Accepted Manuscript

Co-precipitation preparation of LiNi0.5Mn1.5O4 hollow hierarchical microspheres with

superior electrochemical performance for 5 V Li-ion batteries

Dongsheng Lu, Libei Yuan, Zhixiang Chen, Ronghua Zeng, Yuepeng Cai

PII: S0925-8388(17)33368-6
DOI: 10.1016/j.jallcom.2017.09.306
Reference: JALCOM 43362

To appear in: Journal of Alloys and Compounds

Received Date: 10 May 2017

Revised Date: 26 September 2017
Accepted Date: 27 September 2017

Please cite this article as: D. Lu, L. Yuan, Z. Chen, R. Zeng, Y. Cai, Co-precipitation preparation of
LiNi0.5Mn1.5O4 hollow hierarchical microspheres with superior electrochemical performance for 5 V Li-
ion batteries, Journal of Alloys and Compounds (2017), doi: 10.1016/j.jallcom.2017.09.306.

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 ACCEPTED MANUSCRIPT
Co-precipitation preparation of LiNi0.5Mn1.5O4 hollow hierarchical
microspheres with superior electrochemical performance for 5 V Li-ion
batteries
Dongsheng Lua,*, Libei Yuan, Zhixiang Chena,Ronghua Zenga, Yuepeng Caia,b

a
Institute of chemistry and environment, South China Normal University, Guangzhou,

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510006, China;
b
Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, Guangzhou,
510006, China

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Abstract
In this work, a NH4HCO3 co-precipitation method was used to prepare the precursor

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of LiNi0.5Mn1.5O4 (LNMO). An orthogonal experiment method was applied to analyze
the effects of synthetic conditions such as concentration and molar ratio of Mn2+ and

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Ni2+ in initial solution, reaction temperature, concentration of NH4HCO3, addition speed
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of NH4HCO3 on the molar ratio of Mn/Ni in the sediments, through which the
co-precipitation process was also optimized. It was found that both Mn and Ni are not
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completely precipitated from the NH4HCO3 solution, and the precipitation rate of Ni2+ is
much lower than that of Mn2+. Among these synthetic conditions, the molar ratio of
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Ni/Mn in the mixed metal ion solution has the greatest impact on the molar ratio of
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Mn/Ni in the precursor. A LNMO spinel with precise stoichiometric Ni/Mn and classic
Fd3m structure was obtained by using a precursor prepared under the optimal synthesis
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conditions. Additionally, the prepared LNMO has a spherical hierarchical morphology,

composed of submicron primary particles with a chamfered polyhedral structure. This
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LNMO shows superior electrochemical performance. It delivers a high reversible

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capacity of ∼110 mAh/g and superior capacity retention of 68.2% after 900 cycles at 1 C.
Even at a higher discharge rate of 10 C, the LNMO material still shows a reversible
capacity of 84 mAh/g.
Keywords: Li-ion battery; LiNi0.5Mn1.5O4; Hollow hierarchical microspheres; orthogonal
experiment method; NH4HCO3 co-precipitation process

*
Corresponding author. Tel:+86-020-39310212
E-mail address: dhx@scnu.edu.cn

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1. Introduction
LiNi0.5Mn1.5O4 (LNMO) spinel is an attractive cathode candidate for next generation
lithium-ion batteries as it offers high power capability with an operating voltage of ~ 4.7
V and a capacity of ~ 135 mAh/g. LNMO has been synthesized by a solid-state
method[1-3], co-precipitation method[4-6], sol-gel method[7-8], hydrothermal

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method[9-10], etc. Among the various synthesis methods, the co-precipitation method
is the most effective to prepare pure LNMO with high electrochemical performance

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because the starting ingredients (Ni and Mn) can be mixed at the atomic level [11-12].
Due to the merits of facile morphology control and environment friendliness,

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ammonium hydrogen carbonate (NH4HCO3) is often used as a precipitator to prepare the
precursors of LNMO [4, 6, 13]. The following reactions are speculated in the
co-precipitation process [13-14]:
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NH 4 HCO3
NH +4 + HCO 3- (1)

HCO 3-
H + + CO 32- (2)

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6Mn 2+ + 2Ni 2+ + 8CO32- + 2.5H 2 O → Ni 2 (OH) 2 CO3 ⋅ 6MnCO3 ⋅1.5H 2 O ↓ + CO 2 (3)

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However, part of Ni2 (OH) 2CO3 can dissolve following Eq. (4):
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Ni 2 (OH) 2 CO3 + 12NH +4 → 2Ni(NH 3 ) 62+ (Soluble) + 3H 2 O + CO 2 + 8H + (4)

Dissolution of Ni2 (OH) 2CO3 usually impedes the deposition of Ni2+ and in turn causes
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a severe Ni-deficit in the final LNMO product. However, no study has been focused on
the precipitation rates of Mn2+ and Ni2+ in the co-precipitation reaction. In this paper, the
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precursors of LNMO were synthesized by a co-precipitation reaction of Mn2+ and Ni2+

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in NH4HCO3 solution. The orthogonal experiment method was used to analyze the
effects of synthetic conditions such as concentration and molar ratio of Mn2+ and Ni2+ in
initial solution, reaction temperature, concentration of NH4HCO3, addition speed of
NH4HCO3 on the molar ratio of Mn/Ni in the sediments, through which the process was
optimized. Finally, the hollow LNMO microspheres with precise stoichiometric Ni/Mn
and classic Fd3m structure were prepared at the best synthesis conditions, and then
characterized by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and

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electrochemical method.

2. Experimental
The precursors of LNMO were firstly prepared by the co-precipitation process as
follows: 100 mL Ethanol (AR) was added to 1 L mixed solution of NiSO4·6H2O and

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MnSO4·H2O (M solution) under stirring, and then 1 L NH4HCO3 solution was added
into the metal ion-ethanol solution in 25 °C water bath under vigorous stirring. After the

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addition of all NH4HCO3 solution, the obtained suspension was maintained at 25 °C for
4 h under vigorous stirring and then aged for a certain time. The precursor powder was

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finally obtained through filtering, washing, and drying in a vacuum oven overnight. To
obtain the precursors with precise stoichiometric Ni/Mn, an orthogonal experiment

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method was adopted to investigate the influences of synthetic conditions on the molar
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ratio of Mn/Ni in the precursors. Those synthetic conditions include the following seven
factors: total concentrations of Ni2+ and Mn2+, concentration of NH4HCO3, reaction
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temperature, and molar ratio of Mn/Ni in the M solution, addition speed of NH4HCO3,
ethanol/M solution volume ratio and aging time. An OA18 (37) was employed to assign
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the considered factors as shown in Table1 which is an orthogonal array of seven factors
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and three levels. Eighteen trials were carried out to achieve the optimization condition
according to the OA18 (37).
Ni and Mn content in the precursors of LNMO were determined by a Complexometric
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titration method. (1) Separation of Ni from Mn: About 0.2 g of the precursor powder
was weighed accurately and dissolved in 10 ml concentrated hydrochloric acid under the
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heating condition. Next, 200 ml deionized water and then 5 g tartaric acid were added
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under stirring. The PH of mixed solution was adjusted to 7~8 with about 8 ml
concentrated ammonia solution, and then 60 ml solution of 1% diacetyldioxime in
alcohol was added slowly at 70 °C to precipitate Ni2+ as nickel dimethylglyoxime.
After further stirring for 5 min, the precipitate was separated from the solution by
vacuum filtration and washed with hot water, the washings being collected. (2)
Complexometric titration of Ni: The samples to be titrated were prepared by dissolving
the collected precipitates in concentrated hydrochloric acid, evaporating the solutions to

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nearly dry up, adding 50 ml deionized water and 3 ml concentrated ammonia solution,
diluted to 200 ml. 50 ml of the samples were pipetted into a 200 ml conical flask, 2 g of
Murexide indicator were added and then mixed thoroughly. Finally, the contents of the
conical flask were titrated with a 0.05 mol/L EDTA standard solution until the color
changed from golden yellow–red to purple.(3) Complexmetric titration of Mn: 50 ml of

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the collected solutions (concluding the filtrate and washings) were pipetted into a 200 ml
conical flask and, after in-order addition of 5 ml 20 wt. %tartaric oxalic acid, 0.2 g

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ascorbic acid, 2 ml concentrated ammonia solution , 10 ml NH4Cl–NH3·H2O buffer
solution (PH=10) and 4-5 drops of Eriochrome Black T indicator solution, the

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Mn-containing solutions were titrated with a 0.05 mol/L EDTA standard solution until
the color changed from purple to blue.

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The precursor obtained at the optimal synthesis conditions was mixed with a
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stoichiometric amount of LiOH·H2O. The LNMO sample was obtained after the
precursor was sintered at 850 °C for 24 h in air and then calcined at 650 °C for 10 h in
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air. The morphology of the obtained samples was observed using scanning electron
microscopy (SEM, Ultra 55, Carl Zeiss). Powder X-ray diffraction (XRD, D8 advance,
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Bruker) measurement using Cu Kα radiation were employed to identify the crystalline

phase of the LNMO sample with a scan rate of 12°/min from 10° to 80°. X-ray
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photoelectron spectroscopy (XPS) was performed by an Axis Ultra DLD (Kratos, U.K.)
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instrument, and the spectrum was collected with a monochromatic Al Kα source (1486.7
eV) under ultrahigh vacuum condition. Charge-discharge test was performed with coin
type cell (CR2032) assembled in an argon-filled glove box. A slurry consisting of 80 wt%
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LNMO sample, 12 wt% super P carbon black and 8 wt% polyvinylidene fluoride (PVDF)
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in N-methyl-2- pyrrolidone solvent was coated onto an aluminum foil and dried at
110 °C under vacuum for 12 h. The coin cell was comprised of an LNMO cathode and a
lithium metal anode separated by a porous polypropylene film (Celgard 2400). The
electrolyte used in the test cell was composed of 1 M LiPF6 salt in a mixture of ethylene
carbonate (EC) and ethyl methyl carbonate (EMC) solution (3:7, by volume).
Galvanostatic charge/discharge test was carried out in the voltage range of 3.5-4.9 V
with a Land-CT2001A battery test system at room temperature.
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All chemicals used were of analytical-reagent grade.

3. Results and discussion

3.1 Analysis and optimization of synthetic conditions
The molar ratios of Mn/Ni in the precursors under different factors and levels are
listed in Table 1. With the direct observation analysis from the result (RC > RD > RF > RA >
RG > RE > RB), the influence factors of the molar ratios of Mn/Ni in the precursors are

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listed in this order as follows: molar ratio of Mn/Ni in the M solution (C) > reaction
temperature(D) > ethanol/M solution volume ratio (F) > total concentrations of Ni2+ and

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Mn2+ (A) > aging time (G) > addition speed of NH4HCO3 (E) > concentration of
NH4HCO3. Obviously, the impact of factor C on the molar ratios of Mn/Ni in the

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precursors is much greater than that of the other six factors. As can be seen from Table 1,
when molar ratios of Ni/Mn in the M solutions are fixed at 1/3, Mn/Ni ratios in the

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obtained precursors are 8.55, 5.42, 5.74, 6.41, 6.24 and 5.49, respectively, in Exp.1, 4, 9,
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11, 15 and 17, corresponding to the Mn-Ni precipitation rates of 82.3%-28.9%,
80.0%-44.2%, 80.5%-42.1%, 79.9%-37.4%, 81.6%-39.2% and 83.3%-45.5%. It is found
that both Mn2+ and Ni2+ are not completely precipitated from the mixed solution, and the
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precipitation rate of Mn2+ is much higher than that of Ni2+ because the complexing
constant (β) of [Mn (NH3)2]2+ (logβ = 1.3) is much lower than that of [Ni (NH3)6]2+ (logβ
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= 8.74)[13,15]. In addition, the optimal synthesis conditions for the preparation of the
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precursors of LNMO with precise stoichiometric Ni/Mn are also listed in Table 1.
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Table 1 Orthogonal arrays for experimental design and test results.

Exp. no. Synthesis conditions Results

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(A) (B) (C) (D) (E) (F) (G) Mn/Ni
Total concentrations Concentration of Molar ratio of Reaction Addition speed Ethanol/M Aging molar ratio
of Ni2+ and Mn2+) (Scoresa )

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NH4HCO3 Ni/Mn temperature of NH4HCO3 solution time
mol/L mol/L in the M solution /°C r/min volume ratio /h

1 0.0143 0.143 1/3 25 45 5 3 8.55 (43.7)

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2 0.0143 0.286 3/5 40 25 10 6 4.56 (83.6)
3 0.0143 0.429 4/5 60 10 20 12 2.92 (100)

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4 0.0286 0.143 1/3 40 25 20 12 5.42 (75)

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5 0.0286 0.286 3/5 60 10 5 3 2.18 (92.6)
6 0.0286 0.429 4/5 25 45 10 6 4.49 (84.3)

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7 0.0429 0.143 3/5 25 10 10 12 2.76 (98.4)

D
8 0.0429 0.286 4/5 40 45 20 3 3.11 (98.1)
9 0.0429 0.429 1/3 60 25 5 6 5.74 (71.8)
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11
0.0143
0.0143
0.143
0.286 TE 4/5
1/3
60
25
25
10
10
20
3
6
2.38 (94.6)
6.41 (65.1)
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12 0.0143 0.429 3/5 40 45 5 12 4.75 (81.7)
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13 0.0286 0.143 3/5 60 45 20 6 2.65 (97.3)

14 0.0286 0.286 4/5 25 25 5 12 3.75 (91.7)
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15 0.0286 0.429 1/3 40 10 10 3 6.24 (66.8)

16 0.0429 0.143 4/5 40 10 5 6 1.87 (89.5)
17 0.0429 0.286 1/3 60 45 10 12 5.49 (74.3)
18 0.0429 0.429 3/5 25 25 20 3 4.18 (87.4)

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Table 1 (continued)

Kb1

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468.7 498.5 396.7 470.6 479.4 471 483.2
K2 507.7 505.4 541 494.7 504.1 502 491.6

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K3 519.5 492 558.2 530.6 512.4 522.9 521.1
c
k1 78.1 83.1 66.1 78.4 79.9 78.5 80.5

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k2 84.6 84.2 90.2 82.5 84 83.7 81.9
k3 86.6 82 93 88.4 85.4 87.2 86.9

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d
R 8.5 2.2 26.9 10 5.5 8.7 6.4

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a
Score = 100 − 2.92 − ( Mn Ni )m.r. × 10 , ( Mn Ni )m.r. : molar ratio of Mn/Ni in the precursor.
b
K1, K2 and K3 are the sum of the scores of molar ratio of Mn/Ni in the precursors for each factor at levels 1, 2 and 3.

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c
k1 = K1/6, k2 = K2/6, k3 = K3/6
d
R: range is the difference between kmax and kmin for each factor.

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Optimum conditions: total concentrations of Ni2+ and Mn2+ (0.0429 mol/L); concentration of NH4HCO3(0.286 mol/L); molar ratio of Mn/Ni
in the M solution(4/5); reaction temperature (60 °C ); addition speed of NH4HCO3 (10 r/min); ethanol/M solution volume ratio (20%); aging

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time (12 h)
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3.2 Preparation and characterization of hollow LNMO microspheres
Fig.1 shows SEM images under different magnifications of (a-b) the precursor of
LNMO obtained at the optimal synthesis conditions of Table 1 and (c-e) the final
product of LNMO. According to Fig.1a, the precursor of LNMO is basically in the
shape of uniform microspheres with a size of around 5 µm. Moreover, the

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high-magnification image (Fig.1b) focusing on a single microsphere reveals its
surface is closely constituted by a host of nanoneedles. The complexometric

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titrationanalysis shows that Mn/Ni molar ratio of the precursor is 3.01, which is very
close to the theoretical stoichiometric ratio of 3. However, the ratio value from XPS

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analysis of the particulate surface is 2.87. This result shows that Ni segregation may
occur on the particulate surface. Fig.1c presents the panoramic perspective of the final

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LNMO product. It can be seen that the expected spherical particles are retained indeed
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with a smaller diameter than the precursor. As clearly shown in Fig.1d, theses large
spherical particles are composed of many small crystal grains with a size in the range
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of tens to hundreds nanometers. From the images of the broken spheres (Fig.1e), those
small crystal grains are chamfered polyhedrons and stack into a spherical hierarchical
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structure. HRTEM images of different crystal planes of the primary particle indicate
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that the submicron primary particles are not a common octahedral structure (showing
only one type of {111}surface), but a chamfered polyhedral structure (possessing
extra surfaces{400}, {220} and so on) (Fig.2).
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The XRD pattern of the final LNMO product is shown in Fig.3a. All peaks in the
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XRD pattern can be indexed as the spinel LiNi0.5Mn1.5O4phase (JCPDS no. 80-2162),
such as (111), (311), (400) and (440). No obvious reflection observed at 2θ = 37.6°,
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43.7°, and 63.5° is from a common concomitant impurity phase LixNi1-xO [16]. The
XRD pattern also exhibits no peaks of (110), (320), (510) or (522) diffraction
attributed to the P4332 structure, indicating that the LNMO sample in this work have
the disordered spinel structure with the Fd3m space group [17-18]. The Mn2p XPS
spectrum is presented in Fig.3b. The Mn2p spectrum includes two peaks that can be
ascribed to Mn 2p3/2 at 642.4 eV and 2p1/2 at 654.1 eV with a spin-energy separation

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of 11.7 eV [19]. According to MnO2 and Mn2O3 spectral lines, both of the Mn 2p3/2
and 2p1/2 regions can be deconvoluted into two peaks. The peaks at 642.0 and 643.5
eV (as marked) of the Mn2p3/2 spectrum in Fig.3b are attributed to Mn3+ and Mn4+,
respectively, as are those at 653.2 eV for Mn3+ and 654.5 eV for Mn4+ in the Mn 2p1/2
spectrum[20-21]. It is generally believed that one part of Mn4+ in LNMO can be

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reduced to Mn3+ due to the loss of lattice oxygen accompanied by the formation of
nonstoichiometric LNMO (LiNi0.5Mn1.5O4-δ) during thermal treatment process [18].

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The cycling performance of the final LNMO product is shown in Fig.4a. It can be
seen that the LNMO sample exhibits a high reversible capacity of ∼135 mAh/g and a

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superior capacity retention of 95% after 100 cycles at 0.5 C. The discharge capacity is
about 120, 118, 114 and 108 mAh/g, corresponding to the discharge rate of 1 C, 2 C,

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3 C and 5 C, respectively (Fig.4b). Moreover, even at a higher discharge rate of 10 C,
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the LNMO material still shows a reversible capacity of 84 mAh/g. It is generally
known that a good high rate capability is especially important for the power batteries
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of electric vehicles (EVs) and plug-in hybrid electric vehicles (PHEVs). In order to
characterize the electrochemical reaction of the LNMO, Fig.4c shows a typical
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differential capacity vs. potential curve between 3.7 and 4.9 V obtained from a
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charge-discharge curve. The two pairs of peaks appearing in the potential of 4.69/4.73
V and 4.70/4.77 V are attributed to the two-step oxidation/reduction of Ni2+/Ni3+ and
Ni3+/Ni4+, respectively [22-23], which contributes to the major electrochemical
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capacity. The small peaks at 3.98/4.07 V are ascribed to the redox reaction of
Mn3+/Mn4+, indicating that the obtained LNMO product is of Fd3m structure [16,
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24]. This is in good agreement with the result obtained from the XRD result. It can
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also be seen from Fig.4c that the potential difference between the charge and
discharge plateaus corresponding to the reactions of Ni2+/Ni3+ and Ni3+/Ni4+ are 0.04
V and 0.07 V, respectively, indicating a fast Li+ extraction/insertion kinetics. Fig.5
shows the long-term cycling performance of the LNMO product at a high rate of 1 C.
The discharge capacity of the electrode decays from 110 to 95 mAh/g after 500 cycles,
corresponding to a high capacity retention of 86.4%. Even after 900 extended long
cycles, its capacity retention is still as high as 68.2%. Usually, commercial
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specifications require batteries with a loss of capacity less than 20% for 500 cycles
under normal use.
The electrochemical properties of spherical LNMO have been reported in some
literatures. The spherical LNMO prepared by an ammonium oxalate-carbonate
composite co-precipitation method delivers a discharge capacity of 125 mAh/g and its

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capacity retention is 94% after 200 cycles at 1C [11]. Another spherical LNMO by
using ammonia-mediated carbonate precipitation shows a discharge capacity of 134

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mAh/g after 20 cycles at 0.1C [25]. The spherical LNMO prepared by microwave
method has capacity retention of 97% after 50 cycles at 0.1C [26]. The LNMO

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spheres via hydrothermal synthesis maintain 71% capacity retention after 70 cycles at
0.1C [27]. The difference in microstructure of these LNMO spheres may be one of the

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reasons for their different electrochemical properties. Therefore, the spherical
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hierarchical morphology may play an important role in improving the electrochemical
performance of the LNMO material. Sphericalparticles provide an isotropic diffusion
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path for Li+ transferring between the particle bulk and surface [11, 28]. Besides, this
three-dimensional hierarchical structure is favorable for obtaining good rate capability
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due to the submicron primary particles having provided a short Li+ diffusion path [29].
It is believed that the chamfered polyhedral LNMO have a fast Li+ diffusion path and
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can also suppress the lattice strain and Mn dissolution during the charge–discharge
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process [10, 30].

4. Conclusions
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Using NH4HCO3 co-precipitation method to prepare the precursor of LNMO, both

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Mn2+ and Ni2+ are not completely precipitated from the NH4HCO3 solution, and the
precipitation rate of Mn2+ is much higher than that of Ni2+. Among all the factors
studied, the molar ratio of Ni/Mn in the mixed metal ion solution has the most
significant impact on the molar ratio of Mn/Ni in the precursor. A precursor of LNMO
with precise stoichiometric Ni/Mn can be obtained by optimizing the co-deposition
reaction conditions. The final LNMO product prepared by the above precursor has a
spherical hierarchical structure and exhibits superior electrochemical properties. The

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developed preparation process of LNMO is simple and suitable for large-scale

production, which has positive implications for improving LNMO technology.

Acknowledgements
The authors acknowledge financial support by the National Natural Science

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Foundation (No.21571069), the Scientific and Technological Plan of Guangdong
Province (No. 2015B010135009).

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Figure Captions

Figure.1 SEM images under different magnifications of (a-b) the precursor of LNMO
obtained at the optimal synthesis conditions of Table 1 and (c - e) the final LNMO

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product.
Figure.2 (a) TEM image of a primary particle of LNMO microsphere. (b-d) HRTEM

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images of different crystal planes of the primary particle.

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Figure.3 (a) XRD pattern and (b) XPS of Mn2p peak for the final LNMO product.

Figure.4 (a) Cycling performance of the final LNMO product. The charge and

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discharge current was 0.5 C, and the voltage range was 3.5-4.9 V. (b) Rate capability
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of the final LNMO product. Charge at 0.2 C and discharge at 1 C, 2 C, 3 C, 5 C and
10 C. (c) Typical differential capacity vs. potential curve between 3.7 and 4.9 V
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obtained from a charge-discharge curve.

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Figure.5 Long-term cycling performance of the LNMO product. The charge and
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discharge current was 1 C, and the voltage range was 3.5-4.9 V.

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a) b)

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c) d)

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e)
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Fig.1.
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a)

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b) Position 1

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{111}}
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c) Position 2
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{400}}
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d) Position 3
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{220}}

Fig.2.

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(111) (a)

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(400)
Intensity/a.u.

(311)

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(440)
(333)

(622)
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(222)
(331) (531)

(533)
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

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Two theta/degree
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Mn2p (b)
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2p3/2
2p1/2
3+
4+ 4+ Mn
Mn Mn
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Intensity/a.u.

3+
Mn
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675 670 665 660 655 650 645 640 635 630
Binding Energy/eV
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Fig.3.

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160 105
152
100
144
136 95

128 90

Specific capacity/mAh/g

Charge efficiency/%
120
85
112
104 80
96 75
88
70
80
charge capacity

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72 65
discharge capacity
64 60
56
(a) 55
48
40 50

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0 10 20 30 40 50 60 70 80 90 100
Cycle number

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140

130

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120
-1

1C
Discharge capacity/mAh⋅g

2C
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110
3C
100 5C

90

80
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10C
70

60 (b)
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50
0 5 10 15 20 25 30 35 40 45 50
Cycle number
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0.02
EP

0.01
C
-1

0.00
dQ/dV/Ah⋅V
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0.0003

-0.01 0.0002

0.0001
-1
dQ/dV/Ah ⋅V

0.0000

-0.0001

-0.02 -0.0002

-0.0003

3.5 3.6 3.7 3.8 3.9 4.0 4.1 4.2 4.3 4.4 4.5
(c)
Potential/V

-0.03
3.7 3.8 3.9 4.0 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 5.0
+
Potential/V,vs.Li/Li

Fig.4.

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120

110

100
Specific capacity/mAh/g

90

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80

70
Charge capacity

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60 Discharge capacity

50

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40

30
0 200 400 600 800
Cycle number

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Fig.5.
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Highlights

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• A spherical hierarchical LiNi0.5Mn1.5O4 (LNMO) has been reported for the first time.

• The LNMO exhibits excellent cycling performance and high-rate property.

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• An orthogonal experiment method was applied to obtain precise stoichiometric Ni/Mn.

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