FULL PAPER
Lithium-Ion Batteries
Tuning Anionic Redox Activity and Reversibility
for a High-Capacity Li-Rich Mn-Based Oxide Cathode via
an Integrated Strategy
Qingyuan Li, Dong Zhou, Lijuan Zhang, De Ning, Zhenhua Chen, Zijian Xu, Rui Gao,
Xinzhi Liu, Donghao Xie, Gerhard Schumacher, and Xiangfeng Liu*
When fabricating Li-rich layered oxide cathode materials, anionic redox
chemistry plays a critical role in achieving a large specific capacity.
Unfortunately, the release of lattice oxygen at the surface impedes the
reversibility of the anionic redox reaction, which induces a large irreversible
capacity loss, inferior thermal stability, and voltage decay. Therefore,
methods for improving the anionic redox constitute a major challenge
for the application of high-energy-density Li-rich Mn-based cathode
materials. Herein, to enhance the oxygen redox activity and reversibility in
Co-free Li-rich Mn-based Li1.2Mn0.6Ni0.2O2 cathode materials by using an
integrated strategy of Li2SnO3 coating-induced Sn doping and spinel phase
formation during synchronous lithiation is proposed. As an Li+ conductor,
a Li2SnO3 nanocoating layer protects the lattice oxygen from exposure at
the surface, thereby avoiding irreversible oxidation. The synergy of the
formed spinel phase and Sn dopant not only improves the anionic redox
activity, reversibility, and Li+ migration rate but also decreases Li/Ni mixing.
The 1% Li2SnO3-coated Li1.2Mn0.6Ni0.2O2 delivers a capacity of more than
300 mAh g−1 with 92% Coulombic efficiency. Moreover, improved thermal
stability and voltage retention are also observed. This synergic strategy may
provide insights for understanding and designing new high-performance
materials with enhanced reversible anionic redox and stabilized surface
lattice oxygen.
Dr. Q. Li, Dr. R. Gao, D. Xie, Prof. X. Liu
Center of Materials Science and Optoelectronics Engineering
College of Materials Science and Optoelectronic Technology
University of Chinese Academy of Sciences
Beijing 100049, P. R. China
E-mail: liuxf@ucas.ac.cn
Dr. D. Zhou, Dr. D. Ning, Dr. X. Liu, Prof. G. Schumacher
Helmholtz-Center Berlin for Materials and Energy
Hahn-Meitner-Platz 1, Berlin 14109, Germany
Prof. L. Zhang, Prof. Z. Chen, Prof. Z. Xu
Shanghai Synchrotron Radiation Facility
Shanghai Institute of Applied Physics
Chinese Academy of Sciences
Shanghai 201204, P. R. China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.201806706.
DOI: 10.1002/adfm.201806706
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1. Introduction
Lithium-ion batteries (LIBs) are criti-
cally important components in portable
artificial intelligence devices, electric
vehicles (EVs), and smart grid storage
systems.[1] More than ever before, safe,
stable, and high-performance LIBs are
urgently needed, as the rise of global EVs
continues, because the specific capacity
of the current LIBs cannot meet the
demands of the market.[2] In LIB sys-
tems, the weight and cost of the cathode
materials account for ≈40–50% of the
entire battery, and the specific capacity
of the cathode materials is significantly
lower than that of the anode materials
used in the current study. Therefore,
cathode materials remain the main bot-
tleneck and to overcome this challenge,
high-energy-density cathode materials
are highly desired.
Among various cathode mate-
rials, Li- and Mn-rich layered oxides
(LMLO), which can be described as
xLi2MnO3 · (1−x) LiMO2 (M = Ni, Co, Mn,
etc.), have attracted an increasing amount
of attention as the most promising candi-
dates due to their high specific capacity (≈300 mAh g−1) and
high energy density (≈1000 Wh kg−1).[1a,3] In addition to the
well-known redox behavior of the transition metal (TM) ions
used for charge compensation during Li+ insertion/extraction,
the anionic redox chemistry that occurs in Li-rich layered oxide
cathode materials also plays a critical role in the large specific
capacity, as confirmed by several research groups.[3a,4] Unfor-
tunately, the irreversible release of lattice oxygen at the sur-
face impedes the reversibility of the anionic redox, which can
also induce a large irreversible capacity loss, inferior thermal
stability, and even voltage decay.[5] Therefore, approaches
for improving the anionic redox chemistry (O2−→O2n−) while
suppressing the irreversible O2 release are a big challenge for
the continued development of high-energy Li-rich cathode
materials.[3a,4e,6]
Although some have reported that the incorporation of
precious 4d (Ru) and 5d (Ir) TM ions can mitigate the O2
gas loss,[4f,7] in contrast, cheap 3d (Ni and Mn) TM ion-based
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cathode materials are urgently needed to obtain the high spe-
cific capacity and excellent cycle performance required for
enhanced LIB performance. In such cases, the ions contribute
to these properties by regulating the reversible oxygen redox
chemistry. However, the low-cost 3d TM-based cathode mate-
rials, such as Li- and Mn-rich layered oxide cathodes, suffer
from several intrinsic drawbacks, such as a low lithium ion
conductivity, structural instability, and corrosion of the TM
elements in the electrolyte.[3b,8] These drawbacks cause an
inferior rate capability and poor cycling performance, signifi-
cant voltage fading, and low Coulombic efficiency. In LMLO
cathodes, the transformation from a layered structure to a
spinel phase results in a crystal instability when the cathode
materials are charged to 4.8 V. Although the high voltage is
conducive to improving the energy density because of the elec-
trochemical reaction of the Ni2+/3+ and Ni3+/4+ couples that
occurs at ≈4.7 V,[3a,9] nonetheless the voltage also causes sev-
eral undesirable side reactions. For example, as the fraction
of material in the spinel phase increases during prolonged
cycling, the capacity and voltage fade due to the dissolution
of bivalent manganese near the 3 V plateau.[8,10] However,
some reports have demonstrated that the electrochemical
performance of Li-rich layered cathodes benefits from the
integration of a tiny amount of spinel phase during mate-
rial synthesis.[10c,11] Moreover, to suppress the dissolution of
Mn2+ and release of oxygen, several strategies, such as bulk
doping and surface coating, have been reported.[5,12] However,
with regard to lattice doping, surface modification and spinel
integration, the overall contributions of oxygen redox chem-
istry continue to receive little attention due to the complicated
nature of these processes.
In this work, we propose a facile strategy that simultane-
ously combines the advantages of doping, surface coating, and
spinel phase integration to improve the oxygen redox activity
and suppress the irreversible loss of lattice oxygen as well as
alleviate the other drawbacks of LMLO. A nanolayer of Li+-
conductive Li2SnO3 is coated on the surface of LMLO using a
synchronous lithiation strategy. During lithiation, Sn ions dif-
fuse into the surface of the LMLO cathode materials in a pillar
shape, and a small amount of spinel phase forms simultane-
ously. In this process, the nano-Li2SnO3 coating layer not only
has a higher Li+ conductivity than other conventional metal-
oxide coatings but also induces Sn doping and the formation
of a spinel-layered heterogeneous phase. The synergistic effect
of Sn doping, nano-Li2SnO3, and spinel phase integration
enhances the reversible anionic redox activity and suppresses
the lattice oxygen loss from the surface. Aberration-corrected
scanning transmission electron microscopy (AC-STEM) and
neutron diffraction with Rietveld refinement were used to
verify the existence of the spinel phase and the reduction
of Li/Ni mixing. Ex situ soft X-ray absorption spectroscopy
(XAS), ex situ X-ray photoelectron spectroscopy (XPS), and
differential scanning calorimetry (DSC) were applied to probe
the enhancement of anionic redox reactivity and reversibility.
We believe that the proposed synergistic strategy could give
new insights into the design of high-performance Li+, Na+,
and other types of battery cathodes by regulating the anionic
redox of bulk phase and protecting the lattice oxygen at the
surface.
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2. Results and Discussion
2.1. Crystal Structure and Morphology
X-ray diffraction (XRD) was used to determine the phase com-
position of the pristine and Li2SnO3-coated samples (1%, 3%,
and 5% LSO). As shown in Figure  1a, the main peaks of the
four samples are similar due to the common hexagonal R3m
lattice. In particular, the intensities of the (003), (104), and (101)
peaks of the pristine materials are stronger than those of the
1%, 3%, and 5% LSO, which indicates that the coating layer has
been prepared successfully. A few broad superlattice reflections
appear at ≈20–25° with a space group of C2/m and are caused
by the ordering of Mn and Li atoms in the TM layers, indicating
the presence of Li2MnO3.[13] In addition to the similar diffrac-
tion peaks of the layered cathode materials, the peaks of the
spinel phase can be clearly identified in the 1%, 3%, and 5%
LSO coating samples. The strong cubic spinel diffraction peaks
of the 1%, 3%, and 5% LSO samples are readily indexed as the
space group of the Fd-3m structure.[9,11f ] The spinel phase in
the 3% and 5% LSO samples is more obvious than in the 1%
LSO sample based on the intensity of the diffraction peak at
≈44°.[12k,14] In addition, as the content of the Li2SnO3 coating
layer increases, new peaks appear at 25–35° in the 3% and 5%
LSO samples, to which we ascribe the tetragonal SnO2 phase
with a space group of P42/mnm.[15] Furthermore, to clearly
demonstrate the differences between the XRD patterns of the
pristine, 1%, 3%, and 5% LSO samples, enlarged plots of
the 003 peaks are shown in Figure 1b. Compared with the
pristine material, the 003 peak of 1% LSO shifts to a lower
2θ angle, which indicates that the 003 slabs have expanded
due to the doping and migration of Sn4+ during the coating
process.[12e,16] This expansion is beneficial to the lithium inser-
tion/extraction process. However, the peaks of 3% LSO and
5% LSO clearly show a shift to higher angle, which indicates
a decrease of the interplanar spacing of the 003 crystal plane.
This phenomenon may be caused by the dissolution of Li+ out
of the bulk phase from the uneven coating layer during the
high-temperature synchronous lithiation reaction,[16b] which
is confirmed by elemental mapping images obtained by trans-
mission electron microscopy (TEM) (see below).
Rietveld refinement was performed to further confirm
the effects of Sn4+ doping in the 1%, 3%, and 5% LSO sam-
ples. The fitting curves and Rietveld refinement data of XRD
powder diffraction data are shown in Figure S1 and Table S1
(Supporting Information). Based on the Rietveld refinement,
the contents of the layered and spinel phases in 1% LSO are
≈79.5% and 20.5%, respectively. As shown in Table S1 of the
Supporting Information, the lattice parameter c of the pris-
tine material is 14.2688 Å, whereas that of the 1% LSO with a
uniform coating layer increases to 14.2758 Å, suggesting that
Sn has diffused into the bulk phase from the coating layer.
Interestingly, with the increase of the coating content, the lat-
tice parameter c of the 3% and 5% LSO samples gradually
decreases to 14.2506 and 14.2444 Å, respectively, which may
be due to an uneven coating layer. Importantly, this change is
consistent with the results from the XRD analysis. The slab
thickness (S(MO2)) and the interslab thickness (I(LiO2)) for the
layered phase can be calculated by the following two formulas
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Figure 1.  XRD and Rietveld refinement patterns from neutron powder diffraction. a) Overall XRD patterns of the pristine, 1% LSO, 3% LSO, and 5%
LSO samples; b) magnified patterns of the four samples between 18 and 19.5°. Rietveld refinement of the neutron powder diffraction patterns for the
c) pristine material and d) 1% LSO sample. Rwp values for the pristine material and 1% LSO sample are 5.62% and 6.14%, respectively.

(S(MO2)  = 2[(1/3) – zox] c; I(LiO2)  = (c/3) − S(MO2)).[16b] According
to this equation, the I(LiO2) values of the pristine material and
1% LSO are calculated to be 2.1728 and 2.1790 Å, respectively,
which further demonstrates that Sn has diffused into the sur-
face and bulk phase and that doping with Sn4+ has induced
the spinel phase and expanded the interslab space. Enlarge-
ment of the interslab space can reduce the Li activation energy,
which can significantly enhance the rate of Li+ diffusion. The
S(MO2) values of the pristine sample and 1% LSO are calcu-
lated to be 2.5835 and 2.5796 Å, respectively. Compared with
the pristine sample, the decreased S(MO2) value of 1% LSO is
conducive to the stability of the layered structure. However,
with the increasing coating content, the values of S(MO2) and
I(LiO2) change irregularly because of the nonuniform coating
thickness. Furthermore, the value of I(003)/I(104), which is an
indicator of Li/Ni cation mixing, is also affected. It is believed
that the higher I(003)/I(104) value means a lower degree of
Li/Ni cation mixing, which is beneficial to the rate capability
and the cyclic capability. According to the XRD results, the
I(003)/I(104) value of the pristine specimen is 1.7293, which
is lower than 2.1333 in 1% LSO. This suggests that 1% LSO
has a lower degree of cation mixing than the pristine sample. It
is noteworthy that the I(003)/I(104) value of 3% LSO is higher
than that of the pristine material, which could be responsible
for its slightly better cycle performance at low rate. From these
results, we can conclude that the uniform Li2SnO3 nanocoating
induced trace Sn4+ doping in the surface and a small amount
of spinel phase formation by the synchronous lithiation route.
The combined effect of Sn doping and spinel phase formation
has increased the interslab spacing, which can reduce the polar-
ization of the redox reaction because of the lower Li activation
energy.
Although XRD patterns can give important structural infor-
mation, they are not sensitive to the light Li atom. Because Li+
(0.72 Å) and Ni+ (0.69 Å) have similar ionic radii, Li/Ni mixing
is inevitable, but the degree of mixing cannot be quantita-
tively analyzed by XRD. Instead, neutron diffraction is needed
to quantitatively detect Li occupancy. Figure 1c,d shows the
refinements of the neutron powder diffraction patterns for
the pristine material and 1% LSO sample. The Rwp values of
Rietveld refinement of the pristine sample and 1% LSO are
6.14% and 5.62%, respectively. The Rietveld refinements show

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Figure 2.  Morphological and structural characterization of the 1% LSO sample. a) TEM image of 1% LSO. b) HRTEM image of 1% LSO, from the inset
rectangle in (a). c,d) The SAED pattern and identities of the different diffraction rings, corresponding to the layered, spinel, and Li2SnO3 structures,
respectively. e–i) STEM image and EDS maps of O, Mn, Ni, and Sn.

that the Li/Ni mixing of the pristine and 1% LSO samples are
5.4% and 1.3%, respectively, with the detailed site occupancy
information presented in Table S2 (Supporting Information).
This result clearly illustrates that an appropriate amount of
Li2SnO3 coating can induce Sn doping and spinel phase forma-
tion. These changes can significantly suppress Li/Ni mixing,
which is beneficial for Li+ diffusion and rate performance. The
reduced Li/Ni mixing can also be inferred from the following
AC-STEM results.
The morphologies of the four samples were characterized
by the field emission scanning electron microscopy (FESEM)
(Figure S2, Supporting Information). All samples exhibit spherical
particles with diameters of ≈1–2 μm, with the smaller particles
observed at the sample surface. The pristine material particles
have rough surfaces with a small amount of particle aggregation
(Figure S2a, Supporting Information). Compared with pristine
material, the 1% LSO sample exhibits more spherically shaped
particles and a smoother surface (as shown in Figure S2b of the
Supporting Information). However, the 3% and 5% LSO samples
shown in Figure S2c,d (Supporting Information) possess rougher
surfaces with larger particles. As a result, sample morphology
obviously changes with the increasing content of Li2SnO3 coating,
which might result from the uneven coating thickness.
Figure 2a shows a TEM micrograph of the morphology of 1%
LSO, which was found to exhibit uniform spherically shaped
nanoparticles on its surface. These shape observations agree
well with the imaging results obtained with FESEM presented
in Figure S2b (Supporting Information). Figure 2b shows a
high-resolution TEM (HRTEM) image captured in the region of
the red rectangle in Figure 2a. A heterostructure with three dis-
tinct layers can clearly be observed in Figure 2b. The thickness
of the outermost layer is ≈2 nm, and the lattice fringe spacing
is 0.26 nm, which is attributed to the (−131) planes of Li2SnO3.
The interslab spacing of the intermediate layer is 0.24 nm,
whereas the spacings of the innermost layers are 0.47 and
0.25 nm; the former corresponds to the (222) plane of the spinel
phase, and the latter to the (003) and (101) planes of the layered
structure. A selected-area electron diffraction (SAED) image of
this region (Figure 2c) and the corresponding diffraction pat-
tern (Figure 2d) further verified this heterostructure. Three
diffraction rings are clearly visible in the SAED pattern, corre-
sponding to the (101), (222), and (−131) planes of the layered
structure, spinel phase, and Li2SnO3, respectively. All of these
results support the interpretation of a high degree of structural
compatibility between the layered phase and the spinel struc-
ture, due to the close cubic packing of these structures.[11c] To

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Figure 3.  HAADF-STEM images of the pristine material and 1% LSO sample. a) HAADF-STEM image of the pristine material. Bright spots represent
transition metals (Ni or Mn); the dark spots represent Li layers; the inset rectangle and the histogram represent the mixing of Li/Ni. b) Crystal structure
models of the layered phase with Li/Ni mixing. c) HAADF-STEM image of the 1% LSO sample. The bright dots with arrows illustrate the Sn doped into
the TM layer in the inset color image; the green rectangle represents the spinel structure. d) Crystal model of the spinel phase.
directly observe the distribution of the Li2SnO3 nanocoating on
the surface of the materials, EDS mapping was also employed
while analyzing the samples using TEM, and the results are
presented in Figure 2e–i and Figure S3 ii and iii (Supporting
Information). Accordingly, all TM elements are uniformly
distributed in the 1% LSO specimen. HRTEM images of the
pristine, 3% and 5% LSO samples are also shown in Figure S3
(Supporting Information). Three phases are demonstrated in
Figure S3 II and III of the Supporting Information, revealing
a structure similar to that of the 1% LSO specimen. In com-
parison, Sn is not distributed uniformly on the surface of the
3% and 5% LSO samples, which could deteriorate the electro-
chemical performance of these materials.
To obtain more detailed information about the degree of Sn
doping and spinel phase formation, AC-STEM with HAADF
detector was also employed. When using this technique, Mn,
Ni, and Sn atoms appear brighter than Li and O atoms, due
to the differences in atomic numbers. As shown in Figure  3a,
the HAADF-STEM pattern of the pristine sample reveals a
perfectly layered structure. The TM layers are indicated by
the bright spots, which reside in a straight line (plane), with
the lithium slabs located between these TM layers.[17] Obvious
bright spots appear within the Li slabs (dark dots), as identi-
fied with the rectangle, indicating a degree of Li/Ni mixing in
the pristine materials.[3b] In addition, clear contrast peaks in a
corresponding histogram also illustrates the existence of Li/Ni
mixing. Figure 3b shows an atomic model of Li/Ni mixing in
the layered phase. Figure 3c shows an HAADF-STEM image
of 1% LSO. Several bright contrast spots can be observed
between two bright spot sites, as marked with white arrows,
which stand out structurally when compared with the pris-
tine material (inset in Figure 3c), implying that the Sn atom
is only doped into the TM layer rather than the Li slabs. This
structure promotes Li+ diffusion and leads to the high diffusion
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rate property of this material.[12e] Moreover, Figure 3c confirms
the existence of the spinel phase at an atomic level based on
observations consistent with the typical atomic arrangement
of the spinel structure (Figure 3d). Since the spinel structure
possesses 3D diffusion channels that are available to Li+, this
feature also improves the rate performance of the material.
Based on the above HRTEM analyses and XRD results, we can
conclude that the Li2SnO3 nanocoating has induced the forma-
tion of a spinel phase, as well as a doping effect that expands
the lattice spacing, decreases the degree of cation mixing and
reduces the activation energy of Li+ migration due to the elec-
trostatic interactions.
2.2. Electronic Structure Analysis
To further explore the surface states of the samples, XPS
analy­ses of bare and coated samples were performed (as shown
in Figure S4 of the Supporting Information). According to
Figure S4a of the Supporting Information, the existence of
Sn4+ is proven by the peaks corresponding to Sn 3d3/2 and
3d5/2, which are located at 494.8 and 486.4 eV, respectively,
and confirm that the Li2SnO3 structure is coated on the sur-
face of the materials.[16a] In Figure S4b of the Supporting
Information, two O 1s peaks can be observed for the pristine
material. The main peak and its shoulder peak are located at
529.3 and 531 eV, respectively. The main peak is attributed
to the lattice oxygen, whereas the shoulder peak is associ-
ated with the absorbed oxygen on the surface of the material,
which corresponds to species of Li2CO3 and LiOH.[4e] Com-
pared with the pristine material, the shoulder peaks of the
coated samples have extremely low relative intensities, which
means that very little Li2CO3 and LiOH exist on the surface of
the coated material. In addition, the increased binding energy
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of O 1s is related to the doping of Sn4+ in the coated mate-

rials, which is caused by the stronger bonding between O
and Sn4+ (△HfSn-O = 548 kJ mol−1>△HfMn-O = 402 kJ mol−1 or
△HfNi-O  = 391.6 kJ mol−1) and the associated higher electron-
egativity of this bond; this feature indicates a higher degree
of protection of the layered oxides in Li-rich materials.[16a]
Figure S4c,d of the Supporting Information shows the Ni 2p
and Mn 2p XPS spectra of the four samples. Compared with
the peaks observed for the bare material, the Ni 2p peaks of the
1% Li2SnO3 nanocoated samples are clearly shifted to a lower
binding energy, which implies that the valence state of the Ni
has been reduced, as well as the covalence of NiO. This result
is attributed to the doping of Sn4+ and the need for electric
neutrality to be maintained in the material,[18] which changes
the local geometry of the electronic structure. The peak of Mn
2p is located at ≈642.3 eV in all four samples, corresponds to
Mn4+, and this does not obviously change, which reflects the
stability of the layered structure.
To further study the relationship between the surface and
bulk material of the four samples, soft XAS was also applied,
allowing for the electronic structures of the TMs to be com-
pared between the bare and coated samples. The L-edge XAS
spectra of Ni and Mn were measured in TEY mode (a probe
depth of ≈5 nm) are shown in Figure 4a,b. The L2 and L3 edges
of Ni in the coated materials shift to lower energy compared
with those of the bare samples. The L2 and L3 edges correspond
to the transitions from the 2p3/2 and 2p1/2 core levels to unoc-
cupied 3d holes.[19] The shift of these peaks to lower energies
implies that both the covalence of the NiO bond and the
valence of Ni have been reduced.[19a] This result can be ascribed
to the effect of Sn doping near the surface, which changes the
local electronic structure due to the stronger covalent bond of
SnO and the requirement to maintain charge balance; fur-
thermore, this result is consistent with the results of XPS.
Figure 4b shows the Mn L2 and L3 edge spectra. There is no
obvious change in the L2 and L3 peaks of Mn, indicating the sta-
bility of the structure due to the Mn4+ valence state. Figure 4c
shows the O-K edge spectra recorded for the four samples in
TEY mode. The features in these spectra can be attributed to
the transition of O 1s to the hybridized state of O 2p and TM 3d
orbitals with peaks below ≈534 eV. Similarly, the broad peaks at
energies greater than 534 eV can be ascribed to the transition
of the O1s electron to the hybridized state of TM 4sp and O
2p orbitals.[19a,b] In addition, the intensity of the O K-edge peak
is strongly related to the covalence of TMO bonding.[19a,20]
The associated peaks of the 3% and 5% LSO samples present
at ≈538 eV are stronger than those of the bare and 1% LSO
samples, indicating the strong covalency between the TM and
O in the 3% and 5% LSO samples; this strong covalency is
detrimental to battery performance because of the evolution
of O2.[19a] Moreover, to verify whether the nanocoating modi-
fied only the surface of the pristine materials and not the bulk
phase, XAS spectra were collected in FY mode (a probe depth
of ≈100 nm), as shown in Figure S5 of the Supporting Infor-
mation. According to this figure, no changes were observed
for the TM and oxygen atoms, which means that the electronic
structure is stable in the bulk phase; this stability is beneficial
to the desired cyclic performance and reversible oxygen redox Figure 4.  XAS Spectra of the four samples in TEY Mode. a) Ni L2,3 edge.
chemistry.[12c,19b] b) Mn L2,3 edge. c) O K edge.

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The above analyses clearly illustrates that the Li2SnO3 nano-
coating was deposited successfully onto the surface of the Li-
rich Li1.2Mn0.6Ni0.2O2 substrate during the lithiation process. In
addition, the analyses indicate that part of the Sn has diffused
into the bulk phase, decreasing the covalence between the TM
and oxygen species, which can improve the properties of the
battery by alleviating oxygen evolution. Furthermore, the 1%
LSO nanocoating with a modified surface structure is condu-
cive to the electrochemical performance and charge compensa-
tion via oxygen.
2.3. Electrochemical Performance
The initial charge–discharge curves of the pristine and
coated materials were tested at a current density of 0.05 C
(1 C = 250 mAh g−1) and a voltage of 2–4.8 V, as shown in
Figure  5a and Figure S6 (Supporting Information). During
charging, the voltage plateau below 4.5 V corresponds to Li+
extraction from the layered structure of the sample and the oxi-
dation of the extremely few Mn3+ ions in the spinel structure,
as observed for all samples.[21] The prominent plateau at ≈4.5 V
indicates the irreversible removal of Li and O atoms from
Li2MnO3, and the activation of this layered component.[11a]
The plateau is longer in the pristine material, implying that
the activation is more complete in the first charge process. It is
noteworthy that there are two short plateaus at ≈4.75 V, corre-
sponding to the Li+ deintercalation from the 8a tetrahedral sites
and the oxidation of Ni2+ to Ni4+ in the spinel phase; this pheno­
menon is also apparent during the discharge process in com-
parison with the pristine material.[22] The typical discharge curve
characteristics of the spinel structure are shown in Figure 5a
and Figure S6 (Supporting Information). In addition to the
discharge profile at ≈4.75 V, as discussed above, the voltage
plateaus (≈2.7 and 2.2 V) can be clearly observed in the coated
materials but are not present in the pristine sample, indicating
that the nanocoating has successfully induced the formation of
a spinel phase. These two discharge plateaus can be ascribed to
a phase transition and the reduction of Mn4+ to Mn3+.[23] The
initial discharge capacities of the pristine and nanocoated (1%,
3%, and 5% LSO) samples are 247, 244, 125, and 106 mAh g−1,
respectively. The discharge specific capacity gradually decreases

Figure 5.  a) Initial charge–discharge curves at 0.05 C for the pristine sample and 1% LSO; b) The rate performance. c–e) The cyclic performance at 0.2,
1, and 5 C under room temperature, and f) the cyclic performance at 1 C at 55 °C. g) The average discharge voltage profile versus long-term cycling
at 1 C. h) DSC profiles of the pristine and 1% LSO samples charged to 4.8 V. i) Li+ diffusion coefficient during the charge–discharge process for the
pristine and 1% LSO samples.

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with increasing Li2SnO3 content, because the Li2SnO3 is electro-
chemically inactive whereas Li2MnO3 is partially activated due
to the presence of the nanocoating layer during the first cycle.
However, the initial Coulombic efficiency (≈92%) of the 1% LSO
is higher than that of the pristine sample (≈72%). Moreover,
the specific capacity of the nanocoated samples are improved
by the third cycle. In particular, the 1% LSO has a specific
capacity of up to 315 mAh g−1. In comparison, the capacity of
the pristine material has decreased to 225 mAh g−1. All of these
observations indicate that the reversible redox properties of
the material have been improved in the nanocoated samples.
Cyclic voltammograms (CVs) were recorded for the pristine
and 1% LSO samples (Figure S7, Supporting Information). As
shown in Figure S7a of the Supporting Information, the two
oxidation peaks of the pristine material, occurring at ≈4.0 and
≈4.6 V, can be ascribed to the oxidation of Ni2+ and the extrac-
tion of Li+ from the layered structure with oxygen release,
respectively. In the cathodic scan, the two distinct reduction
peaks at 3.75 and 3.3 V can be attributed to the reduction of
Ni4+ and Mn4+. The current associated with the reduction peaks
increases in the second and third cycles, which means that a
continuous activation process has been established in the ini-
tial cycles. However, as the cycle number is increased, the peak
at ≈4.6 V becomes weaker, indicating the irreversible release
of oxygen. The CV curves of 1% LSO (Figure S7b, Supporting
Information) show some distinct differences. Three obvious
peaks are present at ≈3 and ≈4.7 V during the oxidation pro-
cess, corresponding to the oxidation of Mn3+ and Ni2+ from the
spinel phase. As the scan is recorded for the reduction process,
three apparent peaks develop due to the high voltage spinel
phase. The redox peaks of Ni cations at ≈4 V and the removal
of Li+ at 4.6 V are not obvious due to the overlap of the sloped
region and the small amount of oxygen released.[10c] In addi-
tion, it should be noted that in the first three cycles, the CV
curves of 1% LSO change only slightly, which further confirms
the structural stability and high reversibility of 1% LSO.
Figure 5b shows the rate performances of the four samples.
The charge–discharge current densities are recorded for 0.1,
0.2, 0.5, 1, 2, and 5 C. The 1% LSO sample demonstrates the
highest capacity at these different current densities, recorded at
approximately 255, 233, 208, 188, 164, and 125 mAh g−1 from
0.1 to 5 C, respectively. Collectively, these results are better
than those recorded (212, 184, 166, 141, 123, and 99 mAh g−1)
for the pristine material. The 5% LSO performs the worst of
the four samples, which is consistent with the characteristics
of the initial charge–discharge curves. This poor behavior can
be attributed to the presence of an impurity phase (SnO2) and
the uneven nature of the coating, as shown in Figure 1 and
Figure S3 (Supporting Information). It is noted that the specific
capacity of 1% LSO remains the highest and is the most stable
when the current density returns to 0.1 C after 5 C, due to
its high charge–discharge rate, which is associated with the
stability of its structure. This superior rate capability can be
ascribed to the following points. First, the uniform nanocoating
can be formed by a small amount of Li+ conductor derived from
the Li2SnO3 layer during the synchronous lithiation process,
which is beneficial to the rapid migration of the Li ion; simi-
larly, this nanocoating can protect the layered structure from
electrolyte corrosion and the evolution of oxygen gas. Second,
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the spinel phase can be induced by the Li2SnO3 nanocoating,
leading to the formation of 3D Li+ transport channels within
the spinel structure, which promote the rapid diffusion of Li+ at
high charge and discharge rates. Third, during the coating and
synchronous lithiation process, trace amounts of Sn can diffuse
into the bulk phase from the nanocoating, thereby expanding
the interslab spacing and promoting Li+ migration.[24] Finally,
the excellent capacity is partly derived from the reversible
anionic redox activity that is activated by the nanocoating-
induced Sn doping and spinel structure. We further elucidate
this point with the detailed results of soft XAS and DSC.
To investigate the predominant rate capability in more
detail, the cyclic performances of the pristine and nanocoated
materials were measured at 0.2 C, 1 C, and 5 C between 2
and 4.8 V and at room temperature, as shown in Figure 5c–e.
The 1% LSO sample retains a specific capacity of 220 mAh g−1
after 100 cycles, with a Coulombic efficiency of 99% at 0.2 C.
In comparison, the specific capacity of the pristine material is
only 177 mAh g−1 after 100 cycles, and the remaining capacity
is only 90% of its initial value. The specific capacity of 3%
LSO is better than that of the pristine sample, which retains
196 mAh g−1 and is consistent with the rate property. The high
rate capacities of 3% and 5% LSO are worse than those of 1%
LSO and the pristine material because of the uneven nature of
the coating and impure SnO2 phase. The specific capacity of the
1% LSO is 190 mAh g−1 with a discharge capacity of 98% after
200 cycles at the current density of 1 C. In contrast, the pristine
material delivers a specific capacity of 138 mAh g−1, showing
a capacity maintenance of 89%, as shown in Figure 5d. At the
current density of 5 C, the 1% LSO exhibits the best cycle sta-
bility with a capacity retention of 98.2% after 500 cycles, as
shown in Figure 5e. Moreover, the cycle stability test conducted
at the current density of 1 C at 55 °C is shown in Figure 5f. The
specific capacity of each sample type sharply increases during
the initial cycles, which may be caused by the more thorough
activation and more vigorous kinetics of Li+ at this compara-
tively high test temperature relative to room temperature.[25]
Interestingly, the discharge capacity of all materials is substan-
tially improved at 55 °C in comparison with that of room tem-
perature. For example, the capacity of the 1% LSO sample is
≈300 mAh g−1 at the fifth cycle, with a remaining capacity of
235.1 mAh g−1 after 70 cycles at 1 C. This may be due to faster
Li+ kinetics at 55 °C, more anions in the redox reaction, and the
enhanced layered structure stability associated with the Li2SnO3
nanocoating layer. Moreover, the electrochemical performance
of 1% LSO was observed for a series of Li1.2Mn0.6Ni0.2O2, as
shown in Table S3 (Supporting Information). The excellent
cycle performance of this material can be ascribed to the syner-
gistic effect of Li2SnO3 nanocoating-induced Sn doping and the
formation of the spinel phase heterostructure during synchro-
nous lithiation; this synergy enhances the anion redox activity
and stabilizes the surface lattice oxygens.
According to the above analysis, we find that the 1% LSO
sample shows the best performance in terms of the rate and
cycle stability of all four samples. There is almost no reduction
in the discharge capacity of 1% LSO at the current densities of
0.2, 1, and 5 C. It is worth noting that voltage fading is a critical
problem in Li-rich Mn-based oxide cathode materials. Figure 5g
shows the average voltage decrease of the four samples over
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www.advancedsciencenews.com
200 cycles at the current density of 1 C. Clearly, the discharge
average voltage plateau of the 1% LSO is higher than that of
the others, with less fading than the pristine material. This phe-
nomenon can be observed at the different discharge rates, as
shown in Figure S8 (Supporting Information). This result can
be attributed to the lower degree of cation mixing and disso-
lution, the mitigation of oxygen release and the enhanced sta-
bility of the structure relative to that of the pristine material,
due to the nanocoating-induced doping and the development of
the spinel phase.
The excellent cycle stability is closely related to the mate-
rial’s structure. To confirm the presence of lattice oxygen and
the thermal stability of the material, DSC was carried out.[6b]
Figure 5h shows the DSC profiles of the pristine and 1% LSO
samples upon charging to 4.8 V. The exothermic peak of the
pristine sample appears at 287 °C with a high amount of heat
generation (371.7 J g−1). In contrast, the main exothermic peak
of 1% LSO appears at 293 °C with a lower degree of heat release
(207.2 J g−1). These results indicate that the 1% LSO sample has
a better thermal stability and more stable lattice oxygen, which
may be ascribed to the protective ability of the nanocoating and
the reduced TMO covalence caused by Sn doping. As a result,
both the cycle performance and the safety property have been
significantly improved.
To further understand the excellent electrochemical perfor-
mance of 1% LSO, potentiostatic intermittent titration tech-
nique (PITT) and electrochemical impedance spectroscopy
(EIS) were conducted, as shown in Figures 5i, S9 (Supporting
Information), and Figure 6. The Li+ diffusion coefficient can be
determined based on the following formula, used with PITT
analysis[26]
DLi = − d ln (I ) /dt ][
⋅ 4L2 /π 2 
Figure 6.  EIS Spectra of the four cathode materials. a) EIS spectra of the four samples before cycling. b) Magnified image of (a) before cycling. c) EIS
spectra of the four samples after 200 cycles. d) Magnified image of (c) after 200 cycles.
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www.afm-journal.de
Accordingly, we can clearly see that the DLi value of the 1%
LSO is superior to that of the other materials, whether during
charging or discharging. This result is in agreement with
the analysis presented above. The EIS values of all samples
are shown in Figure 6. Figure 6a,b present Nyquist plots of
the samples before cycling, and Figure 6c,d shows the plots
after 200 cycles. From this comparison, we can determine that
the resistance of the 1% LSO sample is the smallest of the four
samples, which indicates the side reaction that typically occurs
between the electrode surface and electrolyte in 1% LSO has
been prevented by the nanocoating. As a result, the nanocoated
layer has stabilized the lattice oxygen and improved the electro-
chemical performance of the material.
In addition, the in situ and ex situ XRD patterns of the pris-
tine and 1% LSO samples under different charge and discharge
conditions are shown in Figure 7. The (003) peaks first shift to
the left and then to the right during charging and discharging;
in this analysis, the movement of the peak corresponding to the
pristine material is larger than that of 1% LSO. Moreover, the
changes in unit cell volume of the pristine and 1% LSO mate-
rials were derived from refined ex situ XRD data and are plotted
in Figure 7g. It can be seen that the variation in cell volume
of the 1% LSO sample is much smaller than that of the pris-
tine sample, which is primarily attributed to the nanocoating-
induced Sn doping and development of the spinel phase.[11a]
The (311) and (101) peaks of the 1% LSO sample were observed
by in situ XRD, as shown in Figure 7h, where both peaks
exhibit only small shifts in position. Collectively, these results
indicate that the structure is stable because of the small vari-
ation in its unit cell volume and the associated property of a
reversible redox reaction.
To further reveal the origin of the improved specific capacity
and stability of 1% LSO relative to the pristine material, O
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Figure 7.  XRD Patterns and changes in cell volume for the pristine material and 1% LSO sample. a) Ex situ XRD spectra of the pristine material.
b, c) Magnified images of (a) at 17.5–19.6° and 36–37.25°, respectively. d) Ex situ XRD spectra of the 1% LSO sample. e, f) Magnified images of (d) at
17.5–19.6° and 36–37.25°, respectively. g) Cell volume evolution of the pristine and 1% LSO samples at different charge–discharge states. h) Selected
in situ XRD peaks, (311) and (101), for 1% LSO during the first cycle.

K-edge ex situ XAS of both materials was conducted. As is
shown in Figure  8a,b, the 3d band pre-edge peak at ≈529 eV
shifts to a lower energy during the charging process, which is
attributed to the oxidation of TM ions. Of interest is the fact
that the pre-edge peak did not return to its original position
when discharging to 2 V in the pristine material. In contrast,
the pre-edge peak of the 3d band of the 1% LSO sample shifted
to a higher energy after discharging to 2 V, which indicates
the reversible nature of the charge compensation mechanism
during oxygen redox in the Li2SnO3-coated sample relative to
that of the pristine sample; this result is consistent with the
excellent cyclic performance observed for 1% LSO.[4g,h] More-
over, the eg peak (≈531 eV) of the pristine sample is more criti-
cally distorted than that of the 1% LSO sample at 4.8 V. This
distortion may be related to the structural rearrangement
during oxygen evolution, which further indicates that the lattice
oxygen of the 1% LSO sample is more stable than that of the
pristine sample.[27]

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Figure 8. Ex situ soft XAS at different voltage states in FY Mode.
a,b) represent O K-edge soft XAS spectra collected at different states of
charge for the pristine and 1% LSO samples, respectively. c) A comparison
of the relative integrated intensity for the pristine and 1% LSO samples in
the lower energy region (shaded regions in (a) and (b)).
The integrated intensity of low energy peaks with different
charge states can supply important information about the unoc-
cupied hole states of the oxygen 2p orbitals, was previously
verified with soft XAS by Bruce and and co-workers and Yoon
et al.[4g,h,19b] The integrated intensity of the pre-edge peak was
calculated between 525 and 534 eV, and the results are shown
in Figure 8c (the shaded region). By comparing the variation
of the integrated intensity of the O K-edge when using the FY
mode applied to the pristine and 1% LSO samples at different
charge states, the peak intensity of 1% LSO is seen to be greater
than that of the pristine material, as shown in Figure 8c; this
observation indicates that more oxygen redox chemistry occurs
in the 1% LSO sample.[4g,h,19b,27] It is worth noting that the
integrated intensity of the 1% LSO sample returns closer to
the starting state than that of the pristine material when dis-
charging to 2 V, which further indicates the better reversibility
of the charge compensation behavior of the oxygen redox
activity in the 1% LSO sample relative to that of the pristine
material. To further confirm the oxygen redox activity and
degree of reversibility, we also performed ex situ XPS of the
electrodes under different charge–discharge states (as shown
in Figure S10 of the Supporting Information). Figure S10a,c
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of the Supporting Information shows the XPS spectra of the
pristine and 1% LSO samples, respectively. The red area rep-
resents the existence of O2− 2 species at 530.5 eV.[4e,28] The
larger areas of the 1% LSO sample demonstrate the higher
oxygen redox activity. Furthermore, to exclude any interfer-
ence from the surface coating layer, both the pristine and 1%
LSO electrode samples charged at 4.8 V were also etched at
50 and 100 nm, respectively, and then were analyzed by XPS. As
shown in Figure S10b,d of the Supporting Information, the red
areas of the etched samples of 1% LSO (50 and 100 nm, respec-
tively) are also larger than those of the pristine samples etched
at the same thickness, which indicates the higher oxygen redox
activity of 1% LSO than the pristine sample. The above analysis
confirms that both the oxygen redox reactivity and its revers-
ibility are enhanced in the 1% LSO sample.
3. Conclusion
The oxygen redox reactivity and reversibility of LMLO were
enhanced by applying an Li2SnO3 nanocoating layer, which
induced the formation of a spinel phase and Sn doping during
the synchronous lithiation process. The crystal structure
of the material was studied by XRD and neutron diffraction.
Our analyses revealed that the 1% LSO sample exhibited a
lower degree of cation mixing, a more stable structure, and
a lower degree of volumetric expansion compared with the
pristine material and other Li2SnO3-coated samples. HRTEM
analysis revealed the spatial distribution of the Li2SnO3 nano-
coating and spinel phase. The nanocoating promoted the sta-
bility of surface lattice oxygens, as well as Li+ diffusion, and
STEM revealed the doping of Sn atoms within the TM layers
and an expanded interslab spacing due to the pillar structure.
Soft XAS spectral analysis clarified that the 1% LSO sample
possessed a weaker covalence of TMO and an enhanced
reversible oxygen redox reaction, both of which resulted in
a better electrochemical performance than that seen from
others. The specific discharge capacities for 1% LSO were 222,
190, and 122 mAh g−1 at the current densities of 0.2, 1, and
5 C under room temperature, respectively, and the Coulombic
efficiency was ≈99%. The maximum specific capacity was as
high as ≈300 mAh g−1, even at 55 °C. This synergistic strategy
combines the advantages of a nanocoating, Sn doping, and
spinel phase formation and may open the door to significant
gains in our understanding and the design and synthesis of
high-performance cathode materials with enhanced reversible
anionic redox properties.
4. Experimental Section
Material Synthesis: The precursor was synthesized by our previous
method.[11a] To synthesize Mn0.6 Ni0.2 CO3 @SnO2, the precursor (1 g)
was first dissolved in absolute ethanol (10 mL). According to the weight
of the precursor, stoichiometric amounts of SnCl4 dissolved in solution
were dropped into the corresponding precursor solution. Then, the
mixed solution was dried overnight at 80 °C after vigorously stirring
at 700–800 rpm for 12 h to mix thoroughly. A stoichiometric amount
of LiOH·H2O (5% excess) was mixed into the precursor, and then the
mixture was calcined at 900 °C for 12 h (5 °C min−1). The obtained
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
samples were labeled as pristine, 1% LSO, 3% LSO, and 5% LSO
according to the respective amount of Sn in each.
Material Characterization: The crystal structures of the as-prepared
samples were characterized using XRD (Ultima IV, Cu Kα) in the 2θ
range of 10–80°. Data were recorded at a step size of 0.02° and a scan
rate of 10° per minute. Neutron diffraction data were collected at the
research reactor BER II at Helmholtz-Zentrum Berlin für Materialien
und Energie (HZB) using the FIREPOD powder diffractometer (E9).
Scanning electron microscopy (SEM, Hitachi SU-8010) and TEM
(Tecnai G2 F30) were used to observe the morphologies of the samples
and to obtain detailed lattice spacing measurements of the phases
within the samples. Aberration-corrected scanning transmission
electron microscopy JEM ARM200F (JEOL, Tokyo, Japan) was
performed, aided by two CEOS (CEOS, Heidelberg, Germany) probe
aberration correctors, to probe the structure at the atomic scale. XPS
was measured using a Thermo Escalab 250Xi with a monochromatic
X-ray source (E (Al Kα)  = 1486.6 eV). Each spectrum was normalized
using the region of the C 1s (284.6 eV) peak as the line position of
adventitious carbon. Soft XAS of powdered material was performed
at the Russian–German Beamline of the synchrotron Bessy II, Berlin,
Germany. Data were obtained in both total electron yield (TEY) and
fluorescence yield (FY) modes at room temperature under ultrahigh
vacuum (10−9 Torr). The total number of electrons emitted from the
sample were counted in TEY mode, and the energy-dispersive Bruker
XFlash fluorescence detector was used in FY mode. Soft XAS was
performed as an ex situ experiment at beamline BL08U1-A at the
Shanghai Synchrotron Radiation Facility (SSRF).
Electrochemical Measurements: The positive electrodes were formed
from the active materials (80 wt%), carbon black (10 wt%), and
polyvinylidene fluoride (10 wt%), mixed in N-methyl pyrrolidinone.
The slurry was deposited onto an Al foil and then dried under vacuum
at 120 °C for 12 h. The mass of the active materials loaded on each
electrode was ≈2 mg. All electrode cells were assembled in a glovebox
under an Ar atmosphere with oxygen and water contents of less than
0.1 ppm. The PITT and cyclic voltammograms were performed on
an electrochemical workstation (Metrohm-Autolab, PGSTAT 302N)
instrument. EIS was performed on an electrochemical workstation
(Metrohm-Autolab, PGSTAT 302N) instrument with an amplitude of
5 mV and a frequency range from 100 kHz to 0.1 Hz. Galvanostatic
charge–discharge cycling was performed between 2.0 and 4.8 V (vs Li/
Li+) by using a battery tester (NEWARE) at different current densities.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (Grant No. 11575192), the Natural Science Foundation of Beijing
(Grant No. 2182082), the Scientific Instrument Developing Project
(Grant No. ZDKYYQ20170001), the International Partnership Program
(Grant No. 211211KYSB20170060), the Strategic Priority Research
Program (Grant No. XDB28000000), and “The Hundred Talents Project”
of the Chinese Academy of Sciences. The authors also thank the staff
at the BL08U1-A beamline of SSRF for their support. The allocation of
beamtime at RGBL beamline, BESSY-II, Berlin, Germany, is gratefully
acknowledged.
Conflict of Interest
The authors declare no conflict of interest.
Adv. Funct. Mater. 2019, 29, 1806706 1806706  (12 of 13)
www.afm-journal.de
Keywords
Li-rich cathode, lithium-ion batteries, neutron diffraction, oxygen redox,
soft X-ray absorption spectra
Received: September 21, 2018
Revised: December 5, 2018
Published online: January 7, 2019
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