Materials Letters 253 (2019) 136–139

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

V2O5 modified LiNi0.5Mn1.5O4 as cathode material for high-performance

Li-ion battery
Jing-Jing Pan a, Bin Chen a, Ying Xie b,⇑, Ning Ren c,⇑, Ting-Feng Yi a,d,⇑
a
School of Chemistry and Chemical Engineering, Anhui University of Technology, Maanshan, Anhui 243002, PR China
b
Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, PR China
c
Zhejiang Chilwee Chuangyuan Industry Co., Ltd, Changxing, Zhejiang 313100, PR China
d
School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004, PR China

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

Article history: LiNi0.5Mn1.5O4 (LNMO) and V2O5-modified LNMO materials with P4332 structure were prepared by etha-
Received 21 February 2019 nol assisted co-precipitation process. The discharge capacities of V2O5-coated LiNi0.5Mn1.5O4 is 131.4,
Received in revised form 10 June 2019 122, 111.1 93.8 and 52.1 mAh g 1 at 0.2, 0.5, 1, 2 and 5 C charge-discharge rates, respectively. The dis-
Accepted 17 June 2019
charge capacities of pristine LNMO are only 125.7, 107.3, 86.2, 69.7 and 37.6 mAh g 1 at homologous
Available online 18 June 2019
rates. The V2O5 modification can be considered as an efficient way to enhance the rate capability of
LNMO. The improved rate capability of V2O5-coated LNMO material could be ascribed to the enhanced
Keywords:
lithium-ions diffusion coefficient and reduced charge-transfer reaction resistance.
Oxidation
LiNi0.5Mn1.5O4
Ó 2019 Elsevier B.V. All rights reserved.
Rate performance
Energy storage and conversion

1. Introduction 2. Experimental

Spinel LiNi0.5Mn1.5O4 (LNMO) and Li-rich materials show rela-
tively high operating voltage, and then improve the energy density
when used as cathode in LIBs [1]. Unfortunately, several secondary
reactions in the LNMO/electrolyte interface and oxidation of elec-
trolyte are usually found because of the high charge voltage of
about 5 V [2]. These main shortcomings of LNMO limit the large-
scale application. Doping and surface coating have been regarded
as an effective strategy to figure out the above-mentioned issues
[1,3]. The advantage of surface modification is that the direct con-
tact between active materials and electrolyte can be avoided, and
then decrease the secondary reactions [4]. V2O5 can be a good
choice to modify LNMO because V2O5 has a relatively higher ionic
conductivity and Li-ions diffusion coefficient than most metal oxi-
des and metal fluorides, and has been proved to be an attractive
coating material for LIBs cathodes [5]. Hence, V2O5 may be consid-
ered as a satisfactory coating material to enhance the electrochem-
ical performance of LNMO. With this consideration, the purpose of
this work is to improve the electrochemical performance of LNMO
by using V2O5 coating.
MnSO4
H2O and NiSO4
7H2O with a molar ratio of 3:1 were
dissolved in a mixed solution of deionized water and ethanol.
NH4HCO3 solution was added to the mixed solution drop by drop,
and then was transferred to a 200 mL Teflon-lined stainless-steel
autoclave and maintained at 180 °C for 8 h, and then the precipi-
tate was then gathered. The precursors and Li2CO3 were pre-fired
at 500 °C for 4 h, and then sintered at 850 °C for 12 h and at
600 °C for 6 h. For the synthesis of V2O5-coated LNMO, the
Ni0.5Mn1.5(CO3)2 precursors, Li2CO3 and NH4VO3 were mixed, and
then sintered in air at 500 °C for 4 h, at 850 °C for 12 h and then
at 600 °C for 6 h, respectively. The amount of V2O5 was 5% of the
total weight of the composite. The slurry was prepared by mixing
80 wt% of cathode material with 10 wt% of PVDF and 10 wt% of SP
carbon in NMP. The cathode and Li wafers were separated inside
the coin cell using Celgard 2400 membrane prepared in a glove
box. The electrolyte consists of LiPF6 (1 mol L 1) in a 1:1 (by
volume) mixture of EC and DMC. The structure, morphology and
performances are characterized by XRD, FT-IR, SEM, CV, EIS and
charge-discharge measurements, respectively.

⇑ Corresponding authors at: School of Chemistry and Chemical Engineering, 3. Results and discussion
Anhui University of Technology, Maanshan, Anhui 243002, PR China (T.-F. Yi).
E-mail addresses: xieying@hlju.edu.cn (Y. Xie), rnrm040412@163.com (N. Ren), Fig. 1(a, b) indicates the SEM pictures of LNMO and V2O5-coated
tfyihit@163.com (T.-F. Yi). LNMO materials. All samples show uniform particle size

https://doi.org/10.1016/j.matlet.2019.06.062
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
 J.-J. Pan et al. / Materials Letters 253 (2019) 136–139 137

Fig. 1. SEM pictures of (a) LNMO and (b) V2O5-coated LNMO, (c) refinement model of XRD.

distribution with irregular morphologies between 500 and
1000 nm. Hence, the differences of electrochemical performance
between LNMO and V2O5-coated LNMO materials caused by parti-
cle size or morphologies can be excluded.
Fig. 2a indicates XRD patterns of LNMO and V2O5-coated LNMO
powders. The diffraction peaks of both samples represent the stan-
dard card of LNMO, revealing that V2O5 modification does not
change the crystal structure. The impurity phases such as LixNi1-xO
(0  x  1) cannot be observed in both powders, revealing that
both samples show stable spinel structure [6]. The absence of the
(2 2 0) peak indicates that there are no heavy metal ions at the
tetrahedral 8a sites. From the local XRD pattern of Fig. 2b, slight
secondary V2O5 phases marked with asterisk can be found, indicat-
ing that a successful synthesis of V2O5-coated LNMO material.
Fig. 1c is the refinement model, and the result can be also con-
firmed by the XRD Rietveld refinement profiles of LNMO and
V2O5-coated LNMO materials (Fig. 2c, d). It can be found that the
Bragg position corresponding to the spinel LNMO have been syn-
thesized successfully. Moreover, the lattice constants of both sam-
ples are similar, revealing that the V2O5 coating does not alter the
crystal structure of LNMO. It is difficult to clearly distinguish struc-
tural difference of LNMO between P4332 and Fd-3m space groups
because of the similar scattering factors of Mn and Ni [7]. FT-IR
spectroscopy was considered as one of an effective way to solve
the cation ordering qualitatively. The peaks at about 593 and
557 cm 1 in the P4332 phase are more intense than in Fd-3 m
phase, and 3 new diffraction peaks at about 650, 470 and
432 cm 1 are absent in Fd-3m structure (Fig. 2e) [8]. Hence, LNMO
and V2O5-coated LNMO materials in this work is P4332 phase.
Fig. 2f indicates the first charge-discharge profiles of LNMO and
V2O5-coated LNMO materials. V2O5-coated LNMO material exhibits
larger discharge potential plateau than the pristine one, indicating
that V2O5 modification improves the energy density of LNMO.
Fig. 3a indicates the rate capability of LNMO and V2O5-coated
LNMO materials at different rates. it can be found that the dis-
charge capacities of V2O5-coated LNMO is 131.4, 122, 111.1 93.8
and 52.1 mAh g 1 at 0.2, 0.5, 1, 2 and 5 C rates, respectively. The
discharge capacities of pristine LNMO are only 125.7, 107.3, 86.2,
69.7 and 37.6 mAh g 1 at corresponding rates. Obviously,
V2O5-coated LNMO composite indicates higher specific capacities
than pristine LNMO at each rate. In addition, the capacity retention
rate of the V2O5-coated LNMO is near 100% of initial value when
the current density was restored to 0.2 C. Fast charging and
discharging property have been considered as one of the most

Fig. 2. (a) XRD patterns and (b) local XRD patterns, (c, d) Rietveld refinement profiles, (e) FT-IR and (f) initial charge-discharge profiles at 0.2 C of (i) LNMO and (ii) V2O5-
coated LNMO.
138 J.-J. Pan et al. / Materials Letters 253 (2019) 136–139
Fig. 3. (a) rate performance, (b, c) cycling performance, (d) CV curves, (e) Nyquist plots and (f) diagram of Zre plotted against x
(ii) V2O5-coated LNMO.
significant electrochemical performance of high-power Li-ion bat-
teries. Fig. 3b shows the cycle performance of both samples for 100
cycles charge-discharged 1 C rate. The initial specific capacities of
LNMO and V2O5-coated LNMO materials at 1 C are 89.7 and
112.8 mAh g 1, respectively. After 100 cycles, the specific capaci-
ties drop to 54.3 and 108.9 mAh g 1, and the corresponding capac-
ity retention ratios are 60.9% and 96.6%, respectively. In order to
investigate the effect of V2O5 modification on the charge-
discharge property of LNMO, Fig. 3c gives the cycle performance
of both samples for 100 cycles at 2 C charge-discharge rate. The
first specific capacity of V2O5-coated LNMO material is 97.6 mAh
g 1, and the discharge capacity also reaches 83.3 mAh g 1 corre-
sponding a capacity retention ratio of 85.3% after one hundred
cycles, which is obviously higher than pristine LNMO. V2O5-
coated LNMO shows more outstanding rate capacity and cycling
durability cycled at large current density than the pristine one.
Compared with other modified LNMO, such as AlPO4 coated LNMO
[1], Al2O3 coated LNMO [2], Y-doped LNMO [3], etc, and the
V2O5-coated LNMO cathode also shows excellent rate capability.
Fig. 3d shows cyclic voltammetry profiles of LNMO and
V2O5-coated LNMO materials. Both cathodes show oxidation-
reduction peak and similar shape of profiles, revealing that V2O5
coating does not change the Li-ion intercalation and deintercala-
tion mechanism. The peaks in the cyclic voltammetry profile from
LNMO correspond to the oxidation of divalent nickel ion and
trivalent nickel ion. In the P4332 structured LNMO, the Ni plateau
at 4.7 V is continuous with no obvious break between the
Ni2+/Ni3+ and Ni3+/Ni4+ reactions, supporting the premise that a
two-phase mechanism dominates rather than a solid-solution
regime [4]. The Ni atoms change directly from 2+ to 4+. Hence,
the two cathodic peaks are overlapped to a broad peak due to very
incommodious potential gap between peaks form the ordered
arrangement of Ni in LNMO with P4332 space group and look like
a broad peak [9]. In addition, the oxidation of Mn3+ is not found,
0.5
at low frequency region for (i) LNMO and
further revealing the prepared spinels are dominant P4332 space
group. The voltage difference of cyclic voltammetry peaks repre-
sents the polarization degree of the electrodes. The potential differ-
ence of V2O5-coated LNMO cathode is smaller than that of pristine
one (Fig. 3e), revealing a reduced polarization and enhanced elec-
trochemical kinetics due to the V2O5 coating, also these results
are well consistent with the above charge and discharge results.
To illuminate the effects of the V2O5 coating on the dynamics per-
formance of LiNi0.5Mn1.5O4, EIS test was given in Fig. 3f. It can be
found that V2O5-coated LNMO indicates smaller charge transfer
resistance (133.9 X) than that of pristine one (359.5 X), revealing
that V2O5 coating decreases the Rct value at the cathode/electrolyte
interface, and thus enhances the conductivity of LNMO. The
small charge-transfer resistance often means high electronic
conductivity. Hence, V2O5-coated LiNi0.5Mn1.5O4 composite shows
more excellent electronic conductivity than the pristine one. The
electrochemical kinetic parameters DLi (Li-ion diffusion coefficient)
are estimated from the Warburg factor (r) gained from the
gradient between Zre (real part of impedance) and x 1/2 (Fig. 3f).
The Li-ion diffusion coefficients of LNMO and V2O5-coated LNMO
are estimated to be 3.69  10 16 and 8.55  10 16 cm2 s 1,
respectively. It can be found that V2O5-coated LNMO cathode
shows larger diffusion coefficient of Li-ion than the unmodified
one. The result shows that V2O5 coating benefits the improvement
of Li-ion diffusion dynamics. As acid oxide, V2O5 is a fast ion
conductor (LixV2-x/5O5) when the potential exceeds 3.7 V [10].
Therefore, V2O5 not only serves as an acidic isolated protective
layer preventing the dissolution of the Ni and decreasing the con-
tact between LNMO and electrolyte, but also be a rapid conducting
layer, concurrently. The EIS results verify that the V2O5 enhances
the electrical conductivity of the LNMO cathode and highly
improve rapid transfer of ions and e during cycling, leading to
an obvious enhancement of discharge capacity. Hence, the
architecture greatly alleviates the polarization of the cathode in
 J.-J. Pan et al. / Materials Letters 253 (2019) 136–139
charging and discharging process, and promotes the transport of
Li-ions and electrons, and thus enhances the rate performance of
LNMO. Obviously, the wonderful rate-capability of V2O5-coated
LiNi0.5Mn1.5O4 comes from the reduced polarization but most
mainly from the tremendously improved electronic conductivity
and Li-ion migration ability.
4. Conclusion
In general, LNMO and V2O5-coated LNMO with P4332 space
groups were synthesized by an ethanol assisted co-precipitation
process. V2O5 coating was proved to be helpful to the cycling dura-
bility as well as rate performance of LNMO. The V2O5 modification
can be considered as an effective strategy to enhance the rate capa-
bility of LNMO. The improved rate performance of V2O5-coated
LNMO material can be ascribed to the enhanced lithium-ion diffu-
sion coefficient and reduced charge-transfer reaction resistance.
The excellent electrochemical performance suggests that LNMO
material has a significant potential for application in LIBs.
Declaration of Competing Interest
The authors declare that they have no conflict of interest.
139
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (nos. 51774002, 21773060), the Fun-
damental Research Funds for the Central Universities (no.
N182304014), Natural Science Foundation of Heilongjiang Pro-
vince (E2016056) and Young Scholar Project of Long Jiang Scholars
Program (Q201818).
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