Li Co MN O2

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Ceramics International 37 (2011) 665668

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Short communication
Hydrothermal synthesis of LiNixCo1 xO2 cathode materials

Junlan Xie, Xiang Huang *, Zhibin Zhu, Jinhui Dai
Institute of Materials Science and Engineering, Ocean University of China, No. 238 Songling Road, Qingdao 266100, China
Received 20 June 2010; received in revised form 17 July 2010; accepted 22 September 2010
Available online 28 October 2010
Abstract
Ultrafine powders of LiCoO2, nonstoichiometric LiNiO2 and LiNi0.9Co0.1O2 were prepared under mild hydrothermal conditions. The influence
of the molar ratio of Li/Co, Li/Ni and Li/(Ni + Co) was studied. The final products were investigated by XRD, TEM and EDS. To synthesize a
stoichiometric LiNiO2 under mild hydrothermal conditions was found to be a big challenge. Transmission electron microscopies (TEM) revealed
the formation of well-crystallized LiCoO2 and LiNi0.9Co0.1O2 with average size of 100 nm and 10 nm, respectively.
# 2010 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: Hydrothermal synthesis; LiNixCo1 xO2; Cathode materials
1. Introduction
Recent achievements in the development of miniature
portable electronic devices such as cellular phones, computers
and camcorders require a new high-energy compact batteries.
As compared with conventional systems, lithium rechargeable
batteries exhibit higher energy density, higher voltage and
longer shelf life [1].
LiCoO2 remains one of the most attractive positive
electrode materials for secondary lithium batteries due to its
excellent electrochemical properties, such as high output
voltage, long cycle life and easy preparation [2]. However,
this material suffers from high cost, toxicity and relatively
low practical capacity, which limits its further application
[3,4]. LiNiO2 appears to be one candidate as a cathode
material because of the high-specific capacity and low cost.
However, this material has poor cycle life and thermal
instability and it is very difficult to synthesize a stoichiometric LiNiO2 [5]. In an attempt to overcome the problems
associated with LiCoO2 and LiNiO2, iso-structural solid
solutions of LiNixCo1 xO2 have been studied for their
excellent performances, such as lower cost, less toxicity and
higher reversible capacity [612].
In this investigation, we report a novel route to synthesize
LiNixCo1 xO2 via the mild hydrothermal method. It does not
* Corresponding author. Tel.: +86 532 66781690; fax: +86 532 66786519.
E-mail address: sunny_huangx@yahoo.cn (X. Huang).
need troublesome processes such as preparation of precursors

and subsequent heat treatments.
2. Experimental
2.1. Materials and process
The starting materials were analytical reagents: LiOHH2O
(>90%), NiCl26H2O(99.0%), Co(NO3)26H2O(99.0%), and
NaClO (Cl wt% 10% solution). The hydrothermal synthesis
process was carried out as follows. Firstly, a desired amount of
LiOHH2O was added to distilled water to get lithium hydroxide
aqueous solution. Co(II) aqueous solution was prepared by
dissolving an appropriate amount of Co(NO3)26H2O. Then
Co(II) aqueous solution was added dropwise under vigorous
stirring to the lithium hydroxide aqueous solution. The molar
ratio of Li/Co was varied from 10:1 to 50:1 for 4 M LiOH
solution, respectively. Similarly, in order to synthesize LiNiO2
and LiNi0.9Co0.1O2, equal molar LiOHH2O and NiCl26H2O or
mixture of NiCl26H2O and Co(NO3)26H2O (the molar ratio of
Ni(II)/Co(II) = 9.0:1.0) were added to distilled water and went
through the same process as described above. The experiment
conditions were shown in the Table 1.
Reactant mixtures with different Li/Co, Li/Ni and Li/
(Ni + Co) ratios were hydrothermally treated at 220 8C for
10 h in a Teflon-lined autoclave with 0.85 filling factor and
presence of moderate sodium hypochlorite. After the sample
was cooled, the precipitate was washed with distilled water
0272-8842/$36.00 # 2010 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
doi:10.1016/j.ceramint.2010.09.053
[()TD$FIG]
J. Xie et al. / Ceramics International
37 (2011) 665668
666
Table 1
Hydrothermal experiment conditions of LiNixCo1 xO2.
Group
Group
Group
Group
1
2
3
4
Li/Co
Li/Ni
Li/(Ni + Co)
NaClO (ml)
Li+ (mol/L)
10
20
30
50
10
20
30
50
10
20
30
50
20
20
15
10
4
4
4
4
(108)
(110)
(104)
(105)
(101)
(003)
[()TD$FIG]
Li/Co=50
(113)
(009)
(107)
Li/Co=30
(005)
(108)
Li/Co=20
20
Fig. 3. XRD patterns of LiNi0.9Co0.1O2 powders from different starting Li/

(Ni + Co).
3. Results and discussions

Li/Co=10
40
60
80
2-Theta( )
Fig. 1. XRD patterns of LiCoO2 powders from different starting Li/Co.
to remove unreacted lithium. It was then dried at 80 8C

for 3 h.
The XRD patterns of the as-prepared products are shown in

Figs. 13. Fig. 1 revealed the formation of LiCoO2. All the
XRD patterns had sharp peaks indicated a high degree of
crystallinity. Especially the group of Li/Co = 20, the XRD
patterns displayed the hexagonal doublets (0 0 5)/(1 0 8),
[()TD$FIG](0 0 9)/(1 0 7) and (1 0 8)/(1 1 0) with a clear splitting, which
2.2. Test method

The crystalline phase, chemical composition and morphology were characterized by X-ray powder diffraction (XRD;
Model D/max, Rigaku Co., Japan) with Cu Ka radiation
(40 kV, 150 mA), energy dispersive X-ray spectroscopy
(Oxford Instruments INCA EDS system), and transmission
electron microscopy (TEM; Model JEM-840,JEOL Co, Japan),
respectively.
[()TD$FIG]
Fig. 2. XRD patterns of LiNiO2 powders from different starting Li/Ni.
Fig. 4. EDS of LiNi0.9Co0.1O2 powders with Li/(Ni + Co) = 50.
[()TD$FIG]
J. Xie et al. / Ceramics International 37 (2011) 665668
667
Fig. 5. TEM of LiCoO2 (a) and LiNi0.9Co0.1O2 (b) powders.
indicated a high degree of crystallinity and good hexagonal

ordering (Fig. 1). The synthesis experiment of LiNiO2, instead
of stoichiometric LiNiO2, nonstoichiometric LiNiO2 and NiO
(Fig. 2) were obtained. Consequently it was very difficult to
synthesize stoichiometric LiNiO2 under mild hydrothermal
conditions. Fig. 3 presents the X-ray diffraction patterns of
LiNi0.9Co0.1O2 powders. Pure LiNi0.9Co0.1O2 phase was
obtained which had almost identical XRD patterns. There
was a good agreement with the reported results so far [13,14].
The adding of Co(II) ion conduced to synthesize stoichiometric
LiNiO2 under mild hydrothermal conditions. A relatively large
increase in the I(0 0 3)/I(1 0 4) ratio was observed along with
the Li/(Ni + Co) ratio rise. According to Gao et al. [15], an
increase in the I(0 0 3)/I(1 0 4) ratio indicated that the sample
had good cation ordering. The good cation ordering was also
evident from the well-separated (1 0 8) and (1 1 0) reflections
(Fig. 3) [16,17].
The EDS spectra of the synthesized LiNi0.9Co0.1O2 powders
were displayed in Fig. 4. According to that, the final products
consisted of Ni, Co, and O (Li could not be detected by EDS),
the spectra of carbon were derived by the striking of the
conductive glue substrate by the electronic beam. The EDS
results corresponded to the XRD results, further demonstrating
that the final product was LiNi0.9Co0.1O2.
The morphology of LiCoO2 and LiNi0.9Co0.1O2 powders
observed by TEM were shown in Fig. 5. The particle shape of
LiCoO2 powders was ununiform as shown in Fig. 5(a). They
had an average particle size of 100 nm. The LiNi0.9Co0.1O2
powders had regular shape with an average particle size of
10 nm (Fig. 5(b)).
4. Conclusions
LiCoO2, nonstoichiometric LiNiO2 and LiNi0.9Co0.1O2
powders were successfully synthesized by hydrothermal
method at 220 8C for 10 h. The test results of XRD, EDS
and TEM indicated that under mild hydrothermal conditions
ultrafine LiCoO2 and LiNi0.9Co0.1O2 powders could be
obtained. The adding of Co(II) ion was good for the synthesis
of stoichiometric LiNiO2 while only received nonstoichiometric LiNiO2 or mixture of nonstoichiometric LiNiO2 and
NiO when Co(II) ion was absent. The final products
LiNi0.9Co0.1O2 had regular shape and homogeneous size while
the LiCoO2 powders were ununiform. The I(0 0 3)/I(1 0 4) ratio
increased with the Li/(Ni + Co) ratio indicated that the sample
LiNi0.9Co0.1O2 had good cation ordering.
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Available online at www.sciencedirect.

Ceramics International 37 (2011) 665668

Hydrothermal synthesis of LiNixCo1 xO2 cathode materials

need troublesome processes such as preparation of precursors

Fig. 3. XRD patterns of LiNi0.9Co0.1O2 powders from different starting Li/

3. Results and discussions

to remove unreacted lithium. It was then dried at 80 8C

The XRD patterns of the as-prepared products are shown in

2.2. Test method

Fig. 2. XRD patterns of LiNiO2 powders from different starting Li/Ni.

Fig. 4. EDS of LiNi0.9Co0.1O2 powders with Li/(Ni + Co) = 50.

J. Xie et al. / Ceramics International 37 (2011) 665668

Fig. 5. TEM of LiCoO2 (a) and LiNi0.9Co0.1O2 (b) powders.

indicated a high degree of crystallinity and good hexagonal

J. Xie et al. / Ceramics International 37 (2011) 665668

[6] S. Venkatraman, Y. Shin, A. Manthiram, Phase relationships and chemical

[12] S. Yang, H. Yue, Y. Yin, J. Yang, W. Yang, Microwave-assisted synthesis

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