Nano Energy 83 (2021) 105854

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Nano Energy
journal homepage: http://www.elsevier.com/locate/nanoen

Review

Fundamental and solutions of microcrack in Ni-rich layered oxide cathode

materials of lithium-ion batteries
Shouyi Yin, Wentao Deng, Jun Chen, Xu Gao, Guoqiang Zou, Hongshuai Hou, Xiaobo Ji *
State Key Laboratory of Powder Metallurgy, College of Chemistry and Chemical Engineering Central South University, China

A R T I C L E I N F O A B S T R A C T

Keywords: Ni-rich layered transition metal oxide is one of the most promising cathode materials for the next generation
Ni-rich cathode lithium-based automotive batteries due to its excellent electrochemical performances. Nevertheless, its further
Microcrack applications are capped by the structural/interfacial instability during the prolonged charging/discharging,
Lithium-ion batteries
leading to severe performance fading and serious safety concerns. Here, we provide a comprehensive review
Failure mechanism
about challenges and solutions to modify Ni-rich layered cathodes specifically for microcrack failure. Firstly, the
Optimized methods
mechanism of microcrack formation and evolution are concluded thoroughly. Secondly, recent advances in
stabilizing the structure/interface of Ni-rich cathodes are summarized such as surface coating, cation/anion
doping, composition tailoring, morphology engineering and electrolytes optimization. Furthermore, strategies to
mitigate the microcrack and then boost the electrochemical performance of Ni-rich cathodes at the chemical &
mechanical engineering level are presented. More importantly, outlook and perspectives to facilitate the prac­
tical application of Ni-rich layered cathodes toward electrical vehicle application are provided as well.

1. Introduction
In the last decade, global application of electric vehicles (EVs) has
been increasing speedily with the encouragement of government regu­
lations. For instance, the number of passengers electric vehicles carried
has already reached 5.4 million in 2018 [1–5]. Lithium-ion batteries
(LIBs), currently the dominant power source for EVs will replace the
internal combustion engine of vehicles in terms of environmental
friendliness, however, they are insufficient to support the
next-generation EVs due to several technological difficulties [6–9].
Recently, the technological difficulties of LIBs are their structural sta­
bility and energy density, which are principally expressed by the cath­
ode materials [10–14]. These restrictions have provided a powerful
motivation for the evolution of adequate cathode materials for
high-performance EVs. Layered Li[NixCoyMn1− x-y]O2 (NCM) and Li
[NixCoyAl1− x-y]O2 (NCA) are promising cathodes for EVs batteries
because of their comparatively low cost, extreme reversible capacity and
superior rate capability [15], and they have been researched extensively
since the beginning of 21st century [16]. However, they suffer from
structural instability due to the Ni-rich character, and the increase of Ni
content in the composition will distinctively reduce the lifetime of the
corresponding cathode [15,17]. In detail, the failure reasons of Ni-rich
cathode material are reflected at the surface and bulk phase structure
[18,19]. The reaction between the Ni4+ species (discharge state) and
electrolyte will damage the cathode surface, leading to the collapse of
cathode structure followed by transition metal ion dissolution, phase
transition and lattice oxygen evolution [20–23]. Besides, the bulk
structural changes originated from the high Ni content can produce
anisotropic forces leading to the formation of microcracks. The formed
microcracks expose new surfaces which were inside the particle and
further accelerate the deterioration of the cathode, as illustrated sche­
matically in Fig. 1 [21]. The higher the nickel content is, the more
serious the damage of microcracks will be, especially when the Ni
content exceeds 80% (Fig. 2a and b) [18]. In brief, it can be concluded
that the main reason for the decline in the life of Ni-rich cathodes is
attributed to the microcracks which can decrease the thermal stability,
structural stability, and cyclic stability of the cathode simultaneously
(Fig. 2c) [18].
In order to reduce the generation of cracks, currently, general
strategy is to operate the Ni-rich cathode at a limited depth of discharge
(DOD) (e.g. 50%− 80% of the full battery capacity). Nevertheless, DOD
restrictions will increase the battery deadweight, reduce the energy
density, and increase the cost of EVs [24,25]. Therefore, enormous ef­
forts are still needed to modify and improve the Ni-rich cathode

* Corresponding author.
E-mail address: xji@csu.edu.cn (X. Ji).

https://doi.org/10.1016/j.nanoen.2021.105854
Received 18 December 2020; Received in revised form 25 January 2021; Accepted 2 February 2021
Available online 4 February 2021
2211-2855/© 2021 Published by Elsevier Ltd.
S. Yin et al.
reasonably to enhance the life and stability of electric vehicle batteries
[26].
In this review, we have discussed the mechanism of microcrack
formation, and the relationship between structure evolution, surface
degradation, and microcrack formation during the prolonged cycle.
Also, several effective strategies which can mitigate the microcrack
generation from the aspects of surface chemical modification,
strengthening the bulk phase structure and mechanical structure sta­
bility are proposed. Through the discussion, a conclusion is drawn that
constraints from both chemical level and the structural level should be
taken into account in order to solve the issues of Ni-rich cathode, thus to
provide ideas for a new generation of high-energy-density battery
materials.
2. The mechanism of microcrack formation
Now, it is widely accepted that the main reason for the capacity
fading of Ni-rich cathode is the structural degradation which is specif­
ically caused by intergranular fracture due to the interface mechanical
stress. It leads to the disintegration and pulverization of primary parti­
cles [17,18,20,27–35], which can accelerate the side reactions between
the electrolyte and the formed microcracks of cathode materials, and
Fig. 1. The degradation of Ni-rich cathode material and the effect of microcrack.
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Nano Energy 83 (2021) 105854
finally result in the failure of materials [23,33]. Cracks can be divided
into two types according to their positions, namely intergranular crack
and intragranular crack, both of which will damage the structure of
cathode [36]. This section mainly explains the characteristics, the
influencing factors and generation mechanism of these two kinds of
cracks.
2.1. Formation of intergranular cracks
Intergranular cracks are mainly caused by the anisotropic shrinkage
and expansion of primary particles originated from the H2→H3 phase
transition. Forming intergranular cracks is considered to be the most
crucial degradation mechanism of the cathode (its effect on the cathode
is more substantial than forming intragranular cracks), due to the
following reasons: (1) cracks can reduce the connection between parti­
cles, resulting in low conductivity into the secondary particles, which
brings a more uneven state of charge (SOC). The uneven SOC will reduce
the activity of the material thus powdering and fragmentation of parti­
cles; (2) the occurrence of cracks will expose more active positions inside
the particles to react with the electrolyte, creating new appropriate
conditions for phase transition, corrosion and side reactions, thereby
accelerating the degradation of the battery [36].
S. Yin et al.
2.1.1. Cracks generated through H2→H3 phase transition
At present, researchers generally believe that the primary cause of
intergranular microcracks is the H2→H3 phase transition of the material
with high nickel content (nickel content above 0.8) under a high cut-off
voltage (4.3 V and above). The influences of phase transition can be
classed as the following: (1) anisotropic changes in lattice parameters;
(2) sudden changes in lattice parameters.
Before describing the formation of intergranular microcracks, it is
important to understand the Ni-rich cathode’s phase transition during
charging and discharging. By taking LiNiO2 as an example, the structural
transforms of Ni-rich cathode during charging are: Li1− xNiO2 undergoes
phase transitions firstly with three single-phase regions, i.e. a rhombo­
hedral phase (H1) for 0 ≤ x ≤ 0.25, a monoclinic phase (M) for
0.25 ≤ x ≤ 0.55 and a rhombohedral phase (H2) for 0.55 ≤ x ≤ 0.75;
and then with a two-phase coexistence region i.e. two rhombohedral
phases for 0.75 ≤ x ≤ 0.9 (H2 & H3) [37–39]. Specifically, according to
the difference in atomic arrangement, the H3 phase consists of two
types, H3–1 and H3–2.
There are few reports paying attention to the M phase, conversely,
researchers are more interested in the H1/H2/H3 phase transition. The
reasons for H1/H2/H3 phase transitions are closely related to the local
environment of lithium ions [40]. As an example, the phase transition
process of NCM 811 has been studied. As shown in Fig. 3a, the formation
of the H2 phase is caused by lithium ions extraction near the Mn site (LiM
site), and there is a significant peak shift between Li0.91~Li0.80, proving
the lithium ions extraction from LiM site. After charging, LiM gradually
precipitates from the cathode and finally the active material forms a
phase without LiM, which is the H2 phase. As for the H3 phase, it has two
types (labeled H3–1 and H3–2). From Li0.22 to Li0.15, the peak around
300 ppm shifts to a higher chemical site (Fig. 3a), which indicates that
the lithium ions are far away from the Ni site (LiN site). It proves that the
formation of H3–1 phase is mainly caused by the extraction of lithium
ions near the Ni site along with a decreased lattice parameter c. When
charging is about to end, there is a newly-formed peak observed near
0 ppm, which indicate that the lithium ions rearrange near the Ni site
(LiN) and the H3–2 phase forms [40]. For H3–1, lithium ions have a
tendency to escape from LiN sites, while for H3–2, lithium ions may be
re-ordered, and forms a lithium reordered material (Fig. 3b). Therefore,
the cause of the H1/H2/H3 phase transition can be analyzed from the
perspective of lithium-ion environment in material structure. The
statement that these different phase transition is closely related to the
ion environment is consistent with the researcher by Mao et al.[41] By
studying the Debye-Waller factor of the three elements Ni, Co, and Mn,
Mao and co-workers observed that as the voltage increases, the
Debye-Waller factor of Ni gradually increases. In comparison, that of the
other two elements did not change significantly (Fig. 7d), indicating that
the crystal structure around Ni atoms has changed enormously, that is,
Fig. 2. (a) Summarized the relationship between Ni content, cracks and material properties. Copyright 2019, American Chemical Society. (b) Summary diagram of
the relationship between different nickel content, capacity and stability. Copyright 2019, American Chemical Society. (c) The occurrence of cracks is the main reason
that affects the life of electric vehicles. Copyright 2019, American Chemical Society.
(a) Reproduced from Ref [18]. (b) Reproduced from Ref [19]. (c) Reproduced from Ref [19].
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Nano Energy 83 (2021) 105854
Ni is the leading cause of strain. It also proved that the insertion and
extraction of lithium ions near the LiN site is highly related to the gen­
eration of H3 phase transition [41].
Generally, researchers use the differential capacity vs. voltage (dQ
dV− 1) curve to monitor phase transition, since the peak of the dQ dV− 1
curve represents the phase change corresponding to the contraction/
expansion of the lattice parameter and the order of Li vacancies [38,39,
42,43]. For example, sharp peaks of dQ dV− 1 curves signify an abrupt
and short phase change associated with abrupt and harmful structural
changes. On the contrary, wide and low peaks show a protracted phase
transition, which has the advantage of structural stability.
In fact, H2→H3 phase transition is a unique phenomenon of Ni-rich
cathode, because it trends to happen in the material with Ni content
higher than 0.8. Rye et al. used the dQ dV− 1 curves to analyze the ca­
pacity attenuation of Ni-rich Li[NixCOyMn1− x-y]O2, and concluded that
the H2→H3 phase transition is related to the Ni content [21]. It was
observed that there is no H2→H3 phase transition in the cathode with
nickel content lower than 0.8. When the content of nickel in the material
increases, the intensity of the H2→H3 phase transition gradually in­
creases (a more extensive and larger area under the peak implies this in
Fig. 4b), which indicates that the H2→H3 phase transition only happens
in the Ni-rich cathodes with Ni content higher than 0.8, and the higher
the Ni content, the more sever the phase changes (the peak intensity of
the curve represents the intensity of the phase transition) [21]. In
addition to Ni content, the generation of the H3 phase is also related to
the state of charge (SOC) [31]. Yoon et al. used the initial charge and
discharge dQ dV− 1 curves to study the degree of phase change of H3
under high cut-off voltages (4.1, 4.2 and 4.3 V) and found that for
LiNiO2 (LNO), the delithiation/intercalation looks stable when the
battery charged to 4.1 V, and the phase change of H2→H3 is only
observed at 4.2 and 4.3 V (Fig. 4a) [31,38,44]. In addition, the degree of
phase change produced under different DOD conditions is also different.
Through characterizing the scanning electron microscope (SEM) of the
polished part of the NCA95 electrode material after cycling, it can be
observed that when the DOD of the discharge is higher than 60%, the
Ni-rich cathode is prone to crack, and when the DOD is lower than 60%,
NCA95 remains good structural integrity (Fig. 8i) [45]. Therefore, the
main influencing factors of crack generation and development are Ni
content, cut-off voltage and DOD. At present, many researchers propose
to reduce the charge cut-off voltage, lower the Ni content and the DOD
to mitigate the damage to the structure by cracks [24,25]. But the above
strategies come at the cost of capacity. In the field of EVs, if the cathode
is processed in this way, the energy density of the battery will decrease.
The requirement of reaching 300 miles with a single charge can only be
met by increasing the weight of the battery, which will rise the cost.
In a word, the formation of intergranular microcracks is caused by
harmful structural changes arising from the generation of H3 phase,
S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 3. (a) 6Li spin-echo ex-situ NMR spectra of NCM811 for the first cycle. Copyright 2019, Elsevier. (b) Schematic diagram of the relationship between lithium ion
local environment and phase change. Copyright 2019, Elsevier. (c) Contour diagrams illustrate sudden and dramatic changes in phase. Copyright 2019, Royal Society
of Chemistry. (d) In situ XRD patterns of the (003) reflection in the range of 4.15–4.3 V during charging for LNO and W2-LNO. Copyright 2019, Royal Society of
Chemistry.
(a) Reproduced from Ref [40]. (b) Reproduced from Ref [40]. (c) Reproduced from Ref [32]. (d) Reproduced from Ref [32].

which is resulted from high Ni content, cut-off voltage and DOD. The
phase transition causes intergranular microcracks by inducing aniso­
tropic and sudden changes in lattice parameters.
2.1.1.1. Anisotropic changes in lattice parameters. The emergence of H3
phase corresponds to the mutation of lattice parameter. It is found that
the change of lattice volume is consistent with the changing trend of
lattice parameter c, indicating that the change of volume is mainly
displayed as c parameter variation, as depicted in Fig. 4c [31,32]. The
a-axis lattice parameter of Li[NixCo(1− x)/2Mn(1− x)/2]O2 with x = 0.9,
0.92, 0.94, 0.96, 0.98, and 1.0, decreases monotonically with dein­
tercalation of lithium ion, with a Δa = − 2.0%, and Δc = − 7.9% for LNO
[21]. It indicates that the influence of H2→H3 phase on the lattice pa­
rameters changes in the c-axis is much greater than in other directions
[17], which produce anisotropic and abrupt change in a unit cell [17,18,
28]. In fact, the forces inside the particles are not uniformly distributed,
and the stress is only distributed at some points inside the particles.
Ni-rich layered oxides cathode are generally spherical-like secondary
particles composed of primary particles. Among them, the primary
particles are irregular polyhedrons, thus the direction of anisotropic
deformation of the primary particles due to phase change is random. In
addition, the arrangement of the primary particles is irregular, which
causes the forces generated by the expansion and contraction of two
adjacent primary particles to interact at their grain boundary. As shown
in Fig. 19b and c, the direction of the arrow in the figure is the direction
of deformation, and the red part represents the position of the force.
Therefore, the characteristic secondary particle structure of Ni-rich
cathode causes the stress concentration at the grain boundary during
the charging and discharging process. This force acting on the grain
boundary is the direct cause of intergranular cracks. The as-resulted
anisotropic change in lattice parameters will generate anisotropic
force in the randomly oriented primary particles [17], and the observed
large anisotropy causes the buildup of local stress, which damages the
mechanical integrity of the structure [18]. Therefore, the H3 phase
transition results in the anisotropy of lattice volume, which can lead to
the generation of intergranular cracks [21,22,30,31,46–48].
When giving a deeper understanding of the anisotropic change,
specifically the change of lattice parameter c, it can be noticed that the
change determined by the variation of crystal structure and electronic
structure at high SOC [49]. As depicted in the schematic of Fig. 5c, it can
be observed that the lattice expands first and then contracts sharply at
the c-axis direction during charging. The lattice change in the c-axis
depends on the height of the lithium-oxygen slabs and the transition
metal-oxygen slabs, denoted as hLi-O and hTM-O (Fig. 5a). The hTM-O
decreases with the process of lithium removal(delithiation). In contrast,
hLi-O increases at the beginning of charging (delithiation), but when it
reaches about x = 0.4 in LixTMO2, hLi-O suddenly plummets until the
charging process is completed. In the case of Li ≥ 0.4, the net effect of
the simultaneous expansion/contraction of these two slabs on c-axis is
positive, however, delithiation further continues during charging, when
Li < 0.4 both hLi-O and hTM-O shrinks (Fig. 5b) [18,30,49]. Consequently,
the lattice parameters c shows expansion first and then abrupt
contraction [17,18,28,30,32].
The main reason of lattice parameter c variation (hLi-O and hTM-O
change) is the inherent instability of the Ni3+/4+-O2- structure. Obvi­
ously, it was evident that Ni(III/IV) is oxidized by mixed Ni(II/III) over
the whole x(Li) range [49]. The change of crystal structure causes a
continuous decrease of hTM-O during charging. Kondrakov et al. found

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Fig. 4. (a) The dQ dV− 1 curves at different upper cutoff voltages. Copyright 2017, American Chemical Society. (b) The dQ dV− 1 profiles of Li[NixCoyMn1− x-y]O2
which have different Ni content. Copyright 2018, American Chemical Society. (c) The lattice parameters of c-axis, a-axis and unit cell volumes of LiNiO2 (LNO).
Copyright 2019, Royal Society of Chemistry.
(a) Reproduced from Ref [31]. (b) Reproduced from Ref [21]. (c) Reproduced from Ref [32].

that there is a 12% difference in ionic radius of trivalent and tetravalent
nickel ions, which quantitatively consent with the 15% reduction in
hTM‑O from X-ray diffraction (XRD) [49]. The above-mentioned corre­
lation shows that the generation of high-valence Ni is the domain reason
for the contraction of the TM-O slabs (for charge compensation reasons)
[23,49]. In fact, because of the oxidation of Ni evolves into a higher state
the shrinkage of the TM-O slab happens. Therefore, the length of the
TM-O bond is related to the valence of TM ions (TMs) and corresponds to
the size of the ion radii. During discharge process, hybridization occurs
between the Ni 3d and O 2p, which causes the charge on the Ni atom to
be transferred to the O atom (this problem is illustrated by the A1 peak
enhances with the reduction of lithium ions in Fig. 5d) [50]. Moreover,
the closer to the happening of the crack, the further the electron energy
loss spectrum (EELS) peak of Ni moves towards the lower energy di­
rection, indicating that the Ni exhibits a lower oxidation state in the
structural reconstruction near the crack. In contrast, the O peak gradu­
ally decreases, demonstrating that the redox reaction occurs in divalent
O (Fig. 5e) [51]. Therefore, hLi-O is affected by electrostatic repulsion,
and its size depends on the repulsive force between O atoms, due to its
negative charge [49]. However, a large number of lithium ions can
shield this electrostatic repulsion in the structure. As the lithium
removal proceeding, this electrostatic repulsion decreases, and the hLi-O
increases. But once the charge on the O atom is exhausted, the structure
will collapse (phase transition happens), and hLi-O will shrink suddenly
[38,49,50]. There, the parameter c change caused anisotropic force can
bring the microcracking generation.
2.1.1.2. Sudden changes in lattice parameters. In addition to anisotropy,
there is sudden influence of H3 relative to the crystal structure [30,31].
As it is sudden and intense this usually brings local strain concentration
at grain boundary [32]. There are many approaches to detect this sud­
denness of H3→H2 transition. By drawing the contour maps (Fig. 3c)
and the in-situ XRD pattern (Fig. 3d) of the selected area, the change
characteristics of the H3 phase can be clearly analyzed. It can be
observed that, as shown in Fig. 3c, when the H3 phase formation begins,
the H3 peak of the (003) reflecting surface suddenly appears at an angle

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Fig. 5. (a) The crystal structure of NCM811: TM-O slabs (gray), Li-O slabs (green) and unit cell (white square). Copyright 2017, American Chemical Society. (b) The
relationship between the value of hTM‑O and hLi‑O and the lithium content in the structure. Copyright 2017, American Chemical Society. (c) Changes in lattice
parameter of NCM811 during charging. Copyright 2017, American Chemical Society. (d) Ex-situ O K-edge sXAS spectra obtained on LiNiO2. Copyright 2017,
American Chemical Society. (e) The EELS scanning pathway on high-resolution STEM-HAADF image of Ni L-edge and O K-edge, respectively. Copyright 2020,
Elsevier.
(a) Reproduced from Ref [49]. (b) Reproduced from Ref [49]. (c) Reproduced from Ref [49]. (d) Reproduced from Ref [49]. (e) Reproduced from Ref [51].

more than 1◦ which is higher than the H2 peak. In order to further
confirm the sudden change of the lattice parameters, Ryu et al.[32]
plotted the in-situ XRD pattern of the LNO cathode at the 4.15–4.3 V
electrochemical window during the charging process, as shown in
Fig. 3d, where the change of 003 peak can be observed. The symmetry of
the H2 peaks of the reflecting surface is good, and there is almost no
deviation. But at the beginning of the H3 phase transition, the peak
suddenly shifts about 1◦ . This complete discontinuity reflected an abrupt
lattice mismatch, which was expected to induce a large strain between
the two different crystalline domains. Researchers believe that the
damage to secondary particles caused by this abrupt lattice mismatch is
far greater than the damage caused by slow phase transition [31,32,45].
As shown in Fig. 3d, researchers improve the stability of the material by
slowing down the H2→H3 phase transition [32]. The above analysis
shows that there is abruptness of the phase transition, which produces a
large strain between the two different crystalline domains and leads to
microcracks [21,22,30,31,34,38,52].
2.1.2. Cracks generated from heterogeneous state of charge (SOC) structure
between different primary particles
The heterogeneous state of charge (SOC) will produce oxygen va­
cancies and pores, as well as generate the force between two phases, thus
it is another cause of cracks [41,53–55]. By analyzing the Fig. 6a, it is
easy to observe the characters of the intergranular cracks in a secondary
particle, that is the cracks start from the center of a particle and grad­
ually extend to the surface [53]. Regarding this peculiar phenomenon,
many researchers explored the mechanism of crack formation from the
central part of a particle and found it is related to SOC.
In fact, the SOC distribution in a secondary particle is heterogeneous.
Since the ions that play a role in charge compensation are mainly Ni
ions, that is the valence of Ni in different area of one particle related to
the lithium ion content. Therefore, the distribution of Ni K-edge energy
inside the secondary particles can be used to represent the distribution
of SOC [41,56]. For solid state batteries, it is important to note that
Fig. 6b and c reveals considerably reduced redox activity in the outer­
most layer of the secondary particle as well as in the core. The XZ planes
that are shown resemble onions; the surface (a shell) and the core remain
similarly reduced, while a layer of redox-active sits in between. The
reduced phase in the outermost layer is produced by the destruction of
the solid electrolyte. Structural and chemical damage during the me­
chanical cycle seems to accumulate at the core of secondary particle. By
contrast, the core of the particle does not interface directly with elec­
trolyte, but rather would most be affected by intergranular cracking
causing (partial) isolation of primary particles near the core region [53].
Besides, as shown in Fig. 6d, the area with a high reduction degree (1#)
is located at the surface, and the area with a high degree of oxidation
(4#) is randomly located inside the secondary particle, which also
proves the heterogeneity of SOC distribution [41]. On the other hand, in

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Fig. 6. (a) 3D chemical mapping of a cycled (21 cycles) and fully charged NCA particle, in which the isolated voids are marked with red circles, and the inter­
connected crack network is marked with blue arrows. Copyright 2018, American Chemical Society. (b), (c) Chemical phase maps of the oxidized and the reduced
phase, respectively, over the virtual slices in z-x orientations. Copyright 2018, American Chemical Society. (d) Edge energy map over the XZ plane denoted in (b).
Copyright 2019, Wiley-VCH. (e) 2D mapping of mesoscale SOC heterogeneity in NMC secondary particles that were cycled over 3–4.9 voltage windows. Copyright
2019, Wiley-VCH.
(a) Reproduced from Ref [53]. (b) Reproduced from Ref [53]. (c) Reproduced from Ref [53]. (d) Reproduced from Ref [41]. (e) Reproduced from Ref [41].

conventional LiBs, the electrode-electrolyte interaction on the surface of
secondary particles and the associated electrolyte decomposition lead to
a significant reduction of nickel redox activity at the particle surface.
The charge compensation shows that the lithiation cannot be realized
virtually in the core area, so that the SOC of the central part is lower than
at the surface part, indicating that the SOC is heterogeneous inside the
secondary particle.
Uneven SOC will produce oxygen vacancies and pores. The rela­
tionship between porosity and SOC originates from charge compensa­
tion [57]. According to the charge compensation mechanism, at extreme
delithiation state, the Ni is oxidized, and the O 2 P orbital is exhausted
[54]. The extremely unstable Ni4+ species are reduced to a divalent state
by the electrolyte, which leads the electrons in the O atom to
transferring to Ni [49,51,53]. O loses its electronic leading valence rises
and eventually evolves into oxygen, which is the cause of oxygen va­
cancies. When O is continuously oxidized to create oxygen release
conditions, the active material then produces gas and the porosity in­
creases [54,57].
2.1.2.1. Pore can give rise to intergranular cracks. The particle degra­
dation processes take place under thermal abuse conditions, and the
nanopores propagate in primary NCM particles, and then the pores grow
into larger pores/exfoliations, leading to mechanical breakdown of the
primary particles [57]. In addition, porosity causes the heterogeneity of
SOC to some extent, and this influence mechanism of porosity-SOC is a
vicious circle. In fact, isolated pores are scattered throughout the

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Fig. 7. (a) Schematic diagrams to illustrate the dislocation-assisted crack incubation, propagation and multiplication process. Copyright 2017, Nature. (b) A
schematic diagram showing crack formation in the grain interior due to tensile stress. Copyright 2017, Nature. (c) The relationship between oxygen vacancies and
cracks NMC. Copyright 2018, American Chemical Society. (d) Fitted Debye-Waller factor change upon cycling for Ni, Co, and Mn. Copyright 2019, Wiley-VCH. (e)
SOC is negatively correlated with porosity. Copyright 2019, Wiley-VCH. (f) NCM 111 was analyzed from the NBD data and the diagrams illustrate the change of the
disorientation angles in primary particles along the scanning routes signified as yellow dotted line arrows in (g). Copyright 2019, Wiley-VCH. (g) Crystallographic
direction diagrams and disorientation results of bare NCM 111. Copyright 2019, Wiley-VCH. (h) Low-angle grain boundary corresponding to the blue particles in
Fig. 7g. Copyright 2019, Wiley-VCH. (i) FFT image from an atomic-resolution ABF-STEM image (inset) of region (i). (j)-(k) Atomic-resolution STEM-HAADF images of
areas (iii) and (iv), respectively. Copyright 2019, Wiley-VCH.
(a) Reproduced from Ref [36]. (b) Reproduced from Ref [36]. (c) Reproduced from Ref [57]. (d) Reproduced from Ref [41]. (e) Reproduced from Ref [58]. (f)
Reproduced from Ref [58]. (g) Reproduced from Ref [58]. (h) Reproduced from Ref [58]. (i) Reproduced from Ref [58].

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Fig. 8. (a) and (b) The voids and intragranular cracks distribution of NCM111 after 100 cycles. Copyright 2017, Nature. The distribution of dislocations in (c) pristine
and (d) 100 cycled NMC111. Copyright 2017, Nature. (e) The real cracks and incubation crack of LiNi1/3Mn1/3Co1/3O2 cathode along (001) plane. Copyright 2017,
Nature. (f) HAADF and ABF images and lattice model of dark contract stripe. Copyright 2017, Nature. (g) The vacancy accumulation at dislocation source and the
atomic structure model at early incubation stages. Copyright 2017, Nature. (h) A HAADF image showing an end-on edge dislocation in pristine NMC111, the
corresponding strain map by GPA and the dislocation model of (c). Copyright 2017, Nature. (i) Cross-sectional SEM images of NCA95 cathodes after 100 cycles: lower
DOD of 60% and upper DOD of 60%. Copyright 2018, American Chemical Society. (j) Stress field and atomic distribution in phase transition region. Copyright 2020,
Elsevier.
(a) Reproduced from Ref [36]. (b) Reproduced from Ref [36]. (c) Reproduced from Ref [36]. (d) Reproduced from Ref [36]. (e) Reproduced from Ref [36]. (f)
Reproduced from Ref [45]. (g) Reproduced from Ref [45]. (h) Reproduced from Ref [36]. (i) Reproduced from Ref [45]. (j) Reproduced from Ref [51].

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 9. (a) After tensile stress is utilized, the direction of distortion out-of-plane is different from that in-plane. Copyright 2018, Royal Society of Chemistry. (b)
Stress-strain curves for NCM811 under tensile and compressive distortion for both in- and out-of-plane directions. (c) The value of the tensile strain produced when
forces are applied in- and out-of-plane. Copyright 2018, Royal Society of Chemistry. (d) The value of bond-length when appling different strains. Copyright 2018,
Royal Society of Chemistry. Copyright 2018, Royal Society of Chemistry. (e) The ratio of in-plane to out-of-plane for Young’s modulus and maximum strength of
delithiated NCM811 structures. Copyright 2018, Royal Society of Chemistry. (f) the comparison of maximum strength under tensile, compressive deformation.
Copyright 2018, Royal Society of Chemistry.
(a) Reproduced from Ref [54]. (b) Reproduced from Ref [54]. (c) Reproduced from Ref [54]. (d) Reproduced from Ref [54]. (e) Reproduced from Ref [54]. (f)
Reproduced from Ref [54].

secondary particles (Fig. 6a), and these voids are relevant to the SOC.
For these two reasons: (1) porosity represents a kind of structural
degradation and is also closely related to the nucleation of microcracks;
(2) Increased porosity leads to disruption of lithium diffusion pathways
and hence makes subparticle domains less electrochemically active,
causing a decrease in SOC. Belsi et al. explored the relationship between
SOC and structural degradation by studying the porosity of different
regions of secondary particles [53]. As depicted in Fig. 7e, porosity is
negatively correlated with SOC [53]. Therefore, the SOC of high
porosity area might be lower than the pore-free region, and the porosity
has a promote effect on the degree of crack generation by increasing the
inhomogeneity of SOC.
2.1.2.2. Oxygen vacancies can cause intergranular cracks. In fact, oxygen
vacancies are also one of the reasons of cracks generation, which is
positively correlated with oxygen vacancies [49,51,53]. By using finite
element analysis (FEM), Mu et al. studied the relationship between the
distribution of oxygen vacancies in the cathode particles and the stress
field, as shown in Fig. 7c [57]. Oxygen vacancies increase with the
increased cycles. In addition, with the release of oxygen, the outer shell
rich in oxygen vacancies undergoes more significant expansion than the
vacancies-free inner core, resulting in a surface-near compressive stress
field and a core-near tensile stress field. Oxygen vacancies caused cracks
can be divided into three mechanisms [57]. (1) The stress field gener­
ated by the varying concentration of oxygen vacancies will form inter­
granular cracks due to the shear stress at the grain boundary. (2) The
uneven stress in the particles will cause the occurrence of intergranular
cracks. (3) The connection of voids formed by oxygen vacancies will
cause structural degradation thus form intragranular cracks.
2.1.2.3. A large strain because of the phase mismatch can cause inter­
granular cracks. The SOC will cause the two-phase reaction of the
cathode particles to produce intergranular cracks since the different
phases shrink and expand When the SOC is heterogeneous, it means that
there are Li-deficient areas in the particles. Ni2+ near the Li vacancies
will be oxidized to Ni4+ due to the charge compensation effect. Simi­
larly, as Ni and O will also have a charge compensation effect, O va­
cancies will appear, which reduces the migration barrier of Ni2+ and
makes it easier for Ni2+ to migrate to the Li layer [54]. Since Li-Ni
mixing will generate disordered rock salt facies, the phases of different
regions in the same secondary particle are different. Adjacent particles
of different phases will generate stress concentration at the phase
interface [33]. This is because the adjacent primary particles with
structurally heterogeneous phases will produce a different volume
changes throughout the charge and discharge process. The region of the
layered structure and the region of the adjacent rock salt structure will
produce a force at the crystal boundary of two primary particles, which
can cause intergranular cracks along the boundary.
2.2. Formation of intragranular cracks
Intragranular cracks are the other type of cracks in the cathode
material. The causes of intragranular cracks are relatively complicated.
Due to the cyclic generation and reduction of the H3 phase during the
cycling, the primary particles expand and contract with repeated cycles,
and finally resulting in fatigue cracks. In addition, Li-Ni is mixed to form
a fragile rock salt phase zone and this phase region is usually subjected
to tensile stress to produce cracks. Moreover, heterogeneous SOC
structure produced by uneven delithiation can bring local laminar
exfoliation and crack nucleation. Compared with intergranular cracks,
the size of the intragranular cracks is smaller, but the density is higher
than the former. More importantly, under severe electrochemical con­
ditions, intragranular cracks are not only a mechanical failure but also a
structural degradation.
The intragranular cracks can be divided into three types according to
the crack generation mechanism and morphology: (1) the classical
cracks (pointed by the yellow arrow in Fig. 8e); (2) the dark contrast
stripes (pointed by the pink arrow in the Fig. 8e); (3) fine-serried low-
angle grain boundary (indicated by the white circle in Fig. 10c and
pointed by the yellow arrow in Fig. 7h). In this section, the

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Fig. 10. (a) NCA80 cathode in various SOC. Copyright 2019, American Chemical Society. (b) Four regions marked 1, 2, 3, and 4 of different phase on either side of a
crack. Copyright 2016, Wiley-VCH. (c) The low-angle grain boundary of a crystal in a damaged particle with the diffraction pattern (inset) of the corresponding
region. Copyright 2016, Wiley-VCH. Comparison of particle surface (d) and internal (e) structure changes under the influence of electrolyte. Copyright 2018, Royal
Society of Chemistry.
(a) Reproduced from Ref [18]. (b) Reproduced from Ref [33]. (c) Reproduced from Ref [33]. (d) Reproduced from Ref [22].

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 11. (a) The 3D rendering of the pristine NCM particles and after 50 cycles at diverse rates. Copyright 2018, Elsevier. (b) Changes in the diffusion paths of charge
carriers (green lines), electrons (red lines) and lithium ions (blue lines) under the influence of electrolytes. Copyright 2018, Elsevier. (c) The diagram of mismatch
between the local electric and ionic conductivity. Copyright 2018, Elsevier. (d) The evolution of the probability distribution of the cracking induced lithium-ion
diffusion length increment upon electrolyte infiltration. Copyright 2018, Elsevier. (e) The evolution of the mismatch between the local electric and ionic conduc­
tivity upon electrolyte infiltration. Copyright 2018, Elsevier.
(a) Reproduced from Ref [55]. (b) Reproduced from Ref [55]. (c) Reproduced from Ref [55]. (d) Reproduced from Ref [55]. (e) Reproduced from Ref [55].

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 12. Comparison of crack generation of (a) and 2% Ti-doping LiNi0.8Co0.1Mn0.1O2 (b) after 200 cycles. Copyright 2015, Elsevier. Cross-sectional SEM images
after cycling 1000: (c) NCM90, and (d) NCMA89. Copyright 2019, American Chemical Society. Mosaic scanning-TEM image of the cycled cathode after 1000 cycles in
a full cell (e) Al-1 FCG 76 and (f) Al-2 FCG76. Copyright 2017, American Chemical Society. (g) High-resolution TEM of a cycled Al-1 FCG76 cathode with its
corresponding electron diffraction pattern and (inset) FFT images of regions marked 1–4. Copyright 2017, American Chemical Society. (h) Mosaic scanning-TEM
image of the cycled electrode after 1000 cycles in a full cell FCG 76. Copyright 2017, American Chemical Society. (i) TEM and HAADF images of NCA-NCMA90.
Copyright 2015, Elsevier.
(a) Reproduced from Ref [73]. (b) Reproduced from Ref [73]. (c) Reproduced from Ref [64]. (d) Reproduced from Ref [64]. (e) Reproduced from Ref [137]. (f)
Reproduced from Ref [137]. (g) Reproduced from Ref [137]. (h) Reproduced from Ref [137]. (i) Reproduced from Ref [83].

characteristics and generation mechanism of three kinds of cracks are
mainly summarized.
2.2.1. The characteristics of three types of intragranular cracks
Classic crack possesses classic crack character, which is featured by
two-free-surface as signified by the yellow arrows as shown in Fig. 8e
[36]. Except for the tip, the two free surfaces are parallel with the entire
crack direction and the (003) plane in the layered structure.
The second type of microcrack performs as narrow, dark strips par­
alleling to the (003) planes (the layers) and is distributed arbitrarily with
diverse spacing between the strips as indicated by the pink arrows in
Fig. 8e [36]. The minutest distance between the two belts strips is a
single layer of TM. The (003) interplanar spacing of the general layered
structure is 0.48 nm, and the dark contrast bars correspond to the
broadened TM interplanar spacing, distributing in the range of
0.6–0.8 nm (Fig. 8e). Consequently, these dark contrast stripes forms by
the parallel splitting of two adjoining TM layers, resulting in the broader
c-plane spacing [36].
The third type intragranular crack is the fracture inside the crystal
caused by the mechanical effect, and this mechanical failure is normally
manifested as fine-serried and together-stacked low-angle grain
boundary [33]. Due to the special arrangement morphology of this type
of crack, the Moiré fringes generated by optical interference will be
observed. In addition, the crystal structure corresponding to the Moiré
fringe has a large number of atomic rearrangements and chaotic
small-angle grain boundary (Fig. 7j and k) [58].
2.2.2. Intragranular cracks generated from heterogeneous delithiation
Type one and type two crack, (i.e. the classic crack and the dark
contrast stipes) are caused by the heterogeneous delithiation. It is
observed that the dark contrast stripes are spatially connected with the
classical crack (Fig. 8e) [36]. This phenomenon makes researchers
interested in the relationship between these two cracks. One view is that
dark contrast stripes are premature classical crack [36]. Yan et al. used
high-angle annular dark-field (HAADF) and Annular bright-field (ABF)
spectroscopy to analyze the internal structural characteristics of dark
contrast strips to prove that dark contrast strips are premature classic
cracks [36]. There is a black spot at the position pointed by the pink
arrow in the ABF spectrum, indicating that the black part in the HAADF
spectrum is not an empty but a rock salt structure region produced by
cations-mixing. This long-strip-shape of rock salt region has formed an
extremely lithium-poor region due to the Li sites being substituted by Ni
[51]. In addition, the force field near the dark contrast stripe is unbal­
anced, there is a tensile stress field in the dark contrast stripe, and a

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 13. (a) CV curves for Zr-0 and Zr-0.01 samples of the 1th cycle. Copyright 2018, Wiley-VCH. (b) dQ dV− 1 curves of the 1th cycle of the NC90, NCM90, and
NM90 cathodes. Copyright 2019, Wiley-VCH. (c) Compare the shift of the H2/H3 peak in (b). Copyright 2019, Wiley-VCH. (d) Changes of H2↔H3 phase transition
peak width. Copyright 2019, Wiley-VCH. (e) V The difference of unit cell changes during charge and discharge before and after Ti substitution. Copyright 2015,
Elsevier. (f) Schematic representation of the inter-slab space. Copyright 2015, Wiley-VCH. (g) Multiple doping can combine the advantages of single-ions & single-site
doping. Copyright 2017, Royal Society of Chemistry. (h) Long-term cycling performance of the NCA89, NCM90, and NCMA89 cathodes using pouch full cells at 1.0 C
and 25 ◦ C with a electrochemical window of 3.0− 4.2 V. Copyright 2019, American Chemical Society. (i) Comparison of cathode performance of NCM90 and NM90.
Copyright 2015, Wiley-VCH. (j) Ex situ XRD patterns during the first cycle of the NCA-NCMA90 cathode. Copyright 2019, Elsevier. (k) c-axis lattice parameters of the
NCA89, NCM90, and NCMA89 cathodes. Copyright 2019, American Chemical Society.
(a) Reproduced from Ref [69]. (b) Reproduced from Ref [80]. (c) Reproduced from Ref [80]. (d) Reproduced from Ref [80]. (e) Reproduced from Ref [73]. (f)
Reproduced from Ref [77]. (g) Reproduced from Ref [67]. (h) Reproduced from Ref [64]. (i) Reproduced from Ref [80]. (j) Reproduced from Ref [83]. (k)
Reproduced from Ref [64].

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 14. (a) and (c) Side views of atomic structures and calculated oxygen vacancy formation energy. Copyright 2019, American Chemical Society. (b) and (d)
Surface energies of pristine and B-doped LiNi0.9Co0.04Al0.04O2 (003), (012), (100), and (104) surfaces. Copyright 2020, Elsevier. (e) Formation energy of Li-dopant
exchange and the energy of Li-Ni exchange. Copyright 2017, Royal Society of Chemistry. (f) Formation energy for Li-Ni exchange after doping. Copyright 2017, Royal
Society of Chemistry.
(a) Reproduced from Ref [64]. (b) Reproduced from Ref [28]. (c) Reproduced from Ref [64]. (d) Reproduced from Ref [28]. (e) Reproduced from Ref [67]. (f)
Reproduced from Ref [67].

compressive stress in the area where the crystal structure is complete
(Fig. 8j) [36,51]. The tensile stress acting on the rock salt phase area will
tear the particles along this long strip region (the dark contrast stripe).
Therefore, the transition metal atoms at the tip of the dark contrast strip
bend and align to form a cracked V-shaped tip (Fig. 8f). The reason why
it is called “premature crack” is does not have the free-surfaces. As the
battery continues to cycle, premature cracks will further develop into
real cracks [36]. In addition, Yan et al. constructed a crack development
process model, which describes in detail the stages of the transition
between the type two intragranular cracks (see Fig. 7a) [36]. In the first
stage, as the voltage is increased, the damage to the structure by the
crack gradually becomes serious, indicating that the generation and
development of the crack is electrochemically driven (Fig. 8a and b). In
the second stage, premature cracks are generated by dislocations. In the
third stage, the premature crack gradually develops into a real crack
with two parallel planes (parallel to the (003) plane).

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S. Yin et al.
Fig. 15. (a) The schematic of process and characterization of the NS-NCM. Copyright 2018, Royal Society of Chemistry. (b) Double-modification synthesis process
diagram of NCM811. Copyright 2019, Wiley-VCH.
(a) Reproduced from Ref [101]. (b) Reproduced from Ref [120].
Researchers analyzed the causes of dark contrast stripe from the level
of atomic arrangement. As shown in Fig. 8g, the origin of each dark
contrast stripe is a dislocation [36]. In addition, there is an unbalanced
stress field around the dislocation (Fig. 8h), which will further enlarge
the defects at the dislocation. In order to relieve this stress, Li ions and O
ions will be eliminated from the tensile field where the dislocation
happens(the crystal structure arrangement model Fig. 8g and h) [36]. To
a certain extent, the extraction of Li ions will reduce the stability of the
structure and amplify the intracrystalline strain. This implies that the
dislocation is the source of dark contrast stripe [36]. When the cathode
is cycled under a high cut-off voltage of 4.7 V, a high density of dislo­
cations will be generated, which is the leading cause of the aforemen­
tioned generation of dark contrast strips (Fig. 8c and d) [36].
Through the above analysis, it can be concluded that the uneven
stress field in primary particles and the heterogeneous delithiation
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Nano Energy 83 (2021) 105854
together lead to the classical crack and the dark contrast stripes. In fact,
the extremely lithium-deficient regions caused by uneven extraction of
lithium atoms generally have tensile stress fields distributed in them and
the tensile stress is one of the reasons to the form microcracks. Re­
searchers analyze the changes in the structure of the material after being
stressed from the atomic level to explain the importance of lithium
atoms in stabilizing structure. Min et al. conducted an in-depth me­
chanical analysis of the structure from the micro-level through density
functional theory (DFT) [54]. They mainly concluded by comparing the
in-plane and out-of-plane mechanical effects under tensile stress and
compressive stress, respectively. Under the action of force, the defor­
mation directions of the in-plane and out-of-plane structure are different
(Fig. 9a) [54]. When the stress is the same, the strain produced by the
material in the tensile process is greater than the strain produced by
compression (Fig. 9b), and the maximum in-plane compressive stress is
S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 16. (a) The evolution of secondary ion LiNi0.76Mn0.14Co0.10O2 coating and LPO coating after annealing. Copyright 2018, Nature. (b) Grain boundary modifi­
cation can ensure the structural stability of the cathode better than simple coating. Copyright 2018, Nature. (c) The schematic picture of the morphology of NCM-W0,
NCM-W8, and NCM-D8. Copyright 2020, Elsevier. (d) The mechanism of PEDOT as HF scavenger. Copyright 2018, Nature.
(a) Reproduced from Ref [60]. (b) Reproduced from Ref [122]. (c) Reproduced from Ref [125]. (d) Reproduced from Ref [122].

greater than the maximum out-of-plane compressive stress (Fig. 9f). The
above results show that the tensile stress is the main stress to produces
cracks, and the out-of-plane part of the layered structure is more likely to
form cracks [54]. Since Li-O bonds is the link between out-of-planes, the
strength of the Li-O bond determines the strength of the out-of-plane
part [54]. To explain which of the split mode-bond disconnection or
structural degradation is originated under tension, Min et al. studied the
bond-length variety of Mn− O, Co− O, Ni− O, and Li− O inside the
NCM811 cathode when the tensile strain of 0, 0.16 (in-plane), and 0.14
(out-of-plane) is applied, as depicted in Fig. 9c and d [54]. It is

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 17. (a) Cross-sectional STEM-HAADF image and the corresponding C (b) and F (c) maps (two signature elements from the electrolyte) from the pristine electrode
after 200 cycles. Copyright 2018, Nature. (d) STEM-HAADF image and the corresponding C (e) and F (f) maps from the LPO-infused electrode after 200 cycles.
Copyright 2018, Nature. (g)-(i) From top to bottom, SAED, bright-field TEM imaging, STEM-HAADF imaging. Copyright 2018, Nature. The pristine cathode without
cycling (g) the pristine cathode after 200cycles (h) and LPO-infused cathode after 200cycles (i). Copyright 2018, Nature.
(a) Reproduced from Ref [60]. (b) Reproduced from Ref [60]. (c) Reproduced from Ref [60]. (d) Reproduced from Ref [60]. (e) Reproduced from Ref [60]. (f)
Reproduced from Ref [60]. (g) Reproduced from Ref [60]. (h) Reproduced from Ref [60]. (i) Reproduced from Ref [60].

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 18. (a) The changing of layered and spinel-like structure of pristine NCM111 (left) and 60-PEDOT@NCM111 (right) in the high-voltage (4.3–4.6 V) during C/10
charging. Copyright 2019, Nature. (b) Full range (10◦ ≤2θ≤80◦ ) of time-resolved X-ray diffraction (TR-XRD) patterns of partially deintercalated FCG76 and Al-2
FCG76 cathodes during heating from 30◦ to 600◦ C. Copyright 2017, American Chemical Society. (c) Capacity retention comparisons of the pristine sample, the
LPO@GB sample, and LPO@GB/Surface sample. Copyright 2019, Elsevier. (d) Mass spectra for O2 evolution behavior of delithiated pristine NCM111 and 60-
PEDOT@NCM111 in the presence of electrolyte during heating to 500 ℃. Copyright 2019, Nature. (e) Comparison of the charge transfer resistance as a function
of the number of cycles. Copyright 2018, American Chemical Society. Cell parameters c changes of (f) bare NCM111 and (g) 60-PEDOT@NCM111 as a function of
charge-discharge time. Copyright 2019, Nature. The voltage profile and the cell volume evolution of (h) bare NCM111 and (i) 60-PEDOT@NCM111 cathode.
Copyright 2019, Nature.
(a) Reproduced from Ref [122]. (b) Reproduced from Ref [137]. (c) Reproduced from Ref [121]. (d) Reproduced from Ref [122]. (e) Reproduced from Ref [21]. (f)
Reproduced from Ref [122]. (g) Reproduced from Ref [122]. (h) Reproduced from Ref [122]. (i) Reproduced from Ref [122].

concluded that: (1) In-plane, all bonds become longer, which is caused
by the distorted bonding network. (2) Out-of-plane, the bond size of Li-O
changes significantly. However, the bond size of TM-O does not change
much, indicating that the out-of-plane fracture occur at Li-O and finally
led to layer stripping.
It is obvious that the loss of Li-O bond degrades the inter-plane force.
Under the delithiation process, the amount of Li-O decreases, so that the
interlayer force is weakened, and the structural damage will be serious.
When delithiation is heterogeneous, the extremely poor lithium region
will undergo structural vicissitudes due to the massive loss of Li-O bond
[54]. This will result in the imbalance of lattice parameters between
different regions due to the heterogeneity of the structure, which is one
of the reasons for the stress generation. Therefore, it is possible to reduce
the occurrence of cracks by stabilizing the Li-O layer. For example,
doping with some elements with "pillar effect" can play a role in sup­
porting the Li-O layer [54].
In fact, it is generally believed that the concentration of tensile stress
in the rock-salt phase region is also related to heterogeneous delithiation
to a certain extent. This rock-salt phase is a lattice distortion region,
caused by the chemical cycle, and this phase region is a white line in
field of the low-magnification STEM-HAADF image (Fig. 8j) [36,51].
Corresponding geometric phase analysis (GPA) can be observed that the
phase-transition area is red, indicating the effect of tensile stress, while
the other areas are green, indicating the effect of compressive stress. The
results of elemental analysis through the energy dispersive spectroscopy
(EDS) show that the content of Ni in the white area is relatively high,
indicating that Ni replaces Li sites and cations-mixing can form a rock
salt phase [51]. Therefore, the lithium-deficient structure in the white
line area will cause the concentration of tensile stress. In addition, the
model in Fig. 7b shows the mechanism of intragranular cracks from the
perspective of stress direction and crack formation [36]. As the above
analysis shows, the strength of the lithium-poor rock-salt phase is much
lower than the layered structure [51]. Therefore, under the action of
tensile stress, the rock-salt phase zone fractures, and then cracks form.
Recently, Bi et al. found that some gliding lines on the crystal sur­
faces after 200 cycles with 4.3 V cutting off voltage (Fig. 21e) [59]. As
shown in Fig. 21f, he layered structure is well maintained after the
gliding marks occur. No new boundary is generated and the area on the
sides of the slip surface maintains the same lattice structure and chem­
ical conditions. Surprisingly, after discharging, the majority of single
crystals revert to their original structure and the microcracks disappear
(Fig. 21e). However, the repeated gliding near the crystal surface
eventually will evolve into microcrack, and the electrolyte destroys the
new surface (Fig. 21g) [59]. In fact, the particles with the slip surface
experience stacking-sequence-change phase transformations owing to Li
concentration change, which because stress will be generated during Li+

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 19. (a) The development of concentration gradient cathodes improves cathode stability and capacity by changing the structure. (b), (c) Schematic diagram of
the relationship between stress distribution and particle internal structure. Copyright 2020, Wiley-VCH. Copyright 2019, Wiley-VCH. (d) CSG90 and CC90 cathodes
showing the sustained damage and the morphological difference inside the particles. Copyright 2019, Wiley-VCH.
(b) and (c) Reproduced from Ref [17,126]. (b) Reproduced from Ref [35].

Fig. 20. Comparison of structural stability between single-crystal and poly-crystal material.

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(caption on next page)

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 21. (a) Comparison of phase transformation region and degree between single-crystal and poly-crystal material. Copyright 2020, Elsevier. (b) Comparison of
uniformity of lithium-ion transfer between single-crystal and poly-crystal material in full cell. Copyright 2020, Wiley-VCH. (c) Percentage of crystal facets appearing
on the synthesized NMC crystal samples. Copyright 2019, Royal Society of Chemistry. (d) Comparison of lithium distribution in graphite anode (on the left is the
battery with poly-crystal material as cathode, and the right is battery with single-crystal material as cathode). Copyright 2020, Wiley-VCH. (e) SEM image of single-
crystalline NMC76 initially charged to 4.8 V (versus Li+/Li) and discharged to 2.7 V (after being charged to 4.8 V versus Li+/Li). Copyright 2020, Science. (f) HAADF-
STEM image from around the slicing area. The upper inset is a magnified image of the gliding area enclosed by the red square. Copyright 2020, Science. (g) Schematic
illustration of the structural evolution of single-crystalline NMC76 upon cycling. Copyright 2020, Science. (h) COMSOL-simulated shear stress along the yz direction
during charge (delithiation) and discharge (lithiation) at scaled time of 0.1 T. Copyright 2020, Science.
(a) Reproduced from Ref [130]. (b) Reproduced from Ref [129]. (c) Reproduced from Ref [131]. (d) Reproduced from Ref [129]. (e) Reproduced from Ref [59]. (f)
Reproduced from Ref [59]. (g) Reproduced from Ref [59]. (h) Reproduced from Ref [59].

diffusion after establishing a Li concentration gradient in the lattice
[59]. The shear component of local stress along the yz direction that can
trigger the gliding along the (003) planes is shown in Fig. 21h. The signs
of the shear stress during lithiation and delithiation are opposite, which
corresponds exactly to the reversible gliding. However, the gliding
motion not completely and reversible, the irreversible gliding can be
accumulated into the crack opening over a long cycling time [59]. This is
also one of the main reasons for intragranular cracks.
particles are not single crystals but are composed of real primary par­
ticles with small angles and unique boundaries, and these intracrystal­
line GBs will eventually develop into intracrystalline nano-cracks [58].
This small-angle orientation variation causes the anisotropic force inside
the primary particle, and the Moiré fringe (as indicated by the yellow
arrow in Fig. 7h) is an evidence of this stress mechanical failure.
2.3. Propagation and development of microcracks

2.2.3. Intragranular cracks generated from mechanical failure inside the
primary particles
The third type intragranular cracks (i.e. fine-serried low-angle grain
boundary in primary particles) are mainly formed by mechanical dam­
age caused by stress concentration inside the primary particles. The
reasons for this mechanical degradation can be summarized as the
following three parts:
2.2.3.1. Fatigue strain during cycling. The crack splitting/closing during
charging/discharging is due to the expansion/contraction of primary
particles during the prolonged cycle (Fig. 10a). With the repeated
expansion and contraction of the particles, after several cycles, low-
angle grain boundary will be observed inside the primary particles
(Fig. 10c) [33].
2.2.3.2. Misalignment between primary particles. Fig. 7g demonstrates
the diagrams of crystallographic orientation and significant systematic
data of the primary particles in LiNi0.33Co0.33Mn0.33O2 (NCM111), these
data were obtained with an ASTAR tool (Nano MEGAS) [58]. In addi­
tion, the crystal orientation diagrams are produced, and the disorien­
tation angles inner the primary particles are analyzed based on
precession nano beam electron diffraction (NBD) patterns. The same
scanning prefabricated NBD pattern with different primary particles
makes the corresponding color coded images different, indicating that,
in the same secondary particle, the crystal orientation of primary par­
ticles is different. Therefore, the anisotropy of this crystal orientation
arrangement will cause stress concentration within the crystal during
cycling (Fig. 7g) [58].
2.2.3.3. “False” primary particles with grain boundary. It was reported
that there are grain boundary inside a conventional defined primary
particle and low-magnification ABF-STEM image can be used to observe
the existence of them (the black line in Fig. 7g) [58]. Therefore, it is
called “false primary particle” in some studies. The presence of grain
boundaries (GBs) gives possibilities of internal mechanical failure of the
particle. A fast Fourier Transform (FFT) image (Fig. 7i) can be used to
describe further the case of such GBs in crystals, where the reflection
peak splitting into the planes (002) and (006) indicates that two true
primary particles rotate in the plane of 2◦ in GBs [58]. Moreover, Fig. 7f
is disorientation founded on the scanned precession NBD, which shows
that as the distance from the scanning initial point position gets farther,
the disorientation becomes more serious, indicating that the crystal
orientation in a single crystal particle is constantly changing. Descrip­
tion of the above phenomenon, not only the crystal orientation of
different primary particles is different, but also the crystal orientation of
the same primary particles changes [58]. Therefore, the primary
Once the cracks form, the following damages to the materials are
beyond the effects that cracks themselves make, as the related damage
from the electrolyte on the cracked particles will be another important
reason for the degradation of material structure [60]. The electrolyte
will follow the cracks and penetrate the secondary particles. By
analyzing the distribution of characteristic elements fluorine and carbon
in the particles with electrolyte, it can be found that the electrolyte has
almost been distributed in the entire secondary particles after 200 cycles
(Fig. 17a− c) [60]. The electrolyte will react with the Ni4+ substances
inside the secondary particles, causing the TMs to dissolve and severely
destroy the particle structure. Because of this effect of electrolyte and
cracks, microcracks have become the main cause of the capacity fading
of Ni-rich cathode materials [61]. Once the crack appears on the surface
of the cathode particles, it will provide a channel for the penetration of
the electrolyte. The electrolyte will further damage the internal struc­
ture of the particles irreversibly, make the cracks more serious, and
eventually cause the particles to disintegrate and degrade. Nam et al.
observed the cross-sectional morphology of the secondary particles of Li
[Ni0.8Co0.1Al0.1]O2 (NCA811) cathodes under different charged states
and used image analysis software to evaluate the area of the microcracks
aim to infer the extent of damage (see Fig. 10a) [18]. The cathode
particles began to extend microcracks through charging it to 3.9 V, and
the area of cracks increased with the increase of cutoff voltage reaching
25.7% after being charged to 4.3 V. What is more, these microcracks
penetrated the secondary particles surface at 4.1 V during charging,
which can open channels for electrolyte immerses in the particle inte­
rior. However, the microcracks progressively close upon discharging,
due to the primary grain expansion upon lithiation during discharge
[18,45]. Although the microcracks can be closed during discharge, the
effect of the internal electrolyte is irreversible. According to the chem­
ical electrochemical impedance spectroscopy (EIS) characterization re­
sults, the charge-transfer resistance (Rct) increases as the cycling
continues (Fig. 18e), because the parasitic reaction occurred between
the electrolyte and reactive Ni4+ to form Ni-O like rock-salt phase [21,
22,29,31,32,62–64].
Since the fine structure is different between the inner part and outer
part of a particle, the negative effects of the crack associated with the
electrolyte can be slightly different in degree. The cycled Li[Ni0.95C­
o0.025Mn0.025]O2 (NCM95) cathode can get recovered from the cell after
cycling observed by Yoon et al., and the typical TEM imagines are ob­
tained from the single particles through the focused ion beam to further
study the structural damage in the cyclic process [22]. The mixing of the
3a (Li) and 3b (transition metal) sites (Fig. 10d and e) causes the pres­
ence of Fm-3 m [100], and the strong Fm-3 m peak confirms that the
reaction of electrolyte and cathode will produce amorphous and inac­
tivated NiO-like phase (Fig. 10e). However, in different areas of the

22
S. Yin et al.
secondary particles, the electrolyte has different effects on the structure
[22]. It was observed that the NiO-like phase layer inside the particles
(30 nm) is thicker than the particle surface (6 nm) (Fig. 10d and e) [22].
This varying degrees of structure degradation partially depend on the
extent of lithium residues in different regions of the same secondary
particle [22,34]. Compared with the surface, the lithium content at the
core of the secondary particles is lower, and the reaction with the
electrolyte is more intense. Another reason is that the primary particle at
the core is smaller than the one at the surface. This special structure
makes the specific area of the secondary particle at the core larger than
that near the surface [20]. The large internal specific surface area pro­
vides more reaction sites for the electrolyte, thus the damage of the
electrolyte inside the secondary particles is more serious than that at the
surface.
The NiO-like layer produced after the electrolyte and the Ni-rich
cathode reacts with each others, which increases the impedance of the
material, thereby affecting the uniformity of the SOC. This will produce
more intergranular and intragranular cracks, which make the disinte­
gration and pulverization of particles more serious [21,34,46,47,63].
The increasing impedance is mainly produced by the formation of the
NiO-like layer resulted from the interaction between the electrolyte and
the Ni-rich cathode [55,65]. This high-impedance material will cause
uneven electrical contact inside the secondary particles, thereby dete­
riorating the unevenness of the SOC. It is worth mentioning that fast
charging will amplify the structural damage caused by this in­
homogeneity (Fig. 11a) [55]. This is because fast charging will magnify
the chemical formula change experienced by each particle. Eventually, it
will cause uneven local electric field distribution and more concentrated
mechanical stress. Cracks and electrolyte penetration can cause local
ionic conductivity mismatch, and the more severe the cracks, the more
serious the mismatch effect can be (Fig. 11c) [55]. Therefore, the 3D
diffusion path of lithium ions is strongly affected by the electrolyte. As
the electrolyte penetrates, the 3D diffusion channels of lithium ions
gradually decreases, which will increase the difference in the diffusion
path between electrons and lithium ions (Fig. 11b) [55,65]. In addition,
the influence of the electrolyte on the particle surface will also cause the
same mismatch [55]. Eventually, the effect of the electrolyte on the
inside and surface of the particles will cause SOC heterogeneity, thus the
crack happens and finally lead to the failure of the material [55]. The
blue part (1#) representing the high degree of reduction does not cover
the entire surface. The inhomogeneity of 1# further deteriorates the
carrier diffusion path, thereby further aggravating the inhomogeneity of
the internal charge of the particles, leading to more active 4# generation
and further expansion of cracks [55].
3. Strategies to reduce microcracks
By concluding the above theories, the mechanism of the microcracks
formation include three types: The first one is the volumetric anisotropy
change. Due to the instability of Ni3+/4+-O2-electronic structure,
H2→H3 phase transition occurs, which leads to the anisotropy of lattice
parameters, and eventually the stress concentration produces cracks;
The second one is the SOC unevenness, which is caused by the mismatch
of lithium ion and electron diffusion. This will lead to the formation of
extremely lithium-deficient regions, where cation mixing (Li-Ni mixing)
and O evolution (forming oxygen vacancies) will occur. The third one is
the electrolyte damage to the structure. The electrolyte penetrates along
the GBs, causing the internal lithium-deficient areas to react with the
electrolyte, then the transition metal ions are dissolved, and after that
the NiO-like rock salt phase is formed.
Regarding the above three crack formation pathways, corresponding
strategies can be put forward to reduce the cracks. Firstly, doping and
GBs modification can be applied to reduce the stress concentration,
slowing down H3 phase generation or even increasing the critical
voltage where the phase generation happens to eventually reduce the
volume change. This can also be mitigated by designing a single crystal
23
Nano Energy 83 (2021) 105854
particle to reduce intergranular crack, because in a single crystal there is
no interaction between particles like the polycrystalline material. Sec­
ondly, order the crystal orientation to improve the lithium ions and
electron transport then to even the SOC, and eventually reduce O va­
cancies and the degree of Li-Ni mixing. For last one, the electrolyte can
be prevented from penetrating into the particles by either employing
coating and operating grain boundary modification, or doping to get
strong chemical bonds against electrolyte corrosion, or adding electro­
lyte additives to reduce the harm of HF in the electrolyte. We divide
these versatile methods into two categories, namely chemical properties
modification and mechanically based modification, and the effect of
each method on crack suppression is discussed.
3.1. Chemical properties modification
3.1.1. Heteroatom doping
Heteroatom doping can effectively alleviate the generation of crack
through alleviating the H2→H3 phase transition and the cations mixing.
Heteroatom doping can make the crystal structure durable through
strong bones to delay the H2→H3 phase transition. In addition, intro­
ducing ions with a radius like that of lithium ions in the cathode struc­
ture, increasing the Li-Ni exchange defect formation energy and
reducing oxygen vacancy can inhibit the mixing of cations in terms of
reducing the production and migration of divalent nickel. In this part,
the existing doping methods for specific sites and valences ions doping
are comprehensively reviewed, which may shed new light on developing
crack-free Ni-rich cathode toward mitigating the phase transition and
the cations mixing.
Doping at specific sites can get cathodes with different properties.
Elemental substitutions in LiNi1− yMyO2 (M = Co, Mn, Ti, Mg, Al, etc.)
develop a series of successful cathode, such as Co/Mn co-doping LiNi1− x-
yCoxMnyO2 and Co/Al co-doping LiNi1− x-yCoxAlyO2 [66]. Among them,
Co3+ inhibit cation mixing (Li-Ni), and Mn4+ stabilizes the cathode
structure. At the same time, Al3+ decreases the Jahn− Teller distortion of
Ni3+. When heteroatom doping in the Ni-rich cathode, ions will replace
the original Li, Ni, Co and Mn sites. This kind of doping is easy to destroy
the balance within the materials, and the doped material show strong
site selectivity [67]. For example, at the Li sites, doping it with ions with
radius close to the lithium-ion can prevent the migration of Ni2+. At the
Ni sites: substitution of Ni with other cations has been found to improve
cycling stability due to the reason that TM-O networks are strengthened
to delay phase transitions [68]. However, Li, Ni, as the active species
which provide capacity during cycling substitutions at these two sites,
affect the capacity of the cathode [67]. Co sites doping can improve the
phase stability, homogeneity, and charge transfer, doping at Mn sites,
can inhibit Li-Ni mixing and oxygen evolution [67]. Although Co (Mn)
site doping can alleviate the shortcoming of Co (Mn) ion, it also makes
the disadvantage of Mn (Co) ion more prominent. Thus, by reducing the
disadvantages of a single dopant, multi-atom doping strategy can pro­
vide substantially better overall performance [67].
Stronger bonds than TM-O can be introduced into the Ni-rich cath­
ode for stabilizing the crystal structure and delay the H2→H3 phase
transition [69]. In general, replace Ni by a small number of cations like
Al [68], Zr [69–71], and Ti[72,73] can improve cycling stability and/or
thermal stability [68]. Corresponding to the Gibbs free energies of for­
mation at 298 K, assume that the order of the metal-oxygen bonding
force is Al-O > Mn-O > Ni-O [68]. The strong Al-O bond strengthens the
cathode structure by suppressing the phase transform and brings better
cycling and thermal stability (after 70 cycles of NCM811, the volume
retention rate was 83.5% and increased to 91% after doping with 2%
Al). Compared with NCM cathode, NCMA cathode showed almost no
visible microcracks after 1000 cycles (Fig. 12c and d), indicating that Al
has a significant effect on inhibiting the generation of microcracks [74,
75]. In addition, Al-doping can strengthen the boundary between the
primary particles during the phase transition, and it can effectively
reduce the change of the lattice parameter c, thereby inhibiting the
S. Yin et al.
development of microcracks (Fig. 13k) [64]. In order to further verify
the support of the Al-O bond to the crystal structure, Kim et al. used
density functional theory (DFT) to analyze the oxygen vacancy energy
when 89% of lithium is removed from a single lattice (build a model as
shown in Fig. 14a) [64]. Since the oxygen vacancy of NCA89 has the
highest energy (0.87 eV), the Al-O bond is so strong that oxygen atoms
are most unlikely to be released from the Al-O bond, which is sufficient
to indicate that the Al ion in NCMA89 cathode improved its structural
stability during charging (Figs. 14c and 13h) [64]. The enhancement of
the crystal structure significantly delays the phase transition of H2→H3
(Fig. 13j) and enhances the stability of the structure. The bond energy of
Zr-O is more potent than that of Ni, Co, Mn metal-oxygen, which results
in the improvement of structural stability, similar to the mechanism of
Al doping for optimizing the cathode [70]. Besides, Zr4+ can reduce the
anisotropic stress of the crystal lattice to some extent by reducing the
change of the c-axis of the crystal cell, which can be proved by the shifts
of the (003) peak to a lower degree in the XRD pattern (the c-axis is
familiar to the set of planes of (003) reflections) [70]. In addition, the
phase transition from H2→H3 is reduced weakened after Zr4+ doping, as
Zr4+ doping introduce a strong Zr-O bond, which can inhibit the phase
transition, thus decreasing the volume change of anisotropy and the
formation of microcracks [69]. Another example of Ni site doping is the
introduction of Ti to strengthen Ni-O networks. In a word, a strong M-O
network can stabilize the cathode structure, effectively reduce cell vol­
ume deformation (Fig. 13e) microcracks generated during the cycle
(Fig. 12a and b).
At Li sites: doping the cation with constant valence ion like Mg can
show a stable “pillar effect”. Mg is an auspicious dopant which realizes
the stable “pillar effect” in Ni-rich cathode through replace the Li+ inner
Li layer, since its ionic radius is similar to Li+ (Fig. 13f) [76–78]. In
addition to cation doping, anions can be substituted at the O site, such as
F- it stabilizes the structure and increase the capacity retentions. For
instance, LiNi0.8Co0.1Mn0.1O1.98F0.02 provides capacity retentions of
94.4%, 92.8%, 77.5% and 69.9% at 0.5 C, 1 C, 5 C and 10 C, respec­
tively, compared with the corresponding values of 95%, 92.3%, 74.4%
and 64% for LiNi0.8Co0.1Mn0.1O2 [79]. The excellent electrochemical
performance as the result of the strong F-O bond stabilizes the crystal
structure and protects the secondary particle surface from HF corrosion
[73,79].
Because Mn plays the role of stabilizing lattice in the cathode ma­
terial, Aishova et al. proposed a Co-free high-performance cathode [80].
They synthesized Li[Ni0.9Co0.05Mn0.05]O2 (NCM90) and Li[Ni0.9Mn0.1]
O2 (NM90) cathodes, and then compared the performance of them, and
the result is shown in Fig. 13i. It is evident that the cathode at no Co
condition has a considerable improvement in thermal stability, cycle
retention and structural stability (lattice changes, microcracks, and
compressibility). With the increase of Mn content, the H2↔H3 phase
transition peak shifts to upper potential, and the width of the H2/H3
peak is wider than that of NC90, which means that the harmful H2↔H3
phase transition is delayed and the anisotropic force is suppressed
(Fig. 13b− d) [80]. Therefore, increasing the content of Mn in the Ni-rich
cathode will lead to excellent mechanical stability and inhibit the for­
mation of microcracks (micro-compression tests show that the average
single-particle breaking strength of NM90 is 175 MPa, NCM90 is
140 MPa, and NC90 is 95 MPa) [80].
In addition, doping an excellent structure stabilizer like Li2MnO3,
can suppress the H2→H3 phase transition, and reduce the structural
variation of Ni-rich cathode. It was confirmed by cyclic voltammogram
curve and ex-situ X-ray diffraction by Yang et al.[81] The spinel phase
(Fd-3 m) Li2MnO3 component is evenly distributed in the original
cathode (R-3 m). However, the dopant is struggling to maintain its
initial structure when charged to 4.8 V, and the spinel phase is trans­
formed to spinel-like phase. The above phase transition reaction results
in residual spinel phase, spinel-like phase, and mixing of original cath­
ode three-phase. Spinel phase and spinel-like phase play an essential role
in overcoming the phase transition during cycling at high-voltage. Thus,
24
Nano Energy 83 (2021) 105854
the structural damage caused by excessive volume change is avoided
[81].
Cation mixing mainly occurs in the synthesis process of cathode
calcination process. The difficulty of cation mixing is strongminded by
the Li-dopant exchange defect formation energy: the difference between
the energy of lithium doping and lithium removal. The formula for the
average generation energy of Li-Ni exchange is as follows [67]:
Ef(average) = n2+ 2+ 3+ 3+
Ni Ef (Li-Ni ) + nNi Ef (Li-Ni ) (1)
Where n2+ 3+
Ni /nNi
2+ 3+
is the percentages of Ni /Ni in the doped NCM, and
Ef (Li-Ni ) and Ef (Li-Ni3+) are the formation energy of Li exchanged
2+
with divalent Ni and trivalent Ni, respectively. Li-Mg and Li-Zr exchange
may occur during the synthesis process because the formation energy of
Li-Mg and Li-Zr exchange are similar, while the formation energies of Li-
Ni exchange are relatively close. It has been found that both Mg and Zr
will occupy Li sites throughout the synthesis process, and they also can
migrate to Li sites during electrochemical cycles [67]. Other dopants
such as Al, Ga, Si, Ti, and V are unlikely to exchange with lithium-ions
(especially Al, Ga, and Si) because their formation energy is much higher
(Fig. 14e and f) [67]. In all cases, Ni2+ is more likely to substitute Li+
than Ni3+, which indicates that the ion radius is the most important
factor for cation mixed Li layer and the TM layer. Therefore, in order to
reduce the mixing of cations, it is necessary to reduce divalent Ni or
inhibit the migration of divalent Ni (Fig. 14f). In addition, the doping of
Mg at Mn or Co sites can obtain higher generation energy, which has a
positive effect on inhibiting cation mixing (Fig. 14f, where green rep­
resents the Li-Ni exchange formation energy of divalent Ni, and magenta
represents the formation energy of trivalent Ni) [67].
In addition, reducing the number of particles with a radius similar to
lithium ions can also effectively suppress cation mixing. The similarity
of ionic radius (0.76 Å for Li+ and 0.69 Å for Ni2+) leads to the mixing of
TM (3a) and Li (3b) layer. The migration of cations will rearrange the
atoms in the structure to form a disordered phase, which causes an
irreversible structure transition [67]. Doping Mg and Zr can reduce
cation mixing, and these elements are doped at the Li site because the
ionic radius of Mg2+ and Zr4+ is close to Li+, and the formation energies
of Li-Mg and Li-Zr are comparatively approach that of Li-Ni mixing
[67–70,76,82]. The entry of dopant elements into the Li layer can reduce
the entry of Ni2+, and thus reduce cation mixing. They reduce the
number of Ni2+, which can also reduce Li-Ni exchange through doping
Mg at Mn and Co sites. Moreover, it is Mg and Zr ions increase the Li-Ni
exchange defect formation energy (from 0.2 to 0.3–1.15 eV) that is the
proof of this promotion (Fig. 14f) [68]. In addition, Ti4+, as the substi­
tute cation also has the function of preventing cation mixing. After Ti4+
doping, the refinement of XRD patterns proves the size of Ni-O bond is
decreased, which possesses a high Ni-O bond energy (bond length and
bond energy have an roughly inverse square relation) [72]. This gives
the material a strong Ni-O network to stabilize its structure, reducing the
cation disorder from 2.90% to 1.60% after doping with Ti4+ [72]. This
trend comes from oxygen defects, and stable Ni-O network suppresses
the reaction of Ni3+→Ni2+. The cation mixing occurs near oxygen va­
cancy preferentially, because of the local NiO6 distortion and the steric
of no oxygen impeding, therefore Ti4+ doping can reduce Ni/ Li disorder
by reducing oxygen vacancy [72].
The mechanism of Al substitution to reduce cation mixing through
reducing oxygen vacancy is similar to that of Ti4+ doping [76]. Besides,
the Al doping of the NCA cathode promotes the Li and TM ordering
during insertion/exportation of Li+ [83]. Kim et al. K observed in
NCA-NCMA90 (consisting of a core of Li[Ni0.934Co0.043Al0.015]O2
encapsulated by Li[Ni0.844Co0.061Mn0.080Al0.015]O2) that Li+ in TM layer
occupies half of the TM site and TMs in the Li layer occupies half of the Li
site in every other column [83]. It is a superstructure unit cell in the
cathode. Scan the atomic column along the [001] and [012] directions
can observe a very regular oscillation. In this kind of ordered cation
superlattice structure, cation mixing can be effectively suppressed.
S. Yin et al.
Fig. 12i illustrates the SAED aperture covers an area up to 100 nm in
diameter and is observed in many primary particles, it suggests that
cation ordering is a common structural feature of cathode formation in
the cycle [83]. This phenomenon can avoid the particle surface from
structural degradation.
Selection of dopant and doping sites will produce different results,
and on dopant can solve shortages of Ni-rich cathode altogether at the
same time. On the contrary, sometimes, a single dopant at a single site
will destroy the balance of the original cathode and even lead to the
deterioration of the properties of the cathode [67]. Liang et al. found
that a strong site preference exists by comparing different doing sites,
which indicates that only through multi-component doping strategy the
series of existing problems of materials can be solved [67]. Liang et al.
doped with seven different elements (Al, Ga, Mg, Si, Ti, V, and Zr) for the
Mn and Co site to observe the performance of the cathode in perspective
of the energy density, lattice oxygen evolution, Mn-Co clustering,
voltage step, lattice distortion and Li-Ni exchange [67]. A spider dia­
gram (Fig. 13g) was concluded and reached the following conclusions:
doping Al at Mn site, doping Zr or Ti at Co site and at the same time
keeping Mn/Co ration unchanged can receive a promising cathode.
Doping extrinsic ions will reduce the capacity of the cathode to a
certain extent, especially doping at Li and Ni site, because Li and Ni, as
active components, are used as the primary source of capacity through
redox reaction [67,69,84]. Therefore, doping was proposed. It was first
used by Cho et al., which could avoid the capacity loss caused by bulk
doping, obtain the same surface stability as bulk doping, and decrease
the cost of quantity manufacture [85]. Doping Mn on the NCM811
cathode surface can improve the mechanical strength of the pristine
material. The obtained Mn-NCM811 demonstrated much better tough­
ness than bare-NCM811 (109.9 vs. 51.3 MPa), as the strong Mn-O bonds
enhance the connecting strength among primary particles [85]. Addi­
tionally, residual lithium is used as an additional source of lithium to
promote the generation of a Mn-rich surface, which eliminates the
process of washing surface residual lithium while the capacity is kept
[85]. Furthermore, the Mn-rich surface layer protects Ni-rich cathode
from having side reaction with electrolyte.
Moreover, doping is not the most appropriate approach to suppress
the microcrack generation since the realistic capacity only can be remain
at 200–210 mAh g− 1 (25% of Li) to avoid the H2→H3 phase transition
[67]. That is why it is difficult for ion doping strategies to ensure the
cyclic permanence of Ni-rich cathode at high cut-off voltage [86].
Furthermore, doping extrinsic ions at Li or Ni sites will decrease the ratio
of the active species, leading the lower capacity [87]. Therefore, the
cathode particles should be changed structurally, and microstructural
design engineering are a better strategy to reduce microcracks.
3.1.2. Coating
Coating is a fundamental strategy for suppressing the generation of
microcracks. Surface modification can improve the capacity retention,
multiplication performance and thermal steadiness of the material. The
mechanism of the enhancement is due to: (1) Electron-conducting media
and ion-conducting media; (2) residual lithium removal and surface
chemistry change; (3) a physical protective layer to keep the surface
from direct contact with the electrolyte; (4) acidity of the electrolyte
reduction as HF scavenger; (5) reduce stress inside the cathode particles
(elastic coating).
The transfer rate of the heterogeneous surface charge can be
improved by improving the surface electrical conductivity. Coating
materials with high conductivity can construct conductive channels
between primary particles and between the cathode and the collector
[88]. Carbon [88], graphene [89], and some conductive polymers (PPy
[90–92], PANI[93]) have excellent electrical conductivity and they are
commonly used to enhance the surface conductivity of the cathode.
Lithium-ion conductors like Li2TiO3 [94–96], LiAlO2 [94], LiZrO3 [97],
Li2SiO3，[98] and Li3VO4[99] etc. provide 3D tunnels for lithium-ion
transport, which are the “highway” for lithium-ion.
25
Nano Energy 83 (2021) 105854
Electron-conducting media and ion-conducting media can significantly
improve the rate performance and decrease the impedance. Residual
lithium on the cathode surface can improve the moisture absorption and
increase the pH of the surface. However, then it can be used to generate
the lithium-ion conductor layer during the coating process [92,94,
100–110], for example Li3PO4 [92], LiCoO2[100,111] and LiF[103] can
be obtained by adding (NH4)2HPO4, Co(OH)2 and NH4F, during the
secondary treatment of the cathode particles. By improving the elec­
trical conductivity and changing the chemical properties of the cathode
surface, the inner phase transition can be uniform and the local stress
can be reduced through the SOC inside the uniform particle.
Coating with a combination of physical barrier and HF scavenger can
inhibit the development of microcracks to some extent. As a physical
barrier, the electrochemical passivation coating can: (1) prevent the
cathode surface from direct contact with the electrolyte; (2) reduce the
electrolyte infiltration into secondary particles to destroy the primary
particles, and (3) reduce the phase transition caused by the dissolution
of TM oxides. Therefore, the surface of the Ni-rich cathode can be pre­
vented from pulverizing and disintegrating during the cycle. The elec­
trochemical passivation layer is composed of metal oxides (Al2O3 [112,
113], ZrO2 [102,114,115], SiO2 [116], Y2O3 [117], and CuO[118]),
metal fluorides (AlF3[112]) and phosphates (AlPO4[61]) which have
only one stable oxidation state. At the same time, some of these metal
oxides such as Al2O3 [112], ZnO [112], SiO2 [103], Y2O3 [117], and
CuO[118] can act as the HF scavengers. They produce H2O by reacting
with HF to reduce the acidity of the electrolyte, which can degrade the
occurrence of vice reactions between the Ni-rich material and the excess
HF acid.
Even though, the strategy of coating shelters the cathode surface
effectively, but it cannot solve the problem of microcrack generation
fundamentally. It is because that the crack generally starts from the core
of the secondary particle. Once the crack develops to the surface coating
layer, the electrolyte still flows into the particle to further deteriorate the
crack, and finally causes the structure collapse of the cathode particle.
Therefore, doping coupled with coating as a dual-modification approach
is able to suppress both microcrack in the bulk and the degradation at
the surface [119]. Kim et al. put forward a nano-stabilizer with an
additional structure that can be doped and coated simultaneously
[111]. Firstly, nano Co(OH)2 particles were introduced and filled into
every crack from the surface of the cathode particles. Then, bivalent Co
was oxidized to trivalent Co and reacted with residual surface lithium to
form TM concentration gradient (the surface is Ni-poor and Co-rich), as
shown in Fig. 15a. Moreover, Co3+ entered the lattice during annealing
to complete the doping process. This surface treatment forms a powerful
surface network by combining several actions of surface coating layers
together (reduce surface residual lithium, improve electron and
lithium-ion conductivity, form a physical barrier to prevent parasitic
reactions between electrolyte and electrode surface as well as a HF
scavenger) and the TM concentration gradient inside the cathode par­
ticle can suppress the microcrack generation and block side reactions
with the electrolyte [111].
There are many other examples of this combination strategy. For
instance, Yang et al. designed a smart calcination strategy which can
realize one-step and in-situ combination modification for Ti-doped and
La4NiLiO8-coated NCM811 cathode [120]. The raw materials were
added to an ethanol solution, and then stirred until all the ethanol has
evaporated, and transferred the remaining powder to a tube furnace to
synthesis a dual-modified NCM811 (Fig. 15b) [120]. According to DFT
analysis, it is speculated that during the calcination process, Ti ions tend
to dispersed into the NCM bulk phase, while La ions tend to accumulate
at the surface of the NCM particles, and further react with surface Ni ions
to form a La4NiLiO8 coating [120]. The outstandingly boosted rate and
cycling performance can be attributed to three reasons [120]. First, the
obtained La4NiLiO8 coating shell can promote the surface strength
permanence and interface dynamics behavior. Second, the Ti doping
serves as pillars and electrons accumulators, alleviating the
S. Yin et al.
cation-mixing gradation and damaging phase generation. Third, the
dual modification of Ti and LaMO successfully suppresses the inconsis­
tent evolution of intergranular cracks and structural degradation of
NCM811, which may be because of the synergistic effect of Ti and LaMO.
A stretchy capsule shell with elasticity and flexibility can suppress
the interior microcracks by alleviating the interior pressure and reduce
the volume contraction/expansion. Through SEM characterization,
Chen et al. found that coating NCM811 with Polypyrrole (PPy) could
significantly inhibit the generation of microcracks [92]. Furthermore,
Polyaniline (PANI)-poly ethylene glycol (PEG) coating also shows the
above properties and can reduce the generation of microcracks [93].
In summary, similar to atomic doping, surface coating increases the
inactive weight and decreases the energy density of the NCM and NCA
cathodes. Surface modification can only prevent the further develop­
ment of cracks and the damage of surface structure by improving the
surface chemical properties of the cathode. However, it cannot funda­
mentally solve the problem of phase transition, lattice volume anisot­
ropy change, cation mixing, and stress concentration. Therefore, dual
modification (doping coupled with coating) and the microstructural
design of cathode particles are the most promising ways for suppressing
the microcrack.
3.1.3. Grain boundary modification
Grain boundaries (GBs) modification can produce strong inner layers
into secondary particles, which can provide a stable protective layer for
cathode particles to isolate the destructive effect of the electrolyte and a
fast ion conducting layer for primary particle to even the SOC of the
cathode [121].
Yan et al. used a solid electrolyte, Li3PO4 (LPO) to coat the surface of
the secondary particles [60]. During annealing at 600 ◦ C, the LPO layer
attached at the surface of the secondary particle melted and then flowed
into the grain boundary, as shown in Fig. 16a [60]. The distribution of
fluorine and carbon elements after 200 cycles of LiNi0.76Mn0.14Co0.10O2
cathode are shown in Fig. 17a− f. It can be seen from the figure that the
LPO infuse into the GBs of the secondary particles, which can protect the
particles from being invaded by the electrolyte, thereby reducing the
generation of intergranular cracks [60]. Using LPO to modify the grain
boundary can effectively prevent the change of the crystal structure
(Fig. 17g− i). This is because the grain boundary modification can
effectively prevent the penetration of electrolyte and inhibit the damage
of the electrolyte to the structure, thereby reducing the cracks [60].
Besides, to further reduce the destruction of the electrolyte, 3,4-ethylene
dioxythiophene (PEDOT), a conducting polymer, was used to reduce HF
acid in the electrolyte as it can react with the electrolyte [122,123].
PEDOT can be injected into the grain boundary by using oxidative
chemical vapor deposition (oCVD) technology, and the comparison of
modified grains with the original grain structure after a long cycle
(Fig. 16b) proves that using PEDOT to modify the grain boundary has a
particular effect on reducing cracks [122]. The mechanism for reducing
microcracks of PEDOT is that it can reduce the acidity of the electrolyte
by reacting with HF, and thus to reduce the degradation of the internal
structure of the cathode (Fig. 16d) [122].
Grain boundaries modification can also stabilize the crystal struc­
ture. Xu et al. found that PEDOT skin coating on a single particle can also
inhibit the structural evolution from layer to spinel/rock-salt [122]. At
the end of first charge, for the pristine NCM111, the newly phase
emerged and signified by the gentle peak S, which is circled by dotted
line in Fig. 18a. The S peaks correspond to surface phase generation, like
defective spinel structures with Fd-3 m spatial groups, which are typi­
cally related to oxygen elimination [124]. The oxygen and crystal
structure evolution among the layered, the spinel and rock-salt-phase
structure will produce a mismatch, and this mismatch will result in se­
vere microscopic strain (along with peak broadening) inside the primary
particle, which will worsen the stability of the surface and bulk struc­
ture. In the 60-PEDOT-@NCM111 case (the time of oCVD is 60 min), the
above peak is not seen (Fig. 18b), indicating that the layered structure is
26
Nano Energy 83 (2021) 105854
not destroyed. The effectiveness of PEDOT skin coating (grain bound­
aries modification) on primary particles to stabilize the crystal structure
through constant removal and insertion of Li+ is proved. The PEDOT
skin coating also reduces changes in battery volume during charging and
discharging [122]. The changes of lattice parameters c (Fig. 18f and g)
and lattice volume (Fig. 18h and i) of the 60-PEDOT@NCM111 cathode
during charging were reduced by 50% compared with the naked
NCM111 cathode. The compression can considerably alleviate the
anisotropic volume change of the primary particles and inhibit the
intergranular cracks in the secondary particles.
Grain boundaries modification can also increase the transfer rate of
lithium ions and electrons to make SOC more even. Due to the charge
compensation principle, the uniformity of lithium ions is related to local
oxygen vacancy, and the internal pressure of oxygen release is one of the
causes of intragranular crack. As depicted by the oxygen release curves
of the positively charged pristine NCM111 and 60-PEDOT-NCM111
cathodes in the existence of electrolytes (Fig. 18d), the primary parti­
cles coated with conductive materials can effectively reduce the occur­
rence of cracks [122]. The oxygen release curve of exposed NCM111
demonstrates two peaks at 250 ◦ C and 425 ◦ C, corresponding to the
structure transition from the layered to spinel and rock salt structure
respectively. Fortunately, after constructing the artificial PEDOT skin,
no oxygen was released, and there was no additional internal pressure
due to the release of oxygen. Therefore, the primary particles coated
with conductive material can effectively reduce the generation of cracks
[122]. After filling H3BO3 between the primary particles of NCM811,
Mo et al. studied the diffusion coefficient of Li+ (DLi+) (the obtained
particle morphology is shown in Fig. 16c, the left is pristine NCM, the
middle is a wet synthetic secondary particle, and the right is a dry
synthetic secondary particle) [125]. The Galvanostatic intermittent
titration technique (GITT) experiment proves that the grain boundaries
modification method can increase the lithium-ion diffusion rate [125].
The DLi+ of NCM-W8 is 1.212 × 10− 9 cm2 s− 1, which is developed than
that of NCM-W0 (0.704 ×10− 9 cm2 s− 1 at 4.0 V). The GITT analysis
approves that the Li3BO3 coating synthesized by the wet-chemical
approach makes Li+ diffusion more efficiently, that is to say, uniform
grain boundaries modification can significantly increase DLi+, thereby
even the phase distribution within the particles [125].
3.2. Microstructural design
Microcracks that damage the structure and thermodynamic stability
cannot be completely solved through chemical properties modification.
The method only delay the generation of microcracks but do not
fundamentally solve the problem. It is a creative and forward-looking
idea to suppress the microcrack inner Ni-rich cathode particles from
the perspective of mechanical mechanics [61]. The deep mechanical
mechanism in the crystal is comprehensively reviewed in this section,
which provides an unprecedented idea of the microcrack-free cathode.
From the analysis of the causes of cracks, the anisotropy of structural
grains is an essential cause of cracks, leading to poor rate performance
and short cycle life. In response to these problems, Xu et al. proposed
and synthesized a micron-scale Ni-rich NCM811 secondary cathode
material composed of radially arranged single-crystal primary particles
(as shown in Fig. 19c) [126]. With this exclusive crystallographic
texture, the surfaces exposed are active (010) planes, and the 3D Li+
diffusion channel directly penetrates from the surface to the center,
which significantly improves the lithium-ion diffusion coefficient. Dur­
ing cycling, due to the consistent crystal orientation, the coordinated
change of charge and discharge volume is realized, and the intra­
crystalline stress caused by the volume change is significantly alleviated.
Therefore, the material has an excellent reversible capacity (203.4 mAh
g− 1, 3.0–4.3 V) and superior rate performance (152.7 mAh g− 1, the
current density of 152.7 mA g− 1) [126]. In addition, the structure ex­
hibits outstanding cycle durability and the structure did not degrade
within 300 cycles. The crystal-oriented anisotropic morphology
S. Yin et al.
modulation provides a straightforward, effective, and well-ordered
strategy to optimize the applicability and pertinence of Ni-rich cath­
ode. In fact, it is crucial to control the microstructure of the cathode
particles to attain the qualified cycle permanence, especially for high
nickel cathodes (Fig. 19b) [17]. The radially oriented primary particles
limit the stress in the radial direction, and thus the entire secondary
particles will shrink and expand during the charging/discharging pro­
cess without causing significant stress along the boundary between the
particles [17]. As the primary particles become narrow, this effect be­
comes stronger, because a larger proportion of the inter- grain boundary
of per unit volume allows strain energy to dissipate along the inter- grain
boundary more effectively [17]. In this section, the methods for
reducing the formation of microcracks by this kind of radially guided
secondary particle improvement methods are summarized in detail.
3.2.1. Single-crystal cathode
The anisotropic stress of polycrystalline cathode in the cycling pro­
cess is mostly concentrated at the grain boundary, resulting in inter­
granular cracking, which decreases the conductivities of electronic and
ionic [127,128]. More surface structure degradation and side reactions
appear because of the penetration of electrolytes, and the heterogeneous
reaction kinetics deteriorate the structure during the prolonged cycle
[127]. However, fortunately, the cracks can be suppressed by using
single-crystal (SC) cathode since this type of cathode has is excellent
structural retention and the even current flow [129]. The structure
retention comparison diagram of single crystal cathode and poly­
crystalline material is shown in Fig. 20.
3.2.1.1. Excellent structural retention. Single-crystal Ni-rich cathode can
totally prevent morphological collapse with the high mechanical
strength and the GBs-free structure, which brings excellent structural
retention to this type of cathode. Cha et al. found that when 15–45 MPa
was applied to polycrystalline and monocrystalline powders, the
morphology of the latter was better than that of the former [129]. The
main purpose of this study is to exhibit the extraordinary mechanical
strength of SC cathode. In addition, Qian et al. used fracture mechanics
to predict the size of the cracks and found that SC cathode of micron
level have a certain resistance to both intergranular and intragranular
cracks [128]. Through the above related research, the excellent me­
chanical strength of SC has been fully proved.
In addition, the GBs-free structure of SC cathode fundamentally
eliminates the possibility of intergranular cracks. The influence of
intragranular cracks on structural stability is much less than that of
intergranular cracks, thus the cycle stability of SC particles (S83) is
significantly better than that of the poly-crystal (PC) particles (N83)
(Fig. 22j) [119]. This increase in stability comes from the reduction of
side reactions between the electrode material and the electrolyte. This
structure without intergranular cracks can prevent the electrolyte from
intruding into the particles, thereby eliminating the area of phase
change inside the particles due to side reactions. As shown in the
Fig. 21a, compared with PC materials, only a few phase of SC materials
change from a layered structure (R-3 m) to other phase (rock-salt phase
(Fm-3 m) or disordered layer phase), moreover these phase changes are
only distributed on the surface of SC particles [59,130]. The uniform
phase inside the SC particle helps it preserve the integrity of the
structure.
3.2.1.2. Current flow evenly. The uneven distribution of lithium ions
caused by heterogeneous SOC is also one of the reasons why PC mate­
rials are prone to cracks. Overmuch Li+ migrates away from Ni-rich
layered can degrade the inter-layer attachment and diminish the frac­
ture strength of the structure along (001) plane [128]. SC cathode has
more uniform SOC than PC materials, which avoids the generation of
extremely lithium-poor regions inside particles [129]. Generally, the
intercalated lithium in the graphite microstructure cannot completely
27
Nano Energy 83 (2021) 105854
return to the cathode, maintaining bonds with the carbon atoms.
Therefore, the degree of lithium ion distribution in the graphite anode
can be used to estimate the number of lithium vacancies in the cathode
(Fig. 21b). Cha et al. used inductively coupled plasma-optical emission
spectroscopy (ICP-OES) technology to observe the distribution of
lithium in anode graphite to prove the SOC uniformity of single crystal
materials [129]. In this study, with an evolution in the test deepness, the
graphite anode of the PC full-cell exhibited increased amounts of lithium
compounds (colored by red in Fig. 21d). However, there were not many
red areas in the graphite of SC batteries. This shows that the lithium
vacancy in SC cathode is significantly less than PC cathode. Uniform
SOC will help SC cathode reduce the occurrence of cracks.
3.2.1.3. Measures to reduce intragranular cracks in single-crystal cathode.
Although the SC cathode can maintain structural stability by suppress­
ing intergranular cracks, this type of cathode is inevitably attenuated
due to the proliferation of intragranular cracks under high voltage and
high temperature working conditions. Through summary, the existing
single crystal modification measures can be divided into two types: (1)
adjust the orientation of the main crystal plane of the single crystal
particles by crystal face engineering; (2) maintain the surface of layered
structure by eliminating surface chemical reconstruction.
For the first method, Zhu et al. found that the SC cathode with plate-
shaped crystal has relatively stable cycling performance by studying the
properties of SC materials with different crystal forms [131]. This is
because the main crystal face of the plate-shaped SC cathode is (001),
and the chemical stability of the material can be improved to a certain
extent by replacing the active (012) crystal face with an inactive one,
such as (001) or (104) surface, as depicted in the Fig. 21c. The higher
surface energy of (012) family facets makes them more reactive and less
stable during electrochemical cycling [131]. At present, there is not
much research on the orientation of crystal plane. This research provides
a feasible new idea for the field of single crystal materials. To figure out
how effectiveness the crystal face engineering on material properties,
further research is needed.
For the second method, Zhang et al. eliminated the ion mixing at the
surface of the single crystal by adding lithium to the surface of the
material [132]. The electrochemical test shows that the treated single
crystal cathode has good cycling stability and rate performance, which is
attributed to the maintenance of the surface layer structure [132]. It is
because that lithium could redeposit into the SC surface lattice via
oxidation of the rock-salt Ni2+ phase to layered Ni3+, which can restore
the surface to a well-ordered structure.
Overall, the single crystal cathode helps to reduce the generation of
microcracks (Fig. 22d). The single crystalline particles have a great
prospect as a small cathode component [119]. However, the control of
morphology and size is still technically difficult [119,127,128].
3.2.2. Concentration-gradient structure
Considering the instability of the reaction at the cathode/electrolyte
interface and the abrupt structural shrink in the cycling process when Ni
content is higher than 0.8, many researchers have proposed methods to
reduce the surface Ni concentration of particles to obtain the cathode
with better cyclic stability [88,133]. There are three major structure,
core-shell structure (CS) [133–136], core-shell gradient (CSG)[34,35]
full-concentration gradient (FCG) [33,137], and they are used to pro­
mote structural integrity, minimize side reactions and impeding detri­
mental volume change.
3.2.2.1. CS cathode: reduce the internal stress concentration. Core-shell
structure with a high capacity Ni-rich core in a stable shell, such as Li
[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 cathode, is proposed by Sun
et al. in Fig. 22b and f [134]. The cathode exhibits an discharge capacity
of 188 mAh g− 1 at the electrochemical window 3.0–4.3 V [61,134]. In
general, the shell will provide pressure to the inner core, which will be
S. Yin et al. Nano Energy 83 (2021) 105854

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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 22. (a) SEM image of the CSG Li[Ni0.64Co0.18Mn0.18]O2. Copyright 2009, Nature. (b) The EDS image of the Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 particle.
Copyright 2005, American Chemical Society. (c) SEM of a single particle for the and the lithiated material. Copyright 2012, Nature. (d) SEM images of the cross-
sectioned, cycled N83 aggregates and S83 single crystal particles after different cycles between 2.8 and 4.5 V after 100 th cycles. (e) EPMA line scan of the final
lithiated oxide Li[Ni0.64Co0.18Mn0.18]O2. Copyright 2009, Nature. (f) Application of the model for particle design. Copyright 2005, American Chemical Society. (g)
The green area denotes the feasible design region for the core-shell structure. Copyright 2017, American Chemical Society. (h) The Ni-rich particle center and Mn-rich
outer surface are clearly seen from the SEM mapping images. Copyright 2012, Nature. (i) Schematic diagram of the FCG lithium transition metal oxide particle.
Copyright 2012, Nature. (j) Electrochemical performance of the N83 and S83 materials cycling performance between 2.8 and 4.3 V and 2.8–4.5 V. (k) Compressive
stress distribution (minimum principal stress) for CC90 and CSG90 particles at the fully charged state. Copyright 2019, Wiley-VCH.
(a) Reproduced from Ref [139]. (b) Reproduced from Ref [134]. (c) Reproduced from Ref [142]. (d) Reproduced from Ref [127]. (e) Reproduced from Ref [139]. (f)
Reproduced from Ref [134]. (g) Reproduced from Ref [138]. (h) Reproduced from Ref [142]. (i) Reproduced from Ref [142]. (j) Reproduced from Ref [127]. (k)
Reproduced from Ref [35].

balanced by the tensile stress generated by the phase transition of the
Ni-rich cathode, and thus appropriately reducing the stress concentra­
tion and delaying the structural degradation to some extent [35]. The
core shrinks more than the shell because it undergoes a more intense
phase transition, which produces considerable radial stress at the
core-shell interface. This leads to the two-part of the cathode deboned
[136]. Wu et al. found that when designing the CS cathode, the shell
thickness should be less than 0.7 µm, and when the shell is less than
0.18 µm, it should be well-matched with the core with a maximum
radius of 5 µm (shown in the green area in Fig. 22g) [138].
3.2.2.2. CSG: reduce stress concentration in the shell. The concentration
gradient can bring the cathode particles a special radial crystallographic
texture. In order to overcome the shortcomings of the above materials,
Sun et al.[139] proposed CSG materials, where a concentration gradient
exist in the shell (Fig. 22a and e). The concentration gradient in the shell
of CSG cathode smooths the stress change of CS cathode, no core-shell
debone, thus improving cyclic stability. Li[Ni0.90Co0.05Mn0.05]O2 cath­
ode with a Li[Ni0.94Co0.038Mn0.022]O2 core and a 1.5 µm thick CG shell
(surface composition Li[Ni0.841Co0.077Mn0.082]O2) was studied by Kim
et al.[35] The deconvoluted (003) reflections of different SOC is shown
in Fig. 23a, which illustrates a slow phase transition that continues until
the end of the charge of CSG cathode unlike the abrupt H2→H3 phase
transition of Li[Ni0.90Co0.05Mn0.05]O2 CC90. Abrupt changes in the
c-axis lattice parameter are passivated by extending the phase transition
to the charge end (Fig. 23j) [34,35].
Kim et al. calculated the local compressive stress field due to the
anisotropic volume change of the main particle and strategized the
mechanical durability of the cathode in Fig. 22k [35]. On the left is the
pristine particle stress field, and on the right is the CSG particle stress
field. The simulation results show that the compressive stresses (σ comp)
inside the CSG90 cathode particle increases because of shell restraint.
More importantly, the highly arranged shell with geometric shapes
makes the cathode exhibit a uniform stress field, which suppresses the
crack growth inside the shell [35]. The uniform stress field may be due
to the long rod-like grain structure characteristic of CG [33–35,63,137,
140,141]. The firm crystallographic texture and radial primary particles
are able to scatter the force inner particles produced by the abrupt
damaging phase emerging during charging and prevent the electrolyte
from entering the bulk of the particle (Fig. 19d) [127].
3.2.2.3. FCG: eliminate stress concentration at the interface of the core and
shell. Although CSG cathode shows better mechanical properties than
CS cathode, sometimes, the thickness of the shell cannot sustain the
structural stability. Therefore, a full concentration gradient (FCG)
cathode material was proposed [142]. Sun et al. introduced a FCG
cathode, which decreased the concentration of Ni and increased Mn
from center toward the surface of each secondary particles, and the
specific distribution diagram of each component is shown in Fig. 22h
and i. FCG-NCM811 cathode shows excellent cycling stability (after 100
cycles, the volume retention rate is about 85%), with an initial capacity
of 203 mAh g− 1 [143], which proves that CSG structure could optimize
the capacity and cycling stability of cathode materials. The FCG cathode
has a rod-like primary particle parallel structure on the (003) level. This
unique crystal structure reduces the strain concentration caused by the
anisotropic volume change, therefore the FCG structure minimizes the
formation of microcracks (Fig. 12h). which proves that CSG structure
could optimize the capacity and cycling stability of cathode materials.
The FCG cathode has a rod-like primary particle parallel structure on the
(003) level.
3.2.2.4. TSFCG: maximize capacity. The group of Sun expanded the
concept of FCG and reported a two-sloped full concentration gradient
(TSFCG) to maximize average Ni concentration which is the main source
of the capacity [141]. The average composition of the TSFCG is Li
[Ni0.65Co0.13Mn0.22]O2, with a center: Li[Ni0.72Co0.11Mn0.17]O2 and a
surface: Li[Ni0.60Co0.12Mn0.28]O2. Sun et al. tested the electrochemical
performance of the TSFCG, CC Li[Ni0.65Co0.13Mn0.22]O2 (same as
average composition) and NCA Li[Ni0.80Co0.15Al0.05]O2 cathode, and
the results are shown in Fig. 23b. TSFCG has a relatively high specific
capacity, cycle stability, and good rate performance. The high concen­
tration of active Ni2+ and Mn-rich surface suppress the reaction of
Ni2+→Ni4+ and increase the specific capacity [139,144]. It was
observed that rod-shaped primary particles specially grew in the radial
directions with crystallographic texture. This texture reduce the stress
concentration between grain boundary caused by anisotropic volume
change, thus the cycle performance of cathode is optimized [63,140,
141]. In addition, the unique morphology provides a rapid diffusion
channel for Li+ (Li layer plane is arranged along the radial direction),
and the DLi+ of TSFCG is ten times that of CC cathode (Fig. 23e) [141].
3.2.2.5. Al-TSFCG: reduce the cation mixing and enhance crystal
structure. Recently, some researchers have declared that Al-doping
combined with concentration gradient can further optimize the perfor­
mance of cathode from the aspects of surface stability and structural
stability [33,137,140]. Sun’s group has done some research on Al-FCG
[33,66], Al-TSFCG etc., Al-TSFCG[140] etc., and found that Al doping
can reduce the generation of microcracks to a certain extent (Fig. 12h)
[137]. Microprobe compression test was used to verify whether the
reduction of microcrack by Al doping is mechanical strengthening. The
fracture occurring at 113 ± 12 MPa is for the FCG61 cathode, however
the fissure was not detected until 121 ± 11 MPa for the Al-FCG61
cathode [33]. In addition, Kim conducted in situ time-resolution
(TR)-XRD experiments to prove that Al doping can develop the struc­
ture and thermal stability of high nickel cathode, and it was observed
that the cathode of Al-FCG76 (R-3 m) produced rock-salt phase
(Fm-3 m) at 410 ◦ C. In contrast, the cathode of FCG76 (R-3 m) produces
salt phase (Fm-3 m) earlier at about 364 ◦ C, as shown in Fig. 18b [137].
Regarding the ratio of Ni2+ to Li sites, FCG61 is 2.3%, while the cation
mixing of Al-FCG61 is limited to 1.1% before recycling. Therefore, it can
be concluded that Al substitution greatly reduces the cation mixing level
of FCG61 cathode [33]. Cationic mixing (Li+/Ni2+) may cause structural
mismatch and lead to salt rock facies, which will further degrade and
produce cracks during cycling. However, the combination of Al and
concentration gradient can not only improve the structural stability of
CC cathodes, but also improve the stability (the NiO phase of Al-1 FCG76
is limited to 1 nm on the surface as shown in Fig. 12g) [137].
By summarizing the development history of the concentration

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30
 S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 23. (a) (003) reflections of a) CC90, b) CSG90 showing the proportion of existence phase during cycling. Copyright 2019, Wiley-VCH. Electrochemical per­
formance of CC, NCA, and TSFCG cathodes (b) The capacity, cycle stability, and rate performance of NCA, CC and TSFCG. Copyright 2015, Wiley-VCH. Differential
capacity (dQ dV− 1) profiles 1st and 100 th charge and discharge cycles for (c) NCM90 and B1.0-NCM90 cathodes at 55 ◦ C. Copyright 2018, Wiley-VCH. (d)
Normalized peak area of the H2→H3 phase transition during discharging as a function of the number of cycles. Copyright 2020, Wiley-VCH. (e) Chemical diffusion
coefficient, DLi+, of TSFCG, CC, and NCA, as a function of the state of charge. Copyright 2015, Wiley-VCH. (f) Variation in a-axis and c-axis lattice parameters and
unit cell volume as a function of voltage. Copyright 2020, Elsevier. (g) The electrochemical performance of conventional NCA89 and NCM90 cathodes, and newly
synthesized NCB cathode (1.5-NCB90). Copyright 2020, Wiley-VCH. (h) DSC profiles for NCA89 and NCW90 in the delithiated state at 4.3 V. Copyright 2019, Wiley-
VCH. (i) Comparison of the corresponding c-axis lattice parameters representing the lattice mismatch during the H2 / H3 phase transition. Copyright 2019, Royal
Society of Chemistry. (j) The relationship between lattice parameters c of CC90 and CSG90 and the amount of Li+ in the cathode. Copyright 2019, Wiley-VCH. (k)
Differential-capacity peaks of the phase transition from H2 to H3 occurs in the dQ dV− 1 curves. Copyright 2019, Royal Society of Chemistry. (l) Long-term cycling
performance of the NCA89 and NCW90 cathodes at 1 C and 25 ◦ C between 3.0 and 4.2 V. Copyright 2019, Wiley-VCH. (m) the intensity ratio between the (003) and
(104) reflections. Copyright 2019, Royal Society of Chemistry.
(a) Reproduced from Ref [35]. (b) Reproduced from Ref [141]. (c) Reproduced from Ref [62]. (d) Reproduced from Ref [17]. (e) Reproduced from Ref [141]. (f)
Reproduced from Ref [28]. (g) Reproduced from Ref [17]. (h) Reproduced from Ref [29]. (i) Reproduced from Ref [32]. (j) Reproduced from Ref [35]. (k)
Reproduced from Ref [32]. (l) Reproduced from Ref [29]. (m) Reproduced from Ref [32].

gradient cathode, it is found that the structure of the secondary particles
determines the comprehensive properties, as depicted in the schematic
of Fig. 19a. At the first stage, to reduce the stress concentration inside
the particles, CS cathode was proposed. The CS cathode uses the
compressive stress provided in the shell to even the stress concentration
inside the secondary particles, thereby reducing the generation of in­
ternal tensile stress [34,35]. At the second stage, in order to avoid the
stress concentration of the CS cathode in the shell and prevent the
separation of the shell and core, researchers introduced a concentration
gradient in the shell, then a CSG cathode was obtained. A long
rod-shaped crystal structure forms in the shell due to the concentration
gradient. The structure can even the stress in the shell and prevent the
shell from breaking [35]. At the third stage, for the purpose of elimi­
nating the sudden change in concentration at the interface between the
shell and the core in the CSG cathode, the FCG cathode is proposed. This
kind of cathode eliminates the interface between the shell and the core,
and the primary particles are in the shape of long rods and the
cross-sectional area decrease from the surface to the core along the
radius. The spoke-like crystal texture has better resistance to cracks.
However, the average Ni content of FCG cathodes is relatively low [33,
143]. At the fourth stage, in order to maximize the percentage of Ni in
the cathode and maximize the capacity of the cathode, TSFCG was
proposed. This cathode has a double slope and maintains an excellent
structure while keep the best Ni content through the transition of two
concentration gradients [63,140,141]; At the fifth stage, many re­
searchers have proposed doping heteroatoms based on TSFCG, aiming to
introduce strong bonds based on excellent structure. This method can
increase the strength of the lattice or reduce the mixing of cations from
both mechanical properties and structural properties [33,137].
Co-precipitation is a generic preparation method for concentration
gradient cathodes, but the performance of the cathode in connection
with the preparation accuracy [61]. The present preparation process is
extremely sensitive, expensive, and every parameter in the
co-precipitation reaction has a significant influence on the performance.
It is challenging to introduce the full concentration gradient (and thus
the texture microstructure) into the NCM cathode with high Ni content
because the mutual diffusion during the high-temperature lithification
tends to flatten the preexisting concentration gradient of the precursor
[62]. Therefore, the future research direction is to optimize the prepa­
ration route of concentration gradient materials.
3.2.3. Microstructure engineering
In order to meet the requirements of next-generation EVs, the Ni
content in cathode materials should exceed 0.9, and the researchers are
skeptical that the above methods can effectively suppress microcracks at
this Ni concentration [29]. With the increase of Ni content, the forma­
tion of microcracks becomes more and more serious. Therefore, a
comprehensive method needs to be proposed rather than rely solely on
the chemical modification to address the formation of microcracks [17].
Since the volume changes in the lattice are unavoidable during cycling,
and it is only possible to reduce the local stress concentration caused by
the strain. Therefore, Sun’s team proposed microstructure engineering
[17,28,62]. The a-axis direction of each main particle is arranged along
the radial of the secondary particles, forming a strong crystallographic
texture. This structure can make the force distribution uniform and
suppress the local stress concentration that can cause crack nucleation
[17,20,28].
Ryu et al. developed a new type of high nickel cathode, Li
[NixCoyB1− x-y]O2 (NCB), with a unique microstructure, which effec­
tively suppresses the generation of cracks, even after 100 cycles
(Fig. 24g and h) [17]. Experiment results demonstrate that boron ions
can effectively prevent the cathode from structural damage in the
reduction process (Fig. 23d), and it also can bring stable crystallographic
texture to the cathode and make the cathode have good recycling
reversibility (Fig. 23c) [17,62]. Furthermore, to a certain extent, the
more boron is added, the more obvious the optimization effect is
(Fig. 23g) [17].
Boron has a smaller ion radius than Li+, therefore B3+ can occupy the
tetrahedral interstices of the oxygen array in the TM and Li layers. It can
be easily incorporated into the structure [62]. Ryu et al. doped boron
into Li [Ni0.885Co0.1Al0.015]O2 (P-NCA89) to get Li[Ni0.878C­
o0.097Al0.015B0.01]O2 (B-NCA88), and the morphologies of the two
cathodes are shown in Fig. 24a and b [28]. The P-NCA89 cathode is
composed of almost equiaxed polygonal crystals (primary particles),
however, the primary particles of B-NCA88 shows fine needle-like
morphology with a decrease of what toward the center of the particle
[28,62]. The result implies that the spatial correlation microstructure
observed in boron-doped NCM90 cathode is derived from surface energy
modification of primary particles. The surface energies of (003), (01− 2),
(014), and (100) of LiNi0.92Co0.04Al0.04O2 (pristine) and LiB0.02Ni0.90
Co0.04Al0.04O2 (B-doped) are calculated by density functional theory
(DFT) to verify the influence of B doping on the surface energies. Since
the calculation results show that (003) surface is stable as it has the
lowest value of γ, the introduction of boron decrease the surface energy
of (003) (Fig. 14d) [28,62,145]. As crystal growth is determined by the
relative orientation of the low-energy surface, the decrease of surface
energy and maximizes the formation of the (003) surface, which is the
reason for the special radial crystallographic texture [17]. In addition,
boron may segregate to grain boundary during the calcination process
and react with lithium to form the Li3BO3 phase (in Fig. 14b). The three
O anions from the subsurface layer form a curved Li3BO3 layer together
with B dopant, in which the value of B-O bond (1.387 Å) is similar to
that of α- Li3BO3 phase (1.377 Å)) [28], which prevents the coarsening
of primary particles. The grain boundary density of the primary fine
particles in this refined structure is higher, which reduces the stress
concentration in the secondary particles (Fig. 19b) [17]. In fact, boron
does not suppress the inherent volume change during cycling, but it
improves the geometric arrangement of the primary particles to make
the stress uniform [28]. It can be observed that the shrinkage caused by
the H2→H3 phase transition is almost the same after the doping of boron

31
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S. Yin et al. Nano Energy 83 (2021) 105854

Fig. 24. (a) P-NCA89 and (b) B-NCA88 cathode particles’ SEM images of as-synthesized at different magnifications and cross-sectional bright-field scanning TEM
images of as-synthesized particles showing microstructure. Copyright 2020, Elsevier. (c) NCA89 and (d) NCW90 cathode particles’ SEM images with two different
magnifications and bright-field STEM images show part of the particle cross-section. Copyright 2019, Wiley-VCH. Bright-field STEM mosaic image of a cross-section
of (e) NCA89 and (f) NCW90 at charged to 4.3 V. Copyright 2019, Wiley-VCH. Cross-sectional images of the cycled (g) NC90 and (h) 1.5-NCB90 cathode after 100
cycles. Copyright 2020, Wiley-VCH.
(a) Reproduced from Ref [28]. (b) Reproduced from Ref [28]. (c) Reproduced from Ref [29]. (d) Reproduced from Ref [29]. (e) Reproduced from Ref [29]. (f)
Reproduced from Ref [29]. (g) Reproduced from Ref [17]. (h) Reproduced from Ref [17].

(Fig. 23f) [28]. It shows that the microstructure absorbs the anisotropic electrochemical performance (Fig. 23l) [29]. As shown in Fig. 24c and d,
strain during the cycle, and the primary particles arranged in the radial the NCA89 is composed of randomly oriented primary particles of nearly
direction can be uniformly contracted during the charging process, and equal size, and the NCM90 cathode is composed of thin elongated pri­
return to their original size at discharging [28,62]. mary particles toward the surface from the center [29]. The width of
Tungsten doping can improve cyclic stability without sacrificing XRD pattern is inversely proportional to the lattice size, so the
energy density [29,32,146], Ryu et al. substituted W for Al in the Ni-rich normalized XRD pattern of the peak intensity of the (003) peak can be
cathode Li[Ni0.885Co0.10Al0.015]O2 (NCA89) to produce Li used to figure out the size of the particles. Increasing the W content will
[Ni0.9Co0.09W0.01]O2 (NCW90), which showed excellent increase the peak width, and thus that W doping will reduce the size of

32
S. Yin et al. Nano Energy 83 (2021) 105854

the primary particles [29,32]. The W-doped secondary particles are Table 1
comprised of acicular primary particles arranged from the center toward Summary of abbreviations of materials, instruments, and test methods and
the surface (Fig. 24d) [32]. The fine primary particles increase the grain sorted alphabetically by full name.
boundary density of the cathode, and the particular microfractures can Full name Abbreviation
well absorb the strain generated by the anisotropic volume change. Annular bright field ABF
Therefore, W can slow-release the formation of microcracks by changing Charge-transfer resistance Rct
the structure of the secondary particles [29]. The fine primary particles Conventional cathode CC
increase the grain boundary density, and the inter-particle boundaries Core-shell structure cathode CS
Core-shell gradient cathode CSG
serve as an effective barrier to crack propagation, which can make the
Differential capacity vs. voltage curve dQ dV− 1 curve
straight cracks that penetrate the surface of the secondary particles Density functional theory DFT
disperse into a zigzag shape before reaching the surface, as can be seen Depth of discharge DOD
from the comparison between Fig. 24e and f [29]. Differential scanning calorimetry DSC
In addition, the intensity and width of the redox peak in the dQ dV− 1 Energy dispersive spectroscopy EDS
Extended absorption fine structure EXAFS
curve increased with the increase of W content (Fig. 23k) [32]. At the Electron energy loss spectroscopy EELS
same time, it can be clearly seen that after 100 cycles, the distance be­ Electrochemical impedance spectroscopy EIS
tween the peak of H2 and H3 decreases, and the peak of H3 almost Electronic paramagnetic resonance EPR
coincides with that before cycling. Therefore, it can be concluded that Electric vehicles EVs
Full-concentration gradient cathode FCG
doping of W can avoid abrupt phase transition and prolong the phase
Grain boundaries GBs
transition process, thus enhancing the reversibility of H2→H3 phase Galvanostatic intermittent titration technique GITT
transition and maintaining stable structure. This is also demonstrated by High-angle annular dark-field HAADF
continuously varying in situ XRD patterns of (003) reflection (Fig. 3d) Height of the lithium-oxygen slabs hLi-O
[32]. The gently H2→H3 phase transition in the W-doped LNO cathodes Height of the transition metal-oxygen slabs hTM-O
Inductively coupled plasma-optical emission spectroscopy ICP-OES
is probably because of the presence of W6+ ions in the Ni layer, which
LiCoO2 LCO
produces a pillar effect and stabilizes the main structure during cycling LiNiO2 LNO
[32,39,42,147]. Since W protects the cathode microcracks from reach­ Li[NixCoyAl1− x-y]O2 NCA
ing the surface, the degradation of particles by the electrolyte is Li[NixCoyMn1− x-y]O2 NCM
Li[Ni0.8Co0.8Al0.1]O2 NCA811
dramatically reduced, which improves the thermal stability of the
Li[Ni0.33Co0.33Mn0.33[O2 NCM111
cathode. Using differential scanning calorimetry (DSC) can observe this Li[Ni0.9Co0.05Mn0.05]O2 NCM90
phenomenon, which is shown in Fig. 23h [29]. Li[Ni0.95Co0.025Mn0.025]O2 NCM95
Recently, Kim et al. replaced Al with Ta and obtained an ultra-high Li[Ni0.9Mn0.1]O2 NM90
performance material Li[Ni0.9Co0.09Ta0.01]O2, which exhibits 90% ca­ Li[Ni0.9Co0.09B0.01]O2 NCW90
Li[NixCoyB1− x-y]O2 NCB
pacity retention rate after 2000 cycles at full DOD [148]. This excellent
Li3PO4 LPO
performance is achieved by its [003] crystallographic texture, because Lithium-ion batteries LIBs
the special structure inside the secondary particles can reduce stress Li site near Mn site LiM site
concentration. Compared with B and W ion doping, the crystal structure Li site near Ni site LiN site
Nanobeam electron diffraction NBD
obtained after Ta treatment is thinner and longer. Richer grain boundary
Neutron powder diffraction PDF
and stronger crystallographic texture effectively slow down the forma­ Oxidative chemical vapor deposition oCVD
tion of cracks. Table 1. Poly(3,4-ethylenedioxythiophene) PEDOT
Polyaniline PANI
4. Conclusion and perspectives Polypyrrole PPy
Polycrystalline particles N83
Poly-crystal particles PC particles
Among all the cathode candidates for future electric vehicle industry, Selected area electron diffraction SAED
Ni-rich cathode is the most promising one, as it has the obvious Single crystal particles S83
advantage of high capacity to meet the requirements of consumers for Single-crystal cathode SC cathode
State of charge SOC
automobile mileage. However, at its original state, especially when
Scanning transmission electron microscope STEM
cycling under high voltage, its cycle ability, thermal stability, and rate Two-dimensional 2D
capability are not satisfactory. This article discusses the underlying Three-dimensional 3D
mechanism of these drawbacks and corresponding strategies to over­ Transmission electron microscopy TEM
come them. It is found that the key reason for the degradation of Ni-rich Transition metals TM
Transition metals ions TMs
cathode performance is the generation of microcracks during the Time-resolved X-ray diffraction TR-XRD
cycling. Two-sloped full concentration gradient TSFCG
Previous studies have found that the formation mechanism of the X-ray absorption spectroscopy XAS
two types of cracks are different. Intergranular crack is the main reason X-ray diffraction XRD
for the performance degradation of batteries, can formed due to the
H2→H3 phase transition and the heterogeneous SOC between primary
structure.
particles. For intragranular crack, we divide it t into three types through
By summarizing the existing research work, we divide the crack
the related research according to the crack generation mechanism and
suppression methods into two categories according to the different ac­
morphology. These three types are the classical term of crack, the dark
tion principles. One is to produce secondary particles with certain
contrast stripes, and fine-serried low-angle grain boundary. The causes
crystal orientation (the shape and arrangement of primary particle),
of these three kinds of cracks can be summarized as heterogeneous
such as single crystal, concentration gradient, and microstructure
delithiation and mechanical failure inside the primary particles. In
design. The other one is to enhance the particle structure and chemical
addition, once the crack is formed, the electrolyte damage to the cracked
properties, such as doping, coating, modification of grain boundary.
particles is another important reason for the material structure degra­
Although many of these methods have a substantial impact on the sta­
dation. The electrolyte will follow the cracks and penetrate the sec­
bility of battery performance during cycling, even at high cut-off volt­
ondary particles and react with the Ni4+ substances inside the secondary
ages, it remains challenging to solve all the problems at once by using
particles, causing the TMs to dissolve and severely destroy the particle

33
S. Yin et al.
those strategies alone. Therefore, in order to design a high-capacity and
high-stability microcrack-free cathode, we propose a “chemical-me­
chanical mechanism” strategy. It is a multi-channel strategy that utilize
the “chemical-mechanical” approach: (1) microstructure design to
reduce stress concentration, (2) doping to delay the formation of H3
phase, (3) coating to increase the transmission rate of lithium ions and
electrons, (4) grain boundary modification to reduce the generation of
uneven phases while protecting the inner part of particles from the in­
fluence of electrolyte. This “chemical-mechanical” effect may shed new
light on developing crack-free Ni-rich cathode.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially supported by National Key Research and
Development Program of China (2019YFC1907805, 2017YFB0102000),
the Science and Technology Innovation Program of Hunan Province
(2020RC4005, 2019RS1004), Central South University Innovation
Driven Project (2020CX007), and International Postdoctoral Exchange
Fellowship Program (Talent-Introduction Program), China Postdoctoral
Science Foundation (223764).
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Dr. Guoqiang Zou is an Associate Professor at the College of

Chemistry and Chemical Engineering, Central South Univer­
sity. He received his PhD at Central South University in 2018.
Shouyi Yin received his B.S. degree in mineral process engi­ His current research interests are MOF derived materials for
neering from China University of Mining and Technology electrochemical energy storage devices.
(Beijing) in 2019. She is currently working toward the Master
degree in College of Chemistry and Chemical Engineering,
Central South University and his current research involves the
mechanism and improvement of Ni-rich cathode materials.

Dr. Hongshuai Hou is an Associate Professor at the College of

Chemistry and Chemical Engineering, Central South Univer­
sity. He received his PhD at Central South University in 2016.
Dr. Wentao Deng is currently a research fellow at Central His current research interests are electrochemistry and key
South University, Changsha, China. She received master degree materials for electrochemical energy storage devices.
with the supervision of Prof. Xiaobo Ji at Central South Uni­
versity, and got PhD at University of Bath supervised by Dr.
Petra Cameron. Then she did one and half year postdoc
working for Prof. Laurie Peter at University of Bath before
joining Central South University as a research fellow.

Dr. Xiaobo Ji is a “Shenghua” Professor at Central South

Jun Chen is a PhD student in the College of Chemistry and
Chemical Engineering at Central South University under the
supervision of Prof. Xiaobo Ji. His current research focuses on
the design and synthesis of layered transition metal oxide
materials and their applications for Lithium-ion batteries.
University and a Fellow of the Royal Society of Chemistry,
specializing in the research and development of batteries and
supercapacitor materials and their systems. He received his Ph.
D. in Electrochemistry in 2007 under the supervision of Prof.
Richard Compton at the University of Oxford and undertook
postdoctoral work at MIT with Prof. Donald Sadoway.

Xu Gao received his Bachelor (2105) and Master (2018) degree

in Materials Science and Engineering at Sichuan University. He
is now pursuing his PhD degree at College of Chemistry and
Chemical Engineering, Central South University. His research
focuses on the energy storage materials and devices.

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