Electrochimica Acta 55 (2010) 832837

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical properties of nano- and micro-sized LiNi0.5 Mn1.5 O4 synthesized

via thermal decomposition of a ternary eutectic LiNiMn acetate
X. Fang, Y. Lu, N. Ding, X.Y. Feng, C. Liu, C.H. Chen
CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, University of Science and Technology of China, Anhui, Hefei 230026, China

a r t i c l e

i n f o

Article history:
Received 4 July 2009
Received in revised form
15 September 2009
Accepted 15 September 2009
Available online 22 September 2009
Keywords:
Lithium nickel manganese oxide
Eutectic
Low temperature performance
Capacity retention
Lithium battery

a b s t r a c t
Nano- and micro-sized LiNi0.5 Mn1.5 O4 particles are prepared via the thermal decomposition of a ternary
eutectic LiNiMn acetate. Lithium acetate, nickel acetate and manganese acetate can form a ternary
eutectic LiNiMn acetate below 80 C. After further calcination, nano-sized LiNi0.5 Mn1.5 O4 particles can
be obtained at an extremely low temperature (500 C). When the sintering temperature goes above
700 C, the particle size increases, and at 900 C micro-sized LiNi0.5 Mn1.5 O4 particles (with a diameter
of about 4 m) are obtained. Electrochemical tests show that the micro-sized LiNi0.5 Mn1.5 O4 powders
(sintered at 900 C) exhibit the best capacity retention at 25 C, and after 100 cycles, 97% of initial discharge
capacity can still be reached. Nano-sized LiNi0.5 Mn1.5 O4 powders (sintered at 700 C) perform the best
at low temperatures; when cycled at 10 C and charged and discharged at a rate of 1 C, nano-sized
LiNi0.5 Mn1.5 O4 powders can deliver a capacity as high as 110 mAh g1 .
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Lithium-ion batteries are one of the most successful power
sources and have dominated the portable electronic device market for the past two decades. Nonetheless, to keep up with the
fast development of the laptop central processing unit and the
wide application of 3G techniques to cell phones, people have
continued to search for new electrode materials with higher
capacities and more power. Compared to traditional cathode materials, such as LiCoO2 (3.9 V), LiMn2 O4 (4.1 V) and LiFePO4 (3.5 V),
spinel LiNi0.5 Mn1.5 O4 has a higher voltage (4.7 V) [1]. In 1996,
LiNi0.5 Mn1.5 O4 was rst reported to be a 3 V cathode material by
Amine et al. [2]. Later, Dahn and coworkers discovered the 4.7 V
voltage plateau of LiNi0.5 Mn1.5 O4 [3]. The theoretical capacity of
LiNi0.5 Mn1.5 O4 is 146.7 mAh g1 ; due to its high working potential, the energy density of LiNi0.5 Mn1.5 O4 is 20% higher than that of
LiCoO2 . Thus, LiNi0.5 Mn1.5 O4 is seen as a potential cathode material
for use in electric vehicles and energy storage systems in the future.
A variety of synthetic methods for the preparation of
LiNi0.5 Mn1.5 O4 have been reported; these include solid state reaction [4], solgel [5], co-precipitation [6,7], spray pyrolysis [8,9],
electrophoretic deposition [10] and pulsed laser deposition [11].
Kim et al. [12] prepared the well-dened octahedral LiNi0.5 Mn1.5 O4
by the molten salt method starting with the mixture of LiCl

Corresponding author. Tel.: +86 551 3606971; fax: +86 551 3601592.
E-mail address: cchchen@ustc.edu.cn (C.H. Chen).
0013-4686/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.09.046

and Li/Ni/Mn hydroxides; the synthesized LiNi0.5 Mn1.5 O4 powders show excellent cycling performance. In this study, we chose
to use acetates as starting materials; these can form a ternary
eutectic LiNiMn acetate below 80 C. Though acetates have been
widely used in the literature, most studies used a wet-chemical
route assisted by organic materials, such as acrylic acid [13], citric
acid [14], poly(ethylene glycol) [15] and poly(methyl methacrylate) [16]. There are also some reports of studies using the so-called
solgel method. This method involves rst dissolving the acetates
in water and then evaporating the water to obtain a gel [17,18].
We believe that the above method should produce the same ternary
LiNiMn acetate eutectic instead of the real gel. It should be mentioned that prior to our work, Lafont et al. [19] observed this eutectic
phenomenon of LiNiMn acetate, which they called green slurry,
but no extensive investigation was conducted. In Lafonts work, the
capacity at 2 C was observed to be only about 60 mAh g1 . Our work
shows that by simply optimizing the sintering temperature of the
ternary eutectic LiNiMn acetate, we can obtain nano- and microsized LiNi0.5 Mn1.5 O4 particles with a capacity of about 100 mAh g1
at 8 C.
2. Experimental procedures
We mixed 2.488 g (10 mmol) nickel acetate (Ni(Ac)2 4H2 O),
7.352 g (30 mmol) manganese acetate (Mn(Ac)2 4H2 O) and 2.146 g
(21 mmol) lithium acetate (LiAc2H2 O) and milled the mixture by
hand in a mortar. Then, the mixture was calcined at 300 C for 5 h.
After milling by hand again, the powders were sintered in air at 300,

X. Fang et al. / Electrochimica Acta 55 (2010) 832837

833

Fig. 1. Images of the formation of a ternary eutectic LiNiMn acetate: (a) mechanical mixture of LiNiMn acetates; (b) Mn acetate (bottom portion) and Ni acetate (top
portion); (c) the mechanical mixture (left) and MnNi acetates without mixing at 80 C; (d) lying bottle of LiNiMn acetate-mixture at 80 C.

400, 500, 600, 700, 800, 900 and 1000 C for 10 h (with a heating
rate of 3 C min1 ) and allowed to cool naturally. The crystalline
structures of the powders were characterized by X-ray diffraction (XRD, Philips XPert Pro Super, Cu K radiation) with 2 in
the range from 10 to 80 . The morphology and composition of
the powders were determined by scanning electronic microscopy
(SEM, JEOL-6970). The electrochemical characteristics of the products were evaluated with coin cells (CR2032 size) of Li/1 M LiPF6
in ethylene carbonate (EC) and dimethyl carbonate (DMC, with a
weight ratio of 1:1)/LiNi0.5 Mn1.5 O4 assembled in an argon-lled
glove box (MBraun Labmaster 130). The positive electrode laminate
was composed of LiNi0.5 Mn1.5 O4 (84 wt.%), acetylene black (8 wt.%)
and poly(vinylidene uoride) (PVDF, 8 wt.%). The cells were tested
on a multi-channel battery test system (Shenzhen Neware Co. Ltd.)
between 2.8 and 5.1 V (vs. Li+ /Li).

can be attributed to the formation of a ternary eutectic system,

which guarantees the mixing of Li, Ni and Mn atoms at the atomic
level.
The TG-DTA curves of the LiNiMn acetate-mixture are shown
in Fig. 2. There are several thermal steps: (i) the endothermic peak
at 54 C is a result of the formation of a ternary eutectic solution; (ii)
the endothermic peak at 118 C results from the loss of crystallization water, accompanied by a weight loss of 26% (the theoretical
weight loss is 27.7%); (iii) the exothermic peak at 345 C is related
to the decomposition of acetate, with a 41.4% weigh loss (the theoretical weight loss is 37.2%); (iv) the weight is nearly constant when
the temperature is above 370 C; (v) the small endothermic reac-

3. Results and discussion

3.1. Ternary eutectic LiNiMn acetate
The melting points of LiAc2H2 O and MnAc2 4H2 O are 70
and 80 C, respectively. Unlike lithium and manganese acetates,
NiAc2 4H2 O can be directly decomposed, rather than being melted,
with an increase in temperature. In our experiment, we observed
that a mixture of LiAc2H2 O, MnAc2 4H2 O and NiAc2 4H2 O can form
a ternary eutectic solution of LiNiMn acetate at 80 C (Fig. 1a, c
and d). On the other hand, when MnAc2 4H2 O and NiAc2 4H2 O are
put in a bottle one after another without mixing, only MnAc2 4H2 O
melts at an elevated temperature while NiAc2 4H2 O remains a solid
(Fig. 1b and c). Thus, the melting of the LiNiMn acetate-mixture

Fig. 2. TG-DTA curves of the ternary eutectic LiNiMn acetate.

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X. Fang et al. / Electrochimica Acta 55 (2010) 832837

tion at 750 C is a result of the emission of oxygen in LiNi0.5 Mn1.5 O4

(LiNi0.5 Mn1.5 O4 ) [20].
3.2. Structure and morphology
The XRD patterns of the samples sintered at different temperatures (from 200 to 1000 C) are shown in Fig. 3. Due to the similar
diffraction patterns of the spinel and layered structures, it is difcult to differentiate these structures for the samples sintered at low
temperatures (below 500 C). We believe that the samples sintered
at high temperatures (beyond 500 C) are of a pure spinel structure.
This conclusion is supported by the electrochemical test, as shown
below. The peak width at half-height decreases with an increase in
the sintering temperature, which indicates improved crystallinity.
The SEM images of the as-synthesized samples are shown in
Fig. 4. When the temperature is below 700 C, nanoparticles are
obtained. When the temperature increases to 800 C, the particles
grow; at 900 C, the particle size is about 4 m. When the temperature increases to 1000 C, the particle size further increases
to about 10 m. There are some small particles on the surface of
the sample sintered at 1000 C; these particles may have arisen

Fig. 3. XRD patterns of the samples sintered at different temperatures (from 200 to
1000 C).

Fig. 4. SEM images of the as-synthesized samples.

X. Fang et al. / Electrochimica Acta 55 (2010) 832837

835

Fig. 5. Galvanostatic chargedischarge curves (2nd cycle) of the as-synthesized samples (cycled at 25 C, charged and discharged at a rate of 1/3 C).

from the decomposition of LiNi0.5 Mn1.5 O4 at high temperature

[21].
3.3. Electrochemical performance
The galvanostatic chargedischarge curves (2nd cycle) of the
as-synthesized samples are shown in Fig. 5. The sample sintered
at 300 C has a typical voltage prole of a layered-structure cathode (e.g. LiMnO2 ) with a voltage plateau at around 4.0 V [22,23].
This result indicates that Mnn+ ions are only oxidized to trivalence
(LiMnO2 ) at 300 C. When the sintering temperature increases to
400 C, a voltage plateau at 4.7 V appears, indicating the formation
of LiNi0.5 Mn1.5 O4 . At around 3 V another voltage plateau appears
that might be due to the transition from LiMn2 O4 to Li2 Mn2 O4
[24,25]. The powder sintered at 400 C may still have some trivalent
Mn ions. It should be mentioned that in LiNi0.5 Mn1.5 O4 , all Mn ions
should be tetravalent. When the sintering temperature increases
to 500 C, the plateau at 3 V almost disappears, indicating that the
impurity in LiMn2 O4 has been converted into LiNi0.5 Mn1.5 O4 . A
short voltage plateau at around 4.1 V is still observed, however.
This plateau may be attributed to the transition from Mn3+ to Mn4+
in LiNi0.5 Mn1.5 O4 [26]; thus, the real composition should be written as LiNi0.5 Mn1.5 O4 . The plateau at 3 V completely disappears
in the sample sintered at 600 C and due to the oxidation of Mn3+ ,
the plateau at 4.1 V shortens. The sample sintered at 700 C can
deliver a capacity of as high as 127 mAh g1 . When the sintering
temperature is above 700 C, the particle size increases signicantly
to a submicron-size (as shown in Fig. 4). The sample sintered at
800 C can only deliver a capacity of 121 mAh g1 . This result has
been repeated by sintering the sample again. The capacity reduction
at 800 C is likely due to the growth of particles, which increases
the length of the lithium diffusion path. It is also observed that
the plateau at 4.1 V lengthens, due to the reduction of some Mn4+
ions to Mn3+ ions at high temperatures [21]. During the reduction

of Mn4+ ions, the concentration of oxygen vacancy also increases,

leading to an increase in electronic conductivity. Nevertheless, the
increase of electronic conductivity cannot completely compensate
for the adverse effect of increasing the length of the diffusion path,
which reduces capacity. As the temperature further increases to
900 C, the as-synthesized sample delivers the highest capacity of
129.2 mAh g1 , yet 16.6% capacity comes from the 4.1 V plateau.
As a result, the overall output energy is still lower than that from
the sample sintered at 700 C, for which only 7.2% capacity comes
from the 4.1 V plateau. The sample sintered at 1000 C exhibits a
similar voltage prole as that sintered at 900 C, with a capacity of
125 mAh g1 .
Fig. 6 shows the cycling performance of the nano- and microLiNi0.5 Mn1.5 O4 sintered at different temperatures, charged and
discharged at a rate of 1 C, cycled between 2.8 and 5.1 V at room

Fig. 6. Cycling performance of nano- and micro-LiNi0.5 Mn1.5 O4 (at 1 C).

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X. Fang et al. / Electrochimica Acta 55 (2010) 832837

Fig. 7. Rate performance of nano-700 and micro-900 at 25 C.

Fig. 8. Galvanostatic chargedischarge curves (2nd cycle) of nano-700 and micro900 (cycled at 10 C, charged and discharged at a rate of 1/3 C).

temperature. Obviously, the sample sintered at 900 C (micro-900)

exhibits the highest capacity and the best capacity retention during cycling; after 100 cycles, 97% of initial discharge capacity can
still be reached, with a capacity loss of less than 0.04 mAh g1 per
cycle. Although the sample sintered at 700 C (nano-700) also delivers a high capacity, the capacity retention is not as good as that of
micro-900. The large surface area of the nano-700 accelerates the
dissolution of Ni and Mn ions, which results in the loss of capacity of
LiNi0.5 Mn1.5 O4 during cycling [27,28]. The ability to retain capacity
during cycling is: micro-900 submicro-800 > nano-700 > nano600. As nano-700 and micro-900 exhibit higher capacities and
relatively better capacity retention, their rate capability was further
investigated. The rate performance at 25 C of nano-700 and micro900 (charged at a rate of 1 C) is shown in Fig. 7. Both nano- and
micro-sized LiNi0.5 Mn1.5 O4 particles exhibit an excellent rate capability, with a capacity of about 100 mAh g1 at 8 C. At the low rate,
micro-900 displays a better rate capability, though when the rate
increases to 6 C, nano-700 is better. At the low rate, the rate-limiting
factor for the rate performance is the electronic conductivity, which
can be enhanced by the formation of oxygen vacancy at the higher
sintering temperature; thus, micro-900 is better under this condition; at the high rate, the limiting factor is the lithium diffusion in
LiNi0.5 Mn1.5 O4 , and thus nano-700, which has a shorter diffusion
path, is better. Again, for long-time cycling, micro-900 has a better
capacity retention than nano-700.
As a high energy density cathode material, LiNi0.5 Mn1.5 O4 is
seen as a potential cathode material for electric vehicles and hybrid
electric vehicles in the future. Thus, it is necessary to test its performance at low temperatures. We investigated the performance of
nano-700 and micro-900 at 10 C. Fig. 8 shows the galvanostatic
chargedischarge curves (2nd cycle) of nano-700 and micro-900.
The voltage plateau still remains at about 4.6 V, without a signicant drop like that found in LiMn2 O4 [29]. Fig. 9 shows the
rate performance of the two samples cycled at 10 C, charged
at a rate of 1 C (except for the rst 10 cycles, during which the
cells were charged and discharged at a rate of 1/3 C). Nano-700
was found to have a higher capacity, and at 1 C the capacity
was still about 110 mAh g1 . The capacity retention of nano-sized
LiNi0.5 Mn1.5 O4 at low temperatures is much better than those
traditional cathode materials such as LiMn2 O4 [29], LiCoO2 [30],
LiFePO4 [31,32], and even V2 O5 nanobers which has been reported
to be fast Li-ion conductor [33,34]. For micro-900, the capacity
was found to be only about 70 mAh g1 at 1 C. Thus, we believe
that nano-sized LiNi0.5 Mn1.5 O4 perform better at low temperatures.

Fig. 9. Rate performance of nano-700 and micro-900 at 10 C.

4. Conclusions
Nano- and micro-sized LiNi0.5 Mn1.5 O4 particles are successfully
synthesized via the thermal decomposition of a ternary eutectic
LiNiMn acetate. When the sintering temperature is below 800 C,
nano-sized LiNi0.5 Mn1.5 O4 powders are obtained. When the sintering temperature further increases, the particles grow, and nally,
micro-sized LiNi0.5 Mn1.5 O4 powders are obtained. Electrochemical
tests at room temperature show that micro-sized LiNi0.5 Mn1.5 O4
powders sintered at 900 C have the best capacity retention when
cycled at 25 C; after 100 cycles, 97% of initial discharge capacity can still be reached. Nevertheless, nano-sized LiNi0.5 Mn1.5 O4
powders sintered at 700 C exhibit a higher capacity at low temperatures, and at a rate of 1 C it can still deliver a capacity of
110 mAh g1 at 10 C. Both nano- and micro-sized LiNi0.5 Mn1.5 O4
particles exhibit excellent rate capabilities, with a capacity of about
100 mAh g1 at 8 C (at room temperature).

Acknowledgements
This study was supported by National Science Foundation of
China (grant no. 20971117), the Education Department of Anhui
Province (grant no. KJ2009A142) and the Solar Energy Operation
Plan of Academia Sinica.

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