Received: 6 May 2020 Accepted: 18 May 2020

DOI: 10.1002/nano.202000008

REVIEW

Improving LiNixCoyMn1−x−yO2 cathode electrolyte

interface under high voltage in lithium ion batteries

Qian Wu1 Shulan Mao1 Zhuoya Wang1 Yang Tong2 Yingying Lu1

1State Key Laboratory of Chemical

Engineering, Institute of Pharmaceutical Abstract
Engineering, College of Chemical and The demanding for high energy density as well as high safety is still an
Biological Engineering, Zhejiang
important threshold for battery commercialization. Next-generation layered
University, Hangzhou 310027, China
2 High-Tech Research and Development LiNix Coy Mn1−x−y O2 (NCM) cathodes will meet the specific energy required for
Center, Ministry of Science and driving range of at least 300 miles from a single charge to guarantee the success of
Technology of the People’s Republic of electric vehicles. Extending operating voltage of NCM cathode materials is con-
China, Beijing 100044, China
sidered as an effective way to increase energy density of lithium ion batteries.
Correspondence However, unstable electrode electrolyte interface (CEI) limits the electrochem-
Yingying Lu, State Key Laboratory of
ical performance of NCM cathodes when operating at high voltages (>4.3 V).
Chemical Engineering, Institute of Phar-
maceutical Engineering, College of Chem- In this review, underlying factors and mechanisms that result in the failure to
ical and Biological Engineering, Zhejiang form a robust CEI are analyzed, including surface phase reconstruction, stress-
University, Hangzhou 310027, China.
induced cracking, transition metal dissolution, electrolyte decomposition and
Email: [email protected]
oxygen redox reaction. Then, progress on how to improve and stabilize CEI is
Funding information summarized. To bridge the gap between current and next generation automo-
National Key R&D Program of China,
Grant/Award Numbers: 2018YFA0209600,
tive batteries, it is expected that the situation of NCM electrode materials at high
2016YFA0202900; Natural Science Foun- voltage to be fine-tuned with available variables such as nickel content, packag-
dation of China, Grant/Award Numbers: ing density and loading level. Moreover, more detailed work on designing and
21878268, 21676242
studying a reliable CEI can help the application of NCM cathodes under high
voltage.

KEYWORDS
cathode electrolyte interface, high operating voltage, layered LiNix Coy Mn1−x−y O2 cathode,
lithium ion batteries

1 INTRODUCTION further development of LIBs in terms of capital cost,

long-term cycling performance, durability and energy
Since the commercialization in the early 1990s, recharge- density,[5,6] especially for EVs, “range anxiety” remains a
able lithium-ion batteries (LIBs), as the most promising major concern.[6] Generally, as the provider of lithium ion,
energy storage medium, have been widely used in portable cathode materials greatly limit the performance and capac-
electronic devices, electric vehicles (EVs), hybrid EVs, ity of LIBs on account of graphite is the most commer-
and smart grids.[1–4] Rapidly increasing energy demand cial anode.[7] Among current cathode materials, LiCoO2
in modern society has put forward requirements for the (LCO) suffers from low specific capacity of only ≈50% of

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the
original work is properly cited.
© 2020 The Authors. Nano Select published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nano Select 2020;1:111–134. wileyonlinelibrary.com/journal/nano 111

112 WU et al.

F I G U R E 1 A, Cell Wh kg−1 and B, cell Wh L−1 estimations calculated in prismatic hard case format for different cell chemistries. Values
resulting from conservative and competitive electrode designs are indicated by min/max values. Passive materials are not optimized. Repro-
duced with permission.[21] Copyright 2017, American Chemical Society

its theoretical capacity, structural degradation, and oxygen and provide energy by continuously de-intercalating
release at high de-lithiated states.[8–11] Meanwhile, cobalt lithium between anode and cathode. In general, different
resources are scarce and expensive, which limits the large- transition metals have different redox activities at different
scale application of LCO in EVs;[12] LiFePO4 displays high voltages due to crystal-field splitting and differences in
safety characteristic, but operates at low voltage and has electronegativity. The redox reactions of different tran-
low volume specific energy;[13–18] Due to Mn dissolution, sition metals play a crucial role in de-intercalation of
high voltage spinel-like Li2 MnO4 cathode materials suffer lithium ion batteries. For layered NCM electrode, the
from accelerated capacity fading during prolonged cycling Co3+ /Co4+ level is the lowest in energy and it will oxidize
and storage.[19,20] LiNix Coy Al1−x−y O2 (NCA) battery mate- at the highest voltage, the next highest energy levels above
rials have high technical barriers. Moreover, because alu- those of Co are the Ni3+ /Ni4+ and Ni2+ / Ni3+ couples
minum is amphoteric metal which is not easy to precip- followed by that of Mn3+ /Mn4+ redox couple. Hence, the
itate, NCA materials will suffer from thermal runaway de-intercalation of a typical layered Ni-Co-Mn alloy via the
at high temperatures, causing serious consequences.[21–23] oxidation of Ni2+ to Ni3+ , followed by the oxidation of Ni3+
LiNix Coy Mn1−x−y O2 (NCM), layered lithium transition to Ni4+ , and finally the oxidation of Co3+ to Co4+ .[29,30]
metal oxide, is regarded as the most promising cathode Moreover, the Mn4+ maintain constant during the whole
material in the next generation of lithium ion batteries process. Enhancing the working voltage can promote the
due to its large specific capacity, high operating voltage, conversion of Co3+ to Co4+ , thus making NCM cathode
good rate capability, and reasonable cost as the synergis- materials release more capacity. Figure 1 shows a possible
tic effects of transition metals.[2,24–26] In order to satisfy evolutionary roadmap of NCM- and NCA-based cells in
the consumer-threshold of next generation of EVs to travel terms of gravimetric (Wh kg−1 ) and volumetric (Wh kL−1 )
at least 300 miles on a single charge,[24] namely, the cath- energy density.[24] Ni-rich NCMs and particularly NCM811
ode of a battery needs to provide an energy density of 800 (theoretical capacity of 280 mAh g−1 ) is capable to reach
Wh kg−1 .[6] Therefore, it is crucial to further improve the energy density 700 kWh kL−1 and 300 Wh kg−1 at the cell
energy density of NCM cathode. level. This target is possible to achieve with adjustment
At present, ternary NCM batteries (NCMs) containing in some key parameters, such as Ni concentration in
more than 60% nickel have been fully commercialized, but the cathode active material (0.33∼0.90 kmol%), anode
they still cannot guarantee the success of EVs. To realize a material (graphite vs. Si−C anode with a capacity of
high energy density NCM cathode LIB, the main strategy 1000 kmAh kg−1 ), cell upper cutoff voltage (4.2 V vs.
is to enhance the capacity and operating voltage according 4.4 kV), and electrode density (15 kmg kcm−2 , 35% poros-
to the equation: energy density = capacity × voltage. ity, vs. 25 mg cm−2 , 20% porosity).[24] Some novel materials
Running NCM electrode materials at high voltage is an and devices such as Li/S,[31–34] Li/Se,[35] Na-ion,[36–39]
effective way to increase the energy density of the corre- and capacitors[40–42] have been studied to meet energy
sponding batteries.[27] It is deemed that the predominant storage requirements.[4] For sodium ion batteries, the
oxidation states of Ni, Co, and Mn in the NCM compound mass of Na is three times greater than that of Li, resulting
are +2, +3, and +4, respectively with small content of in a lower theoretical capacity.[29,43] Na electrodes tend
Ni3+ and Mn3+ ions.[28] LIBs achieve reversible capacity to have lower average voltages (vs. Na/Na+ ) than Li
WU et al. 113

FIGURE 2 A schematic view of problems and countermeasures of NCM materials when operating at high voltages

electrodes (vs. Li/Li+ ).[44] Intercalation in Na compounds irreversible rock salt phase,[52,53] causing battery’s capac-
generally occurs over a larger voltage window than in ity loss and voltage attenuation, even gas generation and
their Li analogues, which would reduce the practical explosion accidents. Therefore, how to stabilize and opti-
energy density.[45] Besides, as a consequence of larger mize the CEI and reduce the occurrence of side reactions
ionic radius of Na+ (1.16 Å) compared to Li+ (0.76 Å), at interface are of great significance to stabilize the perfor-
the strains associated with (de)intercalation of Na will mance of NCMs at high operating voltage.
be larger, phase transitions upon (de)intercalation are Herein, we review current problems of the CEI of NCMs
much more prevalent in Na compounds.[46] Actually, the under high voltages (>4.3 V), which plays an impor-
limited electrical conductivity and large volume variation tant role in controlling the degree of lithium-ion diffu-
of sulfur, as well as the formation of polysulfides during sion, charge transfer, and parasitic reactions. Degrada-
cycling, are yet to be addressed before lithium-sulfur tion of cathode and corresponding effects on CEI will be
batteries can become an actual reality.[47–49] Particu- discussed. Then, strategies will be postulated on how to
larly, when increasing the upper cutoff voltage above 4.5 V improve and stabilize CEI, such as coating, doping, other
(≈220 mAh g−1 ), and matching with lithium metal anodes, surface treatments, structural modifications, electrolyte
the gravimetric energy density of NCMs can approach additives. Problems and countermeasures of NCM materi-
that of lithium-sulfur batteries, and the volumetric energy als when operating at high voltages are shown in Figure 2.
density will exceed that of lithium-sulfur batteries. The In the end, there will be conclusions on progress of improv-
areal capacity of the sulfur cathode must be controlled at ing the CEI of NCMs, meanwhile, remaining challenges
4∼8 mAh cm−2 to compete with commercial LIBs, but it and future development trends of NCMs are put forward.
cannot be achieved at present.[50] In addition, compared
with NCMs, capacitors are inferior in energy density.[51]
Therefore, considering the comprehensive advantages of 2 REMAINING CHALLENGES
NCMs, it is necessary to study its performance under high
operating voltage. It needs to be aware that higher upper cut-off voltage,
In NCM cathodes, it is widely accepted that Ni2+ migra- larger degree of lithium is utilized in NCM lithium ion
tion has a tendency to occupy Li vacancy during the pro- batteries,[6] which results in a series of degradation prob-
cess of de-intercalation because of similar ionic sizes of lems. Unlike higher nickel incorporation (which also uti-
Ni2+ (0.69 Å) and Li+ (0.76 Å), causing cationic mixing. lizes more lithium ions), electrolyte oxidation and anionic
High operating voltage will aggravate the mixing degree redox caused only by high operating voltage make the
of ions, which will lead to anisotropic changes in crys- cathode - electrolyte interfacial side reactions extremely
tal lattices of different transition metals, making NCM’s complicated, limiting cycle life and safety performance of
spherical secondary particle cracked and transition metal NCMs. Understanding the surface structure evolution of
ions dissolved. The dissolved transition metal ions react NCM materials along with the interfacial side reactions
with electrolyte resulting in the destruction of cathode under high working voltage is significant to design robust
material and the loss of electrolyte. The electrode material cathode electrolyte interface so as to improve electrochem-
changes from layered phase to spinel phase and finally to ical performance.
114 WU et al.

F I G U R E 3 Illustration of the ordered and disordered phase in layered lithium metal oxides and their structural transformation. A, Well
ordered R3̅m structure; B, The cation disorder or cation mixing phase with Fm3̅m structure; C, R3̅m structure with Li vacancies in highly
charged state; D, Partially cation mixed phase with TM ions in Li slab. Reproduced with permission.[53] Copyright 2015 Wiley. E, Qualitative
positions of energy levels in layered Ni–Mn–Co oxide alloys; F, Concentration profile of Li within a particle during charge and discharge.
Reproduced with permission.[54] Copyright 2017, Wiley

2.1 Surface phase reconstruction +3, and +4 respectively.[7,57,58] Because the similarity of
radius between Ni2+ and Li+ ,[53] Ni2+ ions could occupy 3b
As a layered cathode material, NCM have a prototype α- lithium sites in the Li slab easily. Nevertheless, Doeff et al.
NaFeO2 structure with R3̅m space group in which alter- reported that the cation mixing layer consisted of not only
nating layers are consisted of edge-sharing LiO6 and MO6 Ni2+ but also other metal ions, like Mn2+ and Co2+ pro-
octahedra.[54,55] Figure 3A indicates the O3 structure of duced by reduction.[52] The mixing of cations between TM
oxygen-lithium-oxygen-TM-oxygen along the rhombohe- and Li layers will lead to structure reconstruction from lay-
dral[001] direction, with an AB CA BC stacking of oxygen, ered to Fd3̅m disordered spinel and Fm3̅m rock-salt phase
forming a rhombohedrally distorted fcc oxygen framework (Figure 3B).[59,60] Because the spinel and disordered rock-
with three MO2 sheets in the repeat unit.[53] In “O3,” the salt structures are crystallographically related to the O3
“O” indicates that the intercalants are octahedrally coordi- structure in that they all have an fcc oxygen framework,
nated by anions, and the “3” indicates that the repeat unit differing only in their arrangement of Li and TM cations
is three MO2 sheet.[29] over the octahedral and tetrahedral interstitial sites.[29]
Given the fact that Mn3+ will spontaneously donate elec- Theoretically, when one quarter of the metal ions migrate
trons to Ni3+ , yielding Mn4+ and Ni2+ according to crystal- from the transition-metal layer to particular octahedral
field theory,[56] Ni3+ is unstable because of the unpaired sites in the Li layer and metal ions ordering within the fcc
electron spin of the eg orbitals. As a consequence, when oxygen framework and cubic symmetry, O3 will transform
content of Mn is lower than Ni in the lithiated NCM, the to spinel. Note that the spinel-like structure generated dur-
predominant oxidation states of Ni, Co, and Mn are +2, ing phase reconstruction is far from well-ordered spinel.
WU et al. 115

F I G U R E 4 Atomic resolution annular dark-field in the scanning transmission electron microscopy (ADF-STEM) images of NCM parti-
cles. A, After electrolyte exposure (the exposure time is ∼30 hours, equivalent to the time used for one full cycle in this study); B, After 1 cycle
(2.0−4.7 V). the blue arrow indicates the surface reconstruction layer; C, D, Fast Fourier transform (FFT) results showing the surface recon-
struction layer (Fm3̅m [62] zone axis) and the NCM layered structure (R3̅m [63] zone axis), respectively in panel b; E, Variation of the surface
reconstruction layer thickness on orientation after 1 cycle (2.0−4.7 V); F, Image showing loose atomic layers on an NCM particle, after 1 cycle
(2.0−4.7 V). The blue lines indicate the boundaries between the NCM layered structure and surface reconstruction layer in all images. The scale
bars are 2 nm in all images. Reprinted with permission.[49] Copyright 2014, Macmillan Publishers

In addition, the transformation from layered lithium-lack tioned before, in a high voltage charged state, extraction of
state MO2 to rock-salt structure happen via densification Li from the material increase. As a result, the surface struc-
and release of oxygen, with the Li and TM layers no longer ture of NCM materials become so unstable that TM ions
exhibit long-range periodic order. This process is also sup- migrate from TM layer to Li layer easily. The transition-
ported by Hwang et al. with the discovery of a reduction of metal-ion migration has a tendency to occupy every sec-
the Ni and an increase in the effective electron density of ond Li vacancy because the disordered cations repel each
oxygen.[61] other (Figure 3C,D).
The structure reconstruction phenomenon occurs most The relationship between high voltage Li extraction and
likely on the surface of NCM, especially cycling under high structure reconstruction was supported by Doeff et al.[52]
cut-off voltage. There are two main reasons behind: (1) the They found that the surface reconstruction layer is thicker
concentration of Li at the surface is lower than that in the after first cycle between 2.0-4.7 V than electrolyte expo-
bulk within a cathode material particle during charging sure, and this layer consists of Fm3̅m rock-salt structure
process (Figure 3F) because the concentration gradient is with spinel structure from surface to inside (Figure 4).
needed as kinetic driving force for Li diffusion; (2) as men- Even more noteworthy is that the surface reconstruction
116 WU et al.

F I G U R E 5 HR-TEM Lattice image of the surface region after 50 cycles under A, 3.0–4.5 V conditions; B, 3.0–4.8 V conditions; C,
Degradation mechanisms of LiNi0.5 Co0.2 Mn0.3 O2 and phase transformation after cycle tests under high-voltage conditions. Reprinted with
permission.[58] Copyright 2013, Wiley

is orientation-dependent which occurs primarily along the highly oxidative environment that triggers the oxygen loss
lithium diffusion channels, suggesting that surface recon- from the surface of the material.[61]
struction is promoted by lithium removal during charging. The influence of surface phase reconstruction to electro-
Moreover, Jung et al. discovered that the formation of the chemical performance is probably poor due to the sluggish
rock-salt phase is more dominant under a higher voltage kinetics of electrochemical inactive rock-salt phase.[64]
(≈4.8 V) than 4.5 V (Figure 5), which is attributable to the Besides, the TM ions in Li layer acts as a barrier for Li
WU et al. 117

F I G U R E 6 A, Lattice parameters NCM811 as a function of cell voltage (V) during a single charge/discharge cycle; B, Comparison of change
in cell volume as a function of cell voltage for the different NCM compositions. Reprinted with permission.[64] Copyright 2018, American Chem-
ical Society. C, Calculated lattice distortion of the two NCMs on charge. Reprinted with permission.[65] Copyright 2019, American Chemical
Society

diffusion, causing high polarization and poor rate capa- However, it brings a major problem of intergranular crack-
bility and deteriorating the capacity retention. Neverthe- ing induced by anisotropic volume change under elec-
less, Cho et al. reported a thin cation disordered layer trochemical cycling, especially at high working voltage.
to improve cycling performance in which Ni2+ ions were Operando neutron diffraction is used by Goonetilleke et al.
resided in Li slabs with “pillar effect,” because of Ni2+ ions to elucidate the structural evolution of NCM electrodes.[66]
in the Li sites provide an electrostatic repulsion force to As depicted by Figure 6A, the c lattice parameter initially
hinder further cation migration.[65] increases until ∼4.0 V caused by increasing electrostatic
repulsion between the transition-metal octahedra as the
occupancy of the lithium layer is reduced. Beyond this
2.2 Stress-induced cracking voltage, the c lattice parameter decreases rapidly owing
to cation mixing and phase transformation. This large
NCM layered cathode is often fabricated in the form of amount of lattice contraction/expansion results in greater
spherical secondary particles consisting of densely packed repeated mechanical stress on NCM material which also
primary particles in order to meet the high volumetric exhibits as changes in cell volume (Figure 6B) during
energy density and alleviate interfacial side reactions. charging/discharging. The structure collapse generated by
118 WU et al.

lattice strains will lead to microcrack and pulverization of The correlation between TM dissolution and upper cut-
secondary particles. Li et al. demonstrated that the abrupt off voltage was supposed by Gilbert et al.[74] They found
anisotropic lattice collapse of layered NCM at deep charge that continuous operation of full cells with NCM523 leads
is a universal phenomenon critically dependent on Li to dissolution of TM ions and their migration and incor-
utilization, and not Ni content as commonly believed, by poration into the SEI of the graphite-based negative elec-
combining in situ X-ray diffraction analysis and density trode. These processes correlate with cell capacity fade and
functional theory (DFT) calculations.[67] DFT predicts a accelerate markedly as the upper cutoff voltage exceeds
similar extent of the c-axis lattice distortion up to 83 mol% 4.3 V because the enhanced fracture creates new surfaces
Li extraction between LiNiO2 and LiNi1/3 Co1/3 Mn1/3 O2 and causes increased solvent oxidation and TM dissolu-
(Figure 6C). tion. Among TMs, Mn content in the SEI shows a better
Besides intergranular cracks, intragranular cracks were relationship with cell capacity loss than Co and Ni con-
also observed in several cathode materials after prolonged tents. As Mn ions become incorporated into the SEI, the
cycling. Yan et al. reported unexpected observations on kinetics of lithium trapping change from power to linear
the nucleation and growth of intragranular cracks in a at the higher voltage, indicating a large effect of these ions
commercial LiNi1/3 Mn1/3 Co1/3 O2 cathode and the density on SEI growth and implicating (electro)catalytic reactions.
of intragranular cracks abruptly increases when cycled at Likewise, Li et al. showed that the dissolved transition-
a high cutoff voltage of 4.7 V (Figure 7A-C).[68] More- mental ions cross the electrolyte to the anode and affect
over, Lee et al. revisited the crystal structure of primary the SEI during cycling.[75]
particles of NCM materials with transmission electron
microscopy.[69] They revealed that the so-called primary
particles are in fact polycrystalline secondary particles. The 2.4 Electrolyte decomposition and CEI
low-angle grain boundaries between smaller true primary formation
particles cause the development of nanocracks within the
primary-like particles of NCM cathodes after repetitive One of the challenges for further development of NCM
electrochemical cycles. rechargeable batteries for EVs is safety, which essentially
Cracks can result in poor connections between grains corresponding to electrolyte and interface stability. The
of active materials and current collectors, leading to poor energy gap between the highest occupied molecular orbital
electrical conductivity and even loss of active materials (HOMO) and the lowest unoccupied molecular orbital
due to fragmentation. In addition, cracks create fresh (LUMO) is the electrochemical window of the electrolyte,
surfaces that will be exposed to electrolytes and gener- within which the electrode potential needs to be con-
ate new sites for surface phase transformation, corro- trolled in order to maintain the thermodynamic stabil-
sion and side reactions, consequently accelerating cell ity of the electrolyte.[30] Whereas HOMO and LUMO
degradation.[70] This degradation even occur at first cycle are derived from approximated electronic structure the-
(Figure 7D-G).[71] ory while investigating electronic properties of isolated
molecules, their energy levels do not indicate species par-
ticipating in redox reactions. Therefore Peljo et al. provided
2.3 Transition metal dissolution a correct thermodynamic representation for the electro-
chemical stability of the electrolyte based on redox poten-
Lithium salts like LiPF6 used in current electrolytes can tials and Fermi level of the electron in solution.[76] Due to
react with the few ppm of H2 O present in all commer- the significance and widespread application of HOMO and
cial formulations to form HF. The reaction is presented as LUMO in electrochemical stability, this representation will
follows[72] : be adopted in the following parts.
Ideally, once the electrode potentials exceed the elec-
LiPF6 ↔ LiF + PF5 (1) trochemical window of electrolyte, the electrolyte will be
oxidized on the cathode and reduced on the anode, with
PF5 + H2 O ↔ POF3 + 2HF (2) the generation of CEI and SEI respectively. The CEI and
SEI can passivate the electrode hindering the transporta-
Then HF further corrodes the surface of NCM, leading to tion of electron, so as to stabilize the electrode and elec-
the dissolution of transition-metal species which can poi- trolyte. However, the reality is far more complicated about
son the anodic solid electrolyte interface (SEI) as well as the electrolyte decomposition, parasite reaction and CEI
form a CEI film on the cathode.[73] The fracture of NCM formation under high cut-off voltage.
particles with more surfaces exposed in electrolytes can Recently, Zhang et al. developed an in situ Fourier trans-
accelerate this process. form infrared (FT-IR) method to study the reactivity of
WU et al. 119

F I G U R E 7 A-C, Low magnification HAADF images of LiNi1/3 Mn1/3 Co1/3 O2 after 100 cycles at different high cutoff voltages. The red
arrows indicate voids and the yellow arrows in g indicate intragranular cracks. Scale bars, 500 nm. Reprinted with permission.[66] Copyright
2017, Springer Nature. D, Cross-section of an embedded particle in a coin cell after one charge-discharge cycle. Cracking is observed throughout
the particle and cracks in several locations are indicated by arrows; E, Cross-section of an embedded particle in a coin cell after 4500 charge-
discharge cycles showing extensive cracking; F, Schematic of an idealized particle consisting of several grains indicated by dotted lines. Electrical
contact to the shaded conducting medium surrounding the particle is represented by arrows; G, after cycling, separations at grain boundaries
lead to the loss connectivity and electrical contact between grains. Reprinted with permission.[69] Copyright 2013, Wiley
120 WU et al.

F I G U R E 8 Proposed mechanism and pathways of electrolyte decompositions on NCM811. Electrolyte decompositions include solvent
(EMC and EC) decomposition and coupled salt (PF6 − ) decomposition. Solvent decomposition happened by dehydrogenation first, and de-H EC
could be further decomposed by removing another hydrogen or by oligomeriation. The protic species on surface coming from dehydrogenation
could further attack PF6 − and lead to coupled salt decomposition. The decomposed species (mainly solvent decomposed species) will form a
resistive layer at the EEI and lead to great impedance growth, eventually resulting in capacity loss for NCM811. Reprinted with permission.[30]
Copyright 2020, The Royal Society of Chemistry

the electrolyte on NCM surfaces as a function of volt- and reduction of the TM ions,[79] as well as oxygen release
age, finding unique evidence for dehydrogenation of ethy- and oxidation of electrolytes.[80] A part of the lithium is
lene carbonate (EC) on NCM811 surface at voltages as low chemically bound in the CEI, resulting in the formation of
as 3.8 V versus Li+ /Li. The electrolyte oxidation mecha- lithium oxides, fluorides, and carbonates (Figure 9). The
nism on NCM811 surface is described in Figure 8.[77] EMC observed reduction of the TM ions at the interface is inher-
and EC molecules can dissociate hydrogen and form de- ently related to the formation of the CEI layer, which indi-
H EMC and de-H EC respectively that adsorb on oxide cates that the highly oxidative Co4+ and Ni3+/4+ ions are
surface through a C–O bond. The driving force becomes involved in CEI layer formation. Aurbach et al. reported
even greater during de-lithiation and decreasing of x in that the existence of nickel element in electrodes aug-
Lix MO2 . Then one way of de-H EC is further dissociated mented the nucleophilicity of the surface oxygen.[81] Elec-
a second hydrogen on the other carbon forming vinylene trodes seem to reach passivation in LiPF6 /alkyl carbonate-
carbonate (VC), another is further oxidized to open the based solutions, due to the formation of surface species
ring, or form oligomers with EC-like rings such as C6 H8 O6 , such as LiF, MFx, ROCO2 Li, ROCO2 M, and Polycarbon-
C9 H14 O8 , and C7 H10 O6 . The eventual products of solvent ates. Note that CEI components are not static during
dehydrogenation may be CO2 or CO. These Organic prod- cycling. Li et al. described the dynamic behavior of the
ucts form a passivating layer on the oxide surface with cathode interphase in the common non-aqueous elec-
great impedance growth for Li+ migration during charging trolyte by conducting three-dimensional chemical and
of NCM811 measured by EIS. In addition, the dehydrogena- imaging analysis on LiNi0.7 Mn0.15 Co0.15 O2 , and drew a
tion of EC and EMC generates protic species on the surface, schematic diagram of the microstructure and chemi-
which further trigger reactions with LiPF6 to form HF and cal composition of CEI (Figure 10).[82] Studies shown
less-fluorine-coordinated species such as Lix PFy Oz , tran- that some substances in CEI will decompose in a high-
sition metal fluorides (MF) and PF3 O. The more specific oxidation environment of ∼4.5 V, but the CEI tends to
electrolyte decomposition reactions and possible degrada- stabilized during repeated cycles. Species like MFn, LiF,
tion pathways were investigated and postulated with 13 C3 - RCFx, C2 HO− were detected on LiNi0.7 Co0.15 Mn0.15 O2 sur-
labeled EC by Henschel et al.[78] face after 100 cycles, proving that these components can
During delithiated, a charging potential leads to the fur- withstand 4.5 V to a certain extent. Different from the
ther lowering Fermi Energy EF of the cathode material SEI in anode, the components of CEI are more compli-
below the HOMO of the electrolyte, which is accompa- cated due to the complex environment of cathode and con-
nied by a hole transfer from TM3d states to the HOMO of ductive carbon may also affect the CEI components,[83]
the electrolyte, promoting the decomposition of the oxide so the effective in situ characterizations of exploring the
WU et al. 121

F I G U R E 9 A schematic view of the Li+ deintercalation from the cathode material. A, A removal of Li+ is accompanied by the release of
an electron from the host material leading to the oxidation of TM. This conditioning is valid when EF of LNCMO lies well above of highest
occupied molecular orbital (HOMO) of the electrolyte and the downward shift of EF caused by a charging potential is still above the HOMO,
that is, no hole transfer to the HOMO takes place; B, The lowering EF below the HOMO of electrolyte will result in a hole transfer from the
TM3d states to the HOMO until the solid electrolyte interface (SEI) is formed between the cathode and electrolyte; C, The SEI layer consists of
reduced transition metal oxides and the compounds of the decomposed electrolyte. Reprinted with permission.[78] Copyright 2015, American
Chemical Society

F I G U R E 1 0 A, Normalized (to maximum) depth profiling of several secondary ion fragments of interest at the cycled
LiNi0.7 Mn0.15 Co0.15 O2 surface. Depth is calculated based on the calibrated Csþ sputtering rate of ∼0.03 nms−1 for the active material; B, A
schematic diagram of the microstructure and chemical composition of surface degradation products at the of surface LiNi0.7 Mn0.15 Co0.15 O2 .
The size of regions is not drawn to scale. Reprinted with permission.[80] Copyright 2017, Nature Springer

different components during cycles are needed under high ated by the reduction of ester carbonates at the anode,
voltage. small ester molecules undergo a series nucleophilic chain
In recent years, some researches have developed in situ reaction steps and form polymer/oligomer chains contain-
characterization techniques to reveal the dynamic evolu- ing ester and ether groups which adsorbed on NCM sur-
tion of CEI during battery cycling. Identification of CEI faces. As a result, CEI species containing ester and ether
chemistry and the dynamics changes serve as a basis for chains is more stable in the discharged state. Similarly,
the hypothesis of CEI evolution mechanisms. In order Li et al. used in situ shell-isolated nanoparticle-enhanced
to meet the high specificity and high sensitivity, Chen Raman spectroscopy to examine the changes in the inter-
et al. designed operando surface-enhanced Raman spec- face between NCM and carbonate-based electrolyte.[85]
troscopy (SERS) with strong SERS effect provided by the The protic species on the NCM811 surface resulted from
Au nanocube monolayer.[84] They pointed out that initi- dehydrogenation (De-H) reaction of EC could further
122 WU et al.

attack PF6 − anion to deposit lithium fluorides and oxyfluo- other surface treatments, structural modification, elec-
rides species in the surface layer at 3.8 V. Then these species trolyte additives. It is generally believed that the coating
would grow during charge. In addition Meng et al. devel- layer not only can prevent the direct contact between cath-
oped operando attenuated total reflection-fourier trans- ode materials and electrolyte, it also influence interface
form infrared (FTIR) technique finding that the compo- performance.[88,89] Doping elements can reduce the rear-
nents of CEI basically generate in the first cycle own- rangement of ions[90] to increase the structural stability
ing to EC priority decomposition and the presence of of materials[91] and strengthen the TM-O bond energy to
tris(trimethylsilyl)borate (TMSB) can suppress the decom- suppress the phase transition.[92] And structural design
pose of EC in part, and modify the stability of CEI film.[86] of cathode materials can also be used to stabilize CEI by
reducing the variation in volume anisotropy.[52,93–96] In
addition, the introduction of electrolyte additives can be
2.5 Anionic redox reaction regarded as an effective way to promote the formation of
stable CEI.
Most studies of the anionic redox reactions have focused
on Li-excess layered compounds. Nonetheless, Lee et al.
showed unambiguous evidence of reversible anionic redox 3.1 Coating and other surface treatment
reactions in NCM111 with a detailed quantification on
its reversibility upon electrochemical cycling.[87] There Coating the NCM cathode particles by metal oxides, phos-
are two types of oxygen involvements: One is the typical phate, fluoride, lithium is an effective measure to provide
involvement of O through hybridization with transition a protection layer to suppress side reactions between elec-
metals throughout the electrochemical operation which is trode and electrolyte.[88] The surface coating layers are
enhanced upon charge; the other is the intrinsic O redox considered to improve the cycling stability, rate capability
at high potentials when the de-lithiation rate above 65%, and thermal stability[97] . Metal oxides including TiO2, [63]
which contributes excess capacity but leads to irreversible WO3, [98] SnO2, [99] ZrO2, [100] La2 O3, [101] V2 O5 [102] et al.
O loss and associate surface reactions. have been used as coating substances to reduce the charge
Although it is easier to think of these as separate phe- transfer resistance of material and improve electrochemi-
nomena, they in fact are deeply interconnected. During cal reversibility. Based on previous research, the materials
the battery cycling process, especially under the high are continuously improved. Wang et al. prepared an ultra-
working potential, a variety of problems exist at the same thin Al2 O3 film on NCM622, which facilitated ion diffu-
time. The emergence of one phenomenon will accompany sion dynamic characteristic and improved electrochemical
or even aggravate the emergence of other problems, which stability.[103]
brings great challenges to the research. The surface struc- In addition to exploring the effects of different mate-
ture reconstruction increases the surface resistance of rials, new methods have also been developed. Cao et al.
cathodes and the stress induced cracking exposures fresh identified a green and simple coating way to dispersed
cathode surfaces to electrolyte, leading to more severe side Al2 O3 on the cathode surface, the modified cathode
reactions and inefficient CEI generation. The products of materials has excellent high-voltage performance.[104]
electrolyte decomposition are considered to be the main Jiang et al. explored a novel concept to modify primary
components of CEI, with the part of dissolved transition particles of cathode materials by engineering their exposed
metals participating in. The dissolution of transition surface with Na2 MoO4 coating layer, the functionalized
metal and release of oxygen add to the sophistication cathode shows superior cycling performance.[105] Since
of the interface reactions. The origination can be traced that covalent P-O bonds, phosphates such as AlPO4, [106]
to a large number of Li extraction and the changes of MnPO4, [62] exhibit high stability, and lithium-containing
electronic structure and crystal structure under high volt- compounds Li3 PO4, [107] Li2 SiO3, [108] LiAlO2 [109] that with
age. Fortunately, an improvement strategy may alleviate stable chemical properties are widely used as coating
several problems at the same time and ultimately improve layers for fast Li+ conduction. Fluorides suppressed
the cycling stability of NCM batteries under high cutoff oxidation decomposition of the electrolyte on the surface
voltage. of cathode materials.[110] However, inorganic materi-
als tend to deposited on cathode material surface and
they always need complex and expensive processing
3 MODIFICATION steps. Therefore, Lee et al. modified NCM cathode with
poly(tris(2-(acryloyloxy)ethyl) phosphate) (PTAEP) gel
To solve the problems mentioned above, many methods polymer electrolyte.[111] The coating layers serve as
have been proposed successively, such as coating, doping, ion-conductive protective film that effectively improve
WU et al. 123

electrochemical performance of the NCM111 at high- degradation and performance deterioration of NCM.[125]
voltage. Neudeck et al. used organophosphates, However, traditional doping elements are generally inac-
specifically tris(4-nitrophenyl) phosphate (TNPP) and tive under the operating voltage, and the first charge capac-
tris(trimethylsilyl) phosphate as surface modification for ity of the battery decreases slightly with the increase of the
NCM622.[112] The results show that molecular coating is a doping amount. Hence, it is important to optimize a proper
useful method for improving cathode materials. doping amount to balance capacity and stability.
Artificial CEI film with high ionic conductivity and elec- In addition, anion doping has also been extensively stud-
trochemical/thermal stability is suitable for Ni-rich NCM ied. Compared with Li-O bond (341 kJ mol−1 ), Li-F bond
cathodes at high voltage to prevent the decomposition of (577 kJ mol−1 ) is stronger, and the stronger bond between
electrolyte.[113] To take advantage of that, some researchers TM and fluorine leads to more stable structure.[126] In addi-
make artificial CEI on the surface of NCM to achieve a tion, the substitution of fluorine at oxygen site can reduce
high interfacial stability. Jang et al. achieved nanoscale- part of the trivalent nickel (0.56 Å) to divalent nickel (0.69
based artificial CEI layers through the reaction of lithium- Å), thereby expanding lattice parameters.[127] Yue et al.
tetra(trimethylsilyl) borate and cathode material.[114] Chae doped NCM811 with fluorine to protect the electrode from
et al. developed an amphiphilic sulfonate-based artificial HF and maintain the structural stability of the electrode,
CEI, which effectively reduces undesired parasite reac- thereby improving its cycle performance.[126,128]
tions, leading to high interfacial stability and cycling However, there are few studies on the impact of doping
retention.[115] On this basis, he further improved the syn- on CEI, and further development is needed in the future.
thesis method by utilizing an organic surfactant with a sul-
fate functional group to provide a sulfate-embedded CEI
on the NCM8111 surface. Results indicate that modified 3.3 Synergetic modification of coating
NCM811 showed better cycling performance and capacity and doping
retention.[116] Most coating materials are detrimental to
electronic and lithium ion conductivities, which is harmful Considering advantages and disadvantages of doping and
to the electrochemical performances of NCMs. coating, researchers combined these two methods to mod-
ify NCM. Chen et al. covered cadmium oxide on the sur-
face of NCM622 particles, at the same time, a part of cad-
3.2 Doping mium oxides diffused into the crystal lattice with gradi-
ent distribution.[120] Li et al. synthesized LiAlO2 -coated
Doping NCM with cations or anions is another way to mod- and Al-doped NCM523 via a facile coprecipitation method,
ify cathode materials. Anion doping improves the ther- electrochemical test results show that Al-modified sample
mal and structural stability of cathode electrode by par- shows better capacity retention and cycling performance
tially replacing O2− , and stabilizes the discharge poten- than pristine NCM.[129] Similar to this, Ran et al. applied
tial platform.[117] Cation dopants can migrate into Ni, Co gradient phosphate polyanion doping and in-suit coating
or Mn sites, but rarely in Li sites.[54] It reported that of nano-scale Li3 PO4 layer to enhance the properties of
substitution of Co sites generally enhances the charge NCM622.[130]
transfer, while substitution of Mn sites hinders evolu- The substitution of metal ion enlarges the inter-layer
tion of gas and mixing of cations.[118] The metal ion may spacing and coating layer acts as a protective shell
have a larger ionic radius and can be used as pillars for and suppresses various adverse effects during cycling,
both lithium ion layer and transition mental layer, and especially under high-voltage. The steps to achieve the
it can also change the valence states of transition metals co-modification of doping and coating are shown in
or oxygen.[119,120] Jia et al. synthesized layered Nd-doped Figure 11.
NCM523, confirmed that Nd3+ expanded Li-ion channels
and strengthen bonding energy, results in improvement of
structural stability and electron transfer.[121] Mg also shows 3.4 Structural modification
the same effect.[122] Schipper et al. combined computation
and experiment to explore the impact of Zr4+ on the elec- 3.4.1 Concentration gradient
trochemical behavior of NCM622.[123] Zhang et al. substi-
tuted oxygen ions of NCM622 with the boracic polyanion to Although it is possible to improve cycling performance
suppress capacity degradation.[124] To alleviate the struc- of NCMs by coating and doping foreign elements, it is
ture degradation of NCM811, Yang introduced low-content far from enough to meet the performance requirements
Li2 MnO3 as structural stabilizer to suppress the phase of maintaining the battery at high operating voltage for
transition and revealed the relationship between structure a long time. To optimize the NCM electrode material
124 WU et al.

F I G U R E 1 1 A, Schematic illustrations of the microstructure evolution and the reaction mechanisms of Cd-modified NCM622. Reprinted
with permission.[118] Copyright 2018, Elsevier. B, Schematic of the synthesis process of LiNi0.6 Co0.2 Mn0.2 O2 -x (PO4 )x @Li3 PO4 cathode. Reprinted
with permission.[130] Copyright 2019, Elsevier. C, Schematic diagram of the synthesis process for different Al-modified LiNi0.5 Co0.2 Mn0.3 O2
samples. Reprinted with permission.[127] Copyright 2018, Elsevier

more rationally, we need to focus on elements that tration gradient (FCG)[139–143] and two-sloped full-
make up the material. The higher the Ni content, the concentration gradient (TSFCG).[141,142,144–147]
larger the capacity of the battery. Co is usually added Core-shell structure means that two or more materials
to improve layered ordering and electrical conductiv- with different chemical structures are used as shell and
ity to enhance rate capability, while Mn is effective in core respectively in a certain way to construct a novel mate-
inhibiting undesirable chemical and structural changes rial, so as to achieve combination advantages of a variety
in the material at high voltage.[7,53,131,132] Therefore, the of materials. By developing a core/shell NCM particle in
NCM electrode material can be designed as Ni-enriched which the surface is enriched Mn thin layer and Ni-rich
interior and Mn-enriched exterior to obtain both large core can combine effects of Ni and Mn, which will signif-
capacity and high stable interface. This concept has icantly improve the structure stability during cycling by
been proposed since 2005[133] and has developed a partially reducing the Ni3+ ions to more thermodynami-
number of configurations involving core/shell,[133–137] cally stable Ni2+ .[147] On the basis of this idea, a fully func-
core/compositionally graded shell,[137,138] full concen- tional microscale core/shell cathode was realized using a
WU et al. 125

F I G U R E 1 2 A, Schematic diagram of positive-electrode particle with Ni-rich core surrounded by concentration-gradient outer layer.
Reprinted with permission.[146] Copyright 2009, Springer Nature. B, Schematic diagram of the FCG lithium transition-metal oxide particle
with the nickel concentration decreasing from the center towards the outer layer and the concentration of manganese increasing accordingly.
Reprinted with permission.[138] Copyright 2012, Springer Nature

coprecipitation method.[139] Sun et al. proposed a spherical rial gradually emerges. Internal and shell material’s ele-
core/shell structure with a high capacity (delivered from ments are not identical and discontinuous in the structure,
the LiNi0.8 Co0.1 Mn0.1 O2 core) and a good thermal stability two or more types of heterogeneous experience different
(achieved from the LiNi0.5 Mn0.5 O2 shell).[133] This mate- changes in lattice volume, and large boundary cracks and
rial delivered a reversible capacity of 188 mAh g−1 with void formation can be observed at their junction, that is,
the cutoff voltage of 3.0–4.3 V versus Li/Li+ and increased the shell is “stripped” from material body, hindering Li+
the onset temperature of the exothermic decomposition migration and electron transfer, and the battery’s perfor-
from 220 °C for conventional NCM811 material to 250°C. mance deteriorates dramatically.[134,137] To alleviate this,
Moreover, the C/Li[Ni0.8 Co0.1 Mn0.1 ]0.8 [Ni0.5 Mn0.5 ]0.2 O2 Sun et al. introduced a concentration gradient at the shell
cell exhibited splendid cyclability with a capacity reten- part (Figure 12A) to weaken incongruous strain between
tion of 98% compared with the C/NCM811 cathode without compositions.[147] This material achieves not only a very
LiNi0.5 Mn0.5 O2 shell which only hold 81% capacity after high reversible capacity of 209 mAh g−1 (55°C between
500 cycles. This core/shell structure can be regarded as an 3.0 and 4.4 V) based on the particle bulk composition of
extension of surface coating, and active materials are often LiNi0.8 Co0.1 Mn0.1 O2 , but also excellent cycling and safety
used as the shell, which can provide partial capacity while characteristics, which are attributed to the stability of
protecting bulk cathode materials. Cho et al. reported a the concentration-gradient outer layer and surface com-
LiNi0.54 Co0.12 Mn0.34 O2 cathode material which consists of position of LiNi0.46 Co0.23 Mn0.31 O2 . Nonetheless, limited
a layered phase core and stable spinel phase shell possesses by thickness of shell, the modified cathode material still
both high energy and safety on account of aforementioned exhibits inadequate structural stability, especially for cir-
two heterostructures.[136] The material demonstrated a culation under high voltage. Based on this, Sun et al. rec-
reversible capacity of 200 mAh g−1 when cycled between ommended a FCG nanostructure (Figure 12B), where the
3.0 and 4.5 V. It retained 95% capacity retention under the Ni concentration decreases linearly whereas the Mn con-
most severe test condition of 60°C and the amount of oxy- centration increases linearly from the center toward the
gen evolution from the lattice in the cathode is reduced by outer layer of each particle.[139] Meanwhile, the Co con-
70% as well. The eminent results of above two works are centration is gradually varied from bulk to surface, which
attributed to integration functions of Ni-rich core and Mn- will minimize the structure mismatch as well. This newly
rich shell materials. High nickel content ensures that the developed material can deliver a specific capacity of up to
cathode material has a high capacity, and Mn-rich stable 215 mAh g−1 which cycled at 0.2◦ C and 2.7–4.5 V. And it
spinel phase shell suppresses the interface reaction at CEI, also maintained 90% capacity retention after 1000 cycles,
ensuring the stability and safety of battery under high volt- which really revealed outstanding cycling stability in a full-
age. However, after long-term cycling under high voltage, cell configuration. The FCG particle composed of elon-
the disadvantage of this kind of combined cathode mate- gated primary particles which had strong crystallographic
126 WU et al.

FIGURE 13 Schematic of the synthesis process of PSB-NCM. Reprinted with permission.[148] Copyright 2016, Wiley

texture and c-axis of the unit cell aligned in the trans- Therefore, this unique structure of the PSB-NCM cathode
verse direction radially aligned toward the particle cen- showed superior structural stability at a high voltage cut-
ter. Hence, the layered planes were oriented along the off of 4.45 V and high thermal stability at 60◦ C. The above
radial direction and formed a unique morphology, facili- research progresses on the concentration gradient of NCM
tating Li+ transport, minimizing contact with electrolyte materials provide references for us to reasonably design
to have a stable CEI under high voltage charging.[138,144,148] the material structure and improve thermodynamic sta-
In order to further improve capacity and stability of NCMs bility. In the end, the CEI is stabilized to reduce parasitic
under high voltage, a TSFCG Ni-rich cathode was devel- reactions and optimize battery performance. However, due
oped to maximum the Ni concentration near the core and to the material preparation process is more complicated,
the Mn concentration at the surface. Sun et al. developed the calcination temperatures of Ni-enriched core and Mn-
a high-performance LiNi0.65 Co0.13 Mn0.22 O2 cathode mate- enriched shell are different, and passivation method to
rial composed of layered lithium transition metal oxide suppress the surface Mn dissolution is also needed,[150] the
with TSFCG within each particle.[141] This material deliv- industrialization of this material requires more advanced
ered a reversible capacity of 200 mAh g−1 (4.3 V cutoff) equipment and higher costs, namely, the problem of
compared with conventional electrode’s 187 mAh g−1 and cost performance needs to be considered. Therefore,
excellent capacity retention of 88% in contrast to 71% of more systematic analyses are needed on the road to
conventional electrode after 1500 cycles at 1 C in full-cell commercialization.
configuration. Each TSFCG secondary particle consisted
of rod-shaped primary particles that radially oriented from
the particle center, further pushing the boundaries. Jaephil 3.4.2 Single crystalline
Cho et al. synthesized a highly stable transition-metal self-
induced concentration gradient LiNi0.6 Co0.2 Mn0.2 O2 cath- For the preparation of traditional polycrystalline NCM
ode exploiting polystyrene beads (PSBs) cluster incorpo- cathode materials, spherical secondary particles formed
rated coprecipitation method without the additional metal from randomly orientated primary particles. In the process
tank, decreasing the process time and capital cost (Fig- of cycling, the volume of primary particles will change in
ure 13).[149] According to the reduction mechanism of Ni anisotropy gradually along with Li+ de-intercalation and
ions and changes of oxidation state of Ni element, other charge compensation between transition metal elements,
transition metal ions can form the concentration gradients resulting in intergranular cracks, secondary particles’
in the primary particles from surface to core direction to rupture and the structure of cathode being destroyed.
balance charge neutrality. In addition, internal pore spaces And high operating voltage and long-term cycling will
which were generated by the thermal decomposition of aggravate rupture. At the same time, the electrolyte
PSBs during annealing process can be a buffer in the sec- also penetrates into secondary particles along the crack,
ondary particles to accommodate the strain generated dur- transition metals dissolve and react with electrolyte,
ing cycling as well as enhance the electrolyte wettability. which intensifies the phase transition of cathode material
WU et al. 127

F I G U R E 1 4 Electrochemical and interfacial stability of the single crystalline cathode. Schematics showing morphological and interfacial
changes of the polycrystalline and single crystalline cathode during the electrode pressing process and electrochemical cycling. Reprinted with
permission.[22] Copyright 2017, Wiley

from layered structure to rock salt phase and hinders the around 2∼3 μm to conventional polycrystalline uncoated
diffusion of Li+ . The impedance of CEI increases and the and Al2 O3 -coated NCM523 (AC-523) materials.[96] It was
battery’s initial Coulomb efficiency is low which cause shown that release of oxygen around 80°C from charged
battery capacity decay. In addition, there is oxygen loss AC-532 and UC-532 materials whereas it was not detected
accompanied with undesired heat release, causing hidden for charged SC-532 samples. Moreover, SC-523 cells pro-
trouble to safety. The working mechanism of monocrys- duce negligible compared with AC-523 cells’ substantial
talline materials as industrial cathodes’ materials is shown amounts of gas during potentiostatic holds at 4.4, 4.5,
in Figure 14.[25] There will be collapsed secondary particles and 4.6 V for a total time of 300 hours at 40°C. In
for the polycrystalline cathode material and could give rise addition, SC-523 cells had a lower mean parasitic heat
to the formation of resistant layer generated by interfacial flow than that of AC-532 cells in all voltage ranges and
side reactions during the electrode pressing process by exhibited a better capacity retention of ∼92% after 1600
high pressure. By contrast, the monocrystalline material cycles at 40°C between 3 and 4.4 V. It is the single crys-
maintains structural consistency and stable morphology, tal material’s superior stability and corresponding sta-
there is no anisotropic volume change in the cathode ble CEI that makes SC-523/graphite cells have outstand-
and void space between each primary particle during the ing performance at high voltage and high temperature.
pressing and battery cycling process. The morphological Yang et al. fabricated and investigated the integrated sin-
robustness could restrain the continuous formation of gle crystalline LiNi0.83 Co0.11 Mn0.06 O2 (SC-NCM) with pri-
resistance layer, which effectively alleviates particle frac- mary particles of 3∼6 μm diameter, and the SiO-C||SC-
ture and gas evolution, reducing impedance and battery NCM pouch-type full cell with a practical loading (8.7 mAh
performance degradation caused by unstable CEI. cm-2 ) achieved a satisfied energy density of 225 Wh kg−1
The stability of single crystal structure ensures excel- and delivered a capacity retention of 84.8% at 1◦ C after 600
lent electrochemical performance and safety of the bat- cycles at 45°C.[151] Additionally, SC-NCM coin cells exhib-
tery under high operating voltage. Dahn et al. compared ited higher discharge capacity of 162.6 mAh g−1 and main-
a single-crystal NCM523 (SC-523) material with grain size tained a capacity retention of 84.5% compared with normal
128 WU et al.

LiNi0.83 Co0.11 Mn0.06 O2 cells’ 135.7 mAh g−1 and 68.3% after like VC,[163] methyl phenyl carbonate, and diphenyl
150 cycles at 2.75∼4.4 V. The improved electrochemical per- carbonate.[164]
formance is mainly attributed to the fact that single crys- Ma et al. proposed that the functional coating at the
tal particles prevent interparticle rupture, avoid undesired positive electrode side may not be needed when appro-
interface contact between electrode and electrolyte, stabi- priate additives are used.[161] They evaluated the ODTO
lize CEI and inhibit irreversible phase transition of elec- as a novel electrolyte additive which has similar struc-
trode materials. To date, although single crystalline cath- ture to MMDS in both uncoated and coated single crys-
ode materials of high purity have been successfully synthe- tal LiNi0.5 Mn0.3 Co0.2 O2 /graphite pouch cells. Cells with
sized, its average particle size is still less than 1 μm, which uncoated NCM532 and additive blends containing 1%
indicates that the power tap/pellet density needs to be low- ODTO along with 1%LiPO2 F2 , 2% VC or 2%FEC showed
ered. In addition, limited by intrinsic structure, single crys- virtually identical cycling performance to cells with coated
tal materials cannot achieve reversible capacity compara- NCM532 and the same electrolytes. This result illustrates
ble to those of polycrystalline materials. Moreover, some that a coating layer is formed in situ on the surface of NCM
synthetic methods are not suitable for large-scale produc- cathode by these additives.
tion because of the use of volatile and toxic solvents. More Owing to single additive cannot always satisfy the
methods and resources are needed to solve the above prob- demands in practical application, the synergy effect
lems in the process of industrialization of single crystalline between various additives is needed to improve the per-
cathode. formance of the high-voltage NCM batteries.[165,166] In
this regard, J.R. Dahn et al. did a series of work to eval-
uate the blended electrolyte additives in the past few
3.5 Electrolyte additives years.[160,163,167,168] As shown in Figure 15, The charge
end-point capacity slippage, capacity fade, coulombic effi-
In addition to the improvements in the NCM cathode ciency, impedance change during cycling, gas evolution
materials, the interface problems under high voltage can and voltage drop during “cycle-store” testing were com-
also be effectively modified with the electrolyte additives. pared to gain an understanding of the effects of these
Adding a small amount of additives (typically 0.1∼5.0% promising electrolyte additives or additive combinations
by mass or volume fraction) to current commercial elec- on the different types of pouch cells. They found out that
trolytes is more economical and facile compared with 2 wt% PES+ 1 wt% TTSPi+ 1 wt% MMDS (PES-211) can
those strategies to design a new electrolyte formula or improve NCM111/graphite and NCM442/graphite cell per-
to coat on materials surface with annealing. Therefore, formance up to 4.4 V and even to 4.5 V by controlling
it is suitable for large-scale industrial production and impedance growth and improving capacity retention dur-
practical application. Analogous to anode additives, these ing long-term cycling. Nevertheless, further studies sug-
additives in high-voltage batteries mostly have higher gested that PES-211 is not suitable for the high nickel
HOMO level than the solvents, oxidizing prior to the NCM811 cathodes, indicating that there is a complex inter-
electrolytes. Then a stable cathode-electrolyte interface action between the additives and the cathode surface, thus
(CEI) layer is formed in situ on the surface of the positive the selection of additives should consider different positive
electrode, so as to prevent the side interface reactions by electrode systems.
avoiding direct contact between electrode and electrolyte. However, the effect mechanisms of these additives and
In order to be easily decomposed and to generate robust blend additives are unknown, thus more efforts are needed
CEI, the additives probably contain active functional to elucidate. It will be helpful to understand the mysteries
groups or unsaturated bonds which can be divided into if advanced characterization technologies like TOF-SIMS
the flowing categories: (1) lithium salts like lithium or operando liquid SIMS with theoretical calculation tools
dioxalate borate(LiBOB),[152] lithium difluoroxalate could be in use. Studying the mechanism of electrolyte
borate (LiDFOB)[153] and lithium difluorobis(oxalate) additives with the relationship between their structures
phosphate (LiDFBOP).[154] (2) boron-containing like and functions will make the optimization and combination
tris(trimethylsilyl)borate (TMSB),[155] trimethoxy borox- more efficiently.
ine (TMOBX).[156] (3) phosphorous-containing like Among the strategies mentioned above, they all have
tris(trimethylsilyl)phosphite (TTSPi),[157] triphenyl- merits and demerits to NCMs under high voltage. Their
phosphine Oxide (TPPO), [158] and 2-(2,2,2-trifluoroethoxy) comparation and main effects to CEI are summarized
-1,3,2-dioxaphospholane 2-oxide (TFEOP).[159] (4) clearly in Table 1. It is known to all that coating is the direct
sulfur-containing like methylene methane disul- way to construct the CEI artificially and controllably which
fonate (MMDS),[160] 1,2,6-Oxadithiane 2,2,6,6-tetraoxide would be promising to address the problems between cath-
(ODTO),[161] and divinyl sulfone.[162] (5) carbonate odes and electrolytes.
WU et al. 129

F I G U R E 1 5 Radar plots summarizing the effects of selected electrolyte additives (combinations) on A, NCM111/graphite, B,
NCM532/graphite, and C, NCM622/graphite pouch cells studied using UHPC and the “cycle-store” procedure to 4.4 V. The axes are normalized
to the worst value being equal to 100% and they consist of the average coulombic inefficiency (CIE) (from 11 to 15 cycles), the average charge
end-point capacity slippage (from 11 to 15 cycles), the impedance (Rct) after UHPC cycling, the gas evolution during UHPC cycling, the capacity
loss after 35 “cycle-store” cycles, the impedance after the whole “cycle-store” process, the voltage drop at 35 “cycle-store” cycle and the gas evo-
lution during the whole “cycle-store” process. Values closest to the center of the radar plot are best. Reprinted with permission.[160] Copyright
2015 Elsevier

4 CONCLUSIONS AND PROSPECTS increased as well. Moreover, the effective components

of electrolyte and electrode material are consumed, and
In this review, in order to pursue higher energy and finally the capacity is attenuated and the battery is dam-
more stable Li-based batteries, we analyzed the perfor- aged. Finding appropriate means to ensure stable CEI
mance of NCMs which is currently considered to be during battery cycling can reduce gas production, improve
the most promising of next generation of lithium ion battery electrochemical and thermodynamic stability, and
batteries under high operating voltage. This review mainly raise safety level. Some strategies have been proposed,
discusses the decay mechanism of electrode materials, including surface coating, element doping, structure
CEI, and solutions to key problems. Stable CEI is the design, utilizing electrolyte additives and so on. Surface
premise that battery can circulate normally under high coating refers to the artificial construction of a stable layer
voltage. But under normal circumstances, in the process on the surface of cathode material to reinforce secondary
of cathode’s charging and discharging, cationic mixing particles. By acting as a physical barrier, the electrode
and secondary particles rupture will occur, resulting material is separated from electrolyte, phase transition and
in the irreversible phase transition of cathode material transition metal dissolution are inhibited at high voltage,
from layered phase to spinel phase and then to rock salt and interfacial side reactions are suppressed. However,
phase. The side reaction between electrolyte and electrode the material type and thickness of coating layer need to be
is intensified, the impedance and gas production are selected and controlled reasonably. The surface material
130 WU et al.

TA B L E 1 The comparation of different modification methods under high voltage

Modification
methods Advantages Disadvantages Main effect to CEI
Coating 1. Act as a physical barrier 1. Material type selection Artificial construction
2. Suppress interfacial side 2. Thickness controlling of CEI
reactions 3. Capacity sacrifice

Doping 1. Maintain a relatively stable 1. Reversible capacity sacrifice Reduce the volume
structure 2. Doping content controlling anisotropy and CEI
2. Suppress the phase transition fracture

Concentration 1. Same trend lattice volume change 1. High requirements for equipment Reduce the volume
gradient 2. Inhibit particle rupture and operating condition anisotropy and CEI
2. Not suitable for industry fracture

Single 1. Good stability nature 1. capacity release, preparation Form stable CEI
crystalline methods and tap density
improvement
Electrolyte 1. Economical and facile 1. Hard selection In situ formation of
additives 2. Easy to applicate in industry 2. Decomposition during cycling CEI

with electron and ionic conductive characteristics and high voltage. The capacity density, preparation methods
reasonable thickness can ensure sufficient protection for and tap density of these particles still need to be improved.
electrode material without lowering capacity and rate Many electrolyte additives have been reported to improve
performance. Otherwise, there will be a capacity sacrifice circulation performance under high voltage, and their
as a consequence of impeding Li+ migration and electron mechanisms are different. All the above problems need to
conduction. At present, methods that can precisely control be solved by more accurate optimization of NCM cathode
the coating thickness, such as atomic layer deposition materials. It is believed that the most popular way to
(ALD) and chemical vapor deposition (CVD), need rel- meet energy demand of EVs for industrial application
atively high cost. Element doping refers to replacing the should be economical, low requirements for equipment
transition metal ions or lithium ions selectively according and production conditions, simple and easy to promote.[6]
to the size of the foreign elements’ ion radius, and making The interface layer is formed in situ by adding a small
the cathode material maintain a relatively stable structure amount of electrolyte additives, and it only needs simple
under high operating voltage through the regulation of operation to realize this process, therefore, electrolyte
lattice parameters at the atomic level. However, due to additives are considered to be more facial and economic
the replacement of some active materials by chemically than other modifications and are more commonly used in
inactive foreign elements, the reversible capacity of some industry.[7] In order to realize the commercialization of
batteries will be reduced, and element doping content high voltage NCMs, our future work will not only focus
needs to be controlled. The synergistic effects of surface on electrode material and electrolyte, but also explore the
coating and element doping can stabilize material struc- CEI that can more safely match the solid electrolyte.
ture and CEI under high voltage simultaneously, but this Next-generation layered NCM cathodes will enable a
will undoubtedly combine negative effects as well, it is specific energy of 300∼350 or 350∼500 Wh kg−1 when
worth considering how to reasonably select parameters. By they are matched with graphite-silicon or Li metal anode
constructing concentration gradient distribution of nickel respectively, with a driving range of at least 300 miles from
and manganese elements in secondary particles, the lattice a single charge.[6] Increasing the Ni fraction, optionally
volume change of each primary particle has the same coupled with extended operating voltages of NCM cath-
trend under high voltage, which inhibits particle rupture ode materials, which will further drive up energy out-
and stabilizes CEI. Whereas the method of concentration put, are considered as effective means to increase the
gradient design has high requirements for equipment and corresponding battery capacity. And high-nickel layered
operating conditions, it is not suitable for large scale pro- oxides under high operating voltage will occupy a major
duction. Particles in single crystalline morphology have position in Li-based automobile batteries at least through
very good stability nature, which is friendly for forming the next decade. Range and safety requirements remain
stable CEI and maintaining the stability of battery under important threshold for battery commercialization. Using
WU et al. 131

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Qian Wu and Shulan Mao contributed equally to this work. Aurbach, D. Major, G. Goobes, M. Dixit, N. Leifer, Energy Env-
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