An Overview On The Advances of LiCoO2 Cathodes For Lithium-Ion Batteries

Review
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An Overview on the Advances of LiCoO2 Cathodes

for Lithium-Ion Batteries
Yingchun Lyu, Xia Wu, Kai Wang, Zhijie Feng, Tao Cheng, Yang Liu, Meng Wang,
Riming Chen, Leimin Xu, Jingjing Zhou, Yuhao Lu,* and Bingkun Guo*
by Prof. John B. Goodenough offers high

LiCoO2, discovered as a lithium-ion intercalation material in 1980 by Prof. conductivity and stable structural stability
John B. Goodenough, is still the dominant cathode for lithium-ion batteries throughout cycling with ≈0.5 Li+ per for-
(LIBs) in the portable electronics market due to its high compacted density, mula unit (de)insertion.[2] To improve
the energy density and reduce the cost
high energy density, excellent cycle life and reliability. In order to satisfy the of LIBs, tremendous efforts have been
increasing energy demand of portable electronics such as smartphones and devoted to developing new cathode mate-
laptops, the upper cutoff voltage of LiCoO2-based batteries has been continu- rials and some of them have been com-
ously raised for achieving higher energy density. However, several detrimental mercially applied, such as LiMn2O4,[1,3]
issues including surface degradation, damages induced by destructive phase LiFePO4,[4] LiNi1−x−yCoxMnyO2 (NCM, 0 <
x, y < 1),[5] LiNi0.80Co0.15Al0.05O2 (NCA),[6]
transitions, and inhomogeneous reactions could emerge as charging to a
and xLi2MnO3·(1−x)LiMO2 (M = Ni, Co,
high voltage (>4.2 V vs Li/Li+), which leads to the rapid decay of capacity, Mn, etc.) compounds.[7] Among them,
efficiency, and cycle life. In this review, the history and recent advances of spinel LiMn2O4, Olivine LiFePO4 are also
LiCoO2 are introduced, and a significant section is dedicated to the funda- stemmed from Prof. Goodenough’s labs.
mental failure mechanisms of LiCoO2 at high voltages (>4.2 V vs Li/Li+). The electrochemical characteristics of
Meanwhile, the modification strategies and the development of LiCoO2-based the most popular cathode materials are
summarized in Table 1. Among them,
LIBs in industry are also discussed. LiMn2O4, LiFePO4, NCM, and NCA have
been used for electric vehicles (EVs),
and large-scale energy storage systems.
1. Introduction Compared to all other cathode materials, LiCoO2 possesses
many unique advantages, including high Li+/electron conduc-
Lithium-ion batteries (LIBs) are the most commonly used tivity, high compacted density (4.2 g cm−3), and excellent cycle
energy storage devices for portable electronics (e.g., mobile life and reliability. As a result, LiCoO2 is still the dominant
phones, laptops, and power tools) and electric vehicles. To a cathode material in the portable electronics market even after
large extent, LIBs have enabled the mobile revolution and satis- nearly 30 years since the birth of LiCoO2-based LIBs. Moreover,
fied our increasing demand on “mobile living,” which could be LiCoO2 also shows great potential for further high energy den-
one of the most important reasons to award the Nobel Prize sity by means of increasing the upper cutoff voltage during
in Chemistry 2019 to John B. Goodenough, M. Stanley Whit- charging. As shown in Table 1, the energy density of LiCoO2 is
tingham, and Akira Yoshino for the development of LIBs. LIBs 740 Wh kg−1 at 4.45 V and increases to 840 Wh kg−1 at 4.55 V,
were first commercialized by SONY in 1991, with LiCoO2 as the which is comparable with Li-rich cathodes. In consideration
cathode, petroleum coke as the anode, and LiPF6 in propylene of the fact that the compacted density of LiCoO2 is far larger
carbonate (PC) as the electrolyte.[1] LiCoO2 that was first dis- than Li-rich cathodes, LiCoO2-based LIBs demonstrate a much
covered as an intercalation cathode material for LIBs in 1980 higher volumetric energy density that is the overwhelming
advantage as power sources in portable devices.[8]
Dr. Y. Lyu, Z. Feng, T. Cheng, Dr. Y. Liu, Dr. R. Chen, J. Zhou, Prof. B. Guo
Materials Genome Institute
Shanghai University
1.1. The History Before the LiCoO2’s Commercialization
Shanghai 200444, China
E-mail: guobingkun@shu.edu.cn The crystallography of LiCoO2 was reported in 1958.[9] It has
Dr. X. Wu, Dr. K. Wang, Dr. M. Wang, Dr. L. Xu, Dr. Y. Lu an α-NaFeO2-type layered structure in which the oxygen atoms
Ningde Amperex Techology Ltd are arranged in a cubic close-packed (ccp) framework and the
Ningde 352100, China Li+ and Co3+ ions are ordered in alternating (111) planes of
E-mail: Luyuh@ATLBattery.com
R-3m space group with the cell parameters of a = 2.816(2) Å
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202000982.
and c = 14.08(1) Å. Delmas et al. identified it as O3-type LiCoO2
in which O represents that the lithium ions occupy the octa-
DOI: 10.1002/aenm.202000982 hedron sites surrounded by six oxygen and the number stands
Adv. Energy Mater. 2020, 2000982 2000982 (1 of 29) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de
for the packing type of oxygen. Herein, “3” indicates the oxygen
packing is ABCABC….[10] In the 1970s, layered transition metal- Yingchun Lyu is an asso-
containing compounds, for example TiS2, were demonstrated ciate professor at Shanghai
in reversible Li intercalation reactions at reasonably high volt- University. He received his
ages.[11] It paved the way to a new class of cathode materials for Ph.D. degree in condensed
energy storage. The requirement for higher voltage and energy matter physics from Institute
density rapidly led to the replacement of sulfide cathodes by of Physics, Chinese Academy
oxides, along with the development of high-voltage stable of Sciences, in 2015. His
electrolytes. In 1980, the electrochemical properties of LiCoO2 research interests focus on
was reported unprecedentedly by Prof. Goodenough et al. as a high energy density cathode
the cathode material with the electrolyte of LiBF4 in PC.[2,12] It materials for lithium-ion bat-
exhibites a high voltage with open-circuit voltages (OCV) lying teries and the energy storage
in the range of 3.9–4.7 V for 0.07 < x ≤ 1 in LixCoO2. Although mechanism of the electrode
all Li in LiCoO2 could be removed electrochemically in theory, materials.
reversible behavior appeared only in the range of compositions
between LiCoO2 and Li0.5CoO2. The layered-structure of LiCoO2 Yuhao Lu is the director of
exists in other analogous of lithium transition metal oxides with Research Institute at Ningde
a generic formula of LiMO2 in which M = V, Cr, Ni, and Fe. Amperex Technology Limited
The successful application of LiCoO2 inspires a wave of efforts (ATL), and responsible for
to explore polymorph cathode materials for LIBs, for example, R&D of advanced electrode
LiNiO2 which is the base of the widely used NCM and NCA materials and cell designs for
cathode materials.[3,13] Besides, various isoforms of LiCoO2 were high performance lithium-
successfully synthesized with different synthetic conditions ion batteries. He has devel-
such as spinel-LiCoO2 by low-temperature sintering,[14] O2-type oped nonaqueous Prussian
and O4-type LiCoO2 by an ion-exchange method.[15] Herein, 2 white sodium-ion batteries,
indicates the oxygen packing is ABACABAC… and 4 indicates lithium/liquid-cathode
the oxygen packing is ABACBABC.... Owning to the same batteries, and lithium/low-
oxygen packing, annealing at high temperature, metastable temperature molten-salt
spinel-LiCoO2 converts to O3-type LiCoO2. O4-type LiCoO2 has batteries. Aside from batteries, he also had industrial and
an intergrowth structure of O3- and O2-LiCoO2 with stacking academic experience in fuel cells and supercapacitors. He
faulted domains. It is metastable and transforms into the ther- achieved his Ph.D. degree from the University of Alabama,
modynamically stable O3-type LiCoO2 at around 350–400 °C.[16] and was once trained as a postdoctoral fellow under Prof.
To understand the electrochemical behavior, the properties Goodenough’s guidance.
of LixCoO2 were comprehensively investigated.[17] Its electronic
structure indicates the relatively high electronic conductivity and
demonstrates its semiconductive property. With the removal Bingkun Guo is a professor
of Li+ from LiCoO2, its electronic behavior dramatically at Shanghai University. He
changes from semiconductor at x = 1 to metallic with x = 0.9–1.0 received his Ph.D. from the
in LixCoO2, and the metallic feature is further enhanced with Institute of Physics, Chinese
decreasing lithium concentration, which favors the process of Academy of Sciences (CAS)
lithium-ions deintercalation/intercalation.[17a] Moreover, the in 2009. After a short stay
chemical diffusion coefficient of LixCoO2 is very high, which in North Carolina State
makes it be a suitable cathode material for LIBs.[17c] Delmas University, he moved to Oak
et al. also found that electrons play a very important role in Ridge National Laboratory as
both thermodynamics and kinetics during the electrochemical a postdoctoral fellow in 2010.
process.[17b] He worked in Prof. John B.
Besides cathode materials, searching for suitable electrolytes Goodenough’s group as a
and anodes is indispensable to practical LIBs. For example, postdoctoral research fellow
Plichta et al. studied the Li/LixCoO2 rechargeable cells with from 2013 to 2015. He is currently working on advanced
several solvents and lithium salts, and LiAsF6 in methyl ace- materials for high-energy density lithium-ion batteries and
tate electrolyte showed the best performance.[18] In 1985, a full solid-state lithium-ion batteries.
nonaqueous electrolyte rechargeable battery using LiCoO2 as
a positive electrode and carbonaceous materials as a negative
electrode was assembled by Yoshino et al.[19] They performed
the first safety test on LIBs over the world, and eliminated the By using electrolyte solution of LiPF6 in propylene carbonate/
concern on the commercialization of such batteries. diethyl carbonate (PC/DEC), their excellent cycle performance
In 1991, Sony released the first commercial LIBs with was demonstrated with only 10–20% capacity degradation after
LiCoO2 cathode and nongraphitizable carbon anode. It delivered 500 cycles, even at a moderately high temperature. Commer-
a high energy density (253 Wh L−1 in 18 650 batteries).[20] cialized LIBs had almost twice energy density as much as
Table 1. Electrochemical characteristics of the cathode materials. Adapted with permission.[7] Copyright 2017, Wiley-VCH.
LiCoO2 LiNi0.80Mn0.10Co0.10O2 LiNi0.80Co0.15Al0.05O2 Li2MnO3LiNixMnyCozO2 LiFePO4 LiNi1/3Mn1/3Co1/3O2 LiMn2O4

Structure Layered Layered Layered Layered Olivine Layered Spinel
Theoretical Capacity 274 275 279 – 170 275 148
[mA h g−1]
Available Capacity 190@4.45V 210 200@4.3V 250@4.6V 160 160@4.3V 110
[mA h g−1]
215@4.55V 210@4.4V 185@4.5V
Electrode Density 3.9 3.2 3.4 2.7 2.3 3.4 3.2
[g cm−3]
Galvanometric Energy 740@4.45V 800@4.4V 760@4.3V 900@4.6V 540 610@4.3V 410
Density [Wh kg−1]
840@4.55V 800@4.4V 730@4.5V
Volumetric Energy 2900@4.45V 2600@4.4V 2600@4.3V 2430@4.6V 1240 2080@4.3V 1300
−1
Density [Wh L ]
3300@4.55V 2700@4.4V 2480@4.5V
Operating Voltage [V] 3.9 3.8 3.8 3.6 3.4 3.8 4.0
Application Mobile IT Power tools Power tools Evs Power tools Power tools
devices Evs Evs ESSs Evs Evs
Power tools Energy storage ESSs (low end) ESSs ESSs
Systems (ESSs)
that of nickel–cadmium or nickel–metal hydride batteries in particular, Prof. Goodenough[1,23] proposed that the funda-
terms of both weight and volume, which facilitated a major mental reason of the intrinsic voltage limit for the layered
reduction in the size and weight of the power supply for port- LiMO2 cathodes is pinning of a redox couple at the top of an
able devices. With balanced merits between energy density anion p-band. As to LiCoO2, the Co4+/Co3+ redox couple at
and reversibility, LiCoO2 was one of the most reliable cath- the top of the O band determines its intrinsic voltage limit.
odes and, as of today, is still the flagship cathode material Once x > 0.5 in the system of Li1−xCoO2, peroxide formation
in the LIB market of billions of dollars, mostly for electronic at the surface results in the loss of O2. Moreover, Co disso-
consumer products.[21] lution is also considered another issue that is closely related
to the capacity decay above 4.2 V.[24] Various strategies, for
example, surface coating, element doping, and comodification
1.2. The Main Progresses of LiCoO2 After the Commercialization approaches have been proposed to overcome those issues and
promote the long-cycling stability of LiCoO2 at high voltage.[25]
Massive efforts have been taken to exploring high-perfor- Nowadays the operating voltage of LiCoO2 in commercial
mance LIBs after their commercialization in 1991. In the prac- applications have been continually increased. With efforts of
tical application of the early LIBs, only 0.5 mol of Li+ ions per nearly 30 years, the upper cutoff voltage of LiCoO2 in com-
formula were extracted from LiCoO2 to avoid rapid capacity mercial LIBs has been increased to 4.5 V during charging,
decay, corresponding to a specific capacity of ≈140 mAh g−1 at achieving a reversible capacity of ≈185 mAh g−1 with practical
the upper cutoff voltage of 4.2 V. To meet the ever-increasing cycling performance. A breakthrough in the voltage limit of
demand of 3C products on high energy density LIBs, both 4.5 V for LiCoO2 is urgently needed to further increase the
academic and industrial worlds exert intensive efforts onto energy density of LiCoO2-based LIBs. Although considerable
increasing the capacity of LiCoO2. Charging to higher volt- progress for 4.6 V-LiCoO2 in the laboratory level has been
ages is the most promising and effective approach to extract
more lithium-ions from LiCoO2, equivalent to higher capacity
(Table 2). For instance, if charging to 4.5 V, the specific Table 2. Energy density of LiCoO2 at different cutoff voltage. Adapted
with permission.[27] Copyright 2018, Elsevier.
capacity and energy density can be increased to 185 mAh g−1
and 733.5 Wh kg−1, with the increase in ratios of 32.1% and Voltage (vs Li/Li+) 4.2 V 4.3 V 4.4 V 4.5 V 4.6 V
34.0%, respectively. Although Tarascon et al.[22] reported −1]
Capacity [mAh g 140 155 170 185 220
that 95% of lithium can be reinserted back to the structure
of completely delithiated LiCoO2, such behavior triggers the Average Voltage [V] 3.91 3.92 3.94 3.97 4.03
severe capacity fading with cycling. The failure mechanism Specific energy [Wh kg−1] 547.3 607.6 669.6 733.5 885.9
of LiCoO2 at high voltage (>4.2 V vs Li/Li+) has been widely Specific energy [Wh L −1] 2299 2552 2812 3081 3721
studied and great progress has been achieved. The key issues Increasing ratioa) 11% 10% 9.5% 21%
focus on the surface degradation, damages induced by detri-
mental phase transitions and inhomogeneous reactions. In a)Increasing ratio of energy density.
made through comodification strategies,[25a,26] it is still facing 2.1. Failure Induced by Bulk Phase Transition
several challenges, especially the long-cycling stability and
safety in the full cells. As shown in Figure 1a, the structure evolution as removing
Li from LixCoO2 is briefly divided into two different regions,
including 0.45 ≤ x ≤ 1 and x < 0.45. The structural changes
2. Failure Mechanisms of LiCoO2 at High in the region of 0.45 ≤ x ≤ 1 contain a solid solution reaction
process and three weak first-order phase transformations.[17a]
Cutoff Voltages
The first phase transformation at x = 0.93–0.75 is generally
The failure mechanisms of LiCoO2 under high-voltage opera- attributed to the electronic delocalization of LixCoO2.[31] The
tion have been widely investigated, which are summarized as structure in this region remains hexagonal structures, but its
follows: failure induced by bulk phase transition, surface deg- electronic property changes from semiconductive to metallic
radation, and inhomogeneous reaction mechanism. For the with the decrease of lithium concentration. The other two
bulk phase transition induced mechanism, complicated struc- phase-transition regions occur at nearly x = 0.5, undergoing
tural evolution and iterative volume change during Li+ deinter- hexagonal, monoclinic, and hexagonal phases in turn. The
calation/intercalation lead to the irreversible phase transition presence of the monoclinic phase transition was reported to
and particle cracks, and subsequently result in capacity loss. give rise to the structure damage, leading to capacity loss above
For surface issues, the impedance growth of LiCoO2 elec- 4.2 V.[32] However, Dahn suggested that the failure occurring
trodes under high-voltage operation is closely related to the at x > 0.4 is mainly due to the surface impedance growth and
surface degradation, including the continuous formation of can be effectively avoided by surface treatments.[29] Further
the cathode electrolyte interphase (CEI), irreversible surface removing Li from LixCoO2 (x < 0.45) causes phase transitions
phase transitions, O2 loss, and Co dissolution. The inhomo- from O3 to H1-3 and to O1 phase. H1-3 structure has been
geneous reaction mechanism indicates that the state of charge confirmed to be a hybrid of the O1 and O3 structures.[29] As
(SOC) at the different particles or different parts of a particle the structure transition from the O3 to H1-3, the shift of the
is inhomogeneous due to the differences in lithium diffusion OCoO slabs along with lithium rearrangement occurs,
dynamics. The inhomogeneous distribution of SOC leads to leading to internal stress generation and structure damage.
deformation and stress generation, which causes the frag- Moreover, Carlier et al. found that the initial Li/Co stoichiom-
mentation of electrodes and particles and subsequent capacity etry in LiCoO2 (1.00 ≤ Li/Co ≤ 1.05) influences the phase-tran-
loss.[28] sition process at high voltage (>4.5 V).[33] The deintercalation
Figure 1. a) The structure evolution of LiCoO2 with different delithiation. Reproduced with permission.[29] Copyright 2004, Elsevier. b) The cell parameter
changes with different delithiation. Reproduced with permission.[24] Copyright 1996, Elsevier. c) The TEM image of particle cycled after 50 cycles at a
voltage range of 2.7–4.7 V. d) The charge–discharge curve of LiCoO2/Li half-cell for the first 50 cycles in voltage of 2.7–4.7 V. Reproduced with permis-
sion.[30] Copyright 2019, The Royal Society of Chemistry.
process of Li1.00CoO2 is more complex and a new intermediate Li content. Besides, as suggested by Prof. Goodenough, per-
phase is detected between H1-3 and O1. Yan et al. con- oxide formation and O2 loss at the surface of LiCoO2 charged
ducted systematic investigations on the failure mechanisms to the high voltage also contributed to the irreversible struc-
of LiCoO2 over 4.7 V and suggested that the capacity loss is tural damage, which will be discussed in the following part.
mainly due to bulk structure degradation.[30] They found that It is seen that the structure change tends to much severer
the stripe-shaped O1 phase in the grain boundaries induced with deeper delithiation, especially over 4.5 V. Even though the
the irreversible structural changes upon high voltage cycling. huge capacity deterioration does not occur immediately after
Mechanical fractures (e.g., cracking) were also observed due completely removing Li from LiCoO2 as reported by Tarascon
to the anisotropic dimensional change of lattice parameters, et al.,[22] stress accumulation and structural damage associating
a and c, as shown in Figure 1b.[34] Lu et al. investigated the with iterative phase transitions, especially the monoclinic and
phase transitions, Li diffusion, and capacity fade properties of H1-3 structural changes at 4.2 and 4.55 V, respectively, induce
LiCoO2 thin film above 4.2 V.[35] Without interference from the particle cracks/pulverization, resulting in subsequent capacity
binder and conductive carbon that exist in conventional elec- decay (Figure 1c,d). For the phase transition of O3 to H1-3, par-
trodes, such thin-film electrode makes it possible to study the ticularly, large lattice (c-axes) and volume shrinkage have been
failure mechanisms very explicitly. The LiCoO2 film showed widely confirmed (Figure 1b), which tremendously increases
good capacity retention at a upper cutoff voltage of 4.5 V, but the risk of structural destruction. Therefore, to break through
it was observed that rapid capacity fade occurred when the the voltage limit of 4.5 V, it is critical to suppress the detri-
charge voltage was over 4.6 V. It was concluded that structural mental phase transitions and enhance the structural stability.
changes between 4.2 and 4.5 V did not account for the capacity
fade, but those between 4.5 and 4.7 V combined with the low Li
diffusivity probably leads to the capacity failure of LiCoO2. The 2.2. Surface Degradation
chemical diffusion coefficient of Li in LiCoO2 became smaller
as Li content decreased in the range of 0.14 < x < 0.4, which is Along with the structure evolution during (de)lithiation, the
attributed to the high activation barrier for Li hopping at a low surface structure and chemistry evolution of the electrode play
Figure 2. a) Charge–discharge curves of LiCoO2 for cycles 5 and 100. Reproduced with permission.[29] Copyright 2004, Elsevier. b) Schematic energy
diagram of LiCoO2 and its relative energy positions with respect to the HOMO and LUMO of electrolytes. Reproduced with permission.[23] Copyright
2013, American Chemical Society. c) The chemical composition of interface layer on LiCoO2 cathode at different charge and discharge states. d) The
CEI index of major CEI components. e) The composition of the SEI layer on Li anode. f) Schematic diagram of the formation of CEI. Reproduced with
permission.[42] Copyright 2018, Elsevier.
key roles in the electrochemical performance of LiCoO2, and organic compounds containing CO and CH bonds. Basing
have essential effects on the failure of LiCoO2.[36] As mentioned on quantitative XPS analysis, they suggested that the evolu-
above, Dahn et al. found that the impedance growth (Figure 2a) tion of the CEI layer can be due to the continuous reactions of
of LiCoO2 under high-voltage operation is closely associated electrolyte and physical migration of SEI fragments from the
with the surface structure and chemistry evolution, for example, lithium anode. They further found that in the LiCoO2/graphite
electrolyte decomposition and the formation of CEI, irrevers- battery, the CEI layer on LiCoO2 is not significantly changed
ible surface phase transitions, O2 loss, and Co dissolution.[29,37] because of the relatively stable SEI layer formed on graphite
As shown in Figure 2b, the working voltage of an LIB is lim- anode. Yan et al. also reported that the voltage fading of LiCoO2
ited by the “electrochemical window” of an electrolyte that is at high voltage is mainly caused by the retarding Li transporta-
determined by the energy gap between its lowest unoccupied tion of the CEI layer.[30] Although the CEI layer retards Li trans-
molecular orbitals and the highest occupied molecular orbitals portation and increases the surface impedance, it also hinders
(LUMO and HOMO). If the electrochemical potential µA of the continuous decomposition of electrolytes and suppresses
an anode is higher than the LUMO energy of the electrolyte, the formation of a space-charged layer on the cathode surface.
reductive reactions definitely happen unless inert domains so- Yan et al. further suggested that the decomposition of organic
called solid electrolyte interface (SEI) layers form on the anode electrolytes and the formation of CEI are inevitable as charging
and suppress the further reactions. Likewise, oxide reactions over 4.5 V, and further studies are need to develop the CEI
occur between a cathode and the electrolyte as long as the layers with high stability and ionic conductive.
cathodic potential µC locates under the HOMO energy. Such Surface phase transformation is another interfacial degra-
reactions could be hindered by electronic-insulated products on dation mechanism. The irreversible phase transformation is
the cathode so-called CEI layers. The electrolyte–electrode inter- observed on the deeply delithiated LiCoO2 surface as a result
faces play an important role in determining the electrochemical of phase degradation from layered to disordered spinel.[30]
properties of LIBs, especially the reversibility of Li+-intercala- The irreversible phase domain becomes thicker as increasing
tion chemistries and the kinetics of overall cell reactions.[38] the cycling voltage and cycle numbers. The domain of LiCoO2
In contrast to the SEI, the studies on the electrolyte decom- cycled in the voltage range of 2.7–4.4 V, for instance, grows
position on the cathode electrodes and the formation of CEI about twice thicker as the upper voltage is cut off at 4.55 V. In
are relatively scarce because organic electrolytes are thermody- addition, the irreversible domain increases from 6 nm at the
namically stable against most of the cathode electrodes. Prof. 1st cycle to 24 nm at the 10th cycle. Takamatsu et al.[43] reported
Goodnough first reported the formation of a polymeric film on that the surface Co3+ is reduced to Co2+ immediately as long
the surface of charged Li1−xCoO2 in 1985 although the compo- as LiCoO2 contacts with electrolytes. Charging to a high voltage
sitions of the surface layer were not confirmed.[39] Kanamura intensifies the local distortions at the surface of LiCoO2 that
et al. investigated the surface chemistry evolution of a LiCoO2 propagate to the interior subsequently. Besides, O2 release and
thin film by in situ Fourier transform infrared spectroscopy Co dissolution further promote the local structure damage and
and organic compounds with carboxylic groups were detected even form corrosion cavities at surfaces. Moreover, the Li-poor
on the surface.[40] Aurbach et al. have comprehensively studied phase at the surface of delithiated LiCoO2 leads to high activa-
the electrochemical behavior and surface chemistry of LiCoO2 at tion energy and vacancy ordering, resulting in low Li diffusivity
25, 45, and 60 °C.[41] They noticed that the material decay during and high surface impedance.[35] Lu et al. investigated the struc-
cycling is associated mostly with LiCoO2 surface degradation ture properties of LiCoO2 at different charging state by scan-
rather than the bulk structure destruction. A surface layer con- ning transmission electron microscopy (STEM). As shown in
taining LiF, polycarbonate s pecies, and ROCO2Li was observed Figure 3a–f, deep delithiation induces Co migrating to Li sites,
on the cycled LiCoO2 surface within LiPF6/alkyl-carbonate solu- leading to the formation of an incomplete rock-salt phase. Kik-
tions, which obviously gave rise to the growth of impedance on kawa et al. noticed that the electrochemical delithiation process
the electrode. The surface layer became thicker at elevated tem- leads to the inhomogeneous Li/Co distribution and Li-poor
perature and/or for a prolonged storage time, leading to larger phase formation at the surface (Figure 3g–i.).[44] CoO phase
electrode impedance. Moreover, they also suggested that the was observed at the topmost surface of Co3O4, and Li-inserted
surface chemistry of LiCoO2 electrode can be to a large extent Co3O4 were identified at the surface region. Moreover, they also
tuned with electrolyte additives that decompose on the electrode proposed that the Li deficiency is a crucial factor of the nano
surfaces (e.g., polymerization) to form stable and steady CEI crack formation in the charged LiCoO2. Recently, Seong et al.
layers. Zhang et al. performed a quantitative analysis on the systematically studied the intrinsic reversibility of LiCoO2 at
LiCoO2 electrode with X-ray photoelectron spectroscopy (XPS) high cutoff voltage (≥4.6 V). It seems that the main reason for
and detected the relative amounts of surface species at different the rapid capacity decay of LiCoO2 at high operating voltage is
states (Figure 2c–e). In Figure 2c, the red curve defines the the continuous formation of spinel phase surface layer.[45] In
boundary between CEI species and other surface species which particular, the resistive surface layer displays poor stability and
contribute to the XPS signals, demonstrating that the CEI com- can be easily etched as charging to 4.8 V. Accordingly, the for-
ponents changes with battery cycling. Figure 2d shows the rela- mation of resistive surface layer associated with the irreversible
tive change of CEI components during the discharge process surface phase changes is one of the key factors of rapid cycling
of LiCoO2 electrode, which is expressed quantitatively by the degradation of LiCoO2 at high cutoff voltage. It is worth noting
CEI index, that is, (discharge ratio–charge ratio)/charge ratio that the formation of resistive surface layer not only derives
× 100%. In addition, Figure 2e shows the main SEI compo- from the irreversible surface phase changes, but also relates to
nents on the fully charged anode, for example, Li2CO3, LiF, and the interaction with electrolytes.
Figure 3. a–f) STEM ABF images of cycled LiCoO2 at different state: a) pristine LiCoO2, b) Li0.85CoO2 (≈3.92 V), c) Li0.5CoO2 (≈4.18 V), d) Li0.91CoO2 (3.0 V),
e) Li0.7CoO2 (≈3.97 V), f) Li0.3CoO2 (4.5 V). Reproduced with permission.[46] Copyright 2019, American Chemical Society. g–i) Chemical and electronic
states at the surface region of 60% charged LiCoO2 particle: g) bright-field STEM image. h) Plot of x from A to A″ in (g). i) Schematic drawing of the
variation of chemical composition. Reproduced with permission.[44] Copyright 2015, American Chemical Society.
Oxygen loss is one of the key reasons to trigger structural on the anode if the voltage was increased to 4.5 V, indicating
degradation from surface to core and then induce thermal that there is a direct relationship between Co d issolution and
runaway issues of LiCoO2.[47] Prof. Goodenough et al. pointed capacity loss at a high voltage. Other researches also proved
out that the charging voltage of LiMO2-based cathode materials that cycling at high voltage induced surface corrosion and leads
is limited by the top of O 2p band because M 3d band over- to the Co dissolution of LiCoO2,[30] which interfered the inter-
laps with O 2p band which is determined by the high cova- face reactions on both electrodes.[57] In addition, the dissolution
lence of MO band,[1,23] for example CoO band in LiCoO2 results in active mass loss and retarded kinetics of the LiCoO2
(Figure 2b). Charging voltages higher than the limited voltage electrode due to the formation of resistive surface layers such
causes the oxidation of O2−, results in peroxide formation and as CEI layers, corrosion cavities, and Li-poor phases.[24]
O2 release from the surface of LiCoO2.[26,48] Various techniques In summary, the surface structure decay and chemistry evo-
have been used to probe the electronic structure of LiCoO2 so lution of the LiCoO2 electrode over 4.2 V significantly retard Li
as to understand the charge compensation behaviors, e.g. XPS transportation and thus increase its surface impedance, leading
and X-ray absorption spectroscopy (XAS). Delmas et al. inves- to its rapid capacity fading. When charging over 4.5 V, not
tigated the Li deintercalation process of LixCoO2 via XPS. The only is the decomposition of electrolyte rapidly aggravated due
results indicated that Co and O simultaneously undergo redox to the high potential, the concomitant highly active Co4+ and
reactions,[49] which is also confirmed by Soft XAS results of peroxide on LiCoO2 surface, but also severe surface structure
LiCoO2.[50] Recently, Long et al. observed that Co mainly con- decay along with O2 loss and Co dissolution propagates from
tributes to the charge transfer blow 4.4 V while it is only O that the surfaces into cores of LiCoO2 particles, leading to dramatic
compensates the charge above 4.4 V,[51] strongly supporting the capacity degradation quickly, even losing their function of Li-
model proposed by Prof. Goodenough et al. Moreover, local O intercalation in several cycles. To promote the cycling stability
2p holes were observed, which accounts for the origin of per- over 4.5 V, it must be considered to completely isolate the active
oxide or even O2 formation. O2 release from LiCoO2 was quan- LiCoO2 from the electrolytes (before cycling or at least after sev-
tified by the in situ differential electrochemical mass spectrom- eral cycles), enhance the surface structure stability, and entirely
etry (DEMS).[52] Although the O evolution process and the con- avoid O transport and O2 release.
tribution degree of O to the charge transfer is still in debate, it
has been validated that peroxide formation and O loss desta-
bilize the surface structure of LiCoO2 and even promote the 2.3. Inhomogeneous Reaction
irreversible phase of Li-poor spinel structure (Co3O4),[30] leading
to large surface impedance and capacity decay.[53] Furthermore, Aside from the issues originated from bulk phase change
partial oxidation of O reduces the covalence between Co and and surface degradation, the inhomogeneous reaction leads
O, leading to the formation of under-coordinated O and OO to the uneven distribution of the state of charge (SOC) at the
bonds that induce O2 release reaction at ≈200 °C, causing different particles and/or different parts of a particle, which
safety issues.[54] The O-related issues are also observed in causes gradual degradation of electrochemical performance
other layered structure oxides such as LiNiO2[55] and LiNi1/3C with cycling. Liu et al.[58] investigated the reaction mecha-
o1/3Mn1/3O2.[56] nism and electrochemical behavior of two LiCoO2 samples
Co dissolution is also associated with the capacity decay above with different particle sizes by in situ neutron diffraction tech-
4.2 V.[24] Tarascon et al. did not find Co at the anode side as a nique (Figure 4). The LiCoO2 with large particles displayed
LiCoO2 cell was charged to 4.2 V but confirmed Co deposition the inhomogeneous distribution of Li content due to sluggish
cycle lead to the particle inhomogeneity. It is worth noting that

the electrochemical behavior of the particle cannot be equiva-
lent to that of a whole-cell, for example, capacity retention. In
addition, the 3D chemical map of a recovered LiCoO2 particle
revealed cracks between the active and inactive domains, indi-
cating a close relationship between morphological defects and
uneven distribution of Li content.
Rational construction of LiCoO2 cathode with enhanced
growth of electrochemically active facets, i.e., {010}, is conducted
to promote Li-ion transportation and thus improve its rate capa-
bility. Density functional theory (DFT) calculation shows that the
electronic structures LiCoO2 are significantly different among its
facets due to altered spin states of surface Co3+ atoms.[60] The for-
mation of CEI is only observed at the LiCoO2 edge plane other
than at its (001) plane.[61] From crystallographic and microstruc-
tural viewpoints, the changes of the anisotropic lattice parameter
during Li+ removal/insertion result in anisotropic lattice strain
and mechanical degradation. The lattice strain usually intro-
duces (003) bulk stripe-defects and cracks in LiCoO2, especially
Figure 4. Representation of the delithiation mechanism of LiCoO2 with at high voltages with deep delithiation.[44,62]
different particle sizes. Reproduced with permission.[58] Copyright 2019, The inhomogeneous reaction at the different particles and/
Wiley-VCH. or different parts of a particle result in deformation and stress
accumulation. That can cause particle pulverization, electrode
Li diffusion, leading to a two-phase reaction mechanism and fracture, and loss of contact between active materials and cur-
poor rate performance. By comparison, the small particle size rent collects, leading to capacity degradation.
sample underwent a solid solution process and thus showed
better rate performance.
Xu et al. examined the cycling of a single LiCoO2 particle via 3. Modifications
the in situ transmission X-ray microscopy and measured the
charging states of each spot in the particle based on the ref- In order to overcome those aforementioned issues and cater the
erences of fully charged and discharged LiCoO2.[59] As shown long-cycling stability of LiCoO2 at high voltage, various strate-
in Figure 5, it can be seen from these mappings that the SOC gies such as element doping, surface coating, and comodifica-
distribution in the particle is inhomogeneous, especially at tion approaches, have been proposed.
high current rates. When discharged to 3 V, the portions of the
LiCoO2 particle is still at charged state (marked by red) instead
of fully discharged state (marked by green). It is noted that a 3.1. Element Doping
higher discharge current makes the green portion smaller. With
cycling at a low current, the recovery percentage of the par- Element doping significantly tunes the basic physical proper-
ticle rebounds to a higher level. Both high rate and long-term ties of materials, especially for the semiconductors, e.g., the
Figure 5. In situ monitoring of the chemical inhomogeneity in a single particle of LiCoO2 up to 20 cycles. The red area represents the domains at the
charged state, and the green area represents the domains at the discharged state. Reproduced with permission.[59] Copyright 2017, American Chemical
Society.
bandgap, cation ordering, charge distribution, and lattice para 200 cycles, 97% of its initial capacity retains, and its rate perfor-
meters. Likewise, doping various elements into electrode mate- mance is obviously improved. The higher lithium-ion mobility
rials improves their electromotive force, structure evolution, is observed during charge/discharge processes as a result of
cation redox, and electronic/ionic conductivity which are closely expansion of interslab distance.[69a] Recent results indicate that
associated with their electrochemical performance. Various only small amount of Ti (<0.15%) can be doped into LiCoO2
doping strategies in terms of doping elements, doping contents, lattice and most of them enrich on the surface/interface of
doping sites have been proposed and most of them were LiCoO2.[26,77] Al is one of the most attractive dopants due to
demonstrated to effectively improve the electrochemical perfor- strong AlO bond, similar valence and ionic radius with Co
mance of LiCoO2 at a high cutoff voltage. The potential effects of in LiCoO2. Ceder et al. first predicted theoretically and dem-
doping can be summarized as follow: 1) suppressing the phase onstrated experimentally that the Al doping is able to increase
transformations that reduces the generation of deformation the open-circuit voltage and working voltage of LiCoO2.[48a,69b]
and stress; 2) inhibiting the redox reactions of O to stabilize the Although the substitution of Co by Al decreases the capacity,
layer structure of LiCoO2; 3) increasing the interlayer spacing to it supresses the Co dissolution and enhances the structure sta-
facilitate the Li+ diffusion; 4) tuning the electronic structure to bility of LiCoO2.[78]
increase the electronic conductivity and working voltage. Mg-doped LiCoO2 was widely researched by several groups
Substitution of transition metal ions to form solid solution is due to its metallic and ceramic characters like high-melting-
the early strategy to improve the electrochemical properties of point, great electrical conductivity, low density, and good
LiCoO2 at high voltage since the LiMO2 family contains a series oxidation resistance. West and Tukamoto et al. reported that the
of isostructural compounds such as LiAlO2, LiNiO2, LiCrO2, exchange of Mg for Co can improve the electrical conductivity of
LiMnO2, and LiFeO2.[63] Some binary and ternary oxides of the primitive LiCoO2, and thus enhance its cycling performance.[79]
generic formula LiMO2 show interesting properties and appli- Effects of the doping content of Mg on the dielectric and wave
cations. A LiNiO2-LiCoO2 system is first recognized by Ohzuku absorbing properties of LiCoO2 were investigated by Yang
et al. and it exhibits the solid-solution behavior at any compo- et al.[80] When the x ≤ 0.11 (LiCo1−xMgxO2), the material pos-
sition because Co and Ni are able to share the same sites[64] sesses a single hexagonal phase with the R-3m space group.[81]
to comply with the rhombohedral crystal system. As for the When the x ≥ 0.13, the second phase of MgO gradually arises.
system, its OCV vary as a function of x in LixNi0.5Co0.5O2 fol- The interlayer spacing and electrical conductivity increase with
lowing a hyperbolic tangent curve rather than an S-shaped the Mg content in the samples. The enhanced electrical conduc-
Nernstian relation. The composition-dependent OCV curve tivity is ascribed to the increased carrier concentrations. Com-
together with the X-ray diffraction (XRD) results indicates that pared with XRD studies on 30 samples, lithium deficient and
the reaction proceeds in a homogeneous phase.[65] Tirado et al. lithium excess Mg2+-doped LiCoO2 were investigated by Dahn
prepared a solid solution of LiAlyCo1−yO2 with a widely com- et al.[82] The single-phase samples have pure lithium layers
positional interval.[66] Powder XRD reveals explicitly the partial without Mg content but transition metal layers with excess Li
substitution of Co by Al element with a fractional occupancy (if present), Mg, and Co based on analysis of atomic absorption
of tetracoordinate sites by aluminum atoms. However, the analysis and Rietveld refinements. AC impedance spectroscopy
slow Li-ion diffusivity due to the presence of Al in both tetra- demonstrates that the charge–discharge processes include two
hedral and octahedral sites makes a trouble for the applica- steps of partially desolvated Li+ adsorbing–desorbing on the
tion of LiAlyCo1−yO2 cathodes. Stemmed from those efforts, electrode surface and an electron insert-loss from the conduc-
the ternary NCM and NCA systems are developed and widely tion band with the diffusion of Li+ in the intercalation site of
deployed to the fields of EVs and energy storage systems. How- lattices. In summary, the Mg-doping can mainly improve the
ever, for those materials with low Co concentrations, their tap conductivity and affect the electrochemical and electronic prop-
densities and the related volumetric energy-densities are sacrifi- erties of LiCoO2.[83] Similar behavior of the electronic structures
cial. Therefore, highly volumetric energy batteries for 3C prod- of Mg-doped LiCoO2 was also demonstrated by Shi et al. using
ucts are still concentrated on LiCoO2 just with a small quantity the first-principle pseudopotential method.[84]
of doping elements. Ni element doping has been developed since 1993 now that
As doping elements are less than 10%, the high tap den- LiCoO2 and LiNiO2 have the same structure.[64c] Such study
sity of LiCoO2 is retained and its advantages are not sacrificed. mainly focus on the Ni-rich materials because Ni doping usu-
Doping into crystal lattice (LiMxCo1−xO2) is usually suggested to ally introduces undesirable cation mixing, which blocked the
achieve a solid solution that is isostructural with LiCoO2, but it lithium diffusion path. Recent research showed that Ni ele-
is not always required. The grain boundary doping has become ment doping reduces initial Coulomb efficiency and reversible
more and more important in recent years.[67] Extensive investi- capacity of LiCoO2.[85] However, a small amount of Ni doping
gations on cation doping using Mg,[68] Al,[69] Ti,[32] Cr,[70] Mn,[71] stabilizes the layer structure of LiCoO2, because some Ni atoms
Fe, Ni,[64c,72] Cu,[73] Zr,[70,74] Sb,[75] and W[76] are readily available. enter Li planes, and reinforce Li planes, Figure 6.[72,86] At the
Partial substitution has also been greatly effective on structural same time, such element doping reduces the charge transfer
stabilization, cycling stability, and thermal stability, even for impedance during charging–discharging so that the electrode
highly delithated LiCoO2. material has demonstrated better cyclic performance. On the
Doping of Zr, Al, and Ti significantly enhances both cycla- other hand, when Ni is doped too much, the structural stability
bility and rate performance especially at higher discharge cur- of LiCoO2 becomes poor, charge transfer impedance increases,
rent densities.[74] Even at a cut-off voltage of 4.5 V, Ti-doped and cyclic performance is deteriorated.[85] With different SOC,
LiCoO2 exhibits a quite high capacity of 205 mAh g−1.[32] After Choi et al. monitored the structure changes and the Ni-doped
Figure 6. a) The changing electrochemical reactivity comparison of LiCoO2, LiCo0.9Ni0.1O2, and LiNiO2 during the charging process. b) The combina-
tion of phase transition schematic diagram and retention of lattice parameter c. Reproduced with permission.[86] Copyright 2017, Wiley-VCH. c) The
structural fading schema of LiCoO2 and LiCoxNi1−xO2. Reproduced with permission.[72] Copyright 2020, Wiley-VCH.
derivatives by the entropymetry.[87] Lithium extraction gives a ical performance at a cutoff potential of 4.4 V. [73] In the case,
monotonic decline of entropy change (ΔS) based on progressive LiCoO2 surface doped by Cu2+ achieves a robust structure with
vacancy over Li sites, and the presence of a monoclinic inter- an excellent cyclability, a high Coulombic efficiency and high
mediate phase inverses the slope of the ΔS profile to reflect its reversible capacity, as shown in Figure 7. The modified LiCoO2
limited atomic configurations with high ordering. Furthermore, demonstrates good capacity retention at a high discharge cur-
Ni-doping decreases the ordering of the monoclinic phase, rent of 20 C as well as shows good cycling performance at high
decreasing the height amplitude of ΔS profile in the monoclinic testing temperature. The full cell, for instance, coupled with a
regime, suggesting that the increased disorder by Ni-doping graphite anode remains 90% of its initial capacity after 1000
can enhance the stability of the lattice framework, and extend cycles.
the cycle life with a high cutoff voltage of 4.6 V. In addition, multiple elements are doped simultaneously
Doping in the surface is another effective method.[73] Mun into LiCoO2 to synergize the performance enhancement of
et al. prepared an egg-shell structural LiCoO2 with a facile LiCoO2 electrodes.[21] Dahn et al. studied Mg/Mn co-doped
ion-exchange process that demonstrated good electrochem- LiCoO2 (LiCo1−2xMgxMnxO2 (0 ≤ x ≤ 0.05)) in virtue of in situ
Figure 7. a,b) Surface doping using an ion-exchange method. Reproduced with permission.[73] Copyright 2017, The Royal Society of Chemistry.
internal strain distribution, which leads to restricting the lattice

oxygen activity and ensures a stable surface charging to high
voltages. And the synergistically effects can availably improve
the electrochemical performance.
Besides metallic elements, doping nonmetals also shows
performance improvement in LiCoO2. Doped B and Si become
cations and interact with oxygen of LiCoO2. The bond energy of
BO (806(5) kJ mol−1) and SiO (798(8) kJ mol−1) are much
higher than most (transition) metal–oxygen bonds (e.g., MgO
(394(35) kJ mol−1), AlO (512(4) kJ mol−1), TiO (662(16)
kJ mol−1), CoO (368(21) kJ mol−1)),[89] which stabilizes the
structure of LiCoO2 during cycling, especially at its highly del-
ithiated state.[5] It is worth noting that Si doping increases the
conductivity and B takes an adverse role.[79] Chen et al. synthe-
sized Si-doped LiCoO2 through a coprecipitation method.[90] Si4+
ions occupy the Co sites and bring some Co3+ ions to Co2+ for
Figure 8. The phase transition of LiyCo(1−2x)MgxMnxO2−z with different
charge neutrality. Meanwhile, Si4+-ions lead to a lower imped-
Li content during the first and second charge–discharge process. ance and better capacity retention in the voltage of 2.8–4.5 V.
Reproduced under the terms of the Creative Commons Attribution B doping stabilizes the structure of LiCoO2 during cycling, and
4.0 license.[88] Copyright 2017, the Authors. Published by ECS. improve its electrochemical performance.[91] Julien et al. stated
that B3+-ions replaced Co3+-ions at the octahedral sites,[92]
XRD.[88] Results show that high Mg/Mn concentrations in and thus prevented the first-order structural transition associ-
LiCoO2 slightly lead to the high initial charge capacity following ated with Li0.5CoO2. However, due to greatly different radii of
a low discharge capacity, suggesting a low initial Columbic effi- B3+ and O2− (0.27 vs 1.4 Å), B3+ is unlikely to stabilize in Co3+
ciency (3.6–4.7 V). It is only 1% Mg/Mn that the doped LiCoO2 sites with BO6 octahedron but triangle BO3 group.[93]
demonstrates remarkably high cycling performance as a result Aside from cations doping, doping anions is another
of suppressing its impedance growth other than the phase tran- approach to modify the electrode materials.[94]Zhou et al.
sitions of O3-O6 (H1-3)-O1. Performance is observed different investigated halogen instead of oxygen of LiCoO2 by means
significantly in LiCoO2 and LiCo1−2xMgxMnxO2 with x = 0.05 of DFT calculations.[95] Results show that the halogen species
at 4.5 V and above. The former one undergoes the O3-O6(H1- enlarge the lithium slabs, which improves the lithium storage
3)-O1 phase transitions but the latter one demonstrates oxygen capacity, increases the lithium diffusion, and decreases the
evolution without such series of phase transitions (Figure 8). lattice and volume change during the (de)lithiation process.
Li et al. doped the La and Al elements into LiCoO2 concurrently Sun et al. reported that codoping of metal and F stabilizes
to deliver a more reversible capacity.[67] In the modified samples, the cycling performance, improves the rate capability and
the La ions distribution along c-axis to stabilize the structure thermal stability, stabilizes the surface, and suppresses Co
and phase transitions, and the Al ions as the center charged dissolution.[96]
positively to enhance the ions diffusion at the high voltage Aforementioned investigation indicates that DFT is an effec-
performance. The products display high reversible capacity of tive method to clarify the mechanism of element doping on
190 mAh g−1, excellent capacity retention of 96% after 50 cycles the structural stability, electronic state, electrode potential, and
and preeminent rate performance at a cutoff voltage of 4.5 V. Li diffusion of LiCoO 2 systems. The method could guide
The high structural stability during the electrochemical cycle the element selection for doping without complicated and
is due to the inhibition effect to H1-3 phase transition and the time-consumed experiments.[95,97] Hoang et al. reported their
elimination of ordered disorder state transition. first-principles studies of LiCoO2 lightly doped with (transition)
Zhang et al.[26] systematically investigated the effect of trace metal ions.[98] Results show that Al3+, Fe3+, and Mn4+ ions are
doping with Ti/Mg/Al (TMA) and demonstrated that trace favorable on the Co3+ sites, while Mg2+ and Ni3+/Ni2+ can occupy
doping is enough to significantly enhance the cycle and rate the Co3+ and/or Li+ sites depending on the synthesis condi-
performance of LiCoO2 at high voltage of 4.6 V with syner- tions. The lattice site preference, for example, is dependent
gistically effect (Figure 9a–c). Transmission X-ray microscopy on both the dopants’ charges and spin state which are coupled
results of the doped sample show that Al, Mg, and Ti are not strongly to the local lattice environment. The dopants’ solubility
uniformly distributed in the particles, as shown in Figure 10. and defect chemistry in LiCoO2 were calculated by Koyama
The results display that Mg and Al elements have been fully et al.[99] Results show that the valences of the dopants are the
doped into lattices, but for comparison even trace amounts of predominant factor for the occupation sites, whereas their ionic
Ti atoms cannot be completely doped into lattices. Among all, radii have a significant effect on the solubility. With simula-
both of Mg and Al can suppress harmful phase transition at tion, Ceder et al. investigated some nontransition metal-doped
above 4.5 V. Even in trace amounts, Ti segregates significantly LiCoO2 samples.[48a] Among them, aluminum substitution is
at grain boundaries and on the surface, modifying the micro- suggested to raise the cell voltage, increase the energy density,
structure of the particles while stabilizing the surface oxygen and reduce the cost of the material. Shi et al. showed that a
at high voltages, as shown in Figure 9d–h. This doping strategy rational amount of Mg-doping in LiCoO2 is helpful to enhance
can enhance the diffusion coefficient of Li+ and uniform the its electronic conductivity.[84] However, they also explained that
Figure 9. a) Cycle performance with bare LiCoO2 and TMA-LiCoO2. b,c) Charge–discharge curves for different cycles of b) bare LiCoO2 and
c) TMA-LiCoO2. d,e) O K-edge RIXS maps obtained in charged-state of d) bare LiCoO2 and e) TMA-LiCoO2 at 4.6 V. f) RIXS contrastive spectra in
different electrochemical states collected on bare LiCoO2 and TMA-LiCoO2. g) O 1s XPS spectra of bare LiCoO2 and TMA-LiCoO2 after 10 cycles.
h) Schemata of surface modification for LiCoO2. Reproduced with permission.[26] Copyright 2019, Springer Nature.
such doping shifts the Fermi level of LiCoO2 into its valence bility of LiCoO2 at high operating voltages. Up to now, there
band due to Co4+ concentration increasing. Overlapping of Co have been still some scientific issues that need to be further
3d and O 2p orbitals becomes more significant with the con- studied such as the doping effects on the oxygen redox and the
tent of Mg, implying high covalent feature. Although cation related electronic structure, the anion doping effects on the
mixing is usually suggested to deteriorate the lithium diffusion electrochemical performance.
in layered cathode materials.[100] Basing on the DFT calcula-
tion, Zhou et al. found that trace Ni atoms in the Li layers do
not severely block Li diffusion in LiCoO2 but act as pillars to 3.2. Surface Coating
support its layered structure, especially at its highly delithi-
ated states.[101] These results were further supported by experi- Surface coating is an effective method to protect the elec-
ments.[72,86,101,102] Zhou et al.’s calculation results showed that trode surface,[37,104] which i) optimizes the electrode surficial
the halogen species in oxygen sites enlarge the lithium slabs, structure; ii) promotes surface charge transfer; iii) reduces
improve the lithium storage capacity, increase the lithium dif- the acidity of electrolyte and suppresses the transition metal
fusion, and decrease the lattice and volume change during the ions dissolution, as HF scavenger; and iv) regulates interfa-
(de)lithiation process.[95] Ouyang et al.’s calculation found that cial response and enhances the kinetics as a physical barrier
the electrical conductivity can be improved upon Li+ doping in between the electrode surface and electrolyte surface.
Co3+ sites.[103] The cell volume expands with distance elongation Cho et al. triggered to coat Al2O3, LiMn2O4, and ZrO2 on the
between Li-doped CoO layers and contraction between adja- surface of LiCoO2.[105] After that, various oxides such as TiO2,[106]
cent Li layers. The structural stability can also be enhanced as ZnO,[107] B2O3,[108] Li4Ti5O12,[109] ZrO2,[110] BaTiO3,[111] metal fluo-
the volume expansion is suppressed upon Li-doping, and the ride,[112] and phosphate[113] were tried as coating layers to protect
average voltage increases. the electrode. However, the mechanism of surface coating has
Above all, doping is an effective approach to improve the not been fully understood as of today.
electrochemical performance of LiCoO2 in a wide voltage range. Al2O3 coating has been systematically studied for decades.[114]
Various dopants reveal distinctive features on tuning the per- In general, it is believed that Al2O3 coating on LiCoO2 is likely to
formance of LiCoO2. For example, Mg doping has been proved form LiAlO2 or LiAlxCo1−xO2 solid solution interphase layers by
to increase the electronic conductivity of host materials, while means of heat-treatment that are thought as kinds of artificial
Al doping has demonstrated effects on stabilizing structure and passivation layers to optimize surficial dynamics.[15,21] Recently,
suppressing Co dissolution. The doping sites also influence the Dogan et al. revealed that formation of the solid solution con-
structural stability of the material at highly delithiated states. sisting of Li, Al, Co, and O initiates at 400 °C on the surface
Mg or Ni substitution at Li sites can suppress phase transition of Al2O3-coated LiCoO2 and completes at 800 °C, Figure 11.[115]
due to the pillar effect. Therefore, Multiple doping strategy is Cui et al. further confirmed the mechanism by the atomic layer
a promising way to synergistically promote the structure sta- deposition with Al2O3 and ionically conductive LiAlO2.[116] The
Figure 10. 3D X-ray computed tomography reconstruction algorithms, element distribution, and volume distribution of TMA-LiCoO2. a–c) Fluores-
cence-yield scanning transmission X-ray microscopy collect 3D spatial distributions of a) Al, b) Co, and c) Ti. Scale bar: 1 µm. d–f) Element distribution
of d) Al, e) Co, and f) Ti. g) Visualized 3D graph of subdomain formation, which distinguish adjacent subdomains by different colors. h) Quantificating
the volume and surface area of different subdomains and the entire particle. i) Volume distribution of the whole subdomains and volume fraction of
each subdomain. Reproduced with permission.[26] Copyright 2019, Springer Nature.
Al2O3 coating shows great charge-transfer resistance during is important for Al2O3 coating process. Recently, Dahn et al.[117]
cycling and leads to poor electrochemical performance. In a predicted that Al2O3 coating layer reacts with LiPF6 in the elec-
commercial verification test at 4.6 V, LiAlO2-coated LiCoO2 trolyte spontaneously to form a kind of electrolyte additive,
delivers a high reversible capacity of 200 mAh g−1 and retains LiPO2F2. Likewise, MgO coating layer shows the same function.
high capacity after 50 cycles, confirming that the formation of Park et al.[118] investigated the internal structure of MgO-coated
LiAlO2 or LiAlxCo1−xO2 solid solution during high temperature LiCoO2 at the nanoscale, which explains the enhancement of
Figure 11. Schemes of the Al-coating layer evolution on particle surface of LiCoO2 at different annealing temperatures. Reproduced with permission.[115]
Copyright 2017, American Chemical Society.
electrochemical performance. Optimizing experiments on and fluorides surpass the limit and thus are promising as
sintering temperature showed that, the distribution of MgO coating materials for high voltage oxide cathodes. Specifi-
coating layers can be controlled by the heating tempera- cally, the AlPO4 coating has shown superior cycling perfor-
ture, which obviously affected the structural stability during mance.[122] The specific capacity and cycling retention of the
the electrochemical process at high voltage. It was 810 °C that the AlPO4-coated LiCoO2 is significantly affected by the con-
heat-treated powder showed a high doping degree of MgO and tent of AlPO4.[123] 1.0 wt% AlPO4 -coated LiCoO2 shows the
exhibited high capacity and retention. Meanwhile, no obvious best cycling stability. Compared with the bare LiCoO2, the
phase transitions happened on the powder surface, coating initial reversible capacity of the coated one increases from

layer or interface between them. 200 to 210 mAh g−1 with a cutoff voltage of 4.8 V, and remains a
As a coating material, Li1.2Mn0.6Ni0.2O2 with high electro- high capacity of ≈150 mAh g−1 after 50 cycles. Moreover, AlPO4-
chemical activity and stability is widely studied at high upper coated LiCoO2 presents attractive improvement on thermal
cutoff voltage of 4.8 V.[119] With the coating ratio increasing stability. In a charged state of 4.7 V, the onset temperature for
from 0.5 to 5.0 wt%, the Li1.2Mn0.6Ni0.2O2 layer gradually grows the electrolyte oxidation with AlPO4-coated LiCoO2 increases
thicker on the surface of LiCoO2 so as to effectively inhibit the from 187 to ≈220 °C, and the overall heat evolution reduces by
dissolution of Co-ions. Cycled in the voltage range of 3.0–4.5 V, a factor of 10 compared with the bare LiCoO2, which improves
appropriate content of Li1.2Mn0.6Ni0.2O2 facilitates LiCoO2 safety of the LIBs dramatically. Although short circuits occur at
having a high capacity retention. For example, with 3.0 wt% 12 V with a 3 C overcharging rate, the LIBs with the AlPO4-
of Li1.2Mn0.6Ni0.2O2 coating layer, LiCoO2 retains 95% of its nanoparticle-coated LiCoO2 does not exhibit any thermal run-
initial capacity in comparison with the bare LiCoO2 of 82.3% away.[124] Combining STEM and XPS studies, Shao-Horn et al.
after 100 cycles. However, much thicker layer degrades the rate suggested that the superior cycling and thermal properties
performance and increases the charge transfer resistance, indi- of AlPO4-coated LiCoO2 are attributed to the unique surface
cating that the coating layer obstacles Li+ intercalation through microstructure.[125] They showed that excess lithium carbonate
particle surface. In conclusion, the surface modification by the (Li2CO3) on bare LiCoO2 particles can react with AlPO4 nano-
Li1.2Mn0.6Ni0.2O2 is beneficial to enhance the electrochemical particles with the heat treatment at 700 °C and then form a
properties and structural stability at high voltages. rough or pitted surface microstructure along the edges of the
In addition, the interaction between the coating layer and coating layer. Finally, AlPO4 disappeares from the surface of
the electrode material plays important roles in promoting “AlPO4”-coated LiCoO2. In the meantime, Li3PO4 and LiCo1-
cycling life.[120] Guo et al. reported a facile approach to form yAlyO2 are observed on active particles. It was expected that
a spinel LiCoxMn2−xO4 coating layer on LiCoO2, as shown in both phases can highly resist Co dissolution and impedance
Figure 12.[34] Due to the same packing pattern of oxygen in growth during cycling at high voltages, which leads to better
those two materials, the in situ formed LiCoxMn2−xO4 coating cycling performance than that of bare LiCoO2. XPS observa-
layer shows better structural stability and compatibility with the tions have shown that the amount Li2CO3 on the surface is
LiCoO2 host. The stable interface between them provides an much less on AlPO4-coated LiCoO2. Moreover, conversion of
efficient pathway for the ionic and electronic migration during Li2CO3 to Li-ion conductor Li3PO4 and LiCo1−yAlyO2 on LiCoO2
cycling. The modified LiCoO2 delivers a significantly improved can highly reduce the resistance of lithium diffusion at the
capacity retention of 82.0% after 300 cycles at 4.5 V compared particle–electrolyte interface, which enhances rate capability
with the bare LiCoO2 of 15.5% capacity retention. In situ sur- remarkably. Furthermore, it is expected that the presence of
face phosphorylation is also applied to improve the cycle per- electrochemically stable and lithium-conducting phases on the
formance of LiCoO2, due to the high stability of phosphates.[113] electrode surface may reduce the overpotential of LixCoO2 and
The modified LiCoO2 shows a long cycle life with a capacity enhance the thermal property of LixCoO2 at high voltages. In
retention of 81% after 500 long-term cycles. addition, AlPO4-coating layer facilitates the formation of metal
4.5 V versus Li/Li+ is considered to be the upper limit fluorides due to the reaction with electrolyte, which can play a
for stable oxides.[121] However, quite stable phosphates role in stabilizing the surface as a passivation film and protect
Figure 12. a) The schemes of the in-situ LiCoxMn2−xO4 coating process on LiCoO2, and the b) cycle and c) rate performance of bare and LiCoxMn2−xO4-
coated LiCoO2. Reproduced with permission.[34] Copyright 2018, American Chemical Society.
LiCoO2 from continuous degradation during long-term cycling Shahbazian-Yassar et al.[130] proposed a method to restrain
in both LiPF6 and LiClO4 liquid electrolytes.[126] oxygen release from LiCoO2 by surface coating with a thin
Charge transfer process is the rate-determining step of the layer of reduced graphene oxide (rGO). DEMS results reveal
charge/discharge reaction. Nevertheless, most metal oxides that oxygen release is significantly suppressed after LiCoO2
such as Al2O3 and MgO, are not Li-ion conductors which a leads is coated by rGO (Figure 13). Further, thermal analysis and in
to high interfacial resistance between the cathode and electro- situ heating STEM and electron energy loss spectroscopy com-
lyte. Thus, surface modification with a Li-ion conductor displays bining with ab initio molecular dynamics calculations demon-
its unique advantages. Among various Li-ion conductors such strate that the rGO layers could hinder the oxygen release effec-
as, Li2ZrO3[127] and NASICON-type Li1+xAlxTi2−x(PO4)3 (LATP) tively as a result of the strong COcathode bond formation at the
with high ionic conductivity and low cost have attracted a lot of interface of rGO/LiCoO2 where low coordination oxygens exist.
attention. The charge transfer resistance, Rct, of Li2ZrO3-coated Besides exerting coating layers onto a single electrode par-
LiCoO2 remains almost constant during cycling but that of the ticle, the coating method can be applied to the whole elec-
bare LiCoO2 rapidly increases even at the first charge. The acti- trode.[109,131] Magnetron sputtering (MS) is a newly developed
vation energy of charge transfer is lower for the Li2ZrO3-coated coating method, and coats materials onto the outermost layer of
LiCoO2 electrode compared with the bare LiCoO2. Morimoto the electrode. For the general particle-surface-coating method
et al. prepared the LATP-coated LiCoO2 through the mechanical as discussed above, every single electrode particle is uniformly
milling approach.[128] Although the large particles of LATP are coated, as shown in Figure 14. By contrast, MS-coating modi-
only distributed on the surface of LiCoO2 rather than generate a fies only the top surface of the electrode while does not affect
continuous layer, the LATP-coated LiCoO2 shows high capacity the interior electrode, and thus minimizes the impact on the
and cycling performance at 4.5 V. In order to achieve uniform electronic conductivity of interparticles. Furthermore, for MS
coating layer, Yu et al. adopted a facile solution-based method to coating, the annealing step is required to transfer precursor
prepare the LATP-coated LiCoO2.[27] to desired coating materials. Such a step is indispensable for
Carbon coating was proved by Cao et al. to reduce charge wet-chemical coating methods. Recently, with MS-coating

transfer resistance and improve the rate capability of LiCoO2.[129] technology, ZnO, TiO2, Li4Ti5O12, Li2CO3, and Al-doped ZnO
Figure 13. a) High-resolution TEM image of an rGO/LiCoO2. b) Raman spectrum of the bare and rGO/LiCoO2 sample. c) XPS scan from C 1s.
d,e) Voltage profile of d) bare LiCoO2 e) and rGO/LiCoO2 cycled at 3.3–4.8 V. f) Differential electrochemical mass spectroscopy (DEMS) results of the
bare and rGO/LiCoO2 during CV measurement. Reproduced with permission.[130] Copyright 2019, Wiley-VCH.
(AZO) have been sputtered onto LiCoO2 electrodes to enhance retention after 20 cycles at 1 C is much lower than that in the
their electrochemical performance at high voltages.[109,131,132] bare sample.[124b]
However, the mechanisms of surface coating are not always In recent years, high-throughput simulations triggered by
accepted by scientists, Delmas et al. showed that the stoichi- large materials databases have been applied to the design and
ometry of LiCoO2 also impacts its electrochemical perfor- development of surface coating materials for LiCoO2.[121,135]
mance. During the synthesis, excess lithium sources balance Wolverton et al. provided a high-throughput thermochem-
the volatilization of lithium within the annealing process, and ical framework to modify coating materials of the cathode
occupy the sites in Co-layers of LiCoO2, which deteriorates the for LIBs.[135] The framework based on high-throughput DFT
performance of synthesized LiCoO2. By carefully controlling describes thermodynamic and electrochemical stabilities
the s ynthesis condition, Delmas et al. have reported the really (Figure 15a), and acid-scavenging capabilities of surface-
stoichiometric Li1CoO2[133] that exhibits better reversibility and coating materials for cathodes. After sifting through over
a high initial Coulombic efficiency of 97%. As a result, they 130 000 oxygen-bearing materials, they suggested some phys-
suggested that the main beneficial effect from such coating is ical and hydrofluoric-acid barrier coating materials, such as
simply to render the LiCoO2 very stoichiometric by inducing LiAl5O8, WO3, and ZrP2O7 and hydrofluoric-acid scavengers
the rapid loss of excess Li2O at a moderate temperature.[133] such as Sc2O3, Li3NbO4, LiBO2, Mg3(BO3)2 Li2CaGeO4, and
Dahn et al. suggested that the impedance growth in the battery Li2MgSiO4. Through a design strategy to ascertain the ther-
is the key reason for the failure of LiCoO2 cycled to 4.5 V.[29] The modynamically optimal coating materials, the hydrofluoric-
impedance mainly resulted from the surface impurities (e.g., acid scavengers such as Li2CaSiO4, Li2SrSiO4, and CaIn2O4 are
Li2CO3), which is detrimental to capacity retention, may have further selected for the layered LiCoO2. These coating mate-
formed on the surface of LiCoO2 during storage. In considera- rials can increase the cycle life of cathodes of LIBs, and show
tion of the fact that LiCoO2 samples are commonly stored in air, the superior performance to conventional coating materials
the surface degradation may result from the adsorption of mois- such as Al2O3, MgO, ZnO, and ZrO2. A comprehensive and
ture and the related surface reactions. Meanwhile, Dahn et al. systematic understanding of the interaction between the
showed that heat treatment or grinding could clean the surface coating materials and cathodes is important to find stable
and thus obtain excellent capacity retention.[29,134]However, the surface coating materials. With thermodynamic analysis,
surface coating is not always effective. For example, although Mo et al. demonstrated that the drastic reactivity of lithiated
P2O5-coated LiCoO2 shows a similar initial capacity at a low and delithiated cathodes largely restricts the possible coating
current density to the AlPO4-coated sample, the capacity
materials which can maintain stability with the cathode
Figure 14. Illustration of a) the “powder-coating” approach, b) “electrode-coating” approach, and c) sputter machine method. d) Illustration of the
changes of the electrodes coated by different ways before and after electrochemical cycling. Reproduced with permission.[109] Copyright 2016, American
Chemical Society.
under high-voltage cycling, as shown in Figure 15b–d.[121] The solid solution layer, usually introduced by the high-tem-
They expected several novel stable materials, lithium phos- perature annealing process, between the coating layer and
phates, and lithium ternary fluorides, which have high oxida- LiCoO2 host may play an important role in the lithium-ion
tion limits. They suggested these new and stable solid-state transfer process, and it is still lack of deep investigations and
materials have the potential to be stable with high-voltage understanding. In addition, co-coating research is still limited.
cathodes. For example, lithium-ion conductor and electron mixed con-
Above all, coating constructs a protective layer to prevent ductor co-coating is suggested to benefit both the lithium-ion
the direct contact between the LiCoO2 and electrolytes. It pro- and electron conductivity of LiCoO2. The relationship between
tects the electrode surface which is usually the start point of the coating effect and the integrity of the coverage should be
the failure process. Although the coating method is properly carefully researched. The debates on whether island coating or
effective in some cases to improve the electrochemical perfor- even coating is more effective, have existed for a long time. It
mance of LiCoO2, some issues still need to be further studied. should be well answered.
Figure 15. a) The flowchart of the high-throughput coating design framework. Reproduced with permission. b) The schematic compares the operating
voltage window of a cathode to charge and discharge potentials (that is, Ec and Ed, respectively) of an electrochemically stable coating. Reproduced
under the terms of the Creative Commons Attribution 4.0 license.[135] Copyright 2016, the Authors. Published by Springer Nature. c–e) Thermodynamic
analysis of the stability between cathode and contacting materials. Reproduced with permission.[121] Copyright 2019, American Chemical Society.
3.3. Multiple Strategies on Material Modifications addition, the long-term cycle capacity of a comodified LiCoO2/
MCMB cell is significantly improved even at a high tempera-
Element doping and surface coating both improve the elec- ture of 60 °C. By studying the phase transition and interface
trochemical performance of LiCoO2 while they show dif- characteristics of cycled LiCoO2, the synergistic effect of the
ferent mechanisms. Efforts have been taken to combine these bifunctional self-stabilized strategy is demonstrated on struc-
two strategies to build a better LiCoO2 cathode. Lu et al. pro- tural reversibility and interfacial stability. Yao et al.[25c] devel-
posed a class of ternary lithium, aluminum, fluorine-mod- oped a facile blow-spinning synthetic method to achieve Mn/
ified method to enhance the cycling stability of LiCoO2 at La codoping and uniform Li-Ti-O coating of LiCoO2 particles
4.6 V (Figure 16a–d),[25a] which reduces the direct contact area simultaneously. They explained that the Mn and La codoping
between liquid electrolytes and LiCoO2 particles and decreases improves the structural stability and increase the lithium-
the dissolution of active cobalt. It also generates a thin doping ion diffusivity of the LiCoO2 host, and the Ti-based coating
layer containing a Li-Al-Co-O-F solid solution which suppresses stabilizes the interface of LiCoO2 particles. As a result, the
the phase transition of LiCoO2 as charging to 4.6 V. Cui et al. comodified LiCoO2 cathode displays much better rate capa-
used a dual-function self-stabilizing strategy with the Al + Ti bility and cycling stability compared with previously reported
bulk codoping and gradient surface Mg doping to enhance LiCoO2 cathodes. Yu et al. introduced a double-layer struc-
the LiCoO2 at 4.6 V, as shown in Figure 16e–j.[25b] Co-modified ture Li1.6Mg1.6Sn2.8O8 to protect Mg-doped LiCoO2 and sup-
LiCoO2 modified by the dual-function self-stabilization strategy press the structure change.[25e] With a simple surface coating
shows an initial discharge capacity of 224.9 mAh g−1, a specific of SnO2 following high-temperature treatment, the interdif-
capacity as high as 142 mAh g−1 even at 10 C and a capacity fusion of Mg2+ and Li+ promotes to generate double-layer
retention rate of 78% after 200 cycles between 3.0 and 4.6 V. In Li1.6Mg1.6Sn2.8O8. At the same time, Co3+ in LiCoO2 is partly
Figure 16. a–d) Cycle and rate performance of bare and LAF-LiCoO2. Reproduced under the terms of the Creative Commons Attribution 4.0 license.[25a]
Copyright 2018, the Authors. Published by Springer Nature. e–j) Electrochemical performance of BLiCoO2 and CMLiCoO2. Reproduced under the terms
of the Creative Commons Attribution 4.0 license.[25b] Copyright 2019, the Authors. Published by Wiley-VCH.
xidized to improve the electronic conductivity. Those treat-

o Suberonitrile (SUN) and lithium bis(oxalate)borate (LiBOB)
ments significantly enhance the capacity retention and rate are applied as binary additives.[138] LiBOB is oxidized before the
capability. decomposition of the reference electrolyte. SUN with a higher
oxidization potential provides better electrolyte stability at the
higher potentials. The electrochemical performance of LiCoO2
3.4. Electrolyte Optimizing is enhanced significantly in the electrolyte with binary additives,
with a capacity retention of 62% after 500 cycles. The improve-
As mentioned, the electrolyte property closely influences the ment is suggested to be resulted from the unique influence
surface stability, thermal stability, cobalt dissolution, and the on the structure and composition of the CEI on LiCoO2. Other
kinetics of Li-ion transfer at the electrode/electrolyte inter- organic molecules, such as diphenyl diselenide (DPDS),[139]
face.[136] Much work has been done to enhance the electrolyte thiophene,[140] phosphonate-functionalized ionic liquid,[141]
compatibility with HV-LiCoO2, based on the perspective of addi- di(methylsulfonyl) ethane,[142] lithium difluoro(oxalato)borate
tives, solvents, and lithium salts. (LiDFOB),[143] 4-propyl-[1,3,2]dioxathiolane-2,2-dioxide,[144] fuma-
Multitudinous electrolyte additives have been developed to ronitrile,[145] and succinic anhydride are also developed as CEI-
protect the interface and thus improve the cyclic stability of forming additives.[146] Inorganic nano-Al2O3 particles are also
HV-LiCoO2. Vinylene carbonate (VC) is a commonly used and applied as electrolyte additives.[147] The electrochemical and
effective surface film forming additive to improve the electro- thermal performance of commercial LiCoO2 is improved by
chemical performance of LiCoO2.[137] Koyama et al. showed that soaking nano-Al2O3 in LiPF6/EC/dimethyl carbonate (DMC)
the interfacial resistance can be effectively decreased in the VC- electrolyte. Wang et al. suggested that the improvement is
added electrolyte, as shown in Figure 17a. The electronic struc- attributed to corrosion of the solid superacids AlF3/Al2O3 and
ture at the electrode/electrolyte interface was also investigated AlF3/Li3AlF6 from the reaction between Al2O3 and HF/PF5 in
to elucidate the mechanism underlying the cyclability improve- the electrolyte. Further work by Dahn suggested that the sponta-
ment using in situ total-reflection fluorescence X-ray absorp- neous reaction of the LiPF6 electrolyte salt with Al2O3 produces
tion spectroscopy, as shown in Figure 17b. Results indicate that LiPO2F2, a well-known electrolyte additive.[117] The LiPO2F2 fur-
the reduction and irreversible change in the electronic structure ther improves the electrochemical performance.
of Co ions at the surface of LiCoO2 are suppressed by the VC Although carbonates are the mostly used electrolyte sol-
additive, during the soaking and successive charge/discharge vents, their oxidation and decomposition occur at high voltage
processes, as shown in Figure 17c.[137b] of > 4.5 V. Nitriles have attracted great interest as high-voltage
Figure 17. a) The interfacial resistance changes with the VC-free and the VC-added electrolyte. b) The absorption energy shifts of the Co K edge surface
XANES spectra during soaking and charge/discharge processes with the VC-free and VC-added electrolytes. c) the schematic diagram of the mechanism
of VC in the electrolyte. Reproduced with permission.[137b] Copyright 2015, American Chemical Society.
electrolyte solvents due to their wide electrochemical window. created an additive library of 7381 structures, containing high-
Cui et al. reported a dual-anion deep eutectic solution (D-DES) throughput quantum chemistry calculations of the HOMO and
based on an elaborately selected combination of nitrile, LUMO energies, vertical ionization potentials, electron affini-
LiDFOB, and LiTFSI.[148] The interactions of succinonitrile ties, and chemical hardness of these structures.[151] The calcula-
with cation/anion endow D-DES with excellent ionic conduc- tions were carried out using the PM3 semiempirical method.
tivity and significantly reactions interface stability. The capacity This additives library is an effective tool to accelerate the
retention of LiCoO2|Li cell is over 70% for 500 cycles with a screening and optimization of electrolyte additives through a
high cutoff voltage of 4.7 V. Succinonitrile, as an electrolyte sol- given chemical design space. Jiang et al. examined the effect of
vent, combining LiDFOB as salt, can stabilize the interface of multiple functionalization on sulfone’s oxidation potential.[152]
LiCoO2 and suppress the cathodic interfacial reaction.[149] Com- They computed oxidation potentials for a series of sulfone-
prehensive modification strategy based on the solvent, additive, based molecules functionalized with fluorine, cyano, ester, and
and lithium salt was reported by Zhao et al.[150] Fluoroethylene carbonate groups using a quantum chemistry method within a
carbonate (FEC) with higher ionic conductivity and oxidative continuum solvation model. Zhao et al. designed an effective
stability was used to replace ethylene carbonate along with type of high-voltage electrolyte based on the guidance of theo-
1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (HFE) retical calculations combined with the advantages of different
added to obtain a trisolvent electrolyte system of 1.2 m LiPF6 solvents.[153] The electrolyte is composed of fluoroethylene
in FEC/dimethyl carbonate/HFE (1:1:1 by volume). In addition, dipropyl ether which is excellent in antioxidation and antireduc-
0.15 m LiDFOB was added as a film-forming additive to further tion, FEC which is excellent in antioxidation and has a better
stabilize both the cathode and anode. The new electrolyte ena- film forming property on the negative electrode surface, the
bles LiCoO2|Li batteries to maintain nearly 84% capacity after dimethyl sulfone (DMSO2) which preferentially oxidizes on the
300 cycles when charged to 4.5 V under the current density of cathode electrode and participates in CEI formation, and the
200 mA g−1. low-viscosity DMC as a solvent. This designed electrolyte can
High-throughput calculations are applied to screen new elec- not only greatly improve the cycle performance of LiCoO2|Li
trolyte additives. To discover electrolyte additives, Halls et al. cell at 4.55 V but also has a good compatibility with graphite
anode. Compared with the conventional electrolyte, by use of as separators to enhance the electrochemical performance and
the designed electrolyte, the capacity retention rate increases thermal stability of LIBs.[161]
from the original 38.1% up to 87.1% after 300 cycles, and the Polyvinylidene fluoride (PVDF) is the most widely used
capacity retention rate is also effectively promoted from 21.0% binder for LiCoO2 electrode fabrication. Its molecular weights
to 74.9% after 300 cycles. The experimental results show that influence its adhesion properties. As the molecular weight
use of this electrolyte can effectively inhibit the dissolution of increases, the adhesion strength not only in the electrode
transition metal ions from LiCoO2 materials, thereby ensuring composite, but also at the electrode/current collector interface
the structural stability of the cathode material and greatly increases.[162] The LiCoO2 electrode with a PVDF binder of high
improving the electrochemical performance. molecular weight (1 000 000) shows better electrochemical per-
Besides, aqueous electrolytes,[154] liquid-crystalline electro- formance during cycling tests even at 60 °C.
lytes,[155] and solid-state electrolytes[156] are also developed to Aluminum foils are commonly employed as current collec-
increase the electrochemical performance of HV-LiCoO2. tors for cathode electrodes in LIBs. Numerous strategies are
Above all, the high flammability and low stability at high- focused on the structural modification to increase the adhe-
voltage of nonaqueous electrolytes are big challenges for the sion between the electrode and the current collectors. Yang
application of HV-LiCoO2. Optimizing electrolyte formulations et al. coupled Al collector with chemical vapor deposition-
and developing new additives can effectively tune the electrode/ grown large-area three-layered graphene.[163] The graphene-
electrolyte interface property. Unfortunately, some candidate induced adhesion strength between the current collector
additives, solvents, and lithium salts are usually much expen- and the active materials contributes to the high mechanical
sive compared to the commercially used ones. Some of them strength of the electrode itself and high density of electrical
do still not match well with graphite anode which is the most path within the electrode, which facilitates effective electron
widely used anode material. Further works on the electrolyte transfer and affords the ability to withstand mechanical stress
modification are still needed. arising from the volume change of active materials during
the charge/discharge process. Moreover, the graphene layers
protect the underlying current collectors from corrosion and
3.5. Other Strategies greatly improved the thermal conductivity; they also improved
the safety of the energy-storage devices. Crater-like architec-
Apart from the LiCoO2 particles and electrolytes, separators, tural aluminum foil was prepared by a simple chemical etching
binders, current collectors, and conductive additives are also method with NaOH-based solutions.[164] It is electrochemically
important components that influence the electron transport in stable as the current collector, in contact with other cell
the electrodes and efficiently bridge the internal and external components during the cycling processes. The improved elec-
circuits. trochemical performance is attributed to the good electrical
For nonaqueous LIBs, separators prevent the physical con- contact between cathode material particles and the current
tact of the cathode and anode, and support free Li+ transport collector, which results in efficient electron transfer. He et al.
in the cell. The currently most used separators in LIBs are designed a carbonized melamine formaldehyde foam as a
microporous polyolefin membranes for their excellent mechan- cheap and lightweight current collector and studied its elec-
ical strength and chemical stability. However, their thermal trochemical performance in a Si-LiCoO2 full-cell.[165] The self-
shrinkage at high temperatures usually causes internal short- supported cell assemble strategy is beneficial to improve the
circuit in case of unusual heat generation. To increase the energy density of the whole cell. The energy density of the
thermal stability and cycling performance of LIBs, Kim et al. Si/LiCoO2 full cell achieves 479.5 Wh kg−1 which is obviously
developed a ceramic-coated separator by coating the sides of a higher than that in conventional LIB systems.
porous polyethylene membrane with nanosized Al2O3 powder Various kinds of carbon, including Super P, hollow carbon
and hydrophilic poly(lithium 4-styrenesulfonate) binder.[157] nanospheres,[166] multiwalled carbon nanotubes (CNTs), and
The modified separator exhibits an improved thermal stability graphene,[167] are employed as conductive additives for LIBs.
at high temperatures without significant thermal shrinkage, The effects of different assemblies of Super P, CNTs and gra-
and the cycle performance of LiCoO2|graphite full cell is phene as hybrid conductive additives on the rate performance
improved. In recent years, ceramic-coated separators are widely and cyclic stability of LiCoO2 were systematically investigated
researched,[158] and some new concepts of separators are also by Zou et al.[168] Results indicated that adding graphene, CNTs
developed. Cui et al developed a sponge-like polysulfonamide/ or mixture of them into the conventional Super P conduc-
SiO2 composite membrane as a novel separator of LIBs.[159] It tive agent is effective to reduce the overall mass ratio of the
processes higher porosity, ionic conductivity, thermal stability carbonaceous conductive additives in the LiCoO2 electrode and
and flame retarding ability, and can ensure LiCoO2|Li half-cells improve its rate performance and cycle stability. Yang et al. sys-
work at a high temperature of 90 °C. Goodenough et al. devel- tematically investigated the effects of the graphene nanosheet
oped a low-cost self-assembly SiO2 layer by spray-deposited onto (GN) on the performance of the microsized LiCoO2 cathode.[169]
an electrode surface which can act as a separator.[160] The LIBs Li-ion diffusion hindering effect was not observed in the micro-
with a LiCoO2 cathode show similar performance to batteries sized LiCoO2 electrode system, even with a high loading den-
with a traditional polypropylene separator and improved cycla- sity of 10 mg cm−2. They developed a binary conductive additive
bility with a reduced volume of liquid electrolyte owing to the composed of SP and GN which are responsible for constructing
electrolyte wetting properties of the SiO2 nanoparticles. Electro- short-range and long-range conductive networks, respec-
spun PTFE nanofiber and other polymer films are also studied tively. Only 0.2 wt% GN together with 1% SP can construct
an excellent conductive network, and the battery presents out- breakthrough until 2013 when the second-generation LiCoO2-
standing cycle and rate performance, even better than the com- based LIBs with a cutoff voltage of 4.35 V was launched into the
mercially available battery containing 3 wt% SP. Huang et al. market by several battery companies including ATL. It was only
reported the investigation of surface coating with 2–3 nm of 1 year later that the third-generation LiCoO2-based LIBs were
Al2O3, TiO2 , and Ta2O5 oxides on Super P carbon black via assembled with a higher cutoff voltage of 4.4 V. ATL was one of
atomic layer deposition.[170] Ta2O5 acts as an HF barrier which the pioneers to commercialize such batteries and became one
mitigates the oxidation of electrolyte on the surface of Super P of the global leading companies in the production of recharge-
at high working voltage. able LIB cells, packs, and system integration thanks to its
In summary, the major issue related to HV-LiCoO2 is the strict and effective control for quality and safety of high energy/
serious capacity loss during cycling, resulting from the struc- power batteries. As of today, it has been one of the world’s top
tural instability of the Li1−xCoO2 at highly delithiated state and suppliers of consumer polymer LIBs. The LiCoO2-based LIBs
the accompanying Co dissolution, decomposition of the elec- used in smartphone and tablet is one of its core products which
trolytes. Much work has verified that stabilizing the electrolyte/ are mainly supplied to the top tiers of mobile giants over the
electrode interface and preventing the side reactions between world. Now, ATL is ready to release a new generation of LiCoO2-
the electrode and electrolyte through the element doping, sur- based LIBs with a further higher energy density. In other
face coating, electrolyte optimizing, and other strategies can words, such LiCoO2-based LIBs demonstrate higher voltage
improve the electrochemical performance of HV-LiCoO2 at a and capacity compared with precedents. Although the huge
high cutoff voltage of 4.5 or 4.55 V. However, when increasing progress has been achieved in LIBs, it is still hard to catch up
the cutoff voltage up to 4.6 V, bulk modification method must with the devouring requirement of electronic devices in long
be applied to stabilize the bulk structure and suppress or time operation, fast charge, and high power. Therefore, we are
weaken the O3 to H1-3 or O1 phase transformation which sig- still confronting big challenges to improve the performance of
nificantly changes the oxygen framework and distorts the struc- LiCoO2-based LIBs.
ture. With the development of simulation methods and compu-
tation power, especially after combining with high-throughput
strategy and data science, the theoretical investigations on HV- 4.1. Development of Commercial LiCoO2-Based LIBs
LiCoO2 has become indispensable.
LiCoO2 cathode material has been mainly used in pouch cells
for electronic devices such as smartphones, tablets, ultrathin
4. The History of LiCoO2-Based LIBs portable PCs, and drones. A typical pouch cell composed of
cathode, anode, electrolyte, separators, packing foil, tab, etc.,
in the Industry
is shown in Figure 18. All battery companies are striving for
LiCoO2 was recognized as a promising cathode material by a high energy density of LiCoO2-based LIBs in the portable
Goodenough in 1980.[2,12] Then it was successfully assembled field and acquiring a balance among high energy density, fast
into a practical lithium-ion battery in 1991 by the Sony Corpo- charge, high safety, and low cost. Up to now, the improvement
ration. The LiCoO2 cathode material for LIBs possessed a low of commercial LiCoO2-based LIBs has been ascribed to two cat-
upper cutoff voltage (4.2 V vs graphite) and a low reversible egories: the optimization of cell components (active and inac-
capacity of 137 mAh g−1, indicating a low energy density (Energy = tive materials) and the cell configurations. For the optimization
voltage × capacity). Many efforts were taken to improve the of cell components, the first method is to pair up superior
performance of LiCoO2, but there was no any significant cathode and anode materials with high capacities and proper
Figure 18. The structure composition of LiCoO2-based pouch cells in industry.
voltages so as to reach high energy of LIBs. In consideration for LiCoO2 reported in research papers, the effective tech-
of the volumetric energy density, high energy should be real- nologies in industry have been confirmed to be only Al, Mg,
ized in a certain volume. For example, the compacted density Ti doping, and Al2O3 coating for the overall considerations of
of electrode needs to be enhanced and the ratios of active mate- capacity improvement, doping, and coating homogeneity, cost,
rials in cathodes and anodes are increased. In order to provide and safety. Especially, particle size distribution is very vital to
more effective space for active materials, the thicknesses of improve the volumetric energy density of cells because high
separator and current collectors become thinner and thinner in compacted density of electrode could be achieved.
the pouch cells. However, it is worth noting that aggressively As of now, LiCoO2 cathode material has been rapidly
modifying the inactive components brings up many unex- improved by means of different technology routes as illus-
pected safety issues in cells. Some cell incidents have been seen trated in Figure 19. In the early days, the upper cutoff voltage
in smartphones and laptops. of LiCoO2-based LIBs was limited to 4.2 V. Meanwhile, it was
The second one is to optimize the cell configurations and difficult to process the large LiCoO2 particles to prepare slurry
use different structures of the pouch cells for some specific and coat electrode, and thus the LiCoO2 particles were con-
applications. The novel structure designs of pouch cells can not trolled below 10 µm which resulted in low compacted density,
only improve the energy density but also achieve some new fea- low volumetric energy density, and even safety issues. With the
tures such as fast charge and high power. Over the past decades development of synthetic technology, the compacted density
of years, the energy density limits of LiCoO2-based LIBs have was improved with larger particles (15–22 µm). The compacted
been broken up unremittingly. density of LiCoO2 cathode material was increased from 3.7 to
In the optimization of cell components, it could be observed 4.1 g cm−3, leading to a high volumetric energy density. Mean-
that the cathode materials mainly determine the energy density while, Ti and Mg were introduced to the LiCoO2 to stabilize its
of the pouch cells. Toward the aim of a higher energy density, crystal structure and enhance its electronic conductivity which
the most feasible method is to increase the reversible capacity contributes to the excellent cycling performance of LiCoO2-
of cathodes as well as the operation voltage of LIBs. Battery based LIBs. With increasing the upper cutoff voltage to 4.3 V,
companies have developed many proprietary technologies the reversible capacity was improved accordingly. To ensure the
among which development of electrode materials are mainly cycle stability of LiCoO2 cathode material, the Al2O3 coating
focused. In brief, doping and coating are intensively adopted was used to stabilize the interface of LiCoO2 electrode with elec-
to improve the structure stability of LiCoO2 cathode materials trolytes which was ascribed to the removal residual Li by Al2O3
so as to increase their upper cutoff voltages and energy den- on the surface of LiCoO2. With powder engineering, mixing dif-
sities. A representative patent about LiCoO2 cathode material ferent particle sizes of LiCoO2 increased the compacted density
was published in 2003 by FMC Corporation[171] that claimed a further from 4.1 to 4.15 g cm−3, suggesting a higher volumetric
compound with the formula LiαCoβAγO2 in which “A” is one energy density at 4.35 V. However, such improvement is mar-
or more dopants having an average oxidation state N such that ginal, and the enhancement of voltage should be more effective
+2.5 ≤ N ≤ +3.5, 0.90 ≤ α ≤ 1.10, β > 0, γ ≥ 0. Those dopants to increase the energy of LiCoO2. When the upper cutoff voltage
were stated to improve the electrochemical performance of is further increased, the use of LiCoO2 suffered from more and
LiCoO2 cathode materials remarkably. Although there are also more challenges such as irreversible phase transition, large
many beneficial doping elements and coating compounds lattice expansion, Co dissolution, and O2 evolution,[172] which
Figure 19. The technological development route of LiCoO2 cathode material in industry.
inevitably deteriorated the LiCoO2 performance. Al doping Of course, it is necessary to use highly kinetic graphite anode
was observed to suppress phase transition of LiCoO2 and thus materials and high conductivity of electrolytes as the multiple
stabilized its crystal structure when the LiCoO2 cutoff voltage tab winding cell is able to fully realize its fast charge perfor-
became 4.4 V. Battery material suppliers developed unique syn- mance. The current technology can support the charge/dis-
thesis routes that make it possible to dope a high concentra- charge rate higher than 3C rate.
tion of Al into LiCoO2 homogeneously. However, it is more and Due to superior performance of LiCoO2, the LiCoO2-based
more difficult to achieve the balance of high energy density and LIBs become irreplaceable power sources in the consumer elec-
safety. The higher upper cutoff voltage requires better interface tronic applications, especially for those that need long operation
stability of LiCoO2 and electrolyte. At 4.45 V, the new technology time. In the foreseeable future, the development of LiCoO2-
to coat dense Al2O3 is very critical to alleviate the LiCoO2 cor- based LIBs is still toward higher volumetric energy density, new
rosion by electrolytes. The dense Al2O3 coated LiCoO2 shows battery technologies and new application fields.
improved energy density and excellent cycling performance.
When the cutoff voltage exceeds 4.5 V, the oxygen framework
of LiCoO2 cathode material is extremely unstable. Thus, the sta- 4.2. Risks and Dilemmas of LiCoO2-Based LIBs in the Industry
bilization of O framework in LiCoO2 cathode material is obliga-
tory to realize higher energy density in the future although From the initial recognition of LiCoO2 to its commercialization
many technical solutions have been proposed. for LIBs, and now wide application in consumer electronics,
Aside from the high energy density, fast charge is another the accessible energy density in LiCoO2-based LIBs is still far
important feature for customers to fully charge their cellphones below the theoretical value. There is still a long way to achieve
and tablets in a short time which facilitates battery compa- a high energy density. Up to now, LiCoO2 cathode material has
nies to develop new battery technologies. The design of pouch been the best choice for LIBs due to its high theoretical capacity
cell configuration is a typical solution to boost the kinetics of (274 mAh g−1), high voltage plateau (>3.85 V), high compacted
pouch cells. The typical structure of the pouch cell is shown, for density (4.1–4.2 g cm−3), high initial Coulombic efficiency
example, to describe its configuration improvement as shown (92–94%), and excellent cycle stability. However, the compacted
in Figure 20a, which is so-called winding cell structure. In gen- density has almost reached the margin of LiCoO2 cathode mate-
eral, it has only one tab on the current collector. Although the rial. The upper cutoff voltage of LiCoO2-based LIBs has been
structure provides a high energy density, it leads to an uneven increased to 4.6, 4.7, or even 4.8 V in academic research, but the
current distribution and a high resistance inside the pouch cell, cycling stability is far below the practical standard in industry. Till
which restricts its power density. As a result, the multiple tabs now, no battery companies have released products with a cutoff
shown in Figure 20b are suggested to unify the current dis- voltage higher than 4.45 V. Thus, there are many challenges to be
tribution and improve the charge capability of the pouch cell. circumvented on the way for a higher energy density.
Figure 20. a,b) The schematic illustration of normal winding cell and multiple tab winding cell of LiCoO2-based pouch cells in industry.
The first challenge is the structure degradation of LiCoO2 based LIBs are failed when the upper cutoff voltage is higher
cathode materials. When the LiCoO2-based pouch cells are than 4.55 V. Some possible reasons are proposed as follow. First,
charged to a higher cutoff voltage, the irreversible phase tran- the structure change of LiCoO2 tends to be much more severe
sition, large lattice expansion, Co dissolution, and O evolu- at 4.6 V. In particular, the H1-3 phase transition near 4.55 V
tion of LiCoO2 cathode material become more serious. At not only induces the shift of OCoO slabs, but also leads to a
elevated temperature environment, such degradations are large lattice (c-axes) and volume shrinkage, which tremendously
aggravated. The cell components (electrolytes, conductive addi- increases the risk of structural collapse and cracks formation.
tives, binders, current collectors, separators, etc.), especially Second, when the upper cutoff voltage is higher than 4.55 V, not
electrolytes, decompose under the high cutoff voltage and only the decomposition of electrolyte will be dramatically exacer-
deteriorated under high temperature, which results in higher bated by high voltage, highly active Co4+, and peroxide, but also
requirements for electrolyte technologies. However, the current severe surface structure collapse accompanied by O loss and Co
electrolyte technologies are difficult to support the high voltage dissolution will cause the spread of structure collapse and cracks
cycling. The second one is the interface reactions. The LiCoO2 into particle core, which lead to dramatic capacity loss quickly.
cathode material under high cutoff voltage unavoidably reacts In order to overcome the issues mentioned above, many sci-
with other compositions in pouch cells such as electrolyte sol- entific and technical issues are required to address. 1) Devel-
vents, Li salts, separators, and binders. The inevitable interface oping more effective and precise doping strategies to suppress
reactions result in the rapidly increased impedance, obviously the phase transformations (especially H1-3 phase transition
swelling, poor floating charge, and large heat generation. As near 4.55 V) and O redox reactions. Multiple doping strategies
the tremendous amount of heat is released from LiCoO2-based such as Ti/Mg/Al codoping, have already demonstrated syn-
LIBs, it destroys the ion diffusion pathway and even causes a ergistic effects on enhancing the cycle stability of LiCoO2 over
short circuit between the LiCoO2 cathode and graphitic anode, 4.5 V. To develop more systematic and precise multiple doping
which ultimately results in poor electrochemical performance methods (including multiple elements doping, multiple sites
and leads to the safety risks. doping, and doping into both of lattice and grain boundaries)
could be a promising way to further improve the high-voltage
performance. 2) To promote the cycling stability over 4.5 V, it
5. Conclusions and Future Perspectives must be considered to completely isolate the active LiCoO2 from
the electrolytes (before cycling or at least after several cycles),
Even after nearly 30 years since the birth of LIBs, LiCoO2 still enhance the surface structure stability, entirely avoid O trans-
maintains the position as dominant cathode material for LIBs port, and O2 release. 3) In view of the decomposition of organic
in the portable electronics, due to its high compact density, high electrolytes and the formation of CEI are inevitable as charging
volumetric energy density, and excellent reliability. Charging to over 4.5 V, further studies are needed to develop novel electro-
high voltages is the most effective and promising way to further lyte formulations and additives to form the CEI layers with high
increase the capacity of LiCoO2. Unfortunately, such behavior stability and ionic conductive. 4) Advanced characterization
will inevitably trigger the dramatic fading of capacity, efficiency, techniques such as trace element analysis techniques and in
and cycle life. The failure mechanism of LiCoO2 at high voltage situ/operando characterization techniques, are required to fur-
(>4.2 V vs Li/Li+) has been widely studied and great progress has ther understand the fundamental issues (for example: precise
been made. The critical issues are summarized as follow: 1) com- sites and roles of various dopants, interactions between coating
plicated structural evolution and iterative volume change during layer, and host material/electrolyte during long-term cycling,
Li+ deintercalation/intercalation lead to the irreversible phase the formation mechanism of CEI). Targeting higher energy
transition and particle cracks, subsequently resulting in capacity density and safety has been proven to be a challenging task
loss; 2) the surface structure and chemistry evolution of the in LiCoO2-based LIBs. Over the nearly 30 years after the first
LiCoO2 electrodes in high voltage (>4.2 V vs Li/Li+), including commercialization of LiCoO2-based LIBs, the role that the
CEI formation, inert Li-poor phase growth, structure collapse, LiCoO2-based LIBs played in consumer electronics is still indis-
and defects formation induced by O loss and Co dissolution, sig- pensable and will continue to be in the future. Therefore, com-
nificantly increase the surface impedance of LiCoO2 electrodes, prehensive improvements and deep understandings on LiCoO2
leading to rapid capacity decay; 3) the inhomogeneous reaction cathode material, electrolytes, and other compositions in LiCoO2-
leads to deformation and stress accumulation, which also causes based punch cells are very important as well as necessary.
particles pulverization, electrode fracture, and the loss of contact
between active materials and current collects. Various modifica-
tion strategies, including surface coating, element doping, and Acknowledgements
co-modification approaches, have been developed to overcome
above issues and promote the long-cycling stability of LiCoO2 Y.L. and X.W. contributed equally to this work. This work was supported
by the National Key R&D Program of China (Grant No. 2018YFB0905400),
at high voltage. Up to now, the charging voltage of LiCoO2
Science and Technology Commission of Shanghai Municipality (Grant
has been increased to 4.5 V (vs Li/Li+), achieving a reversible No.18010500300), and 111 project (D16002).
capacity of ≈180 mAh g−1 with acceptable cycling life.
Although an increase in capacity from ≈180 to ≈220 mAh g−1
can be achieved by further increasing the cutoff voltage to 4.6 V,
the modification strategies developed in the past to solve the Conflict of Interest
electrochemical performance and the safety issues of LiCoO2- The authors declare no conflict of interest.
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