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PROGRESS REPORT
Nickel-Rich and Lithium-Rich Layered Oxide Cathodes:
Progress and Perspectives
Arumugam Manthiram,* James C. Knight, Seung-Taek Myung,* Seung-Min Oh,
and Yang-Kook Sun*

cathode materials that have improved

Ni-rich layered oxides and Li-rich layered oxides are topics of much research capacity, stability, rate capability, cycle life,
interest as cathodes for Li-ion batteries due to their low cost and higher and safety, while keeping the cost low.
discharge capacities compared to those of LiCoO2 and LiMn2O4. However, Ni-rich layered oxides (NLOs) and Li-rich
layered oxides (LLOs) are two families of
Ni-rich layered oxides have several pitfalls, including difficulty in synthesizing a
cathodes that have received lots of atten-
well-ordered material with all Ni3+ ions, poor cyclability, moisture sensitivity, a tion as potential next-generation cathodes
thermal runaway reaction, and formation of a harmful surface layer caused by for LIBs. The prime advantage of these
side reactions with the electrolyte. Recent efforts towards Ni-rich layered oxides materials is their high discharge capaci-
have centered on optimizing the composition and processing conditions to ties (200 – 220 mAh g−1 for NLOs and
250 – 300 mAh g−1 for LLOs) and energy
obtain controlled bulk and surface compositions to overcome the capacity fade.
densities, as they represent a significant
Li-rich layered oxides also have negative aspects, including oxygen loss from improvement over the most common com-
the lattice during first charge, a large first cycle irreversible capacity loss, poor mercial LIB cathodes: LiCoO2 (140 mAh g−1),
rate capability, side reactions with the electrolyte, low tap density, and voltage LiNi1/3Co1/3Mn1/3O2 (160 mAh g−1), and
decay during extended cycling. Recent work on Li-rich layered oxides has LiMn2O4 (120 mAh g−1). The other ben-
focused on understanding the surface and bulk structures and eliminating the eficial trait of these layered oxides is their
lower cost due to a reduction in Co con-
undesirable properties. Followed by a brief introduction, an account of recent
tent. Although both NLOs and LLOs are
developments on the understanding and performance gains of Ni-rich and Li- similar in their basic composition and
rich layered oxide cathodes is provided, along with future research directions. structure, they differ significantly in their
electrochemical behavior/properties and
crystal chemistry. NLOs suffer from the
challenge of maintaining all Ni in the 3+ oxidation state during
1. Introduction
synthesis, capacity fade, detrimental side reactions with the
Li-ion batteries (LIBs) have become prevalent in modern day electrolyte caused by the high cycling voltage, and safety issues
society, as they power cell phones, laptops, and electric vehi- resulting from thermal runaway reactions. The structure of
cles (EV), among other items. Significant research attention is LLOs is described by researchers as either a solid solution or
focused on them in order to expand their use in the EV market a nanocomposite of Li2MnO3 and LiMO2, where M is a collec-
and for possible deployment in grid storage applications for tion of metals, most often Mn, Ni, and Co. The high discharge
renewable power sources, such as wind, solar, and geothermal. capacity of LLOs is derived from its unique first charge-dis-
One of the most explored areas of research in LIBs is designing charge cycle that consists of transition-metal (TM) oxidation fol-
lowed by the oxidation and loss of oxide ions from the lattice
during charge, which leads to a compensatory Mn reduction
Prof. A. Manthiram, Dr. J. C. Knight during discharge. Unfortunately, a myriad of challenges are
Electrochemical Energy Laboratory also associated with LLOs. The LLOs suffer from oxygen loss
McKetta Department of Chemical Engineering from the lattice during first charge, high first cycle irreversible
The University of Texas at Austin
Austin, TX 78712, USA capacity loss (IRC), poor rate capability, low volumetric energy
E-mail: manth@austin.utexas.edu density due to a low tap density, and a substantial voltage decay
Prof. S.-T. Myung over extended cycling due to a transformation to a spinel-like
Department of Nano Engineering phase. These issues will be discussed in further detail here.
Sejong University
Seoul 143–747, South Korea
E-mail: smyung@sejong.ac.kr
Dr. S.-M. Oh, Prof. Y.-K. Sun 2. Ni-Rich Layered Oxides
Department of Energy Engineering
Hanyang University 2.1. LiNiO2
Seoul 133–791, South Korea
E-mail: yksun@hanyang.ac.kr LiNiO2 has the α-NaFeO2 structure with the oxide ions forming
DOI: 10.1002/aenm.201501010 a cubic close-packed arrangement (Figure 1a). LiNiO2 was first

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introduced by Dyer et al. in 1954.[1] After the successful launch

of the Li-ion battery in 1991, which used LiCoO2 as the cathode Arumugam Manthiram is
material, LiNiO2 has sparked a great deal of interest due to its a Professor and holder of
cost effectiveness and structural similarity to LiCoO2. However, the Cockrell Family Regents
it is rather difficult to synthesize the stoichiometric LiNiO2 with Chair in Engineering in
a Li:Ni ratio of 1:1. The synthesis often results in the formation the Materials Science and
of a lithium-deficient Li1-xNi1+xO2 with part of the Ni present Engineering Program and
as Ni2+ and cation mixing between Ni and Li, as it is difficult Department of Mechanical
to maintain all Ni as Ni3+ at the high synthesis temperatures Engineering at the University
of >700 °C.[2] The presence of Ni in the Li layer can impede Li+ of Texas at Austin. He is
diffusion and lower rate capability.[3] Nonetheless, Dahn et al. also the Director of the
demonstrated the feasibility of coupling Li0.96Ni1.04O2 with coke Texas Materials Institute and
as the anode, which could operate for 300 cycles (Figure 1b).[2a] the Materials Science and
Ohzuku et al. evaluated the relationship between the crystal Engineering Program. His research interests are in the
structure and electrochemical performance,[4] i.e., the integrated area of rechargeable batteries, fuel cells, and solar cells,
intensity of I(003)/I(104) is a key parameter that represents including novel synthesis approaches for nanomaterials
the degree of mixing of Ni and Li ions. Minimization of such and nanocomposites.
disorder resulted in a high capacity and good reversibility
James C. Knight received his
(Figure 1c). Carrying out the synthesis in a flowing oxygen
B.S. degree from the William
atmosphere or using excess Li precursor in the initial reaction
G. Lowrie Department of
mixture is helpful to decrease the amount of Ni2+, although not
Chemical and Biomolecular
completely successful to keep as all Ni3+, and obtaining over
Engineering at The Ohio
200 mAh g−1 with good cyclability.[5]
State University in 2009.
He received his Ph.D. from
the McKetta Department of
2.2. LiNi1-xMxO2 (M = metal)
Chemical Engineering at the
University of Texas at Austin
The above-mentioned results indicate the difficulty of syn-
(UT-Austin) under the super-
thesizing stoichiometric LiNiO2. These drawbacks could be
vision of Prof. Arumugam
greatly mitigated by substituting other ions such as Co,[5c,6]
Manthiram. His research focused on Li-rich layered oxides
Fe,[7] Mn,[5c,7b,8] Ti,[5c,9] Mg,[9c,10] and Al[9d,e,10g,11] for Ni. Substitu-
and spinel materials for Li-ion and other advanced battery
tions impact the layeredness of the structure, its stability upon
applications.
lithium deintercalation, the capacity, and more importantly, the
thermal properties at highly delithiated states.
Yang-Kook Sun obtained
his Ph.D. degree from
Seoul National University,
2.2.1. Co Substitution
South Korea, and has
been a Professor of Energy
The LiNi1-xCoxO2 solid solution is interesting in terms of struc-
Engineering at Hanyang
ture and electrochemical performance due to its ease of synthesis
University, South Korea, since
and the similar redox potentials of Ni3+/4+ and Co3+/4+, which
2000. His research interests
enables high voltage operation. Indeed, flowing oxygen was nec-
are synthesis of new electrode
essary to prepare LiNiO2 to minimize the formation of Ni2+ and
materials for lithium-ion bat-
cation disorder. For the synthesis of the LiNi1-xCoxO2 solid solu-
teries, sodium-ion batteries,
tion, however, oxygen is not necessarily required to produce a
lithium-sulfur batteries, and
well-defined rhomboheral layered structure. Zhecheva et al. and
lithium-air batteries. In particular, he is developing next-
Delmas et al. showed that Co substitution was highly effective
generation cathode metals such as core–shell, core–shell
in lowering the cation mixing between the Li and TM layers.[6b,c]
with concentration gradient, and full concentration gra-
Although a multistep phase transition occurs in LiNiO2 during
dient transition-metal oxides for lithium-ion battteries.
charge–discharge, improvement in the initial structural integrity
simultaneously stabilizes the structure during cycling, leading
to a single-phase reaction for LiNi0.5Co0.5O2 during repetitive Li+ amounts of Fe and Ni present in the Li layers and the real com-
de-/intercalation.[2d,6d] As a result, the capacity loss was not sig- position exists as Li1-x(Ni1-yFey)1+xO2, as proved by the Rietveld
nificant for Co-doped LiNiO2 (Figure 1d). refinement results obtained from X-ray diffraction (XRD) and
magnetic studies, lowering the rate capability.[7a] The material
2.2.2. Fe Substitution also exhibits a large irreversible capacity in the first cycle and
its capacity retention is unacceptably low, which can be ascribed
In terms of cost, Fe is one of the best candidates because of its to the structural disorder with serious cation mixing in the Li
abundance in the earth’s crust. However, there are always large layers.[7c]

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Figure 1. a) Schematic drawing of O3 type α-NaFeO2 crystal structure:
red circles denote Li and blue octahedra (M) represent transition metal
layers. b) V(y) for Li/Li1-xNiO2 cells: (solid curve) first charge and dis-
charge to 2.0 V, (small dashed curve) second charge and discharge to
1.7 V, (large dashed curve) third charge. Reproduced with permission.[2b]
Copyright 1990, Elsevier. c) Electrochemical activity of Li1-xNiO2 pro-
duced by conventional ceramic method through calcination of LiNO3
and NiCO3 at 750 °C in O2 stream. Reproduced with permission.[2d]
Copyright 1993, The Electrochemical Society. d) Cycle number versus
energy plot of Li/LixNi0.7Co0.3O2. Reproduced with permission.[6c] Copy-
right 1993, Elsevier. e) Electrochemical stability of LiNi1-xTixO2 (x = 0.025
– 0.2). Reproduced with permission.[9b] Copyright 2001, Elsevier. f) Cycla-
bility of Mg doped LiNiO2 cycled in the voltage range of 3.1–4.4 V at
a constant current of 0.25 mA cm−2. Reproduced with permission.[10a]
Copyright 2000, The Electrochemical Society. g) Continuous charge and
discharge curves of LixNi0.89Al0.16O2 cycled at C/20 rate. Reproduced with
permission.[11b] Copyright 2003, Elsevier. Thermal gravimetric analyses for
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PROGRESS REPORT
2.2.3. Mn Substitution
As an alternative substituent, Mn is worthy because of its low
cost and the similarity of the ionic radii of Mn3+ (0.65 Å) and
Ni3+ (0.60 Å). The solid solution of LiNi1-xMnxO2 is isostruc-
tural with LiNiO2, but the diffraction profiles indicate merging
of the (006)/(102) and (108)/(110) pairs, which is close to cubic
symmetry.[8a] The Rietveld refinement analysis suggests cation
mixing between Li and Ni due to the internal redox reaction
Mn3+ + Ni3+ → Mn4+ + Ni2+ as the Mn3+/4+ energy lies above
the Ni2+/3+ energy. The creation of Ni2+ leads to increased Li/
Ni interlayer mixing due to the smaller size difference between
Ni2+ (0.69 Ǻ) and Li+ (0.76 Ǻ) ions. The cation mixing results
in a degradation of the electrochemical properties, although the
thermal stability is improved at the highly delithiated state.[5c]
2.2.4. Ti Substitution
Earlier studies reported the failure of Ti substitution because
cation mixing was more progressed in the Li layers. Because Ti
exists as Ti4+ in layered oxides, Ni2+ ions are formed to main-
tain charge neutrality, leading to increased cation disorder.[9a]
Kim and Amine suggested that the introduced tetravalent Ti
renders the structure rigid.[9b] This is a reasonable assumption
because the Gibbs energy for the formation of TiO2 at 25 °C
(–888.8 kJ mol−1) is sufficiently low to stabilize the crystal struc-
ture. The Ti substitution leads to good electrochemical perfor-
mance (Figure 1e) at low doping levels (≈5%), but above which
the resulting crystal structure becomes seriously disordered
with a low c/a ratio and broadened full-width of half maximum
values of the diffraction peaks. A few later studies also demon-
strated the effects of Ti on the structural and electrochemical
performance.[9e,f ]
2.2.5. Mg Substitution
Another approach to minimize the occupation of divalent Ni
in Li layers is to replace the divalent Ni present in Li1-xNi1+xO2
by Mg. In addition, Mg is known to improve the electric con-
ductivity in LiCo1-xMgxO2 as a result of the formation of holes
in the Co3+/4+ t2 band.[12] Rietveld refinement of the XRD data
shows that the lithium deficiency space is filled with Mg2+ ions
due to the similarity of the ionic radii of Li+ (0.76 Å) and Mg2+
(0.72 Å), which does not participate in the redox process.[10c,d]
Hence, the crystal structure is less affected by severe shrinkage
of the interlayer spacing upon lithium deintercalation.
These structural aspects endorse the significant improvement
of the cycling behavior (Figure 1f). The general characteristics
of the substitution of divalent ions include i) improvement of
the thermal stability, ii) durability during high voltage opera-
tion, and iii) good cyclability.[10a,b] In addition, it is expected that
in the charged state, the Mg doping prevents the decomposition
h) Li0.30Ni1.02O2, i) Li0.30Ni0.89Al0.16O2, and j) Evolution of the chex/ahex ratio
versus temperature for Li0.50Ni1.02O2, Li0.50Ni0.89Al0.16O2, Li0.30Ni1.02O2,
and Li0.30Ni0.89Al0.16O2. Panels (h–j) reproduced with permission.[11c]
Copyright 2003, American Chemical Society.
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of Lix<0.3NiO2 into a spinel-like phase or into LiNiO2 and NiO
with the release of oxygen. The effect of Mg can be summa-
rized as follows: i) the presence of inert species on the TM site
helps prevent overcharging during charge and ii) the doped
Mg reinforces the interatomic bonding in the NiO2 layers. As a
result, the exothermic reaction could be reduced and the main
reaction temperature shifts toward a higher temperature. These
phenomena are associated with structural stabilization achieved
by Mg substitution.
2.2.6. Al Substitution
Replacement of Ni with Al is advantageous because the
atomic weight of Al is lighter than that of other TM ions, so
LiNi1-xAlxO2 has an increased theoretical gravimetric capacity
for a given amount of Li extraction. It is generally known that
Al replacement for the TM site is not easy because of the for-
mation of undesired oxide phases such as β-LiAlO2, Al2O3,
and γ-LiAlO2 when calcined above 600 °C. This is because the
phase formation reaction rate of Al progresses slower than
those of Li and Ni when a conventional solid-state reaction
method is employed. For this reason, coprecipitation,[11b,c] sol-
gel,[11d] or solution-based synthesis methods[11e] are preferred
to obtain phase-pure LiNi1-xAlxO2. Since α-LiAlO2 (a = 2.800 Å,
c = 14.22 Å) has a smaller a-axis and larger c-axis than LiNiO2
(a = 2.880 Å, c = 14.19 Å), an anisotropic change of the lattice
parameters is natural, provided that a solid solution is formed.
LiNi1-xAlxO2 suppresses all of the phase transitions observed for
the LiNiO2 system,[11a,b] i.e., the unit cell volume change was
only about 2.5% when Li+ was extracted up to Li0.2Ni0.75Al0.25O2,
maintaining the original rhombohedral structure throughout
Li+ extraction.[11a] This impressive structural stabilization is
observed only for the LiNi1-xAlxO2 system. In addition, the
reduction in the amount of the electro-active species Ni3+, made
through direct replacement with Al3+ in the TM site, negates
the benefits of the weight reduction and results in a capacity
decrease. The cycling performance, however, is significantly
improved due to structural stabilization (Figure 1g).
Interestingly, an additional voltage plateau is observed in the
range of 4.5 – 4.8 V for LiNi0.75Al0.25O2. Manthiram and Goode-
nough showed the influence of the inductive effect in increasing
the redox energy of the Fe2+/3+ couple when going from an oxide
such as Fe2O3 to a polyanion cathode such as Fe2(SO4)3.[13] In
that case, the stronger S–O bond weakens the Fe-O bond and
thereby increases the operating voltage of the Fe2+/3+ couple in
Fe2(SO4)3 compared to that in Fe2O3. By applying similar con-
siderations, the increase in the operating voltage with Al substi-
tution in LiNi0.75Al0.25O2 could be due to the weakening of the
Ni–O bond by the stronger Al–O bond through the inductive
effect. On Li+ extraction from LiNiO2, there is a formation of an
increasing amount of unstable Ni4+ in the electrode. The Ni4+ is
reduced to Ni3+ at an elevated temperature (300 °C), accompa-
nied by oxygen evolution from the host structure. Importantly,
the presence of Al3+ that is strongly bonded with oxygen sup-
presses oxygen release from the crystal structure (Figure 1h,i).
This would inhibit cationic migration, which delays the exo-
thermic phase transformation from rhombohedral to cubic
spinel with increasing temperature to 300 °C (Figure 1j).
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2.3. LiNi1–x–yMxM′yO2 (M, M′ = metal)
2.3.1. LiNi1–x–yMgxM′yO2 (M′ = Ti and Al)
The Ti and Al substituents do not seriously affect the crystal
structure, in particular Ni occupation in the Li layer, because
of the differences in the ionic radii, where the smaller Al3+
(0.535 Å) and Ti4+ (0.605 Å) preferentially locate in the TM
layers rather than in the Li layers. As mentioned previously,
Mg2+ is effective in increasing the electrical conductivity. Ti4+
compensates for the charge deficiency caused by the divalent
Ni in the TM layers. These synergetic effects greatly improve
the structural integrity. Apart from the structural aspect, the
addition of these electroinactive moieties tends to lower the
delivered capacity because of the reduced amount of the elec-
trochemically active Ni3+/4+ in the oxide matrix. The electro-
chemical results of the Li[Ni0.75Mg0.125Ti0.125]O2 cathode include
retention of 89% of its capacity over approximately 85 cycles in
the voltage range of 3.0–4.5 V, although the initial capacity was
reduced due to the presence of redox-inactive elements in the
compound, as expected.[14] The co-doped LiNi0.90Al0.05Mg0.05O2
exhibited good reversible capacity with excellent capacity reten-
tion (Figure 2a).[11e] This may result from the presence of the
strong Al–O bond, which renders the oxide matrix more rigid.
These systems were found to show significantly improved
thermal behavior at the expense of capacity. The inert elements
prevent the complete removal of all the lithium, which mini-
mizes possible structural collapse and oxygen evolution from
the highly delithiated host structure. This is achieved by the
improved structural integrity originating from the effects of
strong Al–O and Ti–O bonds on the crystal structure, which
suppresses oxygen evolution.
2.3.2. LiNi1–x–yCoxAlyO2
Co-doped LiNi1-xCoxO2 was identified to possess improved
electrochemical properties, which was supported by the forma-
tion of a better layered structure, as described in Section 2.2.1.
Additionally, this system requires less severe synthesis condi-
tions. However, Abraham et al. pointed out that the formation
of an insulating LixNi1-xO-type layer on the particle surface is
the main reason for the 43% power fade of the LiNi0.8Co0.2O2
cell.[15] Based on the studies of Al3+ substitution, it is clear
that Al3+ substitution favors stabilization of the crystal struc-
ture, which significantly affects the electrode performance and
thermal stability. Guilmard et al. reported that the occupation
of Ni2+ in the Li layer could be dramatically reduced below
1% in LiNi0.70Co0.15Al0.15O2.[16] With the help of the additional
Co3+/4+ redox, the material can possess a high capacity and
reversibility associated with a decrease in polarization, in which
Al substitution occurs by forcing more electronic exchange
between lithium and the oxygen network, as suggested by Ced-
er’s group.[17] Thermal degradation of chemically delithiated
Li0.45Ni0.8Co0.15Al0.05O2 occurred in several steps, primarily due
to oxygen evolution from the delithiated material (Figure 2c).[18]
The original rhombohedral structure transforms to spinel-like
at 265 °C and it further evolves to a rock salt type structure in
the end (Figure 2d). The main exothermic reaction is deeply
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Figure 2. a) Cyclability of LiNi1-x-yAlxMgyO2. Reproduced with permission.[11e] Copyright 2006, Elsevier. b) Charge and discharge capacity of
LiNi0.7Co0.15Al0.15O2 measured at C/20 in the voltage range of 3–4.15 V. Reproduced with permission.[16] Copyright 2003, Elsevier. c) Thermal gravi-
metric analysis of Li0.45[Ni0.8Co0.15Al0.05]O2 cathode conducted under purified air atmosphere. Reproduced with permission.[18a] Copyright 2006, Elsevier.
d) Evolution of XRD patterns recorded at room temperature on Li0.45[Ni0.8Co0.15Al0.05]O2 samples that were subjected to TGA shown in (c). Reproduced
with permission.[18a] Copyright 2006, Elsevier. e) DSC curves of Li0.53[Ni0.8Co0.15Al0.05]O2 cathode in the presence of 1.2 M LiPF6 in EC-EMC (3:7 in by
v/v). Reproduced with permission.[18b] Copyright 2006, The Electrochemical Society.

related to the oxygen evolution during the phase transforma-
tion from the rhombohedral structure to spinel-like (Figure 2e).
In this temperature range, self-heating is also accelerated,
resulting in thermal runaway of the cathode.[19]
2.4. Li[Ni1–x–yCoxMny]O2
Li[Ni1–xMnx]O2 was first introduced by Dahn’s group.[8a] It is a
solid solution below x = 0.5, but its electrode performance dete-
riorates with increasing Mn content. Sphar et al. reported the
formation of single-phase Li[Ni0.5Mn0.5]O2 formed at 700 °C.[20]
The temperature was too low for optimized electrochemical
performance and its capacity decreased from 150 mAh g−1 to
125 mAh g−1 after 25 cycles. Ohzuku et al. revisited the mate-
rial and demonstrated a constant capacity of 150 mAh g−1
(Figure 3a).[21] The formal charges of Ni and Mn are 2+ and 4+,
respectively, in Li[Ni0.5Mn0.5]O2.[22] Interestingly, only the Ni2+/4+
redox couples are electrochemically available (Figure 3b).[22b]
Meanwhile, the tetravalent Mn is electrochemically inactive, but
provides significant structural stability. Because Mn is tetrava-
lent, there is no concern for the occurrence of the Jahn–Teller
effect associated with Mn3+. Kang et al. replaced Mn with Ti to
produce Li0.9Ni0.5Ti0.5O2, resulting in a rock salt structure.[23]
This demonstrates that tetravalent Mn plays a key role to stabi-
lize the α-NaFeO2 layer structure. This is further confirmed in
the thermal stability results (Figure 3c). The onset exothermic
temperature of charged Li1-x[Ni0.5Mn0.5]O2 with a smaller par-
ticle size (3 µm) was slightly lower (295 °C) than that of the
sample with a larger particle size (10 µm, 302 °C).[24] This
behavior proves that the electrochemically inactive Mn4+ por-
tion provides significant structural stability at the delithiated
state, even though the particle diameter is as small as 3 µm.
However, a large amount of Ni2+ (≈10%) present in the Li
layers impedes Li+ diffusion in Li[Ni0.5Mn0.5]O2.[25] Another
aspect that should be resolved is the low electrical conductivity.

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Figure 3. a) Charge-discharge curves of Li[Ni0.5Mn0.5]O2 in the voltage range of 2.5–4.3 V at a rate of 0.17 mA cm−2 at 30 °C. Reproduced
with permission.[21b] Copyright 2003, Elsevier. b) Ni K-edge spectra of Li[Ni0.5Mn0.5]O2 charged to 4.9 V at a rate of C/50. Reproduced with
permission.[22b] Copyright 2003, American Chemical Society. c) Comparison of DSC traces of Li1-δ[Ni0.5Mn0.5]O2 with different average particle
sizes. Reproduced with permission.[24] Copyright 2003, Elsevier. d) Charge–discharge curves of Li[Ni1/3Co1/3Mn1/3]O2 in the voltage range of
2.5–4.6 V at a rate of 0.17 mA cm−2 at 30 °C. Reproduced with permission.[28b] Copyright 2003, Elsevier. e) Amount of Ni in the lithium layers of
Li[NixCo1–2xMnx]O2 as Co content varies. Reproduced with permission.[26] Copyright 2002, The Electrochemical Society. f ) Initial charge-discharge
curves, g) cyclability, and h) rate capability of Li[Ni0.5CoxMn0.6-x]O2 (x = 0.1 – 0.4). Panels (f–h) reproduced with permission.[29] Copyright 2007,
The Electrochemical Society.

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2.0 4.5

Normalized intensity / A.U.

x in Li[Ni1-2xCoxMnx]O2
x = 0.1
(a) (b)
1.5 x = 0.2 4.0
x = 0.25

Voltage / V
x = 0.3
1.0 NiO
LiNiO2 3.5
x = 0.1
0.06 x = 0.2
x = 0.25 x in Li[Ni1-2xCoxMnx]O2
0.5 x = 0.3
NiO x = 0.1
LiNiO2 3.0 x = 0.2
0.03 x = 0.25
x = 0.3
0.0
8330 8332 8334 8336 0 50 100 150 200
-1
Capacity / mAh g
8330 8335 8340 8345 8350 8355 8360 8365
Thermal Stability
Photon energy / eV Capacity Retention
20 -1 320 Preferred 100
x=0.85, 971.5 J g Li[Ni1/3Co1/3Mn1/3]O2 Perfor

Capacity Retention / %
4 . 3 V cut-off

Thermal Stability / oC
-1 o
x=0.8, 904.8 J g 225 C -mance 95
-1

-1
300
Heat Flow / W g

x=0.7, 826.3 J g
15 -1
x=0.6, 721.4 J g
o
232 C Li[Ni0.5Co0.2Mn0.3]O2 90
-1
x=0.5, 605.7 J g o
280
242 C
-1
x=1/3, 512.5 J g o
85
264 C
10 290 C
o
260 Li[Ni0.6Co0.2Mn0.2]O2 80

o Li[Ni0.7Co0.15Mn0.15]O2 75
306 C 240
5 Li[Ni0.8Co0.1Mn0.1]O2 70
(c) 220
(d) 65
Li[Ni0.85Co0.075Mn0.075]O2
0
150 200 250 300 350 160 170 180 190 200 210
o
Temperature / C Discharge Capacity / mAh g-1
Figure 4. a) Ni K-edge XANES spectra of Li[Ni1–2xCoxMnx]O2 and b) the resulting first charge and discharge curves obtained at a current of
20 mA g−1 between 3–4.3 V at 30 °C. Panels (a,b) reproduced with permission.[31] Copyright 2007, The Electrochemical Society. c) DSC results of the
Li1-δ[NixCoyMnz]O2 materials (x = 1/3, 0.5, 0.6, 0.7, 0.8, 0.85) charged to 4.3 V and d) correlation among discharge capacity, thermal stability, and
capacity retention for Li1-δ[NixCoyMnz]O2 materials (x = 1/3, 0.5, 0.6, 0.7, 0.8, 0.85). Panels (c,d) reproduced with permission.[34] Copyright 2013,
Elsevier.

Based on the experience of the familiar LiCoO2, which has of Co is preferred to yield a better rate capability because of
a high electric conductivity and almost no cation mixing, the high electrical conductivity characteristics of LiCoO2. The
Li[Ni1-xCoxMnx]O2 (x = 0 – 0.5) obtained by the addition of Co to oxidation states of the TM ions in Li[Ni0.5Mn0.5]O2[22a,b,30] and
Li[Ni0.5Mn0.5]O2 could successfully stabilize the layered crystal Li[NixCo1–2xMnx]O2 (x = 0–0.5)[31] are Ni2+, Co3+, and Mn4+.
structure.[26] These compositions were first introduced by Liu By increasing the upper cut-off voltage to 4.6 V, the Co sub-
et al. and Yoshio et al.[27] The occupation of Ni2+ in the Li layer stitution for Ni and Mn gave rise to an increase in the initial
could be reduced to 2.4% in Li[Ni0.5Co0.3Mn0.2]O2, delivering a discharge capacity. However, the replacement brought about
reversible capacity of ≈150 mAh g−1 to 4.3 V. Soon after, Ohzuku severe capacity fading during extensive cycling. This data
et al. fabricated Li[Ni1/3Co1/3Mn1/3]O2, which delivers a revers- raises an issue regarding the capacity versus retention, where
ible capacity of ≈150 mAh g−1 to 4.2 V and 220 mAh g−1 to 5 V it is important to possess good capacity retention along with a
(Figure 3d).[28] MacNeil et al. discovered a continuous solid solu- high capacity. The highest capacity obtained was approximately
tion of Li[NixCo1–2xMnx]O2 (x = 0–0.5), which obeys Vegard’s 170 mAh g−1 for Li[Ni0.4Co0.4Mn0.2]O2.
law in that both the a- and c-axis parameters decreased linearly A higher level of Ni incorporation leads to a higher reversible
with increasing Co content (Figure 3e).[26] Interestingly, the capacity in Li[Ni1–2xCoxMnx]O2 because Ni2+ can be fully oxi-
delivered capacities increased to 170 mAh g−1 as the amount of dized to Ni4+, while it is hard to oxidize Co beyond Co3.6+ without
Co is increased (Figure 3f,g) when charged to 4.3 V.[29] This is oxidizing O2– ions and Mn4+ remains inactive.[29,31,32] As can
due to the contribution of the additional redox reaction associ- be seen in Figure 4a, when x = 0.3 in Li[Ni1–2xCoxMnx]O2, the
ated with Co3+/4+. At high rates, there is an obvious variation photon energy shift is close to that of NiO. The pre-edge spec-
of the delivered capacity (Figure 3h) where a higher content trum of Li[Ni0.4Co0.3Mn0.3]O2 is also nearly identical to that of

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NiO, as shown in the inset of Figure 4a. For x = 0.2 and 0.25 in
Li[Ni1–2xCoxMnx]O2, the inflection is slightly lower compared to
that in LiNiO2. However, it is still higher than that in NiO. The
main inflection (8330–8365 eV) of Ni for Li[Ni0.8Co0.1Mn0.1]O2
is almost identical to LiNiO2, indicating that the oxidation state
of Ni is close to 3+. This means that reduction of the Co and
Mn contents brings about partial formation of Ni3+ from Ni2+.
This confirms that almost all of the Ni2+ in Li[Ni0.4Co0.3Mn0.3]O2
changed to Ni3+ in Li[Ni0.8Co0.1Mn0.1]O2. The initial discharge
capacity increases with increasing Ni content due to the
increasing redox-active species of Ni3+/4+, Co3+/4+, and Mn3+/4+
with 165 mAh g−1 for x = 0.3, 173 mAh g−1 for x = 0.25,
177 mAh g−1 for x = 0.2, and 200 mAh g−1 for x = 0.1 (Figure 4b).
The operating voltage in the initial charging stage decreases as
the Mn content in the total amount of TM ions decreases. How-
ever, the discharge voltages are similar for all of the composi-
tions. This indicates that the capacities of Li[NixCo1–2xMnx]O2
and Li[Ni1–2xCoxMnx]O2 are strongly dependent on the Ni con-
tent, reaching approximately 200 mAh g−1 for Li[Ni0.8Co0.1Mn0.1]
O2, which is comparable to conventional Li[Ni0.8Co0.15Al0.05]O2
(190 mAh g−1 at 4.3 V charge cut-off).[33]
The Ni-rich materials always suffer from oxygen evo-
lution from the oxide lattice in the temperature range of
150–300 °C when deeply delithiated.[11c,18a,b,19,29,31,34] The exo-
thermic decomposition temperature gradually shifts to lower
temperatures accompanied with higher heat generation as
the Ni content increases. As summarized in Figure 4d, the
Li[Ni1/3Co1/3Mn1/3]O2 cathode exhibits the best capacity reten-
tion and thermal stability among the Li[Ni1–2xCoxMnx]O2
samples. By contrast, its discharge capacity is limited due to
the lower amount of Ni. The Li[Ni1–2xCoxMnx]O2 (x = 0.075)
cathode that contains the highest Ni content experiences severe
capacity fading. The capacity fading mechanism is believed to
be due to the overall volume expansion of the electrode during
cycling and surface structural degradation (transformation to
the rock salt structure). Hence, the composition and micro-
structure of Li[Ni1–2xCoxMnx]O2 needs to be further optimized
or modified by heteroelements, in particular the surface, to
attain an ideal cathode material with high capacity and thermal
stability.
To date, several coating approaches have been introduced to
improve the cycle retention, rate capability, and thermal stability
of cathode materials. The coating materials include carbon,
metal oxides, metal carbonates, metal aluminates, metal phos-
phates, metal fluorides, metal oxyfluorides, and metal hydrox-
ides.[35] Surface coating of these materials results in improve-
ments of the cathode materials, which can be attributed to the
following: i) protection of the cathode surface from undesired
chemical reactions with the organic electrolyte and the conse-
quent suppression of solid-electrolyte interphase (SEI) layer
formation, and ii) scavenging by the coating materials of trace
amounts of HF present in the electrolyte.
2.5. From Core–Shell to Full Concentration-Gradient Samples
Even though a surface coating can effectively improve the struc-
tural and thermal stabilities of cathode materials, it is not easy
to completely encapsulate the active particles with thin coating
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layers, which sometimes causes the formation of an island-like
coating. Therefore, a new concept was introduced to satisfy the
requirements for Ni-rich materials to provide high capacity
and good thermal properties. Sun’s group proposed the con-
cept of core-shell cathode materials with a Ni-rich core and a
Mn-rich shell (Figure 5a,b).[36] The Ni-rich Li[Ni0.8Co0.1Mn0.1]
O2 core has a high capacity but poor structural stability due
to unwanted surface reactions with the electrolyte. On the
other hand, the shell part of Li[Ni0.5Mn0.5]O2 has good struc-
tural and thermal stabilities, but a low specific capacity and
poor rate capability. These properties can be hybridized in a
particle, namely, a core–shell structure with a composition of
Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2. The core–shell electrode
demonstrated superior cyclability in full-cell tests, which is
ascribed to the stabilized structure derived from the presence of
tetravalent Mn in the Li[Ni0.5Mn0.5]O2 shell. If the core material,
Li[Ni0.8Co0.1Mn0.1]O2, is present in the shell part, such extraor-
dinary electrode performance would not be achieved due to the
structural instability of the core material.
These core–shell structures, however, also have a fatal lim-
itation of boundary cracks between the core and shell due to
the different volume expansions during cycling. To overcome
this challenge, a new core–shell material with a concentration-
gradient shell was introduced.[37] The end part of the Ni-rich
core is directly connected with the concentration-gradient shell
to produce a continuous compositional change from the core
composition of Li[Ni0.8Co0.1Mn0.1]O2 to the outer composition
of Li[Ni0.46Co0.23Mn0.31]O2 (Figure 5b). This approach was very
effective to enhance the cycle retention of core–shell gradient
(CSG)-type materials due to the minimized formation of micro-
cracks. The CSG material showed good discharge capacity and
excellent cycle retention of 96.5% with a graphite anode over
500 cycles at room temperature.[37a]
The core–shell and concentration-gradient structures miti-
gate the disadvantages of Ni-rich layered cathode materials.
However, these materials still have insufficient stability prop-
erties, especially during cycling testing at elevated tempera-
tures. The CSG material has a thin outer surface layer, which
may affect the thermal stability. Provided that the shell is thick-
ened, good thermal stability and long term cycling properties
can be obtained, whereas the resulting total energy density
of the cathode material would decrease. This motivated the
introduction of full concentration gradient (FCG)-type lay-
ered cathode materials (Figure 5c).[38] Among these FCG-type
materials, FCG-Li[Ni0.75Co0.10Mn0.15]O2 has a high specific
capacity of 215 mAh g−1 at a 0.2 C-rate in the voltage range of
2.7–4.5 V. This result is greater than that of the Ni-rich inner
core (a higher amount of Ni than the average FCG composi-
tion). In addition, FCG-Li[Ni0.75Co0.10Mn0.15]O2 also demon-
strated excellent capacity retention over 1000 cycles at both
25 °C and 55 °C (Figure 5d). The most important feature of
FCG-type materials is the compositional variation of the TM
ions from the inner core to the outer shell. To provide structural
and thermal stabilities, the Mn content also gradually increases
from the inner core to the outer shell.
FCG-type materials have been further improved by modi-
fying the primary particle morphology to nanorods, which can
be radially aligned toward the outer shell within the secondary
micro-sphere particle (Figure 5c,e). The above mentioned
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Figure 5. a) Schematic drawings of core–shell Li[(Ni0.8Co0.1Mn0.1)1-x(Ni0.5Mn0.5)x]O2 particle and the resulting SEM image of fractured core–shell
Li[(Ni0.8Co0.1Mn0.1)0.8(Ni0.5Mn0.5)0.2]O2 particle. Reproduced with permission.[36] Copyright 2005, American Chemical Society. b) Ni-rich core surrounded
by concentration-gradient outer layer and the resulting SEM image of the final Li[Ni0.64Co0.18Mn0.18]O2. Reproduced and adapted with permission.[37a]
Copyright 2009, Macmillan Publishers Limited. c) Full concentration gradient lithium transition-metal oxide particle with the nickel concentration
decreasing from the center towards the outer layer and the concentration of manganese increasing accordingly (center). Reproduced and adapted with
permission.[38a] Copyright 2012, Macmillan Publishers Limited. Cross-sectional TEM image of a full concentration gradient particle composed of long
nanowires (left), and discharge capacity of mesocarbon microbead graphite/full concentration gradient cathode full-cells at room and high tempera-
tures in the voltage range of 3–4.4 V (right). Reproduced and adapted with permission.[38b] Copyright 2013, American Chemical Society.

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core–shell cathode materials were composed of micrometer-
scale spherical particles with a polygonal primary particle
shape. Electrolyte tends to penetrate into the small voids among
the primary particles, which allow diffusion of Li ions along the
grain boundary of each primary particle. Also, the exposed sur-
face area of the FCG-type materials to the electrolyte is large,
which in turn results in increased reactivity at the interface and
can cause deterioration of the electrode performance and infe-
rior safety of the cell. It is interesting that the nanorods point
from the center towards the surface. These nanorod primary
particles are radially aligned for the full concentration-gradient
particle. This configuration of nanorods reduces voids present
in spherical particles so that the contact area with the electro-
lyte is minimized, which enables diminution of side reactions,
in particular when the cathode material is highly oxidized. It
is evident that FCG particles with a nominal composition of
Li[Ni0.75Co0.10Mn0.15]O2 exhibited extraordinary cycling perfor-
mance over 1000 cycles in full cell tests with a carbon anode
(Figure 5e). The capacity retention was approximately 95% at
25 °C and 71% at 55 °C for the short nanorod FCG particles.
Even after increasing the upper cut-off voltage to 4.4 V vs.
carbon, the long nanorod FCG particles showed a high capacity
retention of about 72% over 1000 cycles. It is believed that
this behavior is related to the radial distribution of the long
nanorods, which minimizes the presence of voids among pri-
mary nanorod particles.
Ni-rich compounds usually exhibit a large exothermic peak
in the temperature range of 190–220 °C, whereas the presence
of the shell or concentration gradient shell delays the main exo-
thermic reaction to a temperature as high as 300 °C, where the
differential scanning calorimetry profiles were similar to those
of the outer shell composition.[38] This result clearly indicates
that the stability of the outer shell composition is responsible
for the significant improvement of the thermal properties of the
concentration gradient shell compound. The gradual concentra-
tion change of the stable tetravalent Mn in the concentration
gradient shell resulted in this enhanced thermal stability, which
accentuates the importance of the chemical composition of the
outer shell.
3. Li-Rich Layered Oxides
3.1. Introduction
The roots of LLO research go back to 1991, when Thackeray
et al., inspired by Hunter’s work, produced Li1.09Mn0.91O2 by
acid treatment followed by relithiation of Li2MnO3, and intro-
duced the idea of xLi2MnO3(1 – x)LiMnO2.[39] Years later,
Kalyani et al. discovered that Li2MnO3 could be electrochemi-
cally cycled.[40] Lu et al. put these ideas together and studied
the Li[Li(1/3–2x/3)Mn(2/3–x/3)Nix]O2 series in detail.[41] Research
interest in this topic expanded in the following years, with a lot
of the initial work focusing on improving the electrochemical
behavior by incorporating other metal ions into the structure
or by surface coating, understanding the unique mechanism of
the first charge-discharge reaction, and clarifying the structure
of the materials. The compositions of LLOs are often written
in one of three different notations. The first two notations are
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xLi[Li1/3Mn2/3]O2(1 – x)LiMO2 and xLi2MnO3(1 – x)LiMO2,
while the third notation is Li1+xM1–xO2, where M = Mn, Co,
Ni, etc. One can easily convert among the three notations.
For example, 0.6Li[Li1/3Mn2/3]O2·0.4LiMO2 is the same as
0.5Li2MnO3·0.5LiMO2, which is equivalent to Li1.2Mn0.6Ni0.2O2
if M = [Mn1/2Ni1/2]. This is a common, often investigated, LLO
composition.
3.2. Structure
As with all LIB cathode materials, the structure of LLOs can dra-
matically affect the electrochemical performance, so it is essen-
tial that the structure of LLOs be clarified. LLOs can be thought
of as a combination of LiMO2 and Li2MnO3. LiMO2 has a
rhombohedral R 3m structure, while Li2MnO3 adopts a C 2 / m
monoclinic structure. The two structures, which can be seen in
Figure 6a, are very similar, as Li2MnO3 can be written in the
normal layered stoichiometry as Li[Li1/3Mn2/3]O2. The different
space group of Li2MnO3 arises from the ordering between the
Li+ and Mn4+ ions in the TM layer of the structure. Both LiMO2
and Li2MnO3 have a cubic close packed oxygen array in which
all the resulting octahedral sites are filled by alternating layers
of Li and TM or Li/TM. The peaks in a typical LLO XRD pat-
tern can be indexed to the R 3m space group, with the excep-
tion of some weak reflections in the 20°–25° range, as shown in
Figure 6c. These superstructure reflections are due to Li+/Mn4+
ordering in the TM layer, and they, along with the major peaks,
can be indexed to the C 2/m space group. Reitveld refinement of
powder and synchrotron XRD data provide excellent fits when
using both space groups in their models, but XRD data can
only reveal the average crystal structure.[42] More advanced char-
acterization techniques must be applied in order to study the
local structure of LLO.
Due to the similarity of the LiMO2 and Li2MnO3 phases, the
local structure of LLOs is very complex, difficult to elucidate,
and essential to understanding these materials and their perfor-
mance. To study the local structure, high-resolution transmis-
sion electron microscopy (HRTEM), high-angle annular dark
field scanning transmission electron microscopy (HAADF-
STEM), and electron energy-loss spectroscopy (EELS) analysis
are required. Significant research efforts have been made to dis-
cern the local LLO structure, but there is still no clear consensus
among researchers. Several researchers have found evidence of
solid solution behavior. For instance, numerous studies have
found that LLOs obey Vegard’s law in that their structural
parameters vary linearly with composition.[43] Researchers have
also used advanced TEM analysis to directly show the formation
of a single structure at the atomic level, although some studies
have found R 3m symmetry, while others have found C 2/m
symmetry.[43b,c,44] An HAADF-STEM image of a particle exhib-
iting C 2/m symmetry can be seen in Figure 6b. Other studies
discovered two-phase behavior by showing distinct regions of
monoclinic and rhombohedral symmetry within the same par-
ticle or Mn-rich domains.[45] Perhaps the most widely accepted
model is the nanocomposite model put forth by Thackeray
et al.[46] They posit that because there are not enough Li ions
in the TM layer in most LLO compositions to maintain the 1
Li to 2 TM ratio found in Li2MnO3, there are Li2MnO3-like and
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Figure 6. a) Crystallographic models of the LiMO2 structure (left) with R 3m symmetry and the Li2MnO3 structure (right) with C 2/m symmetry.
Reproduced with permission.[45f ] Copyright 2013, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. b) Aberration-corrected HAADF-STEM image of
Li1.2Mn0.6Ni0.2O2 viewed down the [ 121]NaCl zone axis showing a C 2/m -like arrangement. Reproduced with permission.[48a] Copyright 2014, The
Royal Society of Chemistry. c) XRD patterns of Li1.2Mn0.6–0.5xNi0.2–0.5xCoxO2 (0 < x < 0.2) series showing the typical LLO pattern. Reproduced with
permission.[50b] Copyright 2013, The Royal Society of Chemistry.

LiMO2-like nanodomains that result in short-range order but
not a full solid solution, which has been supported by several
studies.[45c,47] Consensus on the local structure of LLO will most
likely continue to be elusive because the structure has been
found to be sensitive to multiple factors, including Li content,
cooling rate, composition, synthesis temperature, etc.[48]
3.3. First Charge–Discharge Cycle Mechanism
One of the defining features of LLOs is their unique first charge-
discharge cycle mechanism, which is still not fully understood.
The initial charge cycle consists of two regions. During the
first part, Li is extracted due to the oxidation of the TM ions
to the 4+ oxidation state. This process occurs up to ≈4.4 V and
the capacity from this region varies based on the composition
of the material and the charge current. The second phase is a
long plateau that occurs above 4.4 V and consists of Li being
removed concomitantly with oxygen; oxide ions are oxidized
and lost as O2 gas, but LLOs can be thought of as losing Li2O.
In this article, these regions will be referred to as the “sloping
region” and the “oxygen-loss plateau”. The initial discharge
cycle is also complex due to the complicated nature of the first
charge cycle. During the first discharge, the TM ions that were
oxidized during the sloping region are reduced back to their ini-
tial states. Then, because of the lost oxygen ions during charge,
another ion must be reduced, so some Mn4+ ions are reduced
to Mn3+. While this mechanism can explain the high capacities
seen with LLOs (up to 300 mAh g−1), it would require nearly
every Mn4+ ion to be reduced to Mn3+. Other mechanisms, such
as reversible oxygen reduction, side reactions with the electro-
lyte, and/or proton exchange, are also believed to provide addi-
tional capacity.[49] These mechanisms will be further discussed
in later sections.
Numerous studies have focused on the substitution of
different metal ions into a base LLO composition, often
Li1.2Mn0.6Ni0.2O2, in order to alter the length of the sloping
region and oxygen-loss plateau. When substituting an additional
metal ion into the composition, Ni and Mn should be kept in
their 2+ and 4+ oxidation states, respectively, so the new compo-
sitions must be chosen carefully. This means that a 2+ ion, such
as Mg2+, should replace Ni2+, while a 4+ ion, such as Ti4+, should

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Figure 7. a) The first cycle charge-discharge curves of Li1.2Mn0.54-xTixNi0.13Co0.13O2 and Li1.2Mn0.6-xTixNi0.2O2 (x = 0, 0.1, and 0.2) are compared.
b) A qualitative diagram illustrating the relative positions of various energy bands common to LLOs. Reproduced with permission.[52] Copyright 2011,
American Chemical Society.
replace Mn4+. A 3+ ion, such as Al3+, should replace Mn4+ and
Ni2+ equally. Any dopant ion that can be oxidized above 4+ will
significantly increase the length of the sloping region. Examples
of this include Ru and Cr, as they can be oxidized to 5+ and 6+,
respectively.[50] Conversely, substitution of electroinactive ions,
such as Mg2+, Al3+, and Ga3+, markedly decrease the length of
the sloping region.[50b] Ions that maintain the same level of elec-
troactivity, such as Co3+ and Fe3+, cause slight changes in the
length of the sloping region due to changes in conductivity and
whether or not they can be fully oxidized to the 4+ state.[50b,51]
The effect of substituted ions on the length of the plateau
region is not as straightforward, however, as it varies with the
covalency of the metal-oxygen bond. The covalence of this bond
is determined by the position of the metal 3d band relative to
the top of the O2− 2p band.[50b] The overlap of the Co3+/4+ t2g
band with the top of the O2− 2p band leads to Co as the only
dopant found to significantly increase the oxygen-loss plateau
length.[51] Other metal ions, such as Ti4+, reduce the length of
the oxygen-loss plateau upon substitution due to their less cova-
lent metal–oxygen bonds.[52] This is usually an intrinsic prop-
erty of the ion, but sometimes can be caused by other factors,
such as the formation of Ru–Ru dimers.[50a] Figure 7a illustrates
the effect of Co3+ and Ti4+ doping on the sloping region and the
oxygen-loss plateau, while Figure 7b depicts a qualitative energy
band diagram of those materials.
A lot of recent work in this area has focused on better elu-
cidating the oxygen-loss plateau mechanism. Because the
oxygen-loss behavior is derived from the Li2MnO3 character
of the LLO system, one might think that studying the cycling
mechanism of Li2MnO3 would provide insight into the mecha-
nism of LLO. To that end, Li2MnO3 has also been investigated
extensively, where it was found that H+/Li+ ion exchange
accounts for some of the electrochemical activity in the plateau
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region.[49f ] However, Dogan et al. and Croy et al. used nuclear
magnetic resonance (NMR) and X-ray absorption spectroscopy
(XAS) measurements to show that not only ion exchange does
not occur in LLOs during the oxygen-loss plateau, but also the
Li2MnO3 component of LLOs does not behave structurally or
electrochemically like pure Li2MnO3.[53] They did, however,
find the progressive build-up of proton-containing species,
presumably on the cathode surface during extended cycling.
This leaves oxide ion oxidation and subsequent loss of Li2O as
the accepted cause of the oxygen-loss plateau. It has been con-
firmed using differential electrochemical mass spectrometry
(DEMS), synchrotron XRD, EELS, and Rietveld refinement that
oxide ions are oxidized and oxygen gas is evolved during the
oxygen-loss plateau.[41c,47b,54] Recently, however, Delmas et al.
have proposed a more complicated mechanism of irreversible
oxide-ion oxidation and subsequent oxygen loss at the surface
of the particles coupled with reversible oxide-ion oxidation in
the bulk.[44a,49a,b,55] They used electrochemical measurements,
neutron diffraction, chemical analysis, Raman spectroscopy,
and HAADF-STEM to reach this conclusion by showing that
oxygen gas is evolved at the surface, TM ions migrate from the
surface to the bulk in a densification process, but that the bulk
structure does not undergo any significant structural change.
Several studies by Tarascon et al. have focused on Li2RuO3-
based materials that are similar in structure to Li2MnO3 in
order to study the electrochemical mechanism of LLO.[49c,d,56]
They were able to demonstrate that oxide ions can be reversibly
oxidized to peroxide/superoxide-like species and that the pro-
pensity to do so, as opposed to being irreversibly lost as oxygen
gas, can be altered by cation substitution, such as Sn, which
affects the d-sp hybridization of the metal-oxygen bond. Other
work has been done on first cycle mechanism, but it will be dis-
cussed in the sections on IRC and voltage decay.
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Figure 8. a) High-resolution HAADF-STEM images of Li1.2Mn0.6Ni0.2O2 after (from left to right) 0, 5, 45, and 100 cycles showing the gradual growth
of the spinel-like surface layer. Reproduced with permission.[57a] Copyright 2014, American Chemical Society. b) Voltage profiles of Li1.2Mn0.6Ni0.2O2
synthesized using a (from left to right) co-precipitation, sol–gel, and hydrothermal assisted method showing voltage decay during extended cycling.
Reproduced with permission.[62] Copyright 2014, American Chemical Society. c) The 1st (left) and 50th (right) cycle normalized discharge profiles of
Li1.2–xMn0.54Ni0.13+xCo0.13–xO2 (x = 0, 0.05, 0.075, and 0.1) showing the reduced voltage decay at higher x values. Reproduced with permission.[66b]
Copyright 2014, The Royal Society of Chemistry.

3.4. Obstacles to Commercialization
While researchers have made great strides in understanding
the structure and properties of LLOs, as well as improving their
performance and mitigating some of their deficiencies, signifi-
cant progress is still required in order for LLOs to become com-
mercially viable. The major challenges associated with LLOs
include voltage decay during cycling, large 1st cycle IRC, poor
rate capability, and low volumetric energy density. A brief over-
view of these issues and some recent progress in overcoming
these challenges is presented in the next sections.
3.4.1. Voltage Decay
Voltage decay, which may also be denoted as voltage fade, is
perhaps the greatest obstacle to LLO commercialization, and
it refers to the fact that during extended cycling, LLOs suffer
from a significant decrease in operating voltage. This in turn
causes a reduced energy density and difficulty in determining
the state of charge of battery cells. It is understood that there
is a gradual structural change to a new phase during extended
cycling, that TM ions migrate into Li sites in both the TM and
Li layers, and a TM-rich and Li-poor surface phase is formed,
where TM ions are reduced and react with the electrolyte.[57]
Though the exact structure of the defect phase is not fully
understood, it is commonly referred to as a spinel-type phase,
which is the term used in this progress report. Numerous pub-
lished reports have shown evidence of the increasing spinel-like
phase growth during extended cycling through dQ/dV analysis,
XAS, and HRTEM, some of which are shown in Figure 8a.[58]
Because of these observations and others, some studies con-
clude that the structural change begins at the surface and grows
during cycling.[57a,b] On the other hand, other studies have
found voltage decay to be derived from the bulk and that sur-
face effects are not a huge factor.[53b,59] Density functional
theory (DFT) calculations and neutron diffraction have shown
that voltage decay is promoted primarily by two mechanisms:

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the migration of TM ions from the octahedral sites of the metal
layer through tetrahedral sites to empty octahedral sites in the
Li layer and the formation of Li dumbbell structures, which are
two Li ions trapped in tetrahedral sites above and below a Li
site vacancy in the metal layer.[60] Sathiya et al., however, found
that TM ions migrating to the Li layer was not a major cause of
concern, but instead problems arise when TM ions are trapped
in tetrahedral sites, which can be reduced by using larger TM
ions.[56b]
Extensive work has recently been done at Argonne National
Laboratory to elucidate the voltage decay mechanism.[53b,59,61]
Among many other findings, they propose a mechanism
that leads to voltage decay.[61b] Upon charging, some TM ions
migrate to tetrahedral sites, and then once discharged to ≈3.3 V,
they may follow one of three paths. They may migrate back
to octahedral sites in the TM layer, which leads to an energy
difference that manifests as hysteresis during cycling. They
may become trapped in the tetrahedral sites, which leads to
decreased Li diffusion, increased impedance, and reduced
capacity, or they may migrate to octahedral sites in the Li layer,
which alters the local structure to one with a lower operating
voltage, causing voltage decay. Synthesis technique and condi-
tions can also affect voltage decay, as researchers have reduced
voltage decay by utilizing a hydrothermal assisted synthesis
method instead of the standard co-precipitation and sol-gel
methods to produce greater Ni-homogeneity throughout the
particles.[62] This led to a uniform C 2/m phase particle as
opposed to a mixture of R 3m and C 2/m phases, minimized
the number of Ni4+ ions at the particle surface, which are highly
reactive with the electrolyte, and enhanced the Ni–Mn interac-
tions that have been shown to stabilize the LLO structure.[57a,63]
Figure 8b shows the vast differences in voltage decay pro-
duced by various synthesis techniques. Specific surface facets
can greatly affect the mechanism, as Yan et al. concluded that
surfaces terminating in purely cations or purely anions were
resistant to structural changes, whereas surfaces terminating
in a mix of cations and anions produced a surface layer that
was Mn-rich on the outside but Ni-rich on the inside.[57a] They
proposed that Ni migrated from the bulk to the surface, where
it reacted with the electrolyte at a faster rate than Mn, which led
to voltage decay due to decreased redox capability and a reduc-
tion in stabilizing Mn–Ni interactions.
Other mechanistic studies have found that two competing
rate laws determine the kinetics of voltage decay and that
proton insertion does not play a role in the process.[53b,64] While
it was originally thought that voltage decay arose due to the high
voltage required to activate the Li2MnO3 component of LLOs, Li
et al. have shown that the process occurs even when LLOs are
cycled well below this activation threshold.[65] A simple analysis
to visualize the voltage decay is to just compare the shapes of
voltage profiles of an early cycle to one after extended cycling;
however this method is not always accurate due to differences
in specific capacities and the fact that electrode impedance also
affects voltage decay. Normalizing voltage profiles eliminates
the first issue, while Bettge et al. suggests a testing protocol
focused on the iR-corrected average voltage of materials to over-
come the second.[66]
Researchers are attacking this problem from several different
directions. One of which is intelligently altering the composition
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of LLOs through doping. Lee and Manthiram showed that while
the octahedral site stabilization energy (OSSE) of the TM ions
is a significant factor in the phase transformation of layered
oxides, it does not play as large a role in LLOs due to the dif-
ferences in their dumbbell formations.[66b] On the other hand,
they found that decreasing the length of the oxygen-loss plateau
by increasing the Ni content at the expense of the Li and Co
content is an effective means of reducing voltage decay, which
agrees with another study that shows increasing Li2MnO3 con-
tent increases voltage decay.[61b,66b] This inhibits voltage decay
by reducing the amount of Li ions in the TM layers, so fewer
dumbbells are formed and by creating fewer oxygen vacancies,
which in turn hinders TM ion migration. The voltage decay
reduction produced by their novel LLO series is depicted in
Figure 8c.
Song et al. extended this idea by increasing the sloping
region at the expense of the oxygen-loss plateau even further by
doping with Cr and saw reduced voltage decay.[67] Ates et al. and
Li et al. recently used the addition of Na+ and K+ ions, respec-
tively, to show that monovalent dopants can provide structural
stability to LLOs and block the layered-to-spinel transforma-
tion.[68] Ates et al. published another report that used Ni3+
doping to improve voltage decay by decreasing the amount of
Mn3+ created during the first discharge, which increases the
average discharge voltage and inhibits the growth of the spinel-
like phase.[69] Zheng et al. coated LLO with AlF3 and found that
it reduces voltage decay by providing structural stability and
protecting the electrode from side reactions with the electro-
lyte; however, a previous study did not see any improvement
by various other coatings.[70] Recent attempts at forming com-
posite materials by combining LLOs with high-voltage spinel
materials have had success, as the spinel additive stabilizes
the layered structure and inhibits the additional growth of the
spinel-like phase.[63a,71] Composites can be created by using
less Li than is stoichiometrically required during calcining or
by growing a spinel outer layer on LLO seed particles using a
modified sol-gel process.
3.4.2. Rate Capability
Another significant issue with LLOs is their low rate capa-
bility. This is caused by several factors, including the insulating
nature of Mn4+ ions in the Li2MnO3 component, a large charge-
transfer resistance at the interface between the particle and the
electrolyte, a thick SEI layer that forms during cycling, poor del-
ithiation kinetics (particularly in the Li2MnO3 component), and
the often large particles of LLOs synthesized by researchers.[72]
There are several strategies that researchers have used in
order to increase the rate capability of LLOs. The first and most
prevalent method to enhance rate capability is through surface
modification, which can refer to either coating the particle sur-
face with a compound or treating the surface to enact a struc-
tural change. Surface modification increases rate capability by
decreasing the charge-transfer resistance, increasing particle
conductivity, and/or altering the SEI layer thickness and com-
position. Electrically conductive coatings, which are often made
of polymers, carbon-based materials, or carbon composites,
enhance the rate capability by increasing the conductivity of
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PROGRESS REPORT
Figure 9. a) First cycle charge-discharge profiles of VO2(B)- Li1.2Mn0.54Ni0.13Co0.13O2 composites displaying the reduction of IRC. Reproduced with
permission.[83c] Copyright 2011, The Electrochemical Society. b) TEM image of LLO sample with rGO (4 wt%)/AlPO4 (2 wt%) composite coating. c) Plot
illustrating the increase in normalized rate capability of LLO coated with rGO/AlPO4 composite coatings. Panels (b,c) reproduced with permission.[73g]
Copyright 2014, The Royal Society of Chemistry.

LLOs. Examples of these coatings include carbon, graphene-like
carbon, carbon nanotubes, polyaniline, a polystyrene/polythio-
phene-based polymer (PEDOT:PSS), an Li3PO4/C composite,
and reduced graphene oxide (rGO)/AlPO4 composites.[73] A
TEM image of an rGO/AlPO4 composite coated particle and the
rate capability improvement can be seen in Figure 9b,c, respec-
tively. The remaining coatings can be summarized as metal
oxides and metal phosphates, and their rate capability improve-
ment is derived from lowering the charge-transfer resistance
by creating a different interface with the electrolyte. Therefore,
the coatings also change the nature of the SEI layer forma-
tion, often resulting in thinner coatings that are less insulating
than those on the uncoated materials. CuO, Sm2O3/CeO2,
Pr6O11, V2O5, MnO, and Al2O3 are examples of successful metal
oxide coatings.[74] Some examples of metal phosphate coat-
ings include AlPO4, CoPO4, CePO4, Li3V2(PO4)3, LiNiPO4, and
Co3(PO4)2.[74f,75] One additional coating that has been found to
markedly improve rate capability, along with other electrochem-
ical properties, is AlF3.[76] There are, however, two challenges
when dealing with surface coatings. Special care must be taken
to ensure that the particles are coated uniformly and that the
coating thickness is optimized. With many coatings, there is a
thickness “sweet spot”, where they are thick enough to impart
structural stability but not too thick as to impede electronic and
ionic conductivity. Surface treatment is an additional method of
improving the rate capability of LLOs, which often consists of
exposing the active material to a treatment solution followed by
an annealing step. LLOs treated with Super P carbon, NH4SO4,
and persulfates have been found to increase the rate capability
by removing Li+ ions from the particle surfaces, inducing a
structural change to a spinel phase on the surface.[77] This
improves conductivity and enhances rate capability.
Furthermore, there are several additional methods utilized
to increase the rate capability: altering the synthesis method
in order to make particles with shorter Li ion diffusion paths,
elemental substitution, and forming composites with other
materials. In order to shrink the Li-ion diffusion paths, various
nanostructures are employed. For instance, researchers have

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synthesized micrometer-sized secondary particles made up of
80–200 nm sized primary particles, 30 nm diameter nanowires
made by ion exchange that possess a very impressive 5C dis-
charge capacity of 275 mAh g−1, and nanoplates that preferen-
tially expose the (010) surface plane in order to increase Li-ion
diffusion.[78] The downside to nanoparticles is that they have a
drastically increased surface area, which leads to greater SEI
layer formation, side reactions with the electrolyte, and safety
concerns due to increased oxygen loss.
Elemental substitution is a simple approach to boost rate
capability. Certain dopants are able to reduce the impedance
of the bulk material and may increase lattice parameters if
they have a larger ionic radius, which reduces the energy bar-
rier and promotes Li-ion diffusion. These dopants include Mg,
Al, Co, Cr, Fe, Ru, Na, and F, although F doping may actually
form an LiF coating instead of going into the lattice.[42b,68a,79]
A final method to strengthen the rate capability of LLOs is to
physically blend it with another material to form a composite.
Blending LLOs with high-voltage spinel (LiMn1.5Ni0.5O4) is the
most studied composite, as spinels have excellent rate capability
due to their 3D Li-ion transport, and they also possess the same
cubic close packed oxygen lattice as LLOs.[63a,71b] Moreover,
Gallagher et al. found that mixing LLOs with LiFePO4 enhanced
the rate capabaility and pulse power due to the lower imped-
ance provided by the olivine structure at low states of charge.[80]
3.4.3. First Cycle Irreversible Capacity Loss
A large first cycle IRC, often 60–100 mAh g−1, is a third crucial
issue for LLOs. In the literature, some researchers instead refer
to this issue as a low first cycle Coulombic efficiency, where
values are usually less than 80%, but both phrasings refer to
the same topic. As with most other electrochemical proper-
ties of LLOs, the large IRC is linked to the unique first charge-
discharge cycle.[41c,81] During the oxygen-loss plateau, Li2O is
removed from the structure, leaving oxygen vacancies and Li
vacancies in both the TM and Li layers behind. At the end of
the first charge cycle, some of these vacancies are eliminated
through structural densification caused by TM migration.[82]
Cations in the TM layer migrate through tetrahedral sites to
empty Li sites in the TM layer and in the Li layer, and a corre-
sponding amount of oxygen vacancies are also eliminated. For
every oxygen vacancy eliminated, one Li vacancy is also elimi-
nated. Because of this process, not all of the Li ions extracted
during the first charge can be inserted back into the structure,
causing the high IRC. These excess Li ions are then free to
react with products of the electrolyte decomposition to form a
thicker SEI layer. Researchers have found that most but not all
of the oxygen vacancies are eliminated during the first cycle.[82]
The remaining vacancies could be removed during subsequent
cycles, which could manifest as fading capacity.
Researchers have used several different solutions to combat
the IRC problem. Composite materials can be made by
blending LLOs together with a Li-insertion host in order to
recapture the Li ions that cannot be reintercalated to the LLO
structure. Manthiram’s group pioneered this method, initially
using V2O5, before later investigating LiV3O8, Li4Mn5O12, and
VO2(B).[83] The effect of VO2(B) addition on the first cycle IRC
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can be seen in Figure 9a. They were able to completely elimi-
nate the first cycle IRC using this method, but the addition of
the other hosts decreases the gravimetric capacity. Gallagher
et al. also reported a decreased IRC when they encorporated
LiFePO4 into an LLO composite.[80] The use of Li-insertion
hosts only manages the effects of the IRC mechanism, instead
of trying to solve the underlying causes of oxygen loss and TM
migration. Various methods have been used to attack the root
causes of the large IRC. Surface treatment is again a prevalent
and successful method for reducing the IRC. As mentioned in
the rate capability section, coatings provide structural stability
to LLOs,[82] which also helps maintain more of the vacancies
that are formed, so they reduce IRC via two different pro-
cesses.[82] Nearly all of the coatings mentioned in the rate capa-
bility section reduce the IRC, so they will not be listed in detail
here again.[73a,g,74b,c,f,g,75b,84] One interesting example, however,
is LiV2O5, because it serves as a coating and a Li-insertion
host.[74d] Some of the surface treatments previously mentioned,
such as Na2S2O8 and HNO3, can also reduce the IRC as they
chemically remove Li2O, causing a surface structural transfor-
mation, which essentially serves as a coating layer.[77c,85]
Altering the material composition can also have beneficial
effects in reducing the IRC. Substituting Ru for Mn has been
found to markedly reduce the IRC, presumably due to the
reduced Li2MnO3 character of the material.[86] Tarascon et al.
also significantly reduced the IRC by developing another family
of LLO materials, Sn-doped Li2RuO3.[49d] The low IRC is due to
the large Sn4+ ions that resist TM migration and the ability of
Ru4+ to promote reversible oxide-ion oxidation, which reduces
oxygen loss and vacancy formation. The IRC can also be reduced
by altering the cycling protocol. Van Bommel et al. used step-
wise charging to reduce the IRC by maintaining more oxygen
vacancies after the oxygen-loss plateau.[87] Multiple groups have
also found that cycling at higher temperatures decreases the
IRC significantly, but this may be due to increased side reac-
tions with the electrolyte instead of increased Li reinsertion.[88]
A recent study by Shunmugasundaram et al. used the novel
idea of synthesizing LLO materials with metal site vacancies to
considerably reduce the IRC.[89] By inducing metal site vacan-
cies, they created a material that is Li-rich by having a Li:TM
ratio greater than 1 and exhibiting an oxygen-loss plateau, but
it is structurally analogous to traditional layered oxides due to
the lack of Li+ ions in the TM layer. These built-in metal vacan-
cies still allow for near complete Li reinsertion even after some
structural densification occurs.
3.4.4. Volumetric Energy Density
The final hurdle to LLO commercialization is their low volu-
metric energy density, which is caused by a combination of
voltage decay, capacity fade, and often small particle size.
Voltage decay refers to the gradual structural transformation
of the LLO material to a spinel-like phase, which results in
reduced operating voltage. Readers can refer to Section 3.4.1
for a thorough discussion on this topic. The capacity fade of
LLOs proceeds through multiple mechanisms: Li+ ions react
and become trapped in the SEI layer, HF molecules created by
trace amounts of water reacting with the electrolyte attack the
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particles leading to TM dissolution (primarily Mn3+), repeated
volume change during cycling can lead to material loss, and
the structural transformation to the spinel-like phase.[62,73g,90]
The poor rate capability of LLOs, caused by the low Li diffusion
rate in the Li2MnO3 component, leads researchers to synthesize
smaller particles, which tend to be less dense.[91] These smaller
particles have a higher surface area, which leads to increased
reactivity with the electrolyte, a thicker SEI layer, increased
oxygen loss, and enhanced layered-to-spinel transformation,
which speeds up voltage decay.[90b]
A myriad of solutions have been attempted in order to
improve the volumetric energy density by increasing the par-
ticle density or by minimizing the capacity fade. Two simple
methods, stepwise precycling and the use of electrolyte addi-
tives, do not require altering the LLO material at all. Electro-
chemical precycling has been mentioned before as a way to
reduce the IRC, but the process also reduces capacity fade.
Studies by Ito et al. and Nakahara et al. have shown that step-
wise traversing of the oxygen-loss plateau can reduce microc-
rack formation at the surface and may promote the reversible
oxidation of oxide ions, both of which enhance cyclability.[92]
In order to fully activate the Li2MnO3 component of LLOs,
cells must be cycled above 4.5 V, which is outside of the elec-
trolyte stability window, so it decomposes and reacts with the
cathode, leading to capacity fade and other negative outcomes.
Electrolyte additives have been studied extensively in order
to reduce this issue, as they are a relatively inexpensive and
simple method of improving the cyclability of LLOs. They are
often large organic molecures, and some examples are lithium
organo-phosphates and lithium organo-borates.[93] They pro-
mote better electrochemical performance by inhibiting elec-
trolyte decomposition derived from both the high voltage and
reactions with the superoxide ions created during the oxygen-
loss plateau, acting as an HF scavenger in order to suppress
TM dissolution, and forming a more stable and less insulating
SEI layer.[93b]
Another approach to decreasing the capacity fade is by sur-
face coating. The topic of surface coating should be familiar
to the reader by now, as it has previously been discussed how
surface coating can alleviate the LLO issues of poor rate capa-
bility and large first cycle IRC. With regards to capacity fade,
however, surface coating is effective because it reduces electro-
lyte decomposition, which leads to the creation of a thinner and
more robust SEI layer containing less Li+ ions. It also impedes
surface attacks, such as TM dissolution, etching, and pitting
that lead to material loss, by absorbing HF molecules.[70a] There
are numerous examples of coatings that reduce the capacity
fade, including the previously discussed carbon-based, metal
phosphates, AlF3, and metal oxides.[70a,73e,g,h,74c,d,75a,b,76] One
drawback to coatings, however, is that they often reduce the
energy density compared to the pristine material.
Moreover, the volumetric energy density can also be
increased by altering the synthesis method or parameters in
order to minimize the capacity fade or to create larger and
denser particles without sacrificing rate capability. Researchers
have frequently found that producing particles that are more
uniform in size, morphology, and composition, as well as more
crystalline, leads to an increase in cyclability. The common
methods of LLO synthesis are co-precipitation and sol–gel;
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PROGRESS REPORT
however other techniques, such as combustion, organic co-
precipitation, and hydrothermal-assisted synthesis can enhance
cyclability.[62,66b,94] Zheng et al. used a hydrothermal-assisted
synthesis method with great success.[62] Energy dispersive spec-
troscopy (EDS) showed that Ni segregated to particle surfaces in
the samples made by co-precipitation and sol-gel synthesis. In
the hydrothermal-assisted materials, there was a uniform dis-
tribution of Ni throughout the particles, which led to decreased
side reactions with the electrolyte and excellent cyclic stability.
A more promising area of research is in hierarchical struc-
tures, which are micrometer-sized secondary particles com-
posed of nano-sized primary particles. The aim of these struc-
tures is to combine the often enhanced rate capability of nano-
particles with the decreased electrode/electrolyte side reactions
and higher density of the micrometer-sized particles. Several
studies have found novel ways of synthesizing hierarchical
structures with varying degrees of success of producing high
discharge capacity, rate capability, and cyclability.[91,95] Zhang
et al. utilized an ionic interfusion method to synthesize uniform
spherical secondary particles composed of nanoplates preferen-
tially oriented to expose planes with facile Li+ diffusion paths,
which lead to superior cyclic stability and rate capability.[95a] Oh
et al. used a co-precipitation method followed by hydrazine sur-
face treatment to create dense 10 micrometer particles made of
flake-like primary particles.[91] The hydrazine treatment formed
a spinel-like phase on the surface, and the material exhibited
excellent density and electrochemical performance. Some rep-
resentative images and electrochemical data of Zhang’s and
Oh’s hierarchical structures can be seen in Figure 10.
4. Conclusions and Future Directions
This report has provided a brief account of the progress made
in recent years and the challenges associated with both Ni-rich
layered oxide and Li-rich layered oxide cathodes. A summary of
the progress made and future directions are briefly given in the
next sections.
4.1. Ni-Rich Layered Oxides
Ni-rich layered oxides are being pursued as next generation
Li-ion battery cathodes because of their high discharge capacity
(200–220 mAh g−1) and lower cost than current Li-ion bat-
tery cathodes. They are derived from LiNiO2, which possesses
the typical rhombohedral layered oxide structure. Some chal-
lenges associated with LiNiO2, however, are the difficulty in
maintaining all Ni ions in the 3+ oxidation state as some tend
to reduce to Ni2+, and the consequent presence of Ni2+ ions
in the Li layer, which affects the layeredness of the structure
and reduces the rate capability. It was found that doping with
other cations could improve the structural stability, discharge
capacity, and thermal stability. Researchers then found that the
substitution of two or more metal ions can provide even greater
performance improvement. The two most successful combi-
nations of dopant ions are Co/Al and Mn/Co. The addition of
Mn and Co to LiNiO2 is particularly beneficial, as Mn exists in
the 4+ state, which allows for the formation of more Ni2+ ions.
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Figure 10. a) Field-emission SEM images of Li1.2Mn0.54Ni0.13Co0.13O2
hierarchical structures synthesized using an ionic interfusion method.
b) Cyclability and Coulomic efficiency plots showing the excellent cyclic
stability of particles seen in panel (a). Panels (a,b) reproduced with
permission.[95a] Copyright 2014, American Chemical Society. c) SEM
images of pristine (left) and cross-sectioned (right) Li1.2Mn0.6Ni0.2O2 hier-
achrical structure synthesized using a modified co-precipitation method.
d) Plot illustrating the increased and stabilized energy density produced
by the images seen in panel (c). Panels (c,d) reproduced with permis-
sion.[91] Copyright 2014, American Chemical Society.
While the Mn4+ ions are electrochemically inactive and enhance
structural stability, the Ni2+ ions and their presence in the Li
layer lowers the rate capability.
In order to produce materials with even higher discharge
capacities, researchers are focused on Ni-rich layered oxides,
which consist of layered oxides with Mn, Ni, and Co ions in the
metal layer. The increased Ni content provides greater capacity,
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but also lowers the thermal stability and cyclability. Researchers
have tried to combat these issues with a variety of approaches.
The simplest is to add a surface coating to the cathode oxide
particles. Surface coating can mitigate many of the issues
facing Ni-rich layered oxides, including raising the rate capa-
bility through an increase in electrical conductivity and Li-ion
diffusivity, improving capacity retention, and reducing thermal
instability. The capacity retention and thermal stability enhance-
ments are due to the altered interface with the electroltye. The
coatings decrease side reactions between the active material and
the electrolyte and act as an HF scavenger. Some of the more
successful coatings are metal phosphates and metal oxides.
Altering the particle morphology has also been found to
mitigate some of the issues with Ni-rich layered oxides. Synthe-
sizing nanorod primary particles that are radially aligned to the
outer shell significantly improve cyclic retention because they
reduce the number and size of voids that the electrolyte can fill.
By reducing the interfacial area between the active material and
the electrolyte, side reactions are reduced, leading to superior
cyclability.
Another method of improving Ni-rich layered oxide perfor-
mance is through the use of compositional heterogeneity. The
first form of this was to synthesize a high capacity Ni-rich core
inside of a Mn-rich shell that provided structural and thermal
stability. During cycling, however, the different rates of expan-
sion led to cracks between the core and shell and material
failure. To overcome this problem, Sun’s group has synthe-
sized shell layers that had concentration gradients throughout
them. This enhanced the capacity and cyclability of the mate-
rials, but the thermal stability was still an issue. This led to
full concentration gradient materials, where the composition
varied throughout the entire particle, which are currently being
intensely pursued.
Overall, it remains challenging to achieve both a high
capacity and excellent stability because of the different charac-
teristics of individual TM ions. There is a trade-off relationship
among capacity, cyclability, and thermal properties in Ni-based
layered cathode materials. Therefore, effective mitigation of
these problems requires exploration of the best compositions,
which satisfy application-specific goals. Combining at least
two compositions (e.g., layered-layered or spinel-spinel) seems
to be a better approach to realize the goals through material
design, including the synthesis method, morphology, composi-
tion, and charge balance, involving new concepts from nano- to
microscale modification. Lithium-ion batteries are indispen-
sable power sources in the mobile market, and they could also
become critical for mid- to large-scale applications.
4.2. Li-Rich Layered Oxides
LLOs are a candidate to replace the current crop of Li-ion
battery cathodes due to their large discharge capacity of
250–300 mAh g−1. They have a complex structure, as they
can be viewed as a combination of Li2MnO3 and LiMO2, and,
depending on synthesis conditions and composition, they can
form either a single phase solid solution or a nanocomposite.
LLOs also possess a very unique two-part first charge profile
that consists of an intial region where the TM ions are oxidized,
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which is followed by a long plateau, where oxide ions are oxi-
dized. Some oxide ions are irreversibly oxidized and lost from
the structure, while others are reversibly oxidized and con-
tribute to the high discharge capacity. Some of the oxygen and
Li vacancies created during the first charge are then eliminated
through TM migration, which leads to a large first cycle IRC,
creation of reduced Mn3+ ions, and a gradual transformation
of the material to a spinel-like phase and subsequent voltage
decay.
However, there are considerable challenges inherent to LLOs,
including the aforementioned voltage decay and IRC, as well as
low rate capability due to the Li2MnO3 component and low volu-
metric energy density. Researchers have devised several strate-
gies to resolve these issues. New synthesis methods have been
developed to produce more homogenous particles and hierar-
chical structures that exhibit strong electrochemical performance
and dense particles. The composition can be altered by adjusting
the ratio of the Li2MnO3 and LiMO2 phases or cation substitu-
tions, which, when done intelligently, can have positive impacts
on the voltage decay, IRC, and rate capability concerns. Surface
modification through coating or chemical treatment can signifi-
cantly enhance the electrochemical performance of LLOs by sta-
bilizing the structural framework and protecting the particle sur-
face from negative reactions with the electrolyte. Other solutions
to mitigating the negative properties of LLOs include changing
the cycling parameters, using electrolyte additives, and creating
composite materials by blending LLOs with other compounds.
The approaches mentioned in this progress report have
partially mitigated some of the challenges posed by the LLO
materials; however, substantial improvements are still required
in order for these materials to move to the commercial level.
Multiple studies have investigated the local structure, but there
is still no consensus among researchers. That disagreement
is due in part to the various synthesis procedures and com-
positions used in the studies. A clearer understanding of the
local structure, particularly the Li/TM ordering, with respect
to synthesis conditions and composition is required. This will
require a combination of characterization techniques, such as
HAADF-STEM, neutron diffraction, Raman spectroscopy, and
EDS. Once a thorough understanding of the local structure is
gathered, it can inform the studies of the cycling mechanism
and electrochemical properties. Completely elucidating the
cycling mechanism, specifically the first charge-discharge cycle,
is the next crucial step in LLO development because all of the
electrochemical properties tie back to the unique first cycle
behavior. Specifically, the prevalence and mechanism of revers-
ible oxide-ion oxidation and how it is affected by local struc-
ture and composition is of prime importance. Other points of
emphasis should be the fate of O2 gas and oxide radicals upon
removal from the cathode, figuring out how the various types
of vacancies are created and eliminated, and the process of
TM and Li migration in the structure. One potential method
of investigating the cycling mechanism is to look further into
the results of high temperature cycling. LLOs have exhibited
discharge capacities of 310–350 mAh g−1, which is above the
theoretical limit, when cycled at 55 °C or above.[49e,88a] If this
unexpected capacity is not due to electrolyte oxidation or proton
exchange, then this behavior could provide insight into the
room-temperature mechanism as well.
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Additionally, more work needs to be done to solve the major
drawbacks of LLOs. Surface coating has repeatedly been shown
to improve the discharge capacity, cyclic stability, and rate capa-
bility, while reducing the IRC, but it has not been as effective at
mitigating the voltage decay phenomenon, meaning this pro-
cess also takes place in the bulk material. Other methods need
to be developed to combat the TM migration, vacancy elimi-
nation, and subsequent phase transformation in order to halt
voltage decay. Additional synthesis of hierarchical structures
with new morphologies should be pursued, as they have shown
the most promise in raising the volumetric energy density of
LLOs. Several newer areas of LLO research are also ripe for
further exploration. Electrolyte additives were briefly discussed
previously, but development of new additives could greatly
enhance the electrochemical performance of these materials,
particularly if they were electroactive and could collect oxygen
ions before they partake in negative side reactions. It may be
possible to find enhanced performance and new insights in
materials that are not based on the Li2MnO3-LiMO2 system,
such as how Tarascon et al. have developed Li2RuO3-based
materials.[49c,d,56] Thermal stability is another area that should
be further explored in LLOs. When charged to high voltages,
LLOs have poor thermal stability due to the oxygen lost from
the structure.[96] This effect can be mitigated to some extent
by synthesizing larger particles or coating the particles, both
of which reduce the side reactions that lead to thermal run-
away reactions.[75a,e,76a,96] More in depth research, however, is
required on this topic.
The number of full cell studies is limited, so more should be
undertaken, as this is another obstacle towards commercializa-
tion and phenomena seen in half cells may not always match
those seen in full cells.[57d,97] Unfortunately, this may add to the
list of LLO problems that need to be addressed. Li1.2Mn0.6Ni0.2O2
is often seen as the “base” LLO composition, so it is frequently
the subject of advanced structural studies and new synthesis
techniques. This composition has a lower capacity, however,
due to the lack of Co substitution. Cation substitution can
significantly affect local structure and particle morphology,
so while it is certainly wise to understand the “base” material
before modifying it, more analyses should be completed on
Co-substituted compositions and other higher capacity LLOs,
as they are more likely to be the materials that are of commer-
cial interest. Exploring the synergistic effects of techniques pre-
sented in this report should also be pursued. For example, an
electrolyte additive may eliminate the capacity fade found in a
dense material with superior rate capability produced by a novel
synthesis procedure, thus mitigating multiple shortcomings of
LLOs. Interested readers can find further discussion of the cur-
rent research on LLOs in other review articles.[72a,98]
Acknowledgements
This work was supported by the Assistant Secretary for Energy Efficiency
and Renewable Energy, Office of Vehicle Technologies of the U.S.
Department of Energy under Contract No. DE-EE0006447. This work was
supported by the Global Frontier R&D Program (2013M3A6B1078875)
on Center for Hybrid Interface Materials (HIM) funded by the Ministry
of Science, ICT & Future Planning, and by the Human Resources
Development Program (No. 20124010203310) of the Korea Institute of
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 www.advenergymat.de
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Energy Technology Evaluation and Planning (KETEP) grant funded by the
Korean government Ministry of Trade, Industry, and Energy.
Received: May 22, 2015
Revised: June 25, 2015
Published online: October 7, 2015
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