Materials Chemistry and Physics 249 (2020) 123135

Contents lists available at ScienceDirect

Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

A simple strategy to prepare the La2Li0.5Al0.5O4 modified high-performance

ni-rich cathode material
Jiachao Yang a, c, 1, Yongxiang Chen a, c, Yunjiao Li a, c, *, Shiyi Deng a, c, Shenghong Chang a, c,
Guolin Cao a, c, Dianwei Zhang a, c, Shilei Wang a, c, Wei Li a, b, c
a
School of Metallurgy and Environment, Central South University, Changsha, 410083, PR China
b
Citic Dameng Mining Industries Limited, Nanning, 530028, PR China
c
Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Central South University, Changsha 410083, China

H I G H L I G H T S

� The La–Al co-doping and La2Li0.5Al0.5O4 coating NCM811 cathode material was prepared by a simple method.
� The La and Al were doped in the host material uniformly.
� La2Li0.5Al0.5O4 coating protects the active material from electrolyte eroding.
� The co-modification method contributes to the superior electrochemical performances of NCM811.

A R T I C L E I N F O A B S T R A C T

Keywords: LiNi0.8Co0.1Mn0.1O2(NCM811) is regarded as one of the promising Li-ion battery cathode materials due to the
Li-ion battery high capacity and low cost, but the poor cyclic and rate performances hinder its widespread application. In our
Ni-rich cathode material research, La and Al co-modified NCM811 is successfully prepared by a simple method. XRD and XPS confirm that
High performance
La and Al can not only dope into the NCM811 bulk, but also form the La2Li0.5Al0.5O4 coating layer on the surface.
La–Al co-doping
The La2Li0.5Al0.5O4 coated and La-and-Al-doped NCM811 exhibits an excellent capacity retention of 97.2% at 1C
La2Li0.5Al0.5O4
in the voltage range of 3.0–4.4 V after 100 cycles, 18.5% higher than that of the pristine. As for rate performance,
it exhibits a retention of 95.1% in capacity at 5C after 80 cycles from 3.0 V to 4.4 V, 6.4% higher than that of the
pristine. The enhanced high-voltage electrochemical performances are mainly ascribed to the facts that the La
and Al strengthen the bulk structure by co-doping and the formed La2Li0.5Al0.5O4 coating layer, as the high-Tc
superconducting oxides, not only promotes the diffusion of Liþ but also protect the cathodes from eroding by
with the electrolyte. Meanwhile, the residual lithium is reduced by the formation of La2Li0.5Al0.5O4. The
enhanced electrochemical performance shows that the modification of La2Li0.5Al0.5O4 coating and La–Al co-
doping is a competitive method for industrial production of NCM811 material.

1. Introduction electronics [6,7]. The nickel-rich layer cathodes (LiNixM1-xO2; M ¼ Mn,

With the development of worldwide economics and technology,
there is an increasing demand for energy source [1,2]. Among many
kinds of energy storage devices, lithium-ion batteries (LIBs) are
considered as the most promising power source, due to their high ca­
pacity and stable discharge platform [3–5]. The lithium-ion batteries
have widespread application in electric vehicles (EVs) and consumer
Co and Al; x > 0.5) are considered to be promising choices to meet the
consumer demand because of their advantages of low cost and high
energy density [8–13]. Nevertheless, the cycling performances of Ni-rich
layer materials will be seriously deteriorated at a higher cut-off voltage
and a higher temperature [14]. The Ni2þ ions can be easily reduced from
Ni3þ/Ni4þ in the process of discharging. On account of the similar radius
of Ni2þ(0.69 Å) and Liþ(0.76 Å), the Ni2þ ions could occupy the Liþ site,

* Corresponding author. School of Metallurgy and Environment, Central South University, Changsha 410083, PR China.
E-mail addresses: 904025697@qq.com (J. Yang), 1570661095@qq.com (Y. Chen), yunjiao_li@csu.edu.cn (Y. Li), 530956636@qq.com (S. Deng), 1579063776@
qq.com (S. Chang), caoguolin1983@163.com (G. Cao), 346011128@qq.com (D. Zhang), 740121077@qq.com (S. Wang), 35251011@qq.com (W. Li).
1
Jiachao Yang will handle Correspondence at all stages of refereeing and publication, also post-publication.

https://doi.org/10.1016/j.matchemphys.2020.123135
Received 9 January 2020; Received in revised form 20 April 2020; Accepted 27 April 2020
Available online 29 April 2020
0254-0584/© 2020 Published by Elsevier B.V.
J. Yang et al.
Fig. 1. XRD patterns of the samples and the magnified section at the range from 18.5� to 19� .
Table 1
The lattice parameters of the samples.
a(Å) c(Å) c/a V R
NCM-P 2.873 14.206 4.944 101.53
NCM-1 2.874 14.212 4.945 101.62
NCM-2 2.874 14.213 4.946 101.70
NCM-3 2.875 14.218 4.943 102.05
which leads to the formation of spinel phase and rock salt phase [15,16].
The spinel phase will form at a high rate discharging process and the
rock salt phase will form at a low rate discharging process [17–19]. As
for the chemical characters, the residual lithium, which evolves from
excess lithium and environmental oxygen, and leads to the lower ca­
pacity, aggravated cycle performance and inferior structure stability
[20,21]. And the high-activity electrolyte, at the voltage above 4.3 V,
will aggravate the side reaction with the cathode materials, resulting in
the poor surface character [17].
Many efforts have been made to optimize the performances of Ni-rich
layer materials via surface coating, element doping, design of concen­
trate gradient structure and synthesis of micro-structured materials. The
element doping is an approach of atom substitution to stabilize the
crystalline structure, reduce the side reaction between the cathode
materials and the electrolyte, and enhance the transmission of Li-ion in
the bulk phase. It is proved that various doping elements are effective,
such as Na, Mg, F, Ca, Al, Mn and Mo [21–27]. The surface modification
is another resultful method to increase the structure stability of surface
phase and inhibit the bulk strain of host material, where the secondary
particles are homogeneously coated by some chemical stable com­
pounds like Al2O3, Li4Ti5O12, TiO2 and Li3PO4 [28–31].
To be specific, the single element doping of Al and La in LiCoO2 were
reported ten years ago. Ghosh prepared La-doped LiCoO2 cathode ma­
terial with high rate capacity [32]. Myung explored the effect of Al
doping on the microstructure of LiCoO2 cathode material [33]. More­
over, the Al and La co-doped LiCoO2 was reported, which enhanced the
lithium ion diffusion coefficient [34]. But there is little research about
the La–Al co-doped Ni-rich materials and there should be more attention
about the reaction of Li, La and Al [32,33]. There are two researches
about LaAlO3 coated NCM811 material and co-modified NCM811 ma­
terial of La coating and Al doping [35,36]. Our work proved that La and
Al tended to form stable La2Li0.5Al0.5O4 compound rather than
Materials Chemistry and Physics 249 (2020) 123135
respective oxides in Ni-rich materials. La2Li0.5Al0.5O4 is a kind of
high-Tc superconducting oxides with K2NiF4-type structure, which is
chemically and structurally stable. Moreover, the MeO6 octahedron fa­
cilitates the transport of Li-ion in host structure. Li et al. [36] proved that
1.60 the reaction between La, Al and Li by generating La2Li0.5Al0.5O4 effec­
1.60 tively reduced the residential lithium on the surface of the particles.
1.64
In our research, the one-step solid state reaction is applied to prepare
1.80
the cathode material. Most importantly, this method is a simple route to
prepare high performance Li-ion cathode material, which means the low
cost and less variables. For many synthesis techniques, such as chemical
vapor deposition method and sol-gel method, it is hard to have extensive
application. So the low cost method will be benefit for industry. And it’s
easier to control the preparation process because of the less variables.
The stable crystal of the bulk with doping atoms will form at the high
temperature. Eventually, compared with the astriction of solubility
product in coprecipitation method, this method applies to almost any
element.
Herein, the La–Al co-modified LiNi0.8Co0.1Mn0.1O2 cathode material
was prepared successfully by the solid state reaction. The modified
cathode material shows an excellent electrochemical performance.
2. Experimental
2.1. Material synthesis
The hydroxide NCM811 precursor was obtained from Ronbay
Technology Co., Ltd. The pristine NCM811(NCM-P) material was pre­
pared by calcining the mixture of the precursor and LiOH⋅H2O (with a
Li/Me molar ratio of 1:1.05) at 500 � C for 4 h and then 800 � C for 12 h.
The La–Al co-modified cathode material were prepared by the following
procedures. Firstly, La(NO3)3⋅6H2O and Al(NO3)3⋅9H2O with a La/Al
molar ratio of 4:1 were dissolved in anhydrous alcohol. Secondly, the
precursor was added into the La–Al ethanol solution with the Me(La þ
Al)/precursor mass ratio of 1500 ppm (NCM-1), 3000 ppm (NCM-2) and
4500 ppm (NCM-3), respectively. After the suspensions were totally
dried at 90 � C, the mixture was calcined at 500 � C for 4 h and then at
800 � C for 12 h in an oxygen atmosphere to obtain the La–Al co-modified
materials.
2
J. Yang et al.
Fig. 2. SEM images of (a) NCM-P, (b) NCM-1, (c) NCM-2 and (d) NCM-3.
2.2. Material characterization
The surface morphologies of the particles were characterized using a
scanning electron microscope coupled with an energy dispersive spec­
trometer (SEM/EDS, JEOL JSM-6360LV, Japan). The crystal structure
information was collected by a Rigaku D/max-2500 diffractometer. The
radiation source is Cu Kα and the scan speed was set as 5� /min. The
states information of elements on the several nanometers depth of
samples’ surface was obtained by X-ray photoelectron spectroscopy
(XPS, VG Multilab, 2000).
2.3. Electrochemical test
The positive electrode was made by mixing polyvinylidene fluoride
(PVDF) (10 wt%), active material (80 wt%) and acetylene black (10 wt
%). The mixture was dispersed in N-methyl-2-pyrrolidone (NMP) and
then pasted onto the Al foil and dried at 90 � C for 4 h. The oven-dried
plate was punched into discs of 7 mm in radius as cathode electrodes.
The coin cells were assembled in the Argon-filled glove box employing
the metallic lithium as anode electrodes. The electrolyte was 1 M LiPF6
dissolved in EMC, EC and DMC with the vol ratio of 1:1:1. A Land Test
System was used to investigate the stability of charge/discharge tests at
different rates (1 C ¼ 180 mAh g 1) at the voltages from 3.0 to 4.4 V at
room temperature (25 � C). The multicycle cyclic voltammetry (CV) were
measured at the range of 3.0–4.4 V with a scanning rate of 0.1 mV s 1.
The electrochemical impedance spectroscopy (EIS) was tested over the
frequency range of 0.01 Hz–100 kHz. The amplitude of AC signal was set
as � 5 mV.
3
Materials Chemistry and Physics 249 (2020) 123135
3. Results and discussion
3.1. Structure and morphology
The XRD patterns shown in Fig. 1 demonstrate that all the four
samples exhibit an α-NaFeO2 structure with R3ð—Þm space group. And
the samples with high crystallinity and purity were detected. The clear
splitting of (108)/(110) and (006)/(102) peaks reveals a great ordered
layer structure. The values of the intensity ratio of I(003)/I(104) are
greater than 1.20, reflecting the low cation mixing of Liþ and Ni2þ. It is
important that three peaks at 31.6� , 24.6� and 33.7� , respectively, were
detected in NCM-3, highly corresponding to the characteristic peaks of
La2Li0.5Al0.5O4 (JCPDS #40–1167). The acquired La2Li0.5Al0.5O4 proved
the reaction between La, Al and Li, which could effectively reduce the
residential lithium on the surface of the particles [36]. Moreover,
La2Li0.5Al0.5O4 was found in La2O3-coated and Al-doped NCM811
cathode material [35]. But the XRD patterns of La2Li0.5Al0.5O4 didn’t
appear in NCM-1 and NCM-2 due to the low contents of La and Al.
From the magnified section from 18.5� to 19� , the 2-theta value of
(003) peak decreased gradually, with the increase of La and Al contents.
The phenomenon was possibly attributed to the larger radius of La3þ
(1.061 Å) than those of Liþ (0.76 Å) and Ni3þ (0.56 Å).
The lattice parameters of the obtained samples was summarized in
Table 1. The values of a and c slightly raised, as the increase of La3þ. And
the values of c/a, which are usually used to reflect the degree of layered
structure, are over 4.9, indicating the great layered structure of all the
samples.
The morphologies of different samples were shown in Fig. 2. All the
four samples exhibited well-spherical secondary particles with sizes
distributing in the range of 5–15 μm. No clear size change was observed
among the four samples. The NCM-P sample, as shown in Fig. 2(a),
J. Yang et al.
Fig. 3. EDS line scanning and backscattered electron section images of NCM-2. (a) SEM image on the cross-section of NCM-2; Corresponding EDS (b) line-scanning
result and mapping of (c) Al and (d) La elements.
presented a rough surface of second particles, which might lead to a
larger contact area and induce more serious side reaction eventually. By
contrast, Fig. 2(b–d) indicated that the surface of the modified material
was more smooth with compact primary particles.
The EDS line and mapping analyses of NCM-2 were conducted to
investigate the element distribution after La and Al co-modification. In
Fig. 3(a), the image of cross-section of NCM-2 is chosen for analyzing the
morphology of inner phase. Fig. 3(b) shows that La2Li0.5Al0.5O4 was
coated on the surface of material with the high intensity of La and Al.
Obviously, the Ni content on the surface were decreased due to the
coating of La2Li0.5Al0.5O4. The intensity of La and Al in inner phase was
stable, because La and Al were doped in the host material uniformly. In
general, the curves of La and Al have the similar tendency. The curves of
Co and Mn show that their element contents are similar. To explore the
element distribution of the particles, EDS mapping result of NCM-2 is
presented in Fig. 3(c and d). It is obvious that Al and La were distributed
homogeneously on the surface and cross-section of the NCM-2 particles,
which indicates that La and Al were doped in NCM811 material.
XPS measurement was employed to evaluate the surface element
valance of NCM-2 and NCM-P. As shown in Fig. 4(a and b), the binding
energies of Al and La are 68 eV and 855 eV, respectively, which indicate
that La and Al are distributed on the surface of NCM-2. In Fig. 4(c and d),
the XPS spectrum of Ni 2p3/2 for NCM-P consists of two peaks which
represent the Ni2þ and Ni3þ and locate at 854.7 eV and 855.9 eV,
respectively. According to the fitting results, the ratio of Ni2þ reaches to
43.5% in NCM-P, comparing with 34.6% in NCM-2. The excess Ni2þ will
aggravate the cation mixing of Li/Ni, in which Ni2þ ions occupy the Liþ
sites. After La–Al doping, NCM-2 displayed a less ratio of Ni2þ than the
pristine by 8.9%, which implies that the modified cathode material may
have a better cycle performance.
4
Materials Chemistry and Physics 249 (2020) 123135
3.2. Electrochemical properties
The electrochemical performances of the La–Al co-modified NCM811
cathode materials were depicted in Fig. 5. The initial capacities at 0.1 C
of NCM-P, NCM-1, NCM-2, NCM-3 were 191.5, 192.7, 191.0 and 179.0
mAh g 1, respectively. The reduction of initial capacity may be ascribed
to the more generation of La2Li0.5Al0.5O4, which is electrochemically
inert. Moreover, the radius of La3þ is much larger than those of the
transition metal ions, which may lead to the distortion of crystal struc­
ture. After 100 cycles at 1C, the capacity retentions of the four samples
were 78.7%, 89.8%, 97.2% and 85.6%, respectively. As the present
study show, most pristine NCM811 cathode materials deliver a initial
capacity of around 190 mAh g 1 (198 [37] and 194.7 [38] mAh g 1) at
the voltage range of 3.0–4.4 V and 1 C rate, and the retentions of those
are around 77% (77.2% [37] and 78.7% [38]) after the 100 cycles. And
the retentions of best modified samples are all around 88%. Compared
with those, the electrochemical performance of the pristine material in
our research is normal. And the NCM-2 in our study has a great
improvement. The NCM-2 sample has the highest capacity retention.
The initial charge/discharge curves in Fig. 5 (c) were all smooth, indi­
cating that all of them have steady discharge platforms. The charge/­
discharge curves of NCM-2 were denser than NCM-P, indicating the less
polarization and the better electrochemical performance. As reflected in
Fig. 5 (d), NCM-2 yielded the excellent discharge capacities at 2C, 4C
and 8C, which could be originated from the decrease of the material
impendence. It is proved that the La2Li0.5Al0.5O4 modified cathode
resulted in the enhanced electrochemical performances.
Fig. 6 (a) shows the cyclic performance from 3.0 V to 4.4 V at 5C rate.
The NCM-P yielded 174.7 mAh⋅g 1 for the initial cycle with low
retention of 88.7% after 80 cycles. By contrast, the NCM-2 delivered
181.1 mAh⋅g 1 with the retention of 95.1%, revealing that NCM-2 has
much better electrochemical performance at a higher rate. The EIS tests
were performed at the charged state of 4.4 V to explore the impendence
J. Yang et al. Materials Chemistry and Physics 249 (2020) 123135

Fig. 4. XPS spectra of (a) Al 2p, (b) La 3d3/2 of NCM-2; Ni 2p of (c) NCM-P and (d) NCM-2.

5
J. Yang et al. Materials Chemistry and Physics 249 (2020) 123135

Fig. 5. (a) Cycling performance of samples from 3.0 V to 4.4 V at 1 C and the corresponding (b) initial charge/discharge curves of the four samples. (c) Charge/
discharge curves of NCM-P and NCM-2. (d) Rate performance of NCM-P and NCM-2.

6
J. Yang et al. Materials Chemistry and Physics 249 (2020) 123135

Fig. 6. (a)Cycling performance from 3.0 V to 4.4 V at 5C charge/discharge profile for NCM-P. (b) EIS curves of NCM-2 at the voltage of 3.0–4.4 V before cycling. (d)
CV curves of NCM-P and (d) NCM-2 at the voltage of 3.0–4.4 V

materials, which still suffer from the decay of discharge capacity. In our
Table 2 research, La and Al are not only form the La2Li0.5Al0.5O4 coating layer on
The impendence of NCM-P and NCM-2 before and after 100 cycles. the surface, but also homogeneously dope into the inner phase of
Samples Rs(Ω) Rf(Ω) Rct(Ω) NCM811 materials using a simple solid-state method. Consequently, the
NCM-P 1.76 43.5 164.4
capacity retention of NCM-2 was raised to 97.2% after 100 cycles from
NCM-2 1.21 40.8 150.4 3.0 to 4.4 V at 1C, and 95.1% after 80 cycles from 3.0 to 4.4 V at 5C. And
the XRD results confirmed that in the Li–Al–La system, La2Li0.5Al0.5O4
could be generated at a high temperature over 800 � C. The La–Al co-
of ionic/electronic transfer and the kinetics characteristics. As shown in modified method is believed to be useful for other oxide cathodes. The
Fig. 6(b), the Nyquist plots consist of a small interrupt before a semi­ research provides an important direction to prepare high-performance
circle in the high frequency range, two semicircles in the high/medium- Ni-rich cathode materials.
to-low frequency range and a sloping line in the low frequency range,
corresponding to the solution resistance (Rs), surface film impedance Declaration of competing interest
(Rf), charge-discharge resistance (Rct) and the Liþ diffusion coefficient
(DLiþ), respectively [39]. It can be seen from Table 2 that the Rf and Rct The authors declare there is no conflicts of interest regarding the
were reduced from 43.5 Ω to 40.8 Ω and from 164.4 Ω to 150.4 Ω, publication of this paper.
respectively. It demonstrated that the La2Li0.5Al0.5O4 modification
effectively decreased the resistance of material. Cyclic voltammetry was
CRediT authorship contribution statement
employed to reveal the polarization of NCM-P and NCM-2. As shown in
Fig. 6(c and d), the ΔE of NCM-P between the oxidation peak and the
Jiachao Yang: Writing - original draft. Yong xiang Chen: Writing -
reduction peak was 0.260 V. By contrast, the ΔE of NCM-2 was 0.229 V,
review & editing. Yunjiao Li: Proiect administration. Shiyi Deng:
which is less than NCM-P by 0.031 V, indicating a smaller electro­
Formal analysis. Shenghong Chang: Data curation. Guolin Cao: Soft­
chemical polarization.
ware. Dianwei Zhang: Visualization. Shilei Wang: Supervision. Wei Li:
Resources.
4. Conclusions

Acknowledgments
In summary, both coating and doping are deemed to be useful to
modify the cathode materials for Li-ion batteries. However, the single
The authors are very grateful for the financial support from the
method has limited effects on promoting the performances of the Ni-rich
Government of Chongzuo, Guangxi Zhuang Autonomous Region (GC

7
J. Yang et al.
Joint Special Fund No. FA2019015) and Science and Technology
Department of Guangxi Zhuang Autonomous Region (Guangxi Special
Fund for Scientific Center and Talent Resources, No. AD18281073).
References
[1] L. Pan, Y. Xia, B. Qiu, H. Zhao, H. Guo, K. Jia, Q. Gu, Z. Liu, Synthesis and
electrochemical performance of micro-sized Li-rich layered cathode material for
Lithium-ion batteries, Electrochim. Acta (2016), https://doi.org/10.1016/j.
electacta.2016.06.069.
[2] R.N. Ramesha, C.P. Laisa, K. Ramesha, Improving electrochemical stability by
transition metal cation doping for manganese in lithium-rich layered cathode,
Li1.2Ni0.13Co0.13Mn0.54-xMxO2 (M ¼ Co, Cr and Fe), electrochim, Acta (2017),
https://doi.org/10.1016/j.electacta.2017.08.039.
[3] Y. Zhu, X. Luo, M. Xu, L. Zhang, L. Yu, W. Fan, W. Li, Failure mechanism of layered
lithium-rich oxide/graphite cell and its solution by using electrolyte additive,
J. Power Sources (2016), https://doi.org/10.1016/j.jpowsour.2016.03.090.
[4] Z. Zhou, Y. Ma, L. Wang, P. Zuo, X. Cheng, C. Du, G. Yin, Y. Gao, Triphenyl
phosphite as an electrolyte additive to improve the cyclic stability of lithium-rich
layered oxide cathode for lithium-ion batteries, Electrochim. Acta (2016), https://
doi.org/10.1016/j.electacta.2016.09.008.
[5] F. Zheng, C. Yang, X. Xiong, J. Xiong, R. Hu, Y. Chen, M. Liu, Nanoscale Surface
Modification of Lithium-Rich Layered-Oxide Composite Cathodes for Suppressing
Voltage Fade, Angew. Chem. Int. Ed. (2015), https://doi.org/10.1002/
anie.201506408.
[6] W. Liu, P. Oh, X. Liu, M.J. Lee, W. Cho, S. Chae, Y. Kim, J. Cho, Nickel-rich layered
lithium transition-metal oxide for high-energy lithium-ion batteries, Angew. Chem.
Int. Ed. (2015), https://doi.org/10.1002/anie.201409262.
[7] L. Dong, F. Liang, D. Wang, C. Zhu, J. Liu, D. Gui, C. Li, Safe ionic liquid-sulfolane/
LiDFOB electrolytes for high voltage Li1.15(Ni0.36Mn0.64)0.85O2 lithium ion
battery at elevated temperatures, Electrochim. Acta (2018), https://doi.org/
10.1016/j.electacta.2018.03.108.
[8] Z. Zheng, X.D. Guo, S.L. Chou, W.B. Hua, H.K. Liu, S.X. Dou, X.S. Yang, Uniform Ni-
rich LiNi0.6Co0.2Mn0.2O2 porous microspheres: facile designed synthesis and
their improved electrochemical performance, Electrochim. Acta (2016), https://
doi.org/10.1016/j.electacta.2016.01.092.
[9] K. Du, J. Huang, Y. Cao, Z. Peng, G. Hu, Study of effects on LiNi0.8Co0.15Al
0.05O2 cathode by LiNi1/3Co 1/3Mn1/3O2 coating for lithium ion batteries,
J. Alloys Compd. (2013), https://doi.org/10.1016/j.jallcom.2013.05.134.
[10] Y.K. Sun, D.H. Kim, H.G. Jung, S.T. Myung, K. Amine, High-voltage performance of
concentration-gradient Li[Ni 0.67Co0.15Mn0.18]O2 cathode material for lithium-
ion batteries, Electrochim. Acta (2010), https://doi.org/10.1016/j.
electacta.2010.07.074.
[11] K.J. Park, B.B. Lim, M.H. Choi, H.G. Jung, Y.K. Sun, M. Haro, N. Vicente,
J. Bisquert, G. Garcia-Belmonte, A high-capacity Li[Ni0.8Co0.06Mn0.14]O2
positive electrode with a dual concentration gradient for next-generation lithium-
ion batteries, J. Mater. Chem. (2015), https://doi.org/10.1039/c5ta05657h.
[12] J. Gao, S.Q. Shi, H. Li, Brief overview of electrochemical potential in lithium ion
batteries, Chin. Phys. B (2015), https://doi.org/10.1088/1674-1056/25/1/
018210.
[13] N. Andreu, D. Flahaut, R. Dedryv� ere, M. Minvielle, H. Martinez, D. Gonbeau, XPS
investigation of surface reactivity of electrode materials: effect of the transition
metal, ACS Appl. Mater. Interfaces (2015), https://doi.org/10.1021/am5089764.
[14] S. Shi, J. Gao, Y. Liu, Y. Zhao, Q. Wu, W. Ju, C. Ouyang, R. Xiao, Multi-scale
computation methods: their applications in lithium-ion battery research and
development, Chin. Phys. B (2015), https://doi.org/10.1088/1674-1056/25/1/
018212.
[15] J. Kang, B. Han, First-principles study on the thermal stability of LiNiO2 materials
coated by amorphous Al2O3 with atomic layer thickness, ACS Appl. Mater.
Interfaces (2015), https://doi.org/10.1021/acsami.5b02572.
[16] Z. Shadike, Y.N. Zhou, L.L. Chen, Q. Wu, J.L. Yue, N. Zhang, X.Q. Yang, L. Gu, X.
S. Liu, S.Q. Shi, Z.W. Fu, Antisite occupation induced single anionic redox
chemistry and structural stabilization of layered sodium chromium sulfide, Nat.
Commun. (2017), https://doi.org/10.1038/s41467-017-00677-3.
[17] L. Zou, W. Zhao, Z. Liu, H. Jia, J. Zheng, G. Wang, Y. Yang, J.G. Zhang, C. Wang,
Revealing cycling rate-dependent structure evolution in Ni-rich layered cathode
materials, ACS Energy Lett. (2018), https://doi.org/10.1021/
acsenergylett.8b01490.
[18] F. Wu, J. Tian, Y. Su, J. Wang, C. Zhang, L. Bao, T. He, J. Li, S. Chen, Effect of Ni2þ
content on lithium/nickel disorder for Ni-rich cathode materials, ACS Appl. Mater.
Interfaces (2015), https://doi.org/10.1021/acsami.5b00645.
[19] X. Zhang, M. Van Hulzen, D.P. Singh, A. Brownrigg, J.P. Wright, N.H. Van Dijk,
M. Wagemaker, Direct view on the phase evolution in individual LiFePO 4
nanoparticles during Li-ion battery cycling, Nat. Commun. (2015), https://doi.org/
10.1038/ncomms9333.
Materials Chemistry and Physics 249 (2020) 123135
[20] G.W. Nam, N.-Y. Park, K.-J. Park, J. Yang, J. Liu, C.S. Yoon, Y.-K. Sun, Capacity
fading of Ni-rich NCA cathodes: effect of microcracking extent, ACS Energy Lett. 4
(2019) 2995–3001, https://doi.org/10.1021/acsenergylett.9b02302.
[21] M. Jo, H. Ku, S. Park, J. Song, K. Kwon, Effects of Residual Lithium in the
precursors of Li[Ni1/3Co1/3Mn1/3]O2 on their lithium-ion battery performance,
J. Phys. Chem. Solid. 118 (2018) 47–52, https://doi.org/10.1016/j.
jpcs.2018.02.043.
[22] Z. Huang, Z. Wang, X. Zheng, H. Guo, X. Li, Q. Jing, Z. Yang, Effect of Mg doping
on the structural and electrochemical performance of LiNi0.6Co0.2Mn0.2O2
cathode materials, Electrochim. Acta (2015), https://doi.org/10.1016/j.
electacta.2015.09.151.
[23] Y.C. Li, W. Xiang, Z.G. Wu, C.L. Xu, Y. Di Xu, Y. Xiao, Z.G. Yang, C.J. Wu, G.P. Lv,
X.D. Guo, Construction of homogeneously Al3þ doped Ni rich Ni-Co-Mn cathode
with high stable cycling performance and storage stability via scalable continuous
precipitation, Electrochim. Acta 291 (2018) 84–94, https://doi.org/10.1016/j.
electacta.2018.08.124.
[24] Z. Yang, W. Xiang, Z. Wu, F. He, J. Zhang, Y. Xiao, B. Zhong, X. Guo, Effect of
niobium doping on the structure and electrochemical performance of LiNi 0.5 Co
0.2 Mn 0.3 O 2 cathode materials for lithium ion batteries, Ceram. Int. 43 (2017)
3866–3872, https://doi.org/10.1016/j.ceramint.2016.12.048.
[25] W. Hua, J. Zhang, Z. Zheng, W. Liu, X. Peng, X.D. Guo, B. Zhong, Y.J. Wang,
X. Wang, Na-doped Ni-rich LiNi0.5Co0.2Mn0.3O2 cathode material with both high
rate capability and high tap density for lithium ion batteries, Dalton Trans. (2014),
https://doi.org/10.1039/c4dt01611d.
[26] W. Cho, Y.J. Lim, S.M. Lee, J.H. Kim, J.H. Song, J.S. Yu, Y.J. Kim, M.S. Park, Facile
Mn surface doping of Ni-rich layered cathode materials for lithium ion batteries,
ACS Appl. Mater. Interfaces (2018), https://doi.org/10.1021/acsami.8b13766.
[27] P. Yue, Z. Wang, H. Guo, X. Xiong, X. Li, A low temperature fluorine substitution on
the electrochemical performance of layered LiNi0.8Co0.1Mn0.1O 2-zFz cathode
materials, Electrochim. Acta (2013), https://doi.org/10.1016/j.
electacta.2013.01.018.
[28] Z.F. Tang, R. Wu, P.F. Huang, Q.S. Wang, C.H. Chen, Improving the
electrochemical performance of Ni-rich cathode material
LiNi0.815Co0.15Al0.035O2by removing the lithium residues and forming
Li3PO4coating layer, J. Alloys Compd. (2017), https://doi.org/10.1016/j.
jallcom.2016.10.099.
[29] Y. Di Xu, W. Xiang, Z.G. Wu, C.L. Xu, Y.C. Li, X.D. Guo, G.P. Lv, X. Peng, B.
H. Zhong, Improving cycling performance and rate capability of Ni-rich LiNi 0.8 Co
0.1 Mn 0.1 O 2 cathode materials by Li 4 Ti 5 O 12 coating, Electrochim. Acta 268
(2018) 358–365, https://doi.org/10.1016/j.electacta.2018.02.049.
[30] Y. Chen, Y. Zhang, F. Wang, Z. Wang, Q. Zhang, Improve the structure and
electrochemical performance of LiNi 0.6Co0.2Mn0.2O2 cathode material by nano-
Al2O3 ultrasonic coating, J. Alloys Compd. (2014), https://doi.org/10.1016/j.
jallcom.2014.05.068.
[31] S.N. Lim, W. Ahn, S.H. Yeon, S. Bin Park, Enhanced elevated-temperature
performance of Li(Ni0.8Co 0.15Al0.05)O2 electrodes coated with Li 2O-2B2O3
glass, Electrochim. Acta (2014), https://doi.org/10.1016/j.electacta.2014.05.056.
[32] P. Ghosh, S. Mahanty, R.N. Basu, Lanthanum-doped LiCoO2 cathode with high rate
capability, Electrochim. Acta (2009), https://doi.org/10.1016/j.
electacta.2008.09.050.
[33] S.T. Myung, N. Kumagai, S. Komaba, H.T. Chung, Effects of Al doping on the
microstructure of LiCoO2 cathode materials, Solid State Ionics (2001), https://doi.
org/10.1016/S0167-2738(00)00828-6.
[34] Q. Liu, X. Su, D. Lei, Y. Qin, J. Wen, F. Guo, Y.A. Wu, Y. Rong, R. Kou, X. Xiao,
F. Aguesse, J. Bare~no, Y. Ren, W. Lu, Y. Li, Approaching the capacity limit of
lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping,
Nat. Energy. 3 (2018) 936–943, https://doi.org/10.1038/s41560-018-0180-6.
[35] Y.C. Li, W. Xiang, Y. Xiao, Z.G. Wu, C.L. Xu, W. Xu, Y. Di Xu, C. Wu, Z.G. Yang, X.
D. Guo, Synergy of doping and coating induced heterogeneous structure and
concentration gradient in Ni-rich cathode for enhanced electrochemical
performance, J. Power Sources 423 (2019) 144–151, https://doi.org/10.1016/j.
jpowsour.2019.03.073.
[36] Y.C. Li, W.M. Zhao, W. Xiang, Z.G. Wu, Z.G. Yang, C.L. Xu, Y. Di Xu, E.H. Wang, C.
J. Wu, X.D. Guo, Promoting the electrochemical performance of
LiNi0.8Co0.1Mn0.1O2 cathode via LaAlO3 coating, J. Alloys Compd. 766 (2018)
546–555, https://doi.org/10.1016/j.jallcom.2018.06.364.
[37] Y. Li, J. Zhu, S. Deng, T. Lei, Y. Chen, G. Cao, S. Wang, J. Zhang, J. Guo, Towards
superior cyclability of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium ion
batteries via synergetic effects of Sb modification, J. Alloys Compd. 798 (2019)
93–103, https://doi.org/10.1016/j.jallcom.2019.05.217.
[38] J. Zhu, G. Cao, Y. Li, S. Wang, S. Deng, J. Guo, Y. Chen, T. Lei, J. Zhang, S. Chang,
Nd2O3 encapsulation-assisted surface passivation of Ni-rich LiNi0.8Co0.1Mn0.1O2
active material and its electrochemical performance, Electrochim. Acta 325 (2019)
134889, https://doi.org/10.1016/j.electacta.2019.134889.
[39] Y. Zhang, Z.B. Wang, F. Da Yu, L.F. Que, M.J. Wang, Y.F. Xia, Y. Xue, J. Wu, Studies
on stability and capacity for long-life cycle performance of Li(Ni0.5Co0.2Mn0.3)
O2 by Mo modification for lithium-ion battery, J. Power Sources (2017), https://
doi.org/10.1016/j.jpowsour.2017.05.013.