbert, 2017). Liu et al. also found similar results (Liu et al., 2014),
the time required for the 1D transmission of lithium ions in the
[010] direction of the LiFePO4 material particle to 30 nm was less
than 1 s when the LiFePO4 particles were nanosized, which effec-
tively shortened the diffusion path of lithium ions in the LiFePO4
material particles. In addition, the difference between the output
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Particuology 61 (2022) 18–29
voltage of LIBs with different particle sizes of LiFePO4 material was
indistinctive at 0.2 C. The output voltage only declined by 1% and
the maximum capacity almost unchanged at 0.2 C when the parti-
cle size changed from 0.5 ␮m to 10.5 ␮m, which indicated that the
battery performance of LIBs was barely affected by the change of
the particle size at low discharge rates. On the other hand, the liquid
phase diffusion coefficient of lithium ions under different particle
sizes, the electrochemical reaction rate at the interface of electrode
material and electrolyte, and the Li-ion concentration on particle
surface were calculated by using model equations. The results indi-
cated that the resistance in solid phase was the key factor limiting
the performance of LIBs. The Li-ion concentration on the surface
of the particles increased sharply at high discharge rate, but the
generated lithium was difficult to quickly diffuse into the particles
due to the low solid phase diffusion coefficient in particles, which
limited the electrochemistry reaction speed. When the particle size
decreased, the diffusion path within the particles was shortened,
the transfer of lithium inside the particles had been accelerated,
and the overall current density increased, thus improved the rate
performance of LIBs.
The ternary layered oxides Li[Nix Coy (Al or Mn)1−x−y ]O2 (NCA
or NCM) with high voltage and high specific capacity now play an
important role as cathode materials in EV batteries (Yu & Zhou,
2013). Xing et al. (Xing, Wang, & Yang, 2015) synthesized two differ-
ent particle sizes of ternary materials and studied the effect of par-
ticle size on electrochemical performance of LiNi0.5 Co0.2 Mn0.3 O2 as
cathode material for LIBs. The results showed that the particle size
of the ternary material was closely related to the particle size of the
precursor, the particle size of the ternary material prepared from
the precursor with a large particle size was also large. Meanwhile,
the ternary materials with small particle size (NCM-S) had larger
specific surface area of 1.21 g m−2 , and the specific surface area
of large particle ternary materials (NCM-L) was 0.99 g m−2 . And
the powder resistivity test showed that the powder resistivity of
NCM-L with larger particle size under different pressures was lower
than that of NCM-S, which indicated that the ternary material with
larger particle size had higher electronic conductivity. This may be
due to the fact that electrons had to pass through more particle
interfaces when moving in small particle size powder, resulting in
greater electron conduction interface impedance. The first charge-
discharge curve showed that the gap between the charging and
discharging voltage platforms of NCM-L was greater than that of
NCM-S, indicating a larger polarization of NCM-L. The reason for
the larger polarization of NCM-L was the larger particle size of
NCM-L, which leaded to a longer migration path of lithium ions.
Besides, the first coulombic efficiency of NCM-S was only 80.49%,
lower than that of NCM-L (86.55%), which may be caused by the
side-reactions of small particle size materials with high specific
surface area. In addition, Xia et al. also found the similar results in
LiNi0.80 Co0.15 Al0.05 O2 cathode materials, the sample with smaller
particle size had better cycling performance at high rates but no
obvious advantages at low rates compared with the sample with
larger particle size (Xia et al., 2018). These results again illustrate
the importance of small particle size in improving the rate perfor-
mance of cathode materials, since the Li-ion have the ability of rapid
migration when small particle size shortened the de-intercalation
path, which is more conducive to a high-rate cycle. Likewise, Lu
et al. investigated the effects of the particle size of lithium man-
ganese oxide LiMn2 O4 cathode particles on the electrochemical
performance by comparing four different particle sizes, the average
particle sizes (D50) for four kinds of sieved powders are 19.9, 32.9,
41.9, and 53.8 ␮m, respectively (Lu & Lin, 2001). And the capacity
and coulomb efficiency of LiMn2 O4 cathode particles significantly
increased with a decrease in the average particle size since the
small particles with large interface area provided more Li-ions for
diffusion, thereby resulting in the high ionic current and capacity.
J. Zhang et al.
Fig. 3. (a–d) SEM images of the LiCoO2 particles obtained at various temperatures.
LiCoO2 nanoparticles prepared hydrothermally at (a) 200 ◦ C were further annealed
at (b) 500, (c) 700, and (d) 900 ◦ C for 5 h. (e–h) Voltage profiles of the first cycles at
0.1, 2, 4, and 7 C rates (2C-1 and 2C-50 denote the first and 50th cycles at a rate of
2 C) (Jo et al., 2009).
The importance of the proper particle size
In what concerns nano and micro electroactive particle sizes, it
seems that there are intermediate particle sizes whose electrodes
present better electrochemical performances (Pavoni et al., 2018).
Jo et al. (Jo, Hong, Choo, & Cho, 2009) prepared LiCoO2 nanopar-
ticles with different particle size of 50 nm, 100 nm, 300 nm, and 1
␮m (Fig. 3(a)–(d)), at 200, 500, 700, and 900 ◦ C by hydrothermal
treatment, respectively. And they investigated the effect of LiCoO2
cathode nanoparticle size on high-rate performance in LIBs. The
results of LiCoO2 cathode with a particle size of 50 nm showed
the highest irreversible capacity ratio of 47% and highest surface
areas of 14 m2 g–1 among the samples at 0.1 C (compared with 37%
of 100 nm-sized particles, 14% of 300 nm-sized particles and 6%
of 1 ␮m-sized particles), which indicated that the increased sur-
face area of smaller particle size will result in more side reactions
with the electrolyte, thus forming a thicker solid electrolyte inter-
face. Liu et al. (Liu, Li, Wang, Huang, & Chen, 2006) also found large
irreversible capacity in the first cycle of the LiCoO2 nanoparticles
(30–50 nm), and reported that the reactivity of nanosized LiCoO2
with electrolyte was much higher due to the larger surface area
in comparison with commercial LiCoO2 , which indicated that the
spontaneous reaction between LiCoO2 and electrolyte was “magni-
fied”, thus resulted in a large irreversible capacity. In addition, the
solid electrolyte interface film thickness on the LiCoO2 nanoparti-
cles (30–50 nm) was about 2–5 nm and increased with increasing
surface area of the cathode, which also explained the origin of
the larger irreversible capacity of the smaller particles. However,
in this case, the rate capability tests (Fig. 3(e)–(h)) showed that
the LiCoO2 cathode with particle size of 300 nm demonstrated
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Particuology 61 (2022) 18–29
the best rate capability at higher C rates (instead of 50 nm-sized
particles or 100 nm-sized particles), which was attribute to more
side reactions of cathode with smaller particle size and resulted
in deteriorated rate capabilities at higher C rate. Likewise, the
LiCr0.2 Ni0.4 Mn1.4 O4 electrodes with particles larger than 500 nm
showed the highest capacity retention and better cycling stabil-
ity among LiCr0.2 Ni0.4 Mn1.4 O4 electrodes manufactured with eight
mean particle sizes ranging from 55 nm to 3215 nm (Aklalouch,
Rojas, Rojo, Saadoune, & Amarilla, 2009). Electrodes of porous
nanostructured LiFePO4 particles presented better charge capac-
ities when manufactured under average particle size of 170 nm
compared with that of 600 nm (Choi & Kumta, 2007).
Yang et al. explored optimal particle size of the micron-sized
LiMn0.8 Fe0.2 PO4 with enhanced electrochemical performance as
cathode material for LIBs (Yang et al., 2020). The LiMn0.8 Fe0.2 PO4
cathode with particle size of ∼9.39 ␮m (LM0.8 F0.2 P-9) exhibited
excellent rate performance with the specific capacity of 122 mA
h g–1 at 0.5 C and 106 mA h g–1 at 3 C, which was higher than
that with the particle sizes of ∼2.71 ␮m (LM0.8 F0.2 P-2), ∼3.74 ␮m
(LM0.8 F0.2 P-3), ∼6.41 ␮m (LM0.8 F0.2 P-6) or ∼16.31 ␮m (LM0.8 F0.2
P-16) (Yang et al., 2020). Smaller particles sizes are beneficial to
shorten the Li-ion diffusion path resulting in small electrochemical
polarization, however, the large specific surface area of LM0.8 F0.2 P-
2, LM0.8 F0.2 P-3 or LM0.8 F0.2 P-6 samples (shown in Table 1) would
extend the contact between cathode particles and electrolyte,
which caused the poor cycling performance. For the LM0.8 F0.2 P-16
sample, the large particle size made the Li-ion diffusion path much
longer, which caused the serious polarization phenomenon. The
optimal particle size of the micron-sized LM0.8 F0.2 P-9 cathode
facilitated the fast diffusion of Li-ion, resulting in higher ionic
conductivity and improved electrochemical performances.
Reducing the particle size of the cathode material can effec-
tively improve the performance of LIBs, however, due to their high
surface areas and less-coordinated surface atoms, materials with
small particle size, especially nanoparticles, are more prone to sur-
face reaction and particle dissolution in electrolyte, which may
severely reduce the cyclic and calendar life of batteries (Jamnik &
Maier, 2003). Moreover, electrode material consisting of individual
nanosized grains incorporated into the slurry can produce elec-
trodes that were kinetically slow due to poor electrical conductivity
between nanosized grains and reduced electrolyte penetration into
regions of agglomerated nanoparticles, even though Li-ion diffu-
sion lengths were short (Lesel et al., 2017). On the other hand, the
tap density of small particle material is generally low and the man-
ufacturing costs are often high, leading to low energy density and
high energy cost of LIBs. In addition, smaller particles also required
more supporting materials such as conductive carbon, binder and
current collector in a battery cell (Awarke, Lauer, Pischinger, &
Wittler, 2011). Therefore, in order to obtain the excellent rate per-
formance, we should comprehensively consider the benefits and
the adverse effects in real applications of small particle size cath-
ode materials. The particle size of electrode material needs to be
appropriate, instead of blindly pursuing small particle size. We
can design different particle size cathode materials according to
the different application scenarios for different output voltage and
charge-discharge rate requirements.
Particle size distribution
Since particle size distribution (PSD) represents the particle
packing and polydispersity of electrode materials, which deter-
mines the tap density of electrode materials and the energy density
of LIBs. Chung et al. assessed the impact of particle size polydis-
persity on the electrochemical performance of battery electrodes
by using 3D X-ray tomography data of LiMn2 O4 battery elec-
trode and computer-generated microstructures, which showed
J. Zhang et al.
Fig. 4. (a) Particle size distribution of the LiNi1/3 Mn1/3 Co1/3 O2 secondary-particles
before and after sieving with a 5 mm mesh. Inset indicates the average secondary-
particle diameter and the standard deviation. (b) Nyquist plots showing the
impedance response of the LiNi1/3 Mn1/3 Co1/3 O2 cathodes before and after sieving.
(c) and (d) Enlarged Nyquist plots showing the region where the semicircles are
observed (Nara et al., 2017).
that the particle size polydispersity impacted the local chemical
and electrical behavior of the porous electrode, and the broad
PSD can achieve an enhanced energy density (two times higher)
than monodisperse-sized particles based electrodes for low C-rates
applications (Chung, Shearing, Brandon, Harris, & García, 2014).
However, for high discharge rates, the monodisperse electrodes
delivered higher power density due to their high surface area per
volume ratio.
Early in 1997, Sheu et al. studied the battery performance
with different LiCoO2 PSD by using charge and discharge recy-
cling process, and the results showed that the smaller PSD had
better cycle stability (Sheu, Yao, Chen, & Chiou, 1997). Gupta et al.
showed that particle packing and morphology impacted the aver-
age transport behavior and macroscopic mechanical deformation
in porous electrodes (Gupta et al., 2011), and this spatial effect will
directly affect the deintercalation of lithium ions, thus affecting
the battery performance. Nara et al. designed an equivalent cir-
cuit and investigated LiNi1/3 Mn1/3 Co1/3 O2 cathodes with different
secondary-particle size distribution by electrochemical impedance
spectroscopy (Nara et al., 2017), and the results suggested that
charge-transfer and diffusion impedances were attributed to a PSD
for LIBs. The LiNi1/3 Mn1/3 Co1/3 O2 secondary-particles were sieved
by using the micro-sieve of 5 mm mesh to obtain two different PSD.
As shown in Fig. 4(a), the PSD became narrow after sieving, the aver-
age particle size (diameter, ) decreased from 7.4 ␮m to 5.1 ␮m
Table 1
The particle size (D50 ), specific surface area (SSA) and tap density (TD) of the LM0.8 F0.2 P-2, LM0.8 F0.2 P-3, LM0.8 F0.2 P-6, LM0.8 F0.2 P-9 and LM0.8 F0.2 P-16 samples, respectively
(Yang et al., 2020).
Samples LM0.8 F0.2 P-2 LM0.8 F0.2 P-3
D50 (␮m) 2.71 3.74
SSA (m2 g–1 ) 39.46 37.73
TD (g cc–1 ) 0.57 0.65
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Particuology 61 (2022) 18–29
and the standard deviation () decreased from 3.4 to 1.9. The dif-
ference in the charge-transfer resistances (the semicircle observed
at a lower frequency region in Fig. 4(b)–(d)) of the cathodes with
different PSD can be attributed to the difference in the total active
surface areas of the particles.
Using electrochemical models to simulate and predict electro-
chemical performance of LIBs has important guiding significance
for battery design and the optimization of manufacturing pro-
cesses. A variety of Li-ion electrochemical models have been
reported, including pseudo two-dimensional model (P2D model),
single particle model (SP model) and multiple particle model (MP
model) (Pavoni et al., 2018; Röder, Sonntag, Schröder, & Krewer,
2016; Taleghani et al., 2017; Wang et al., 2018). Taleghani et al.
presented a P2D model which considered the mass and charge
transport in the electrolyte and solid phases, as well as the reaction
kinetics in the electrolyte-solid interface (Taleghani et al., 2017).
The results showed that the volume fraction of small and large
particles had a profound effect on battery performance charac-
teristics such as capacity, voltage and specific power, in addition,
the PSD had a greater effect at higher discharge current densities.
Moreover, the change in the porosity of electrode materials will
led to changes in the voltage curve and battery capacities. With
a large increase in the porosity, a sharp decrease in cell voltage
was observed, which due to the lower amount of active materi-
als, although the amount of electrolytic solution in the pores of the
electrode was increased. And the rapid drop in cell voltage can be
also seen when the porosity decreased beyond a specific value, in
this situation, despite the fact that the amount of active materi-
als increased, there were not enough lithium ions in the solution to
reach the reaction zone leading to a mass transfer limitation. There-
fore, it was of great importance to determine the optimal porosity,
as well as the PSD.
The MP model (Farkhondeh & Delacourt, 2011; Safari &
Delacourt, 2011) is an electrochemical model used to study the
influence of electrode particles on the electrochemical performance
of batteries. In MP model, the electrode is simplified into multiple
particles with different sizes, properties and impedances, the com-
prehensive effect of these particles characterizations can be used to
represent the electrochemical behavior of the entire electrode, thus
achieves predicting the utilization rate of particles of various sizes.
Jing et al. analyzed the impact of PSD on the discharge process based
on the MP model, the electrochemical performance of LIBs was sim-
ulated and the effects of different particles on the whole discharge
process were illustrated (Wang et al., 2018). The study showed that
in the early stage of discharge, the intercalation reaction of lithium
ions mainly occurred on the particles with small size, in the late
stage, the intercalation reaction of small size particles would be
saturated, and particle surface reaction was transferred from small
particles to large particles because they had more internal vacan-
cies. In addition, the local current density was evenly distributed
in the early stage of the discharge, but in the later stage of the dis-
charge, the local current density of particles of different sizes varied
greatly, and the overpotential of large particles was large, which
demonstrated that the polarization of large particles was greater
than that of small particles. Therefore, a uniform PSD of cathode
particles is expected to have better electrochemical performance
since it can reduce the increase in polarization caused by large-size
particles in the later stage of discharge process.
LM0.8 F0.2 P-6 LM0.8 F0.2 P-9 LM0.8 F0.2 P-16
6.41 9.39 16.31
36.31 31.56 8.43
0.62 0.68 0.58
J. Zhang et al.
Overall, the PSD determines the particle packing, polydisper-
sity, and porosity of electrode materials, which directly affect the
mass transfer of lithium ions during charging and discharging, as
well as the final energy density of batteries. Therefore, in battery
industrial manufacture, the advanced battery designs can be real-
ized by engineering the particle size and PSD by customizing it to
meet high energy density applications.
Particle shape
The morphology of the particles plays an important role in the
electrochemical performance of LIBs since it is directly related to
the effective surface are of cathode materials. Many studies veri-
fied the correlation between the morphology and electrochemical
properties (Garcia et al., 2017; Zukalová, Procházka, Lásková, Zukal,
& Kavan, 2018), and showed that the particle morphology affected
the Li-ion diffusion pathway and the kinetic properties of cathode
materials (Li, Ren et al., 2019; Pişkin, Uygur, & Aydınol, 2020). Early
in 2006, Kim et al. investigated the shape and surface morphology
of cathode material on electrochemical properties (Kim, Shim, Han,
& Kim, 2006), they found that the Li(Ni1/3 Co1/3 Mn1/3 )O2 secondary
particles with spherical morphology and a smooth surface had bet-
ter capacity retention, which suggested that the shape and surface
morphology should be one important factor for the electrochemi-
cal performance besides the particle size and distribution. Similarly,
Xiao et al. found that the electrochemical performance of LiMn2 O4
particles with spherical morphology was better than those of the
cubic one, and the middle size spherical particles achieved the best
performance by balancing the contradictory of diffusion length in
solid phase and particle agglomeration (Xiao et al., 2013). In addi-
tion to spherical materials, synthesis of 1D (Liu, Sun et al., 2021) or
2D materials (Mei, Zhang, Liao, Sun, & Dou, 2018) with large surface
area can also significantly improves materials characteristics and
electrochemical performance of batteries. For example, creating a
nanosized Li3 V2 (PO4 )3 composite with a 1D nanofiber morphol-
ogy leaded to a better rate and cycle performance (Lee et al., 2020;
Shin, Yang, Sergey, Song, & Kang, 2017), and the 2D materials are
applicable for high charging capacity and long cycle life for metal-
ion batteries such as MoS2 due to their high surface-volume ratio
(Hwang, Kim, & Cho, 2011). However, for ease of manufacturing,
the prevailing technological forms of cathode materials of LIBs
are secondary particles of nearly spherical morphology contain-
ing many nanocrystallites. Additionally, the high tap density and
energy density of the cathode material with spherical particles
meet the market demand for commercial batteries.
Many drawbacks of Li-rich layered oxide cathode materials can
hardly be overcome by simply changing the shape of cathode par-
ticles into sphere, therefore, there are many other strategies for
structural design had been proposed and optimized to improve the
inherently low conductivity and tardy lithiation kinetics of cath-
ode materials (Jiang & Zou, 2018; Lou et al., 2017; Lu et al., 2019;
Oh et al., 2014), such as doping, coating, surface modification, and
nanocrystallization (Lu, Zhang, Zhang, Cheng, & Chen, 2020). The
doped ions, like Ti4+ , Mg2+ , Al3+ , N3+ , F– , can provide stronger M O
chemical bond than active transition metal (Ni, Co, Mn), which
improved the structural stability of the cathode material by sup-
pressing the precipitation of lattice oxygen under high voltage
(Wu, Ni, & Meng, 2015). Hollowing the particles and/or creating
pores can improve specific surface area and electrochemical per-
formance of the cathode materials. Aida et al. synthesized a series of
LiNi1/3 Co1/3 Mn1/3 O2 cathode materials with different particle sizes
and degrees of hollowness and found that increasing hollowness
both increased the electrochemical reaction area and reduced the
Li-ion diffusion distance, thus improved the cycle durability as well
as the rate capability of LIBs, but also found that hollowing causes
poor tap density, which indicated that hollowing contributes to
23
Particuology 61 (2022) 18–29
lower volumetric energy density of the batteries (Aida, Toma, &
Kanada, 2020).
At the scale of particle, surface coating prevents the direct
contact between active materials and electrolyte to enhance the
performance of cathode materials, and the core-shell structure has
been extensively utilized to develop advanced cathode materials.
On the other hand, the traditional cathode active material par-
ticles are usually prepared as polycrystalline particles consisting
of nanoscale primary grains. The single-crystal cathode particles
reveal an alternative path towards developing better battery cath-
ode materials, beyond the traditional one built upon polycrystalline
materials (Kan et al., 2018; Kong, Zhang, Peng, Zeng, & Zhao, 2020;
Li et al., 2017; Zhu & Chen, 2019). It has been proved that the single-
crystal particles can significantly improve the cycle performance of
cathode materials and obtain an excellent capacity retention by
eliminating the internal grain boundaries and inter-granular frac-
ture (Fan et al., 2020; Li, Li, Ma, & Dahn, 2018; Qian et al., 2020; Zhu
et al., 2020).
Core-shell structure
The formation of a core-shell structure is a promising way to
realize uniform encapsulation of the active materials, and help sta-
bilize the surface structure of the cathode material, prevent side
reactions between the electrode material and the electrolyte, and
improve the cycle stability (Hou, Zhang, Zi, Zhang, & Xu, 2017;
Kalluri et al., 2017; Myung, Khalil, & Sun, 2013; Wang et al., 2019;
Yoo, Jang, & Son, 2015; Yuan, Song, Wang, Gu, & Chen, 2019).
For rechargeable LIBs, criteria for electrode materials that should
be satisfied are capacity and safety. Therefore, it is desirable to
adopt high-capacity materials as the core (such as Li-rich layered
ternary battery material Li[Ni0.8 Co0.1 Mn0.1 ]O2 ) and thermally sta-
ble materials as the shell, which should have a high exothermic
decomposition temperature to ensure their thermal stability.
Various surface modification compounds have been reported,
such as Al2 O3 (Lee, Shin, Kannan, Koo, & Kim, 2015), TiO2 (Tao
et al., 2017), SiO2 (Chen et al., 2017), ZrO2 (Ahn et al., 2019), AlF3
(Park, Kim, & Myung, 2008), etc. Chen et al. (Chen et al., 2017)
coated LiNi0.5 Co0.2 Mo0.3 O2 with a layer of 20−25 nm thick SiO2
(Fig. 5(a)–(b)), and the results showed that after 100 cycles at 0.1
C between 2.5–4.3 V, the specific capacity of modified material
remained 82.5%, much higher than that of the original material of
68% remaining. The reversible specific capacity was 153.4 mA h g–1
(92.4% of the initial specific capacity), and the original material was
only 114.3 mA h g–1 (66% of the initial specific capacity) after 50
cycles at 1 C between 2.8–4.5 V (Fig. 5(c)). The obviously improved
performance was mainly attributed to the coating layers reducing
reactions between electrode and electrolyte, which minimized of
the impact of side reactions. In order to improve the ionic conduc-
tivity of these coating materials, some lithium-ion conductors are
employed as surface coating materials, such as LiPON (Wang et al.,
2016), LiAlO2 (Liu et al., 2018), Li3 PO4 (Song, Kim, Kim, & Park,
2011), and Li2 ZrO3 (Wang et al., 2015; Xu et al., 2016). Liu et al.
(Liu et al., 2018) designed an ultra-thin LiAlO2 coating on NCM for
LIBs (Fig. 5(d)), which can maintain a reversible capacity of more
than 149 mA h g–1 after 350 cycles and exhibited a higher rate
capacity of 142 mA h g–1 at 3 C than traditional metal oxide coated
NCM (131.9 mA h g–1 at 3 C of Al2 O3 -coated NCM, as shown in
Fig. 5(e)). The effectively improved cycling stability and rate capa-
bility were attributed to the stabilization of the average discharge
voltage and the better Li-ion transfer at the engineered interfaces
of LiAlO2 coated NCM.
Except for the common coating materials mentioned above,
the concentration gradient core-shell structure design of cathode
materials, in which the transition-metal cations increase and/or
decrease gradually from particle center to surface, is believed to
J. Zhang et al.
Fig. 5. (a) SEM image and (b) TEM image of 0.5 wt% of the SiO2 -coated
LiNi0.5 Co0.2 Mo0.3 O2 . (c) Cycling performance of pristine and SiO2 -coated samples
at 1 C rate in the voltage range of 2.8–4.5 V. (Chen et al., 2017) (d) Schematic illus-
tration of Al2 O3 and LiAlO2 coatings on NCM. (e) Rate capability of NCM, Al-O-2, and
Li-Al-O-2 at various current densities in the range of 25–750 mA g–1 in a voltage
range of 2.7–4.5 V vs. Li/Li+ . (Liu et al., 2018) (f) Cross-sectional SEM images of the
three LLOs (S1, S2, and S3) with different gradients. (g) Gradients of representa-
tive S1, S2, and S3 semispheres as reflected by the contents of transition metals at
positions 1–7 (see images (f) from the sphere center to the surface. (h) Cycle perfor-
mances of S1–S3 at 1 C between 2.0 and 4.6 V. (i) Rate capacities of S1–S3 at 0.1–3
C (Wu et al., 2021).
further overcome the drawbacks of the core-shell structure, since
a void layer of tens of nanometers between the core and the
shell will appear in core-shell layered cathodes after long cycles,
which blocks the Li-ion migration and the electron transfer during
charge/discharge of LIBs, resulting in the rapid decline of elec-
trochemical properties (Hou et al., 2017; Lim et al., 2015; Yoon
et al., 2018). Recently, Wu et al. (Wu et al., 2021) synthesized
a series of full concentration gradient-tailored lithium-rich lay-
ered oxides (LLO) agglomerated spheres with linearly decreasing
Mn and linearly increasing Ni and Co from cathode particle cen-
ter to surface (three LLOs with zero, medium, and high elemental
gradients, termed S1, S2, and S3, as shown in Fig. 5(f)–(g)). The
gradient-tailored LLO with medium-slope showed the most stable
voltage from 3.61 to 3.45 V within 200 cycles and the best electro-
chemical performance with an average voltage decay of only 0.8
mV per cycle as well as a capacity retention of 88.4% (as shown in
Fig. 5(h)). However, the fracture of S3 spheres caused by the intrin-
sic and electrochemical stress during the cycling had a negative
effect on electrochemical performance and weakened the stability
of the S3 cathode. In addition, Wu et al. considered that there was
also intrinsic stress in the uncharged gradient material (S1) due
to the lattice mismatch. Therefore, it is very important to balance
the concentration gradient of cathode particles in the preparation
of high-energy LLOs. For applications of LIBs, active materials are
required to achieve a higher energy density, and the chemical co-
precipitation method is believed to be one of the most effective
24
Particuology 61 (2022) 18–29
Fig. 6. Schematic preparation process of core-shell and concentration-gradient
cathode materials via a co-precipitation route and solid-state reaction (Hou et al.,
2017).
approaches to synthesizing spherical core-shell and concentration-
gradient structured particles with a high tap density, since the
continuous stirred tank reactor used in this method is capable of
producing spherical precursors (Bommel & Dahn, 2009; Hou et al.,
2014; Sun et al., 2009). Fig. 6 showed the scheme of the preparation
process of core-shell and concentration-gradient cathode materi-
als via a co-precipitation route, which involves two main steps: (1)
the preparation of aimed precursors, (2) the solid-state reaction
with lithium sources at high temperature (Hou et al., 2017). How-
ever, the large-scale industrial production applications still face
challenges due to the difficulties in preparation repeatability and
consistency of concentration-gradient cathodes and the high cost
of the batch-wise system in large-scale industrialization.
Single-crystal structure
The common morphology of typical cathode materials is
micrometer-sized secondary aggregated particles consisting of
nanoscale primary particles. It had been reported that these sec-
ondary particles suffer from cracks within or between particles due
to the anisotropic stress and dislocations after excessive cycling,
which may disrupt connectivity and cause loss of conductivity in
the cathode, resulting in a capacity fade of LIBs (Lima, Chob, & Kim,
2001; Huang, Wang, Yang, Xu, & Gu, 2019; Wang, Wu, Wang, &
Chen, 2005). Compared with these typical cathodes, the single-
crystal form without grain boundaries inside particles is considered
effective against issues like cracks and phase transformations, thus
improving the electrochemical properties of cathode materials (Liu
et al., 2020). In addition, the single-crystal cathode materials are
possible to achieve higher electrode compact density and remain
the microstructure during the pressing because they are less prone
to crack when they are rolled into electrodes (Kim et al., 2018).
A micron-sized single-crystalline LiNi0.83 Co0.11 Mn0.06 O2 cath-
ode (SC-NCM) achieved superior cycling performance at both room
temperature and elevated temperature (55 ◦ C), and the well-
preserved rectangular-like morphology of the SC-NCM particles
without visible cracks after prolong cycling, indicated that the
single-crystal cathode particles can effectively prevent the genera-
tion of intergranular cracks and alleviate the irreversible structural
degradation, as seen in Fig. 7 (Fan et al., 2020). Analogously,
Qian et al. (Qian et al., 2020) reported micro-sized single-crystal
LiNi0.6 Mn0.2 Co0.2 O2 cathode materials with high specific capac-
ity of 183 mA h g–1 at 0.1 C (4.3−2.8 V) and excellent capacity
retention of 94% after 300 cycles at 1C, and confirmed that the
J. Zhang et al.
Fig. 7. Cross section SEM images of (a–b) Normal-NCM and (c–d) SC-NCM electrodes
before and after cycling. (e) Schematic illustration of crack evolution and the internal
morphological difference for Normal-NCM and SC-NCM cathodes during prolong
cycling (Fan et al., 2020).
single-crystal particles were stable against intra-granular fracture
as well under normal operating conditions but the intra-granular
fracture did occur if severely overcharged, which may become a
barrier for high-voltage operation of LIBs. Bi et al. (Bi et al., 2020)
observed reversible planar lattice gliding and microcracking along
the (003) plane in a single-crystalline Ni-rich cathode at high volt-
ages, which was correlated with the localized stresses induced by
a concentration gradient of Li atoms in the lattice and quite differ-
ent from cracking along intergranular boundaries of polycrystalline
particles (Ryu, Park, Yoon, & Sun, 2018). Moreover, they found
that single-crystalline Ni-rich cathode particles can be stabilized
by either reducing the crystal size to below 3.5 ␮m, or simply opti-
mizing the depth of charge without sacrificing much reversible
capacity.
Fig. 8. (a) Schematic diagram of the synthetic route for single-crystal NCM811. (b) Formation mechanism of the Ni0.8 Co0.1 Mn0.1 O1.1 microsphere prepared by spray pyrolysis
method from chloride solution. Cycle performances at room temperature (c) and cycle performances at 4 C (d) of PC-811 and SC-811 (Zhu et al., 2020).
25
Particuology 61 (2022) 18–29
On the other hand, the tedious steps and the high process
requirements of the synthesis of the single-crystal particles limit
the large-scale application of the single-crystal cathode materials,
especially for the Ni-rich ternary cathode materials. The formation
of monocrystal always requires high sintering temperatures during
the lithiation of ternary hydroxides, and the specific size of the
particles are difficult to control during the preparation of the
precursor. Zhu et al. (Zhu et al., 2020) developed a novel strategy
to synthesize single-crystal Ni-rich cathode materials without flux
and multi-stage sintering (Fig. 8(a)–(b)). The hybrid oxides NiO-
MnCo2 O4 -Ni6 MnO8 with fine particle size and porous structure
as the precursor was synthesized by spray pyrolysis method, and
then, the submicron single-crystal LiNi0.8 Co0.1 Mn0.1 O2 (NCM811)
cathode material was successfully obtained at a lower lithiation
sintering temperature by using LiNO3 with fusible feature as the
lithium source and the flux agent. As shown in Fig. 8(c)–(d), the
obtained single-crystal NCM811 cathode (SC-811) delivered better
cycle performance of 157 mA h g–1 after 100 cycles at 1 C and
better capacity retention even at high rate of 4 C than that of
the commercial polycrystalline NCM811 (PC-811). Noteworthy,
single-crystal Ni-rich cathodes with Ni > 0.6 are not much reported
because of the challenges of preparing high-performance single
crystals (Bi et al., 2020; Li, Li et al., 2019; Zhu & Chen, 2019), this
synthetic strategy demonstrated that the crystal crushing process,
flux adding, and repeated sintering were not indispensable for
the synthesis of single-crystal cathode materials, which offered
a succinct pathway for the industrial synthesis of single-crystal
Ni-rich cathode materials.
In view of the current development of monocrystalline mate-
rials and the intra-granular fracture did occur when overcharged,
the further research efforts may should focus on developing surface
coating and doping strategies to suppress the structure collapse
and intra-granular fracture upon deep delithiation. For exam-
ple, Huang et al. (Huang et al., 2020) prepared a single crystal
Ni-rich LiNi0.8 Mn0.1 Co0.1 O2 material with a thin MnO2 layer on
the surface, which effectively suppressed side reactions between
electrolyte and cathode materials and delivered a superior electro-
chemical performance. The single crystal primary morphology of
the LiNi0.8 Mn0.1 Co0.1 O2 cathode material not only shortened the
migration path of lithium ions, but also avoided the generation of
J. Zhang et al.
cracks in particles after circulation, and the MnO2 layer acts as a
protective layer and Ni2+ in lithium slab can be used as pillars to
support the lithium layer to avoid collapse in the delithium state.
Influence of electrode processing
Electrode processing (mixing, coating, drying and calender-
ing) has a significant impact on the electrode microstructure and
property, which will ultimately determine the life cycle and elec-
trochemical performance of LIBs (Liu, Cheng et al., 2021).
In a typical electrode processing, the composite electrodes are
fabricated by coating organic solvent-based electrode dispersions
(i.e. slurry) onto a current collector. The biggest challenge in
slurry preparation is to make the active material and conductive
additive particles stable and avoid agglomeration and sedimenta-
tion (Hawley & Li, 2019). The stability and rheological properties
of electrode dispersions will be affected by the properties of
the electrode components (including electrode material, binder,
conductive additive, etc.) as well as the solids loading (Li, Daniel,
& Wood, 2011). Among others, the solids loading depends on the
mixing method and mixing order, and a proper mixing method and
mixing order can significantly reduce the viscosity of the cathode
dispersion (Kim, Jeon, Chung, & Chang, 1999) and improve the
contact between active material particles and conductive additive.
The lower viscosity slurry helps to coat current collector homoge-
neously, limit air bubble formation, and load more active materials,
resulting in higher energy density and improved electrochemical
performance of the electrode (Hawley & Li, 2019; Schmitt et al.,
2013).
During the electrode drying process, evaporation of the sol-
vent causes the coating liquid to shrink and thus generate stress,
which can lead to cracking, curling, and delamination of the coating
(Hawley & Li, 2019). In addition, it is widely believed that the migra-
tion of binder during the drying process will weaken the mechanical
integrity of the coating and lead to an increase in the internal
resistance of the electrode, i.e., the binder diffuses upward to the
coating surface and hinders the insertion reaction of lithium ions
(Lim, Ahn, & Yamamura, 2013; Stein, Mistry, & Mukherjee, 2017;
Susarla, Ahmed, & Dees, 2018). Compared to drying at room tem-
perature, drying at high temperature will accelerate the diffusion
of solvent to the coating surface, which will aggravate the prob-
lem of non-uniform distribution of inactive materials (Font, Protas,
Richardson, & Foster, 2018; Hagiwara, Suszynski, & Francis, 2013).
Therefore, in order to maintain the electrode microstructure of the
cell, both the drying temperature and speed need to be properly
controlled.
Thickening electrodes are the easiest way to obtain more energy
and power density cells, however, as the electrodes thicken, the Li-
ion diffusion distance become longer and mass transport becomes
difficult (Singh, Kaiser, & Hahn, 2015). Accordingly, the cell perfor-
mance will drop dramatically, especially at high rates, since the
rate-limiting step is the solid-state diffusion of Li-ions through
the electrode material (Singh, Mulder, Abdelkader, & Wagemaker,
2013). Calendering of electrodes can significantly reduce the elec-
trode thickness and increase the electrode density, however, the
strong compaction pressure can lead to a decrease in electrode
porosity and an increase in electrode tortuosity, which affects the
electrolyte penetration in the electrode material and the diffu-
sion of lithium ions (Chung, Ebner, Ely, Wood, & Edwin García,
2013; Shim & Striebel, 2003). Therefore, new designs of electrode
architectures (Li et al., 2011) and new fabrication methods (Shen
et al., 2019) are constantly being reported and developed to create
pore channels and balance the tortuosity and porosity. A practi-
cal lithium battery needs a well-matched positive and negative
electrode, besides focusing on the electrode material itself, the elec-
trode processing is also crucial (Kong et al., 2019).
26
Particuology 61 (2022) 18–29
Conclusions and perspectives
In the working process of lithium-ion battery, the contact
and reaction between electrode material particles and lithium
ions occur continuously, and this process is deeply influenced
by the particle size, particle size distribution and particle shape.
Smaller particles shorten the distance for Li-ion transport within
the particles, thus will increase the rate of Li-ion intercala-
tion/deintercalation, resulting a better rate performance of LIBs.
However, the increased surface area of small size particles usually
causes more side reactions with the electrolyte and the man-
ufacturing costs of small particle material are often high. PSD
determines the particle packing, polydispersity, and porosity of
electrode materials, which directly affect Li-ion transfer behavior
during the charge and discharge process, especially at high dis-
charge current density. A uniform PSD of particles can reduce the
increase in polarization caused by large-size particles in the later
stage of discharge process and always has a better cycle stability.
However, considering the practical application, a relatively broad
PSD and spherical-shape of electrode particles can help to obtain
a higher specific charge capacity and higher energy density, which
is attributed to the better packing density of the particles and the
enhanced particle interconnectivity inside the electrode. Therefore,
we should comprehensively consider the benefits and the adverse
effects in real applications, and flexibly adjust particle size and size
distribution of electrode materials to meet the requirements of dif-
ferent application scenarios. For LIBs, the cost of cathode materials
accounts over 30% of the entire battery cost, the development of
cathode materials is the key to satisfy requirements such as energy
density, cost, and in particular, safety of LIBs. Ni-rich layered oxides
now play an important role as cathode materials in EV batteries,
the single-crystal Ni-rich layered oxide particles reveal an alter-
native path towards developing better battery cathode materials,
beyond the traditional one built upon polycrystalline materials. It
has been proved that the single-crystal particles can significantly
improve the cycle performance and obtain an excellent capacity
retention by eliminating the internal grain boundaries and inter-
granular fracture. In addition, the single-crystal cathode materials
are possible to achieve higher electrode compact density and less
prone to crack when they are rolled into electrodes. At the scale of
particle, surface coating prevents the direct contact between active
materials and electrolyte to enhance the performance of cathode
materials, and building a core-shell structure is considered one of
the most effective means to develop advanced cathode materials.
Therefore, to further improve the energy density and stability of
LIBs, future works are suggested to combine the development of
single-crystal Ni-rich layered oxide cathodes with the design of
core-shell structure.
Conflict of interests
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (Grant No. 22078022)
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