RARE METALS, Vol. 27, No. 6, Dec 2008, p.

575

Effects of synthesis conditions on the structural and electrochemical properties

of layered LiNi1/3Co1/3Mn1/3O2 cathode material via oxalate co-precipitation
method
TIAN Huaa, b, YE Naiqinga, b, LIU Dana, b, and LI Wenqunb
a
Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Ministry of Education of China, Guilin 541004, China.
b
Department of Materials and Chemistry Engineering, Guilin University of Technology, Guilin 541004, China.
Received 3 November 2007; received in revised form 20 January 2008; accepted 5 February 2008

Abstract

The uniform layered LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries was prepared by using (Ni1/3Co1/3Mn1/3)C2O4 as precursor
synthesized via oxalate co-precipitation method in air. The effects of calcination temperature and time on the structure and electrochemical
properties of the LiNi1/3Co1/3Mn1/3O2 were systemically studied. XRD results revealed that the optimal calcination conditions to prepare the
layered LiNi1/3Co1/3Mn1/3O2 were 950qC for 15 h. Electrochemical measurement showed that the sample prepared under the such conditions
has the highest initial discharge capacity of 160.8 mAh/g and the smallest irreversible capacity loss of 13.5% as well as stable cycling
performance at a constant current density of 30 mA/g between 2.5 and 4.3 V versus Li at room temperature.

Keywords: lithium ion batteries; oxalate co-precipitation method; cathode materials; electrochemical performance

ways 2+ and stable in aqueous solution, thereby, very effec-

1. Introductionҏ
Since Ohzuku et al. [1] firstly synthesized the cathode
material LiNi1/3Co1/3Mn1/3O2, it has attracted a great deal of
attentions in the investigation of cathode materials for lith-
ium ion batteries to replace the presently popular LiCoO2,
because the combination of Ni, Co, and Mn can provide ad-
vantages such as stable cycling performance, good thermal
stability, and excellent rate capability [2].
It is well known that the electrochemical behavior of the
cathode materials depends not only on the composition but
also its morphology and structure, which are strongly af-
fected by synthesis method. And the synthesis of homoge-
nous LiNi1/3Co1/3Mn1/3O2 is not easy, so selecting a suitable
preparation method is important to obtain phase-pure final
products. Homogeneous LiNi1/3Co1/3Mn1/3O2 is usually syn-
thesized by the mixed hydroxide method [3-4]. In the hy-
droxide co-precipitation method, Mn ion will precipitate into
Mn(OH)2 and be oxidized gradually, its valence state will
change from Mn2+ into Mn3+(in MnOOH) or Mn4+(in MnO2)
in aqueous solution. Therefore, preparing the precursor re-
productively is very difficult. However, in oxalate
co-precipitation method, the valence state of Mn ion is al-
Corresponding author: YE Naiqing E-mail: yenaiqing@glite.edu.cn
tive for industrial application owing to increased reproduci-
bility.
Cho et al. [5] have successfully synthesized the layered
LiNi1/3Co1/3Mn1/3O2 by oxalate co-precipitation method, but
the precursor synthesized by this method still needed to be
protected in inert gas. So the process is very difficult to op-
erate. In this study, the precursor was successfully synthe-
size in air through an instant reaction dropping way using
Mn(CH3COO)2˜4H2O, Ni(CH3COO)2˜4H2O, H2C2O4˜2H2O,
Co(CH3COO)2·4H2O, and NH3˜H2O as starting materials.
The process is easy to operate and there is no necessity to
wash. In this article, the effects of calcination temperature
and time on the structure and electrochemical properties of
the LiNi1/3Co1/3Mn1/3O2 were systemically studied.
2. Experimental
An aqueous solution of Ni(CH3COO)2˜4H2O,
Co(CH3COO)2˜4H2O, and Mn(CH3COO)2˜4H2O (cationic
ratio of NiCoMn = 111) with a concentration of 2 mol/L
(Solution A) was precipitated by adding H2C2O4˜H2O solu-
tion(aq.) of 2 mol/L (Solution B) and desired amount of
576
NH4OH solution(aq.) (Solution C) separately in air with
continued stirring (Solution A, Solution B, and Solution C
were added into a reaction beaker through an instant reac-
tion dropping way, which is tied the exports of tubes of So-
lution A, Solution B, and Solution C together, the exports of
tubes of Solution A and Solution C are above that of Solu-
tion B, in order to make the cationic of Solution A firstly
react with NH4OH and rapidly react with H2C2O4·H2O, so
that the Mn2+ can be avoided to oxidize in alkaline condi-
tions when the process is not protected by inert gas). The
solution was maintained at 40qC for 1 h and the pH was
controlled to 7-11. Then, the precursor was filtered, not
washed, and dried at 120qC overnight. The obtained pre-
cursor powder was mixed with LiOH˜H2O (10 mol% excess
amount of Li salts was used to compensate for possible Li
loss during the calcinations). The mixed powder was ground
in a mortar and then calcined at 800-1000qC for 10-25 h in
air again to obtain highly crystallized LiNi1/3Co1/3Mn1/3O2.
The transition metal composition of the precursor was
determined by atomic absorption spectroscopy (AAS, Pgen-
eral TAS-990). The crystal phases of the synthesized pow-
ders were determined by X-ray diffraction (XRD, Panalyti-
cal, X’Pert PRO) using Cu KD radiation in the 2ș ranges of
10-70q.
The electrochemical characteristics of the synthesized
powders were determined on a two-electrode test cell. The
cathode was prepared by mixing the active material with
carbon black and polytetrafluoroethylene (PTFE) in a
weight ratio of 85105. The anode, electrolyte, and separa-
tor were lithium foils, 1 mol/L LiPF6-EC/DMC (11 in
volume) and Celgard2400 film, respectively. The test cells
were assembled in an argon-filled glove-box. The
charge-discharge measurements were performed at room
temperature in a voltage range of 2.5-4.3 V at a constant
current density of 30 mA/g using a computer controlled
multichannel battery test system.
3. Results and discussion
The obtained powder from the oxalate co-precipitation
process was used as an oxalate precursor. XRD and AAS
analyses were carried out to investigate structure and transi-
tion metal composition of oxalate precursor. Fig. 1 shows
Table 1. AAS analysis results of oxalate precursor
Analysis results of products / mol%
Nominal composition
Ni Co
Ni1/3Co1/3Mn1/3C2O4 0.330 0.331
Fig. 2 illustrates the powder X-ray diffraction patterns of
the samples calcined at different temperatures, such as 850,
RARE METALS, Vol. 27, No. 6, Dec 2008
X-ray diffraction pattern of oxalate precursor. Fig. 1(a) is a
reference XRD pattern of D-[Ni1/3Co1/3Mn1/3]C2O4˜2H2O
synthesized by oxalate co-precipitation method in an inert
atmosphere, Fig. 1(b) is an XRD pattern of the sample syn-
thesized by an instant reaction dropping way in air, and Fig.
1(c) is an XRD pattern of the sample synthesized by con-
ventional dropping way in air. Fig. 1(b) is similar to the
XRD pattern of monoclinic D-FeC2O4·2H2O (PDF
No.72-1305) without any impurity peaks and is well
matched with Fig. 1(a). Fig. 1(c) includes some impurity
peaks and is not well matched with Fig. 1(a). It shows that
the effect of synthesizing oxalate precursor by an instant re-
action dropping way in air is equal to that of the conven-
tional dropping way in inert atmosphere in oxalate
co-precipitation process. Table 1 shows atomic absorption
spectroscopy (AAS) analysis results of oxalate precursor
synthesized by an instant reaction dropping way in air. It can
be seen from the AAS results that it is almost the same as
the design value. Based on the XRD and AAS results, it is
clear that D-[Ni1/3Co1/3Mn1/3]C2O4˜2H2O with monoclinic
structure has been synthesized successfully through the
process.
Fig. 1. X-ray diffraction patterns of oxalate precursors syn-
thesized by different ways: (a) from Ref. [5]; (b) instant reac-
tion dropping way; (c) conventional dropping way.
Practical composition of products
Mn
0.332 Ni0.330Co0.331Mn0.332C2O4
900, 950, and 1000qC, respectively. Hereafter, the materials
synthesized at 850, 900, 950, and 1000qC are referred as
Tian H. et al., Effects of synthesis conditions on the structural and electrochemical properties of} 577

S85, S90, S95, and S100. All the samples can be indexed to
the hexagonal D-NaFeO2 structure (space group: R 3 m )
without any impurity peaks. In XRD patterns, the integrated
intensity ratio of (003)/(104) peaks and the splitting of
(006)/(012) peaks and (018)/(110) peaks are regarded as the
indications of characteristic of layered structure materials. In
Fig. 2, the splits in the (006)/(102) and (108)/(110) doublets
are observed in all the XRD patterns, indicating that the lay-
ered LiNi1/3Co1/3Mn1/3O2 cathode material has been suc-
cessfully synthesized at all the calcination temperatures in
this experiment. As shown in Table 2, with increasing the
calcination temperature from 850 to 1000qC, the lattice pa-
rameter a, which is related to average metal-metal intra-slab
distance, the lattice parameter c, which is correlated to the
average metal-metal intra-slab distance, the trigonal distor-
tion c/a, and the cell volume V underwent no apparent
change. The lattice parameters are in good agreement with
those reported in Refs. [5-6]. It was reported that the I003/I104
factor was an indicator of hexagonal ordering, the undesir-
able cation mixing would take place if the integrated inten-
sity ratio of (003)/(104) peaks is less than 1.2, and the higher
the I003/I104-value, the better the hexagonal ordering [7-8]. It
can be seen from Table 2 that the I003/I104 values of all the
samples in this work are larger than 1.2, indicating no obvi-
ous undesirable cation mixing takes place. And S95 has the
highest I003/I104 value of 1.81, indicating the best hexagonal
ordering.
In order to further study the influence of the calcination
temperature on the electrochemical performance of
LiNi1/3Co1/3Mn1/3O2, the test cells are operated at a constant
current density of 30 mA/g between 2.5 and 4.3 V versus Li
at room temperature. Fig. 3 shows the initial charge/discharge
curves of the LiNi1/3Co1/3Mn1/3O2 powder synthesized at
various temperatures for 15 h. As seen from the Fig. 3, all
the cells show quite smooth and monotonous
charge/discharge curves. On charging at 30 mA/g, the volt-
age suddenly increased to about 3.7 V and then held at
3.7-3.95 V until the charge capacity reached about 105
mAh/g, which could be attributed to the Ni2+/Ni4+ redox re-
action that occurred in this region [4]. On further charging,
the voltage curves monotonously increased to 4.3 V, which
was similar to that observed by Ohzuku et al. [1].
Charge-discharge capacities and capacity retention ratios of
all the samples are listed in Table 3. The discharge capaci-
ties of 143.4, 145.9, 160.8, and 159.0 mAh/g were obtained
at the first cycle for S85, S90, S95 and S100, respectively.
Further more, their reversible capacity loss of S85, S90, S95,
and S100 were 42.8, 38.4, 25.2 and 30.4 mAh/g, respec-
tively. The smallest reversible capacity loss of 25.2 mAh/g
is also obtained by S95. All the samples have excellent cy-
clic performance. The reversible capacity after 20 cycles
was 140.5 mAh/g (98.0% of the initial discharge capacity),
143.1 mAh/g (98.1% of the initial discharge capacity), 159.8
mAh/g (99.4% of the initial discharge capacity) and 151.4
mAh/g (95.2% of the initial discharge capacity) for S85, S90,
S95 and S100, respectively.

Fig. 2. XRD patterns of samples synthesized at different cal-

cination temperatures.
Fig. 3. Initial charge-discharge profiles of samples synthe-
Table 2. Crystal parameters of LiNi1/3Co1/3Mn1/3O2 synthe- sized at different calcination temperatures.
sized at different temperatures
T / qC a / nm c / nm c/a V / nm3 I003/I104 These results are consistent with the XRD results in
850 0.285966 1.423424 4.9776 0.10054 1.45 which the S95 has the highest I003/I104 ratio of 1.81. As men-
tioned above, it can be concluded that LiNi1/3Co1/3Mn1/3O2
900 0.285746 1.422405 4.9779 0.10058 1.53
reported in this article has good electrochemical perform-
950 0.285702 1.422002 4.9772 0.10052 1.81
ance for the application as the cathode material of lithium
1000 0.285966 1.423424 4.9776 0.10081 1.76
ion batteries, and it can be considered that 950qC is the best
578 RARE METALS, Vol. 27, No. 6, Dec 2008

synthetic temperature of LiNi1/3Co1/3Mn1/3O2 for using method as precursor.

(Ni1/3Co1/3Mn1/3)C2O4 prepared by oxalate co-precipitation

Table 3. The first charge-discharge capacities and the first discharge efficiencies of samples synthesized at different calcination
temperatures.
First charge ca- First discharge capac- Reversible capacity First discharge ef- 20th discharge capac- 20th capacity
T / qC
pacity / (mAh˜g1) ity / (mAh˜g1) loss / (mAh˜g1) ficiency / % ity / (mAh˜g1) retention / %
850 186.2 143.4 42.8 77.0 140.5 98.0
900 184.3 145.9 38.4 79.2 143.1 98.1
950 186.0 160.8 25.2 86.5 159.8 99.4
100 189.4 159.0 30.4 83.9 151.4 95.2

The influence of calcination time on the structural and optimal calcination time for preparing LiNi1/3Co1/3Mn1/3O2.
electrochemical properties of LiNi1/3Co1/3Mn1/3O2 was also
investigated. Fig. 4 shows the X-ray diffraction patterns of
the samples calcined at 950qC in air for 10, 15, 20, and 25 h.
Hereafter, the materials synthesized at 10, 15, 20, and 25 h
were referred as T10, T15, T20 and T25, respectively. The
lattice parameters and other structural parameters calculated
for LiNi1/3Co1/3Mn1/3O2 synthesized at different periods of
time are summarized in Table 4. The layered structure of the
materials was confirmed by the clear splitting of the hex-
agonal doublet (006)/(102) and (108)/(110) as shown in Fig.
4. It can be seen from Table 4 that with increasing calcina-
tion time, the calculated lattice parameters a, c, c/a, and unit
cell volume V showed no obvious change. It is clear from
above results that the hexagonal ordering does not change Fig. 4. XRD patterns of the samples synthesized at 950qC for
different periods of time.
with calcination time. Table 5 shows the charge-discharge
capacities and capacity retention ratios of LiNi1/3Co1/3Mn1/3O2 Table 4. Crystal parameters of LiNi1/3Co1/3Mn1/3O2 synthe-
calcined at 950qC for different periods of time in air. The sized at 950qC for different periods of time
first discharge capacities of T10, T15, T20, and T25 were
t/h a / nm c / nm c/a V / nm3 I003/I104
136.8, 160.8, 149.1, and 141.5 mAh/g. The corresponding
25 0.285979 1.423461 4.9775 0.10058 1.63
efficiencies were 79.5%, 86.5%, 80.9% and 76.0%, respec-
20 0.285748 1.422415 4.9779 0.10055 1.67
tively. The capacity retention ratios of all the samples were
above 94.0% by the 20th cycle. Similarly, the best electro- 15 0.285702 1.422002 4.9772 0.10052 1.81
chemical property was obtained for T15 and so 15 h is the 10 0.285963 1.423414 4.9776 0.10045 1.60

Table 5. The first charge-discharge capacities and the first discharge efficiencies of samples synthesized at 950qC for different pe-
riods of time
First charge capac- First discharge ca- Reversible capacity First discharge 20th discharge ca- 20th capacity re-
t/h
ity / (mAh˜g1) pacity / (mAh˜g1) loss / (mAh˜g1) efficiency / % pacity / (mAh˜g1) tention / %
10 172.1 136.8 35.3 79.5 129.1 94.4
15 186.0 160.8 25.2 86.5 159.8 94.4
20 184.3 149.1 35.2 80.9 146.1 98.0
25 186.2 141.5 44.7 76.0 136.5 96.5

LiNi1/3Co1/3Mn1/3O2 powder was successfully prepared by

4. Conclusion
(Ni1/3Co1/3Mn1/3)C2O4 was obtained via
co-precipitation method and well-ordered
calcination of the mixture of LiOH˜H2O and
(Ni1/3Co1/3Mn1/3)C2O4 at different temperatures. The XRD
oxalate results revealed that the I003/I104 values of all the
layered LiNi1/3Co1/3Mn1/3O2 samples in this work are larger than 1.2,
Tian H. et al., Effects of synthesis conditions on the structural and electrochemical properties of}
indicating no obvious undesirable cation mixing takes place.
Based upon the results of the electrochemical experiments,
the ideal calcination conditions for synthesis of layered
LiNi1/3Co1/3Mn1/3O2 were 950qC for 15 h. The cathode ma-
terial prepared under such conditions has the highest I003/I104
ratio of 1.81, the highest initial discharge capacity of 160.8
mAh/g (2.5-4.3 V, 30 mA/g) and the smallest irreversible
capacity loss of 13.5%, as well as good cycle performance.
Acknowledgement
This project is financially supported by the Natural Sci-
ence Foundation of Guangxi Province, China (No.
GKZ0832256).
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