Journal of Alloys and Compounds 787 (2019) 429e439

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Effects of lithium excess and SnO2 surface coating on the

electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathode material
for Li-ion batteries
Zhicheng Xie, Yingying Zhang, Anbao Yuan*, Jiaqiang Xu**
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China

a r t i c l e i n f o a b s t r a c t

Article history: Four LiNi0.8Co0.15Al0.05-based Li-ion-battery cathode materials, i.e., the pristine LiNi0.8Co0.15Al0.05, Li-
Received 24 October 2018 excess Li1þxNi0.8Co0.15Al0.05, SnO2-coated LiNi0.8Co0.15Al0.05 and SnO2-coated Li-excess Li1þxNi0.8-
Received in revised form Co0.15Al0.05 are prepared via a facile oxalate coprecipitation route, and are studied with respect to the
14 January 2019
effects of Li excess and SnO2 coating on the structure and electrochemical properties. X-ray diffraction
Accepted 10 February 2019
and X-ray photoelectric spectroscopy demonstrate that a small amount of Liþ and/or Sn2þ ions are
Available online 11 February 2019
incorporated into the transition-metal slabs of the modified materials, and hence reduce the cationic
disorder of Liþ/Ni2þ. High-resolution transmission electron microscopy and scanning electron micro-
Keywords:
Lithium ion battery
scopy confirm the formation of a SnO2 surface layer that prevents the growth and aggregation of the
Cathode primary particles during high-temperature solid reaction, and therefore results in formation of the SnO2-
Nickel-rich lithium nickel cobalt aluminum coated materials with nano/submicron sphere-like morphology. Lithium excess and SnO2 coating
layered oxide enhance the electrochemical performance. The SnO2-coated Li-excess Li1þxNi0.8Co0.15Al0.05 exhibits not
Lithium excess only higher specific capacity and better rate capability but also excellent cycling stability. After 400 cycles
Tin dioxide surface modification at 1C rate, the capacity is decreased from 123.7 to 86.7 mAh g1, giving capacity retention of 70.1%. Li
excess is believed to decrease the cationic mixing and SnO2 modification is deemed to restrict the un-
desirable side reaction between the active material and electrolyte.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction are expected to be promising cathode materials for next-generation

Lithium ion battery (LIB) has many advantages, such as high
output voltage, high energy/power density, long cycle life and low
environmental pollution. LIBs have been widely used in small
electronic devices such as mobile telephones and laptop com-
puters. LIBs are also considered to be promising power sources for
all-electric vehicles (EVs) and plug-in hybrid-electric vehicles
(PHEVs) [1]. The energy and power densities of commonly used
LIBs are limited to a large extent by the low specific capacities of the
cathode materials such as LiCoO2, LiFePO4 and LiMn2O4, which are
unable to meet the requirement of high energy density towards
application in electric vehicles. Therefore, it is important to explore
novel cathode materials with higher specific capacities.
LiNiO2 (which is isostructural to layer LiCoO2) and its derivatives
* Corresponding author.
** Corresponding author.
E-mail addresses: abyuan@shu.edu.cn (A. Yuan), xujiaqiang@shu.edu.cn (J. Xu).
LIBs owing to their higher specific capacities over LiCoO2. Unfor-
tunately, it is difficult to synthesize a stoichiometric LiNiO2 due to
the incomplete oxidation of Ni2þ to Ni3þ and the lithium volatili-
zation at high temperatures. These will result in severe cationic
disorder of Ni2þ occupying Liþ sites and formation of non-
stoichiometric Li1yNi1þyO2, or more specifically,
(Li1yNi2þy)3b(Ni2þyNi3þ1y)3aO2 in consideration of cationic mix-
ing and charge balance. Among the various nickel-rich LiNiO2 based
cathode materials, the LiNi0.8Co0.15Al0.05O2 (NCA) has been
considered to be one of the preferred cathode materials of LIBs for
electric vehicles owing to its high specific capacity, lower price and
low toxicity. Although the structural and thermal stabilities of
LiNiO2 can be obviously improved by partial replacement of Ni with
Co and Al [2,3], the fast degradation of capacity during long-term
cycling and the poor storage stability with exposure to air are still
unavoidable problems due to the Liþ/Ni2þ cationic mixing, phase
transformation upon cycling and side reactions at the electrode/
electrolyte interface, and the high alkalinity of active material
surface.

https://doi.org/10.1016/j.jallcom.2019.02.127
0925-8388/© 2019 Elsevier B.V. All rights reserved.
430 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
There are two effective strategies to improve the electro-
chemical performance of NCA, i.e., bulk cation/anion doping/sub-
stitution of other elements such as Mg [4], Fe [5] and F [6], and
surface coating/modification of LiCoO2 [7], LiMnPO4 [8], TiO2 [9],
ZnO [10], SiO2 [11], Li2TiO3 [12], diamond-like carbon [13], Sb-
doped SnO2 [14], Co3O4 [15], LiAlO2 [16], Li4SiO4 [17], FePO4 [18],
few-layer reduced graphene oxide [19] and surface fluorination
[20], etc. Besides, it has been reported that the Li/Ni cation mixing
on the 3b Wyckoff site of the Li-excess Li1þx(Ni1/3Mn1/3Co1/3)1xO2
(x ¼ 0.02, 0.04) layered oxide materials are very small (lower than
2%) and are consistent with the structural model
[Li1yNiy]3b[LixþyNi(1x)/3yMn(1x)/3Co(1x)/3]3aO2. These NCM-
type materials can exhibit good electrochemical performance
[21]. There are also reports of improved electrochemical perfor-
mance of other Li-excess NCM-type materials such as
Li1þyNixCo12xMnxO2, Li1þx(Ni0.3Co0.4Mn0.3)O2d and Li1þx(Ni1/
3Co1/3Mn1/3)O2þd [22e25]. However, the effect of Li excess on the
electrochemical properties of NCA-type cathode material is
scarcely reported.
In this study, a novel and facile synthetic strategy, i.e., syn-
chronous bifunctional modification via oxalate coprecipitation
route is proposed to prepare the SnO2 coated Li-excess NCA ma-
terial. This bi-functionally modified NCA material can not only
exhibit improved electrochemical performance but also exhibit
improved storage stability. The effects of lithium excess and SnO2
coating on the composition, structure and electrochemical perfor-
mance of NCA are investigated and discussed.
2. Experimental section
2.1. Preparation of materials
Four LiNi0.8Co0.15Al0.05O2 (NCA) based cathode materials, i.e.,
pristine NCA, Li-excess NCA, SnO2 coated NCA and SnO2 coated Li-
excess NCA were prepared. Here, we take the preparation of SnO2
coated NCA as an example. All the chemicals used herein are of
analytical grade and were purchased from Sinopharm Chemical
Reagent Co., Ltd. First, a certain amount of lithium nitrate (LiNO3),
nickel nitrate (Ni(NO3)2$6H2O), cobalt nitrate (Co(NO3)2$6H2O) and
aluminum nitrate (Al(NO3)3$9H2O) (with the molar ratio of Li: Ni:
Co: Al ¼ 1.05: 0.8: 0.15: 0.05) were dissolved into 30 mL of ethanol
to form a mixed nitrate solution, wherein, the extra 5 mol% of
lithium source was used to compensate for the loss of lithium upon
high temperature heating. Next, the mixed solution was dropped
into 30 mL of ethanol solution containing a given amount of dis-
solved oxalic acid (H2C2O4$2H2O) under magnetic stirring to form
the oxalate coprecipitation suspension. Afterwards, a certain
amount of tin dichloride (SnCl2$2H2O) dissolved in ethanol was
added dropwise to the suspension and then the resulted system
was stirred for 3 h. The ethanol solvent was evaporated in a water
bath at 80  C followed by further drying in a drying cabinet and the
resultant was well ground into fine powders (precursor). Finally,
the precursor was heated first at 450  C for 4 h and then at 800  C
for 15 h under oxygen flow. After cooling drown to ambient tem-
perature, the SnO2 coated NCA material (with ca. 2 wt% SnO2) was
obtained.
The other samples were prepared under the similar conditions.
No tin dichloride was used for preparation of the pristine NCA and
Li-excess NCA. The extra 10 mol% of lithium source was used for
preparation of the Li-excess NCA and SnO2 coated Li-excess NCA.
For convenience, herein, the prepared pristine NCA, Li-excess NCA,
SnO2 coated NCA and SnO2 coated Li-excess NCA are abbreviated as
NCA, Le-NCA, NCA@SnO2 and Le-NCA@SnO2, respectively.
2.2. Characterization of materials
X-ray diffraction (XRD) patterns were collected on a Rigaku D/
MAX2200 X-ray diffractometer with Cu Ka radiation (40 kV/
40 mA) at a scan rate of 6 min1. X-ray photoelectron spectroscopy
(XPS) studies were conducted on an X-ray photoelectron spectro-
scope (ThermoFisher Scientific ESCALAB250Xi) with mono-
chromatic Al Ka radiation. Morphology and microstructure
observations were performed using a field-emission scanning
electron microscope (FESEM, JEOL JSM6700F) equipped with an
energy-dispersive X-ray spectrometer (EDS), and a high-resolution
transmission electron microscope (HRTEM, JEOL JEM2010F)
coupled with selected area electron diffraction (SAED). Elemental
analysis was operated on an inductively coupled plasma atomic
emission spectroscope (ICPAES, ThermoFisher ICAP6300).
Thermogravimetric analysis was carried out on a thermogravi-
metric analyzer (Netzsch TG 209 F1 Libra®) in air atmosphere with
a heating rate of 10  C min1 from ambient temperature to 800  C.
2.3. Coin-type half-cells assembly and electrochemical tests
Working electrode was fabricated by mixing the active material
(NCA or Le-NCA or NCA@SnO2 or Le-NCA@SnO2), acetylene black
conductive agent and polyvinylidene fluoride (PVDF) binder in the
weight ratio of 80:10:10 in N-methyl-2-pyrrolidone (NMP) solvent,
followed by coating the mixed slurry onto an aluminum foil current
collector before drying at 100  C for 12 h in vacuum. CR2016 coin-
type half-cell was assembled in an argon filled glovebox (MIK-
ROUNA Super 1220/750, Mikrouna (China) Co., Ltd., with O2 and
H2O concentration < 1 ppm) using the fabricated working elec-
trode, metallic lithium foil electrode, separator (Celgard 2500), and
1 M LiPF6 dissolved in a mixture of ethylene carbonate (EC) and
methylethyl carbonate (MEC) (1:1 v/v) containing a small amount
of vinylene carbonate (VC) additive as electrolyte. The active ma-
terial loading in the working electrodes is of ca. 1.6 mg cm2.
All the electrochemical measurements were conducted on the
assembled CR2016 coin-type cells at ambient temperature. Cyclic
voltammetry (CV) and electrochemical impedance spectroscopy
(EIS) measurements were performed on CHI Electrochemical
Workstation (CHI 760C). Specifically, CV measurements were car-
ried out at a scan rate of 0.1 mV s1 within the potential window of
2.8e4.3 V (vs. Liþ/Li). EIS measurements were measured at open
potential at 50% state of charge (SOC) with AC amplitude of 5 mV
over a frequency range from 105 to 103 Hz. Galvanostatic charge/
discharge tests were carried out on Land CT2001A autocycler
(China) at different C-rates (1C ¼ 200 mAh g1) in the potential
range of 2.8e4.3 V (vs. Liþ/Li).
3. Results and discussion
3.1. Physical characterization
The TGDSC curves of the precursors (oxalate coprecipitations)
of Le-NCA and Le-NCA@SnO2 are shown in Figs. S1a and 1b (Sup-
porting Information, SI), respectively. As can be seen, the oxidation
combustion of organic in the precursors takes place at ca. 300  C
and is completed at ca. 450  C. Hence, the first-stage calcination
temperature for preparation of the NCA-based materials in this
work was set as 450  C. Fig. S2 (SI) shows the XRD pattern of the
intermediate product obtained from heating the precursor of Le-
NCA@SnO2 at 450  C for 4 h under oxygen flow. As shown, the in-
termediate product consists mainly of NiO, Li2CO3 and CoO. In the
subsequent calcination process at elevated temperatures, the
layered oxide of solid solution would be produced, and simulta-
neously, the SnO2 would be formed on the surface of layered oxide
 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439 431

particles. According to the reported study [26], the heating process Table 1
for preparing nickel-rich layered oxides involves direct phase Li/Ni molar ratios, cell parameters and volumes, and I003/I004 ratios of NCA, Le-NCA,
NCA@SnO2 and Le-NCA@SnO2.
transformation from rock salt phase to the layered structure. That is
to say, in the early stage of heating process, i.e., when heating at Sample Li/Ni ratio a/Ǻ c/Å Vcell/Ǻ3 I003/I004
relatively lower temperatures, the initial lithiation of the rock-salt NCA 0.998: 0.8 2.8644(0) 14.1812(7) 100.7(7) 0.85
NiO phase will lead to the formation of a Li-deficient layered Le-NCA 1.038: 0.8 2.8630(4) 14.1712(4) 100.6(0) 1.17
phase (LixNi2exO2ed). In this stage, partial Co substitution for Ni can NCA@SnO2 1.017: 0.8 2.8681(4) 14.1942(1) 101.1(2) 1.24
Le-NCA@SnO2 1.053: 0.8 2.8671(7) 14.1889(5) 101.0(2) 1.27
promote the nucleation of Co-rich layered phase, while during
further heating at higher temperatures, the subsequent growth and
stabilization of the solid solution Li(Ni, Co)O2 will take place.
Fig. 1a shows the XRD patterns of NCA, Le-NCA, NCA@SnO2 and temperature heating, a Li-doped (Liþ ions entering into the TM
Le-NCA@SnO2. The diffraction peaks are all characteristic peaks of slab) Li(Li0.5x/(1þ0.5x)Ni0.8/(1þ0.5x)Co0.15/(1þ0.5x)Al0.05/(1þ0.5x))O2d
hexagonal layered LiNi0.8Co0.15Al0.05O2 (NCA), which can be (providing no cationic mixing) would be produced. The x value for
attributed to the a-NaFeO2 structure and is similar to those of Le-NCA is 0.038 (Table 1), and hence the chemical formula should
LiNiO2 (PDF 090063, R-3m space group). No any impurity could be Li(Li0..019Ni0.785Co0.147Al0.049)O2d (providing no cationic mix-
be detected. The Li/Ni molar ratios (determined by ICPAES), cell ing). However, it should be mentioned that the cationic mixing is
parameters and volumes (derived from cell refinement), and I003/ inevitable due to still existence of a small amount of Ni2þ ions.
I004 ratios of NCA, Le-NCA, NCA@SnO2 and Le-NCA@SnO2 samples Nevertheless, a small amount of excess Liþ ions occupying TM 3a
are listed in Table 1. The I003/I004 ratio is often used to indicate the sites would result in less Ni2þ ions (or more Ni3þ ions) available in
degree of cationic mixing of Liþ/Ni2þ (partial Ni2þ ions occupation the layered oxide for charge balance, and in this case the oxygen
on Liþ sites). As can be seen, the I003/I004 ratio of NCA is only 0.85, defect is not necessary. Hence, the degree of cationic mixing of Le-
indicating severe cationic mixing. However, it is increased obvi- NCA should be obviously reduced compared to that of the pristine
ously either by Li excess or by Sn presence, suggesting that the NCA.
cationic mixing can be obviously reduced through these modifi- It should be noted that Li excess for a NCA material is different
cations (this will be discussed later). It can be seen from Fig. 1b that from that of a NCM material. For a NCM material, when lithium is
the (003) and (104) peaks of Le-NCA all shift slightly to larger 2q excessive, Li2MnO3 would be available in the material as a solid
angles compared with those of NCA, suggesting that Li excess could solution component, which is similar to the situation of a Li-rich
decrease the cell parameters. On the contrary, those of NCA@SnO2 layered oxide material, for example, the typical Li-rich layered ox-
and Le-NCA@SnO2 all shift to smaller 2q angles, suggesting that ide cathode material Li1.2Ni0.2Mn0.6O2 (or expressed as 0.5Li2M-
presence of Sn could increase the cell parameters. These findings nO3,0.5LiNi0.5Mn0.5O2) [27]. However, for a NCA material, no
are also reflected by the variations of cell parameters and volumes Li2MnO3 component can be formed because there is no Mn element
listed in Table 1. in the material. Hence, some excess Liþ doping on TM 3a sites can
Fig. 2 presents the Ni 2p3/2 XPS spectra of the four samples. All but decrease the Ni2þ content, resulting in less cationic mixing.
the Ni2p3/2 peaks can be fitted into two peaks of Ni3þ and Ni2þ. As The radii of Liþ, Ni2þ and Ni3þ are 0.76, 0.69 and 0.56 Å,
can be seen, the Ni2þ content of Le-NCA, NCA@SnO2 and Le- respectively. As mentioned above, some excess Liþ ions doping in
NCA@SnO2 are obviously less than that of the NCA. Theoretically, a TM 3a sites results in rise of Ni3þ content and reduction of Ni2þ
stoichiometric NCA should be expressed as LiNi0.8Co0.15Al0.05O2, content, and hence the cell parameters of Le-NCA are slightly
where, Li is þ1 valence, and Ni, Co and Al are all þ3 valence. In fact, smaller than those of the NCA (Table 1), and the diffraction peaks of
for preparation of the pristine NCA under the conditions in this Le-NCA shifts slightly to larger 2q angles (Fig. 1b) compared with
work, an off-stoichiometric (Li1y/2Ni2þy/2)3b(Liy/2Ni2þy/ those of the pristine NCA. As shown in Fig. 2e and f, the Sn 3d5/2
2 Ni3þ
0.8y Co Al ) O
0.15 0.05 3a 2d (providing Li/Ni ¼ 1: 0.8) with some peaks of NCA@SnO2 and Le-NCA@SnO2 can be all fitted into two
Liþ/Ni2þ exchange (occupation disorder of Liþ/Ni2þ) would be peaks of Sn4þ (surface SnO2, major) and Sn2þ (bulk phase, minor),
produced due to serious cationic mixing. Whereas, for preparation suggesting incorporation of a small amount of Sn2þ ions into the
of the Le-NCA (Li/Ni ¼ (1 þ x): 0.8, 0 < x < 0.1), if partial excess Liþ TM slab, and while the majority of Sn2þ ions is oxidized to SnO2
ions could occupy the transition-metal (TM) 3a sites during high- coating layer on the surface of layered oxide particles during

Fig. 1. (a) XRD patterns of NCA, Le-NCA, NCA@SnO2 and Le-NCA@SnO2 and (b) close-up view of (003) and (104) peaks.
432 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439

Fig. 2. Ni 2p3/2 XPS spectra of (a) NCA, (b) Le-NCA, (c) NCA@SnO2 and (d) Le-NCA@SnO2; Sn 3d5/2 XPS spectra of (e) NCA@SnO2 and (f) Le-NCA@SnO2.

calcination (this will be discussed later). From the view point of
charge balance, a small amount of Sn2þ doping on the TM 3a sites
should also lead to increase of Ni3þ content and decrease of Ni2þ
content and therefore reduce the degree of cationic mixing. The
degree of cationic mixing of NCA@SnO2 is indeed obviously smaller
than that of the NCA, which is indicated by the I003/I004 ratios.
Besides, the cell parameters of NCA@SnO2 and Le-NCA@SnO2 are all
larger than those of the NCA (Table 1), and the diffraction peaks of
NCA@SnO2 and Le-NCA@SnO2 shift to smaller 2q angles compared
with those of the NCA (Fig. 1b) because of the larger radius of Sn2þ
(0.93 Å). What is more, the surface SnO2 layer could decrease the
lithium loss during high-temperature heating to some extent, as
can be seen from the differences in Li/Ni ratios of the samples
(Table 1).
Fig. 3 shows the SEM images of NCA, Le-NCA, NCA@SnO2 and Le-
NCA@SnO2. The NCA presents the morphology of big irregular
 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439 433

Fig. 3. SEM images of (a) NCA, (b) Le-NCA, (c) NCA@SnO2 and (d) Le-NCA@SnO2; HRTEM images of Le-NCA@SnO2 showing SnO2 coating layer on the surface of selected particle (e)
and showing lattice fringes of (003) plane of a selected area (f). Inset of Fig. 3(f) displays the reciprocal lattice of selected area electron diffraction (SAED).

aggregates, and the Le-NCA presents the morphology of relatively
smaller irregular aggregates. On the contrary, the NCA@SnO2 and
Le-NCA@SnO2 are all composed of uniform monodisperse nano/
submicron sphere-like primary particles. The EDS elemental map-
pings of Ni, Co, Al and O for NCA and Le-NCA, and Ni, Co, Al, O and
Sn for NCA@SnO2 and Le-NCA@SnO2 in Fig. S3 (SI) shows the uni-
form distribution of respective elements in these layered oxides.
Fig. 3e and f shows the HRTEM images of a selected Le-NCA@SnO2
particle and the bulk-phase crystal lattice fringes, respectively. A
thin SnO2 coating layer (with the thickness of several nanometers,
indicated by the arrows) can be clearly observed on the surface of
the particle (Fig. 3e). Thus a coating layer can be also seen on the
surface of more Le-NCA@SnO2 particles (Figs. S4 and SI). The clear
lattice fringes of (003) plane with interplanar spacing of 0.473 nm
observed in Fig. 3f and the selected area electron diffraction (SAED)
pattern (inset of Fig. 3f) confirm the good crystallinity of the layered
oxide with R-3m symmetry. The spontaneous formation of SnO2
coating layer on the particles during calcination can be explained as
follows: during calcination, the layered oxide phase is formed
gradually, and the Sn2þ ions are hardly to enter into the crystalline
host lattice of the layered oxide phase due to the obviously larger
ionic radius of Sn2þ (0.93 Å). Hence, the majority of Sn2þ ions tend
to be oxidized to SnO2 and spontaneously coated on the layered
oxide particles as a surface phase. Nevertheless, a small amount of
Sn2þ ion is still possible to incorporate into the TM 3a sites of the
layered oxide, as confirmed by the detection of Sn2þ ions (the Sn3d
excitations shown in Fig. 2e and f). Fig. S5 (SI) shows the SnO2
surface coating layer with clear SnO2 lattice fringes that further
confirms the formation of SnO2 coating layer on the surface of the
particles. Thus a surface layer is not observed on the surface of the
layered oxide particles without surface modification.
434 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
3.2. Electrochemical performance
The cyclic voltammograms (CVs) of NCA(A), Le-NCA, NCA@SnO2
and Le-NCA@SnO2 electrodes for the first three cycles at a scan rate
of 0.1 mV s1 over the potential range of 2.8e4.3 V (vs. Liþ/Li) are
presented in Fig. 4ad, respectively. The CV response currents of
Le-NCA, NCA@SnO2 and Le-NCA@SnO2 are obviously higher than
that of the NCA. For all of the electrodes, the anodic peak currents in
the second cycle are all decreased but with different degrees and
the peak potentials are all shifted negatively compared with the
first cycle. Since the first cathodic scan, the CVs are almost coin-
cided. This suggests that the first oxidation process is significantly
different from that in the subsequent cycles. It should be noted that
the Le-NCA@SnO2 shows the most distinguished three pairs of
redox peaks at around 3.8, 4.0 and 4.2 V, respectively, which
correspond to the three phase transitions of hexagonal H1 to
monoclinic M, monoclinic M to hexagonal H2 and hexagonal H2 to
hexagonal H3, respectively, during Liþ extraction, and the corre-
sponding inverse phase transitions during Liþ insertion [28]. This
suggests that the Le-NCA@SnO2 has the best electrochemical ac-
tivity and structural ordering among the four materials.
Fig. 5 shows the first three charge/discharge curves of NCA, Le-
NCA, NCA@SnO2 and Le-NCA@SnO2 at 0.1C rate (1C ¼ 200 mA g1).
The first charge capacities of the four electrodes are 201.6, 211.3,
214.7 and 218.7 mAh g1, and the first discharge capacities are
130.5, 159.2, 146.5 and 163.1 mAh g1, giving coulombic efficiencies
of 64.7%, 75.3%, 68.2% and 74.6%, respectively. The second discharge
capacities are 125.0, 159.1, 145.4 and 162.9 mAh g1, and the
coulombic efficiencies are 94.9%, 98.0%, 95.9% and 97.1%, respec-
tively. The third discharge capacities are 125.8, 157.2, 144.8 and
163.5 mAh g1, and the coulombic efficiencies are 97.8%, 97.4%,
Fig. 4. CVs of first three cycles of (a) NCA(A), (b) Le-NCA, (c) NCA@SnO2 and (d) Le-NCA@SnO2 at a scan rate of 0.1 mV s1.
98.0% and 98.9%, respectively. The charge curves and coulombic
efficiencies of each electrode in the first cycle are significantly
different from those in the subsequent cycles, which is consistent
with the CV results (Fig. 4). The reversible discharge capacities and
cycling stabilities of the modified materials, especially for the Le-
NCA@SnO2 material, are obviously superior to that of the pristine
NCA material.
The rate performances of the four electrodes are displayed in
Fig. 6a and b. The maximum discharge capacities of NCA, Le-NCA,
NCA@SnO2 and Le-NCA@SnO2 at 0.1C rate are 130.5, 159.2, 146.5
and 163.9 mAh g1, respectively. When the current rate is increased
to 2C rate, the maximum discharge capacities are remained 28.9,
109.2, 76.7 and 115.2 mAh g1, respectively, giving capacity re-
tentions of 22.1%, 68.6%, 52.4% and 70.3%, respectively, exhibiting
different rate performances. When the C-rate is decreased back to
0.1C, the discharge capacities of the four electrodes are almost
recovered, especially for the Le-NCA@SnO2 electrode. The Le-
NCA@SnO2 shows the best rate performance, and the rate perfor-
mances follow the order of Le-NCA@SnO2 > Le-
NCA > NCA@SnO2 > Le-NCA.
In order to know the electrode reaction kinetics of the four
electrodes, the cycled electrodes (after 30 cycles of rate perfor-
mance test) are subjected to electrochemical impedance spectros-
copy (EIS) measurements conducted at 50% state of charge (SOC).
The EISs are displayed in Fig. 6c and d. As can be seen, the EISs all
consist of two semicircles and a line. The high-frequency semicircle
should be attributed to the solid electrolyte interphase (SEI) film
resistance and capacitance, and the mid-frequency semicircle
should be ascribed to the charge transfer resistance and capaci-
tance at electrode/electrolyte interface. The low-frequency line
should be assigned to diffusion impedance of Liþ ions in layered
 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
Fig. 5. First three charge/discharge curves of (a) NCA(A), (b) Le-NCA, (c) NCA@SnO2 and (d) Le-NCA@SnO2 at 0.1C rate.
oxide and electrode pores [8]. Besides, the fitted parameters of the
EIS data are listed in Table S1 (SI). The NCA electrode exhibits a
slightly larger SEI film resistance and an obviously larger charge
transfer resistance compared with the Le-NCA electrode, and the
Le-NCA@SnO2 electrode shows the smallest SEI film resistance and
charge transfer resistance. Additionally, the parameter Y0 for War-
burg diffusion (Y0 (W)) follows the order of Le-NCA@SnO2 > Le-
NCA ¼ NCA@SnO2 > Le-NCA. These EIS results should account for
the rate performance results of the electrodes. The alleviated
impedance rise during cycling due to the reduced cationic mixing
caused by Liþ and Sn2þ doping on TM 3a sites as well as the sup-
pressed interfacial side reaction of active material surface with
electrolyte thanks to the SnO2 surface coating should be respon-
sible mainly for the improved rate performance of Le-NCA@SnO2.
On the other hand, the morphology of nano/submicron particles of
the SnO2 coated layered oxides may also contribute to the
improvement of rate capability to some extent. The CVs of the four
electrodes after 30 cycles of rate performance test are presented in
Fig. S6 (SI) for comparison.
After the rate performance test, the four electrodes were sub-
jected to long-term cycling performance test at 1C rate, and the
results are shown in Fig. 7a and b. The initial discharge capacities of
NCA, Le-NCA, NCA@SnO2 and Le-NCA@SnO2 are 54.2, 118.6, 94.8
and 123.7 mAh g1, respectively. After 100 cycles, the discharge
capacities drop to 39.4, 94.7, 83.5 and 112.0 mAh g1, giving ca-
pacity retentions of 72.7%, 79.8%, 88.1% and 90.5%, respectively.
Even after 400 cycles, the discharge capacities of NCA@SnO2 and
Le-NCA@SnO2 still remain 61.7 and 86.7 mAh g1, giving capacity
retentions of 65.1% and 70.1%, respectively. That is to say, the Le-
NCA@SnO2 exhibits not only higher initial specific capacity but also
435
excellent cycling stability.
After long-term cycling performance test, the cycled NCA@SnO2
and Le-NCA@SnO2 electrodes are subjected to EIS and CV mea-
surements, and the results are displayed in Fig. 7c and d, respec-
tively, and the fitted parameters of EIS data are listed in Table S1.
The charge transfer resistance of Le-NCA@SnO2 (0.075 U g) is
significantly smaller than that of the NCA@SnO2 (0.519 U g). For
comparison more fully, the EISs of the four cycled electrodes are
presented in Fig. S7 (SI). As can be seen, the SEI resistances of the
cycled electrodes are almost the same, but the charge transfer re-
sistances are obviously different, following the order of NCA > Le-
NCA > NCA@SnO2 > Le-NCA@SnO2. That is to say, the charge
transfer resistances of NCA@SnO2 and Le-NCA@SnO2 electrodes
after 400 cycles are still significantly smaller than the charge
transfer resistances of NCA and Le-NCA electrodes only after 100
cycles.
To know the variations of EIS of the respective electrodes before
and after long-term cycling, the EISs before long-term cycling (after
rate performance test) and after long-term cycling (after 100 or 400
cycles at 1C rate) of the four electrodes are compared in Fig. S8 (SI).
Evidently, the SEI resistances of the four electrodes are increased
not much after the long-term cycling, but the magnitudes of in-
crease in charge transfer resistance are obviously different,
following the order of NCA > Le-NCA > NCA@SnO2 > Le-NCA@SnO2.
The increment of charge transfer resistance of the NCA@SnO2 or Le-
NCA@SnO2 is obviously smaller than that of the NCA or Le-NCA,
especially for the Le-NCA@SnO2. The CVs of NCA@SnO2 and Le-
NCA@SnO2 after 400 cycles at 1C rate are shown in Fig. 7d.
Apparently, the electrochemical activity of the cycled Le-
NCA@SnO2 electrode is higher than that of the cycled NCA@SnO2
436 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
Fig. 6. Rate performances of (a) NCA and Le-NCA and (b) NCA@SnO2 and Le-NCA@SnO2; EISs of (c) NCA and Le-NCA and (d) NCA@SnO2 and Le-NCA@SnO2 measured at 50% SOC
after 30 cycles of rate performance test.
electrode. Additionally, the CVs of NCA@SnO2 and Le-NCA@SnO2
electrodes at different stages (i.e., as-prepared, after 30 cycles of
rate performance test and after 400 cycles at 1C rate, respectively)
are also presented in Fig. S9 (SI) to show the changes of CV of the
two electrodes with increasing galvanostatic charge/discharge
cycles.
The above results demonstrate that SnO2 surface coating can
significantly improve the cycling performance. In addition, Li excess
can also improve the cycling performance to a certain degree.
Structural stability of Ni-rich layered oxides is closely related to
cation mixing (or cation disorder). The disordered phase has a high
barrier of lithium diffusion activation energy. Because of the hin-
drance of Ni2þ ions in lithium layer, the interslab distance of lithium
layer is smaller, so the diffusivity of lithium is lower. Therefore, with
the increase of cation mixing, the rate capability decreased [29].
The study of the surface structure change of LixNi0.8Co0.15Al0.05O2
during the first charge demonstrated that the surface changes from
layered structure (space group R-3m) to disordered spinel-like
structure (Fd-3m), and eventually to rocksalt-like structure (Fm-
3m). These crystal structure changes are also accompanied by sig-
nificant changes in the electronic structure, leading to a decrease in
Ni and an increase in the effective electron density of oxygen. This
causes an imbalance of charges, resulting in formation of oxygen
vacancies and the development of surface porosity [30]. The
degradation mechanisms of LiNiO2-based layered oxides have been
well reviewed and commented recently with respect to reactions at
the cathode/electrolyte interface, surface transformations from
layered phase to spinel- and rocksalt-like phases and bulk trans-
formation to spinel-like phase, as well as mechanical degradation
related to formation of microcracks on active material surface [31].
In our work, we think that on the one hand, lower-valence Liþ and/
or Sn2þ doping on the TM 3a sites can decrease the cation mixing,
which can not only increase the reversible discharge specific ca-
pacity and rate performance, but also can improve the cycling
performance. On the other hand, the SnO2 coating layer can protect
the active material by preventing the surface reactions with elec-
trolyte. Hence, the Le-NCA@SnO2 material can exhibit improved
electrochemical performance.
3.3. Storage stability of NCA@SnO2 material
The SnO2 coating layer can not only improve the cycling sta-
bility, but also improve the storage stability of the NCA material. In
order to evaluate the influence of SnO2 coating layer on storage
stability of NCA-based materials, the as-prepared NCA and
NCA@SnO2 materials were stored severally in hermetic bags for 3
months (here, the stored materials are named as stored NCA and
stored NCA@SnO2, respectively). Thereafter, the electrochemical
performances of the electrodes fabricated from the stored materials
were tested. The results are presented in Fig. 8 in comparison with
the electrochemical performances of the corresponding electrodes
fabricated from as-prepared NCA and NCA@SnO2 materials
(without storage). As can be seen in Fig. 8a and b, the first charge
potentials of the stored NCA and NCA@SnO2 at 0.1C rate are
increased and while the first discharge potentials are decreased
compared to the corresponding as-prepared NCA and NCA@SnO2
(see Fig. 5a and c). An obvious difference between the stored NCA
and stored NCA@SnO2 materials is that the polarization (see the
 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
Fig. 7. Cycling performances of (a) NCA and Le-NCA and (b) NCA@SnO2 and Le-NCA@SnO2 at 1C rate; (c) EISs (50% SOC) and (d) CVs (1 mV s1) of NCA@SnO2 and Le-NCA@SnO2 after
400 cycles at 1C rate.
potential drops on the end of charge when the charging current is
cut off) of the stored NCA is significantly larger than that of the
stored NCA@SnO2. Besides, the cycling stability of the stored NCA is
obviously poor than that of the stored NCA@SnO2 (see the changes
of first three charge/discharge curves of the two electrodes at 0.1C).
In addition, it can be found from Fig. 8a and b that at the initial
stage of the first charge the potentials of the stored NCA and
NCA@SnO2 all increase quickly to high values beyond 3.8 V and
then decrease again to a stable potential of ca. 3.8 V (plateau po-
tential). While, the plateau potentials of as-prepared NCA and
NCA@SnO2 are all ca. 3.6 V (see Fig. 5a and c). As well known, Ni-
rich layered oxide materials have poor storage stability in air.
Because the active material surface tend to react with CO2, O2 and
water in air, a layer of Li2CO3 and LiOH is usually found on the
surfaces of these materials exposed to air. As reported, long-term
exposure of LiNi0.8Co0.15Al0.05O2 could produce a dense Li2CO3
coating layer (approximately 10 nm in thickness) that could
severely reduce both the accessible capacity and the rate perfor-
mance [32]. According to a recent study [33], the observed high
potential at the initial stage of the first charge is related to the
Li2CO3 and LiOH formed on the surface of NCA particles. This sur-
face impedes ionic and electronic transport to the underlying
electrode, with progressive erosion of this layer during cycling, and
leads to different reaction states in particles with an intact versus
an eroded Li2CO3 surface coatings.
As shown in Fig. 8c and d, the specific capacity and rate per-
formance of the stored NCA are markedly decreased compared to
as-prepared NCA, whereas, those of the stored NCA@SnO2 are only
slightly decreased compared to as-prepared NCA@SnO2. To account
for the above observations, EIS measurements for the stored NCA
and NCA@SnO2 electrodes were conducted after the rate
437
performance test. The results are displayed in Fig. 8e and f in
comparison with the corresponding as-prepared materials, and the
fitted parameters of the EIS data are listed in Table S1. As shown, the
charge transfer resistance of stored NCA (4.557 U g) is remarkably
increased compared with as-prepared NCA (0.550 U g), whereas,
that of the stored NCA@SnO2 is increased only a little (from 0.161 to
0.184 U g) compared with as-prepared NCA@SnO2. These EIS results
should be responsible for the observations shown in Fig. 8ad. It
can be concluded that the surface SnO2 coating layer can act as a
protective layer to protect the surface of NCA directly exposed to air,
thus effectively improving the storage stability of the layered oxide.
4. Conclusions
In this paper, the LiNi0.8Co0.15Al0.05 (NCA) layered oxide cathode
material was modified by Li excess and SnO2 surface coating. For
comparative study, four NCA-based cathode materials, i.e., pristine
NCA (NCA), Li-excess NCA (Le-NCA), SnO2 coated NCA (NCA@SnO2)
and SnO2 coated Li-excess NCA (Le-NCA@SnO2) were prepared
under the similar conditions and characterized as the cathode
materials for Li-ion batteries. XRD and XPS analysis demonstrate
that a small amount of Liþ ion enters into the transition-metal slabs
of the Li-excess layered oxides, and that a small amount of Sn2þ ion
incorporates into the transition metal slabs of the SnO2 coated
layered oxides. These lower-valence ions doping on the transition-
metal 3a sites can decrease the amount of Ni2þ ion and hence
reduce the Liþ/Ni2þ cationic mixing. HRTEM observations confirm
that a SnO2 coating layer is formed on the surface of Le-NCA@SnO2
or NCA@SnO2 particles. SEM observations reveal that the surface
SnO2 layer can prevent the growth and aggregation of the layered
oxide particles upon high temperature calcination, thus producing
438 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439

Fig. 8. First three charge/discharge curves of (a) stored NCA and (b) stored NCA@SnO2 at 0.1C rate; Rate performances of (c) stored NCA and (d) stored NCA@SnO2 in comparison
with those of the corresponding as-prepared materials; EISs (measured at 50% SOC after 30 cycles of rate performance test) of (e) stored NCA and (f) stored NCA@SnO2 in com-
parison with those of the corresponding as-prepared materials.

the nano/submicron monodisperse sphere-like SnO2-coated
layered oxides. The electrochemical investigation results exhibit
that cationic mixing has a significant negative influence on the
electrochemical performance, including first charge/discharge
coulombic efficiency, discharge specific capacity at a lower current
rate, rate performance and cycling performance. Surface SnO2
coating can significantly improve the cycling stability of the layered
oxide. Among the investigated materials, the Le-NCA@SnO2 shows
the best electrochemical performance, for example, the discharge
capacity of Le-NCA@SnO2 is decreased from 123.7 to 86.7 mAh g1
after 400 cycles at 1C rate, with capacity retention of 70.1%. The Le-
NCA@SnO2 exhibits not only higher initial specific capacity but also
excellent cycling stability. That is to say, Li excess and SnO2 surface
coating can significantly improve the electrochemical performance
of the nickel-rich NCA material. Li excess is believed to decrease the
cationic mixing and the SnO2 surface modification is considered to
hinder the unwanted side reactions between the surface of active
material particles and electrolyte and is responsible for the excel-
lent cycling performance.
Declarations of interest
None.
 Z. Xie et al. / Journal of Alloys and Compounds 787 (2019) 429e439
Acknowledgements
This work was supported by the National Key Research and
Development Plan “New Energy Automobile” Key Special Project
(2017YFB0102200) and the Shanghai Municipal Education Com-
mission (Peak Discipline Construction). Instrumental Analysis &
Research Center of Shanghai University is gratefully acknowledged
for XRD, XPS, SEM and HRTEM experiments.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jallcom.2019.02.127.
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