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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
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,
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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).
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Fig. 3. XRD patterns of the samples sintered at different temperatures (from 200 to
1000 C).
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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).
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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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