Solid State Ionics 177 (2006) 3303 – 3307

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Synthesis of LiNi0.6Co0.2Mn0.2O2 cathode material by a carbonate

co-precipitation method and its electrochemical characterization
Yao Zhang ⁎, Hui Cao, Jian Zhang, Baojia Xia
Energy Department, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China
Received 3 November 2005; received in revised form 27 July 2006; accepted 11 September 2006

Abstract

Using Na2CO3 and Me(NO3)2 (Me = Ni, Co and Mn) as starting materials, the precursor of LiNi0.6Co0.2Mn0.2O2 cathode material for lithium
rechargeable batteries has been synthesized by carbonate co-precipitation. The precursor was mixed with Li2CO3 and heated in air.
Thermogravimetric analysis (TG–DTA), laser particle size analysis, X-ray diffraction (XRD) and electron scanning microscopy (SEM) were
employed to study the reaction process and the structures of the powders. The D50 of precursor was 2.509 μm and the distribution was relatively
narrow. The optimum calcination temperature was 850–900 °C. Galvanostatic cell cycling and cyclic voltammetry were also used to evaluate the
electrochemical properties. The initial discharge capacity for the powders calcined at 900 °C was about 180 mA h/g at room temperature when
cycled between 2.8 and 4.3 V at 0.2 C rate.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Lithium-ion batteries; Cathode materials; Carbonate; Co-precipitation; LiNi0.6Co0.2Mn0.2O2

1. Introduction LiNi0.6Co0.2Mn0.2O2 was synthesized by the mixed hydroxide

LiCoO2, as a major cathode material has been widely used in
the commercialized lithium-ion batteries due to its low
irreversible capacity loss and good cycling performance. On
the other hand, its high cost and limited capacity promote the
exploration of substitutional materials. Layered LiNiO2, spinel
LiMn2O4 and olivine LiFePO4 are the potential candidates.
Nevertheless, the synthesis of stoichiometric LiNiO2 is hard, and
multiphase reactions lead to structural degradation during
electrochemical cycling [1–4], while LiMn2O4 shows severe
capacity fading caused by Jahn–Teller distortion [5–8]. Al-
though olivine LiFePO4 has a good thermal stability in the fully
charged state and little hygroscopicity [9–12], the high-rate
performance is not good due to the large impedance [9].
Recently, many researchers have been attracted by the layered
Li–Ni–Co–Mn–O composites for their high capacity, good
cycling stability and excellent safety performance [13–18].
Among them, LiNi0.6Co0.2Mn0.2O2 has been investigated as a
promising cathode material. In our previous studies [18],
⁎ Corresponding author. Tel.: +86 21 62511070 8814; fax: +86 21 32200534.
E-mail address: zy.amethyst@gmail.com (Y. Zhang).
0167-2738/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.09.008
method, and the initial specific discharge capacity could reach
about 168 mA h/g when the battery was charged to 4.3 V.
However, Mn(OH)2 is unstable in aqueous solution with high
pH values and forms a secondary phase of MnOx, which can
substantially deteriorate the electrochemical characters of the
final products [19]. In order to avoid the second phase,
LiNi0.6Co0.2Mn0.2O2 was synthesized by a carbonate co-
precipitation method in this paper.
2. Experimental
Ni(NO3)2·6H2O, Mn(NO3)2·6H2O, Co(NO3)2·6H2O and
Na2CO3 were employed as the starting materials to prepare
the precursor (molar ratio of Ni/Co/Mn = 0.6:0.2:0.2). An
aqueous solution of the transition metal nitrates (1 mol/L) was
slowly dripped into a stirred solution of Na2CO3 (3 mol/L) to
keep a homogeneous cation distribution. The solution pH was
controlled between 7 and 10. Polyvinyl Pyrrolidone (PVP, mass
ratio is 1%) was used as a dispersant. The precipitated precursor
was washed for several times with distilled water to remove the
residual sodium salt till pH reached 7–7.5. The residual sodium
in the precursor was about 0.01 wt.% (vs. precursor). After
3304 Y. Zhang et al. / Solid State Ionics 177 (2006) 3303–3307

Table 1
ICP analysis of precursor synthesized at different pH values
pH Ni/Co Ni/Mn
7.5 3.0366 4.0607
8 3.0429 3.2436
8.5 3.0219 3.1120
9 3.0137 3.0701
9.5 3.0090 3.0453

phase of Ni0.6Co0.2Mn0.2(OH)2 appears [20]. On the other hand,

the content of Mn decreases sharply when pH falls to 7
according to ICP analysis (Table 1). The optimal pH value for
the basic carbonate was between 8 and 9. The samples used for
the characterization below were synthesized at around 8.5.
Fig. 1. XRD patterns of precursors of Ni0.6Co0.2Mn0.2(OH)x(CO3)y at different
3.2. Particle size and morphology of precursor and the final
pH values from 7 to 9.5 and Ni2(OH)2(CO3)·H2O at pH values around 8–8.5.
product

filtered and dried in air at 100 °C for 24 h, the precipitate was SEM images of the precursor and final product are shown in
mixed with Li2CO3 (molar ratio of Li/Me = 1.03:1) before Fig. 2. The particle size of the precursor is quite small and uniform
ground in an automatic grinder, then was heated at 500 °C for
8 h and subsequent heat treatments were carried at 800–950 °C
for 10 h in air.
Thermogravimetric (TG) and differential thermal analysis
(DTA) was carried out using 8 mg of sample at a heating rate of
10 °C/min in the temperature range of 25–1000 °C. The crys-
talline structure of the as-prepared materials was characterized
by powder X-ray diffraction (XRD) using a diffractometer
(Japanese D/max-rA, Cu-Kα radiation). Unit cell parameters
were calculated by least-squares fitting of all peak positions.
The elemental composition was determined by ICP-AES (IRIS
Advantage). The morphology and size of the powder particle
were observed by scanning electron microscopy (SEM, Hitachi
X-650). The particle size distribution was measured by a laser
diffraction analyzer (Mastersize 2000) using anhydrous ethanol
as dispersing medium, at 23 °C.
Electrochemical properties of the synthesized LiNi0.6Co0.2
Mn0.2O2 powders were analyzed with LiNi0.6Co0.2Mn0.2O2/Li
half cells. The positive electrode consisted of a mixture of
85 wt.% LiNi0.6Co0.2Mn0.2O2, 10 wt.% carbon black, and 5 wt.%
polyvinylidene difluoride (PVDF) binder. The electrolyte was
made of 1 M LiPF6 dissolved in a 1:1 volume ratio of ethylene
carbonate (EC) and dimethyl carbonate (DMC) and the anode was
metallic lithium. Coin cells (CR2032 size) were assembled in an
argon-filled dry-box.

3. Results and discussions

3.1. X-ray diffraction analysis of the precursors

X-ray diffraction patterns of various precursors prepared by

carbonate co-precipitation at different pH values are illustrated
in Fig. 1. Though the crystallization is low, the two strongest
diffraction peaks (17°, 33°, 60°) match with the XRD pattern of
Ni2(OH)2CO3·H2O (PDF#380714). As pH value ascends, the
broad Bragg peaks at the low angle shifted to a smaller angle. Fig. 2. SEM images of (a) Ni0.6Co0.2Mn0.2(OH)x(CO3)y by a carbonate
When pH reaches 9.5, the Bragg peak is at around 10° and the precipitation method (pH = 8.5); (b) LiNi0.6Co0.2Mn0.2O2 calcined at 900 °C.
 Y. Zhang et al. / Solid State Ionics 177 (2006) 3303–3307
Fig. 3. Particle size distribution of the precursor powders.
(Fig. 2a), all these qualities are good for the following heat
treatments. Fig. 2b is corresponding to the final product heated at
900 °C, the average particle size of LiNi0.6Co0.2Mn0.2O2 was less
than 1 μm. Small particle size is benefit to the lithium-ion transfer
in the charge–discharge process.
Fig. 3 shows the result of laser particle size distribution of the
precursor powder. The mean diameter, D50, is defined as the
average size at which 50% of the particles are smaller and 50%
of the particles are larger. The D50 of precursor by carbonate co-
precipitation is 2.51 μm while that of hydroxide co-precipitation
is 5.78 μm.
3.3. Thermal behavior of precipitated precursor and Li2CO3
Fig. 4 showed the DTA curves of the precursor reacted with
Li2CO3. A mixture of precursor and Li2CO3, in the molar ratio
of 1.03:1 (Li/Me) is used to investigate the thermal interactions
between the precursor and Li2CO3. Excess lithium compensates
for evaporation, which occurs at high temperatures [21].
The decrease in weight can be divided into three temperature
regions: RT–200 °C, 200–300 °C and 300–700 °C. The weight
loss in the first region is assigned to free and crystalline water
loss. The other two weight loss can be explained as follows: (1)
the decomposition of hydrate; (2) finally the decomposition of
Fig. 4. TG–DTA curves of the precursor reacted with Li2CO3.
3305
carbonate, solid-state reaction of oxides to form LiNi0.6Co0.2
Mn0.2O2. Though the phase transformation will not result in the
weight loss, monoclinic to hexagonal phase transformation
usually occurs in this kind of materials when they are heated to
the high temperature [22], as shown in the DTA curve.
3.4. XRD analysis of the cathode materials calcined at different
temperature
Fig. 5 displays the X-ray diffraction patterns of LiNi0.6
Co0.2Mn0.2O2 prepared at 800–950 °C. All diffraction peaks in
each of the patterns are unambiguously indexed with the space
group. However, the diffraction peaks of the sample calcined at
800 °C are a little broader, which indicates low crystallization of
layered LiNi0.6Co0.2Mn0.2O2. With the increasing of the sub-
sequent calcined temperature, the XRD pattern shows a clearer
split between the 006/012 and 108/110 peaks which mean that
the materials have a better hexagonal structure [23]. Unit cell
parameters are calculated and summarized in Table 2. The
lattice volume increases from 100.452 to 100.974 Å3 with
increasing temperature, which is in agreement with the ele-
mental crystal growth theory. The value of I003/I104 is cor-
responding to the cation ordering and high cation ordering is
benefit to the lithium-ion transfer. Hence, LiNi0.6Co0.2Mn0.2O2
with well-developed crystallinity is obtained at 900 °C for 10 h.
Fig. 5. X-ray diffraction patterns of LiNi0.6Co0.2Mn0.2O2 powders as calcined at
800–950 °C in air.
3306 Y. Zhang et al. / Solid State Ionics 177 (2006) 3303–3307
Table 2
Lattice parameters and I003/I104 of LiNi0.6Co0.2Mn0.2O2 samples calcined at
different temperatures
Samples Heating temperatures a (Å) c (Å) c/a V (Å3)
1 800 °C 2.860 14.181 4.958 100.452
2 850 °C 2.862 14.177 4.954 100.564
3 900 °C 2.866 14.195 4.953 100.973
4 950 °C 2.864 14.215 4.965 100.974
3.5. Electrochemical properties
The cyclic voltammograms of LiNi0.6Co0.2Mn0.2O2/Li
cycled between 2.8 and 4.4 V at a scan rate of 0.01 mV/s for
the first cycle is shown in Fig. 6. It is well known that, LiNiO2
exhibits three sharp peaks in the CV curves due to three distinct
phases [24]. Only one couple of peaks in the region of 2.8–
4.4 V appears in Fig. 6. That is, for LiNi0.6Co0.2Mn0.2O2, no
structural degradation from hexagonal to monoclinic occurs.
The cycling performance of LiNi0.6Co0.2Mn0.2O2 samples
calcined between 800 and 950 °C was also investigated, as
shown in Fig. 7. The cells were cycled between 2.8 and 4.3 V at
0.2 C rate. The sample calcined at 900 °C yields the highest
specific discharge capacity. The first discharge capacity is about
180 mA h/g (corresponding to 83% of its initial charge–
discharge efficiency), which is higher than the reported results
synthesized by hydroxide co-precipitation method [18] and after
30 cycles the capacity retention rate is 82.4%. The reversible
specific discharge capacity of the sample calcined at 800 °C was
less than 140 mA h/g which is fewer than that at 900 °C,
therefore, the volume change for sample at 800 °C is fewer.
Hence, its cyclability seems better than samples at 900 °C. With
the increase of heating temperature, the delivered discharge
capacities were improved. The sample calcined at 850 °C
delivered an initial discharge capacity of 152 mA h/g. However,
when the temperature reaches 950 °C, the first discharge
capacity decreases to 140 mA h/g. Though higher temperature
can improve the crystallization, excessive lithium evaporation is
unavoidable during the high temperature treatment [25]. More-
over, Co3+ and Mn4+ are stable between 700 and 1100 °C, but
Ni3+ is stable at a lower temperature [18]. All these reasons will
Fig. 6. Cyclic voltammogram curve of LiNi0.6Co0.2Mn0.2O2/Li cell for the first
cycle. Voltage scan rate: 0.01 mV/s.
I003/I104
1.323
1.546
1.613
2.045
Fig. 7. Cycling performance of LiNi0.6Co0.2Mn0.2O2 heat-treated at various
temperatures. The cells were cycled between 2.8 and 4.3 V at 0.2 C rate, 25 °C.
deteriorate the electrochemical performance. Compared with the
samples synthesized by hydroxide co-precipitation, the samples
synthesized by carbonate co-precipitation have a higher initial
discharge capacity due to the small particle size. Smaller particle
size ensures shorter mean length of Li diffusion pathways from
its position in the LiNi0.6Co0.2Mn0.2O2 lattice to the cathode–
electrolyte interface.
4. Conclusion
LiNi0.6Co0.2Mn0.2O2 as cathode materials in lithium batteries
has been prepared by a carbonate co-precipitation method. The
crystal structure of the precursors and the electrochemical
properties of final powders have been investigated. XRD
patterns have shown the precursors obtained between pH = 8–9
with a Ni2(OH)2CO3·H2O structure. The sample calcined at
900 °C shows the highest initial discharge capacity (180 mA h/g)
which is higher than that the sample synthesized by a hydroxide
co-precipitation method. Besides, it is easier to control pH value
of the solution with Na2CO3 as starting material, which is at-
tractive for the future industrialization.
Acknowledgement
We would like to express our appreciation to Mr. Ning Ding
for his assistance on the paper discussion. We are also grateful
for the support of SIMIT of CAS for the funding of this work.
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