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Effect of Calcination Temperature on the Structure and Electrochemical

Performance of LiMn1.5Ni0.5O4 Cathode Materials

Article in Bulletin of the Korean Chemical Society · January 2013

DOI: 10.5012/bkcs.2013.34.1.59

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Structure and Electrochemical Performance of LiMn1.5Ni0.5O4 Materials Bull. Korean Chem. Soc. 2013, Vol. 34, No. 1 59
http://dx.doi.org/10.5012/bkcs.2013.34.1.59

Effect of Calcination Temperature on the Structure and Electrochemical

Performance of LiMn1.5Ni0.5O4 Cathode Materials
Seo Hee Ju and Dong-Won Kim*

Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea. *E-mail: dongwonkim@hanyang.ac.kr
Received September 3, 2012, Accepted October 2, 2012

Spinel LiMn1.5Ni0.5O4 cathode powders with different morphologies were synthesized by a co-precipitation
method using oxalic acid. The calcination temperature affected the morphologies, crystalline structure and
electrochemical properties of the LiMn1.5Ni0.5O4 powders. The LiMn1.5Ni0.5O4 powders obtained at a
calcination temperature of 850 oC exhibited the highest initial discharge capacity with good capacity retention
and high rate capability.
Key Words : Cathode, Lithium nickel manganese oxide, Lithium-ion battery, Calcination temperature, Elec-
trochemical performance

Introduction lithium acetate dihydrate [Li(CH3COO)·2H2O, Aldrich], man-

ganese(II) acetate tetrahydrate [Mn(CH3COO)2·4H2O, Aldrich]
Lithium-ion batteries are attractive power sources for port- and nickel(II) acetate tetrahydrate [Ni(CH3COO)2·4H2O,
able electronic devices, electric vehicles and energy storage Aldrich] were dissolved in de-ionized water. The solution
systems due to their high energy density and long cycle life.1 was stirred continuously under heating at 60 oC. The oxalic
Lithium manganese oxide (LiMn2O4) with a spinel structure acid solution was added to the homogeneous solution drop
has been considered one of the promising cathode materials by drop. The mole ratio of oxalic acid to metal was 5.0. The
for rechargeable lithium batteries, owing to its low cost, solution was stirred at 90 oC for 2 h and further dried
environmental friendliness, high voltage operation and high overnight at 110 oC. The dried precipitate was preheated at
safety. However, stoichiometric LiMn2O4 materials exhibit 450 oC for 3 h to decompose the organic components. The
large capacity fade on cycling because of the Jahn-Tell precursor powders were calcined at different temperatures
distortion of trivalent Mn ions and the dissolution of Mn into (700, 800, 850, 900, 950, 1000 oC) for 15 h in air atmo-
the liquid electrolyte, especially at elevated temperature.2-6 sphere. The morphological characteristics of the LiMn1.5Ni0.5O4
In order to overcome these problems, several cationic sub- powders were investigated using scanning electron micro-
stitutions to produce LiMn2-yMyO4 (M =Cr, Fe, Co, Ni, and scopy (SEM, JEOL JSM 6701). Energy dispersive spectro-
Cu) have been studied in the literature.7-13 Among these scopy (EDS) and elemental mapping were performed using
materials, LiMn1.5Ni0.5O4 is of great interest as a cathode the same instrument. Powder X-ray diffraction (XRD, Philips
material for 5 V lithium-ion cells because of its high specific X’PERT MPD) using Cu Kα radiation was used to identify
capacity and its dominant plateau at around 4.7 V, which the crystalline phase of the LiMn1.5Ni0.5O4 powders. The
arise from the presence of a Ni2+/Ni4+ redox pair.14-17 Various cathode was prepared by coating an N-methyl pyrrolidone
synthetic methods such as sol-gel, molten salt, co-precipi- (NMP)-based slurry containing LiMn1.5Ni0.5O4 powder, poly-
tation and composition emulsion drying have been applied (vinylidene fluoride) (PVdF) and super-P carbon (85:7.5:7.5
to the preparation of cathode active materials for lithium-ion by weight) on an aluminum foil. The thicknesses of the elec-
batteries. The co-precipitation method is known as a simple trodes ranged from 50 to 55 μm after roll pressing, and their
way to prepare fine, highly pure and homogeneous powders active mass loading corresponded to a capacity of about 1.2
of single or multi-component oxide materials.18-20 mAh cm−2. The lithium electrode consisted of a 150 μm-
In this study, we synthesize spinel LiMn1.5Ni0.5O4 cathode thick lithium foil that was pressed onto a copper current
powders using the co-precipitation method at different cal- collector. A CR2032-type coin cell composed of lithium
cination condition in order to achieve the best electro- anode, a polypropylene separator (Celgard 2400) and
chemical properties. We investigate the effect of the calci- LiMn1.5Ni0.5O4 cathode was assembled with an electrolyte
nation temperature on the morphologies, crystalline structure solution. The liquid electrolyte used in this study was 1 M
and electrochemical properties of spinel LiMn1.5Ni0.5O4 LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC)
cathode powders. (1:1 by volume, battery grade, Soulbrain Co. Ltd.). All cells
were assembled in a dry box filled with argon gas. Charge
Experimental and discharge cycling tests of the Li/LiMn1.5Ni0.5O4 cells
were conducted at different current density over a voltage
LiMn1.5Ni0.5O4 cathode powders were synthesized by co- range of 3.0-4.9 V with battery testing equipment at room
precipitation using oxalic acid. A stoichiometric amount of temperature.
60 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 1 Seo Hee Ju and Dong-Won Kim

Results and Discussion

The LiMn1.5Ni0.5O4 powders with different morphologies

were prepared by co-precipitation method with oxalic acid at
different calcination temperatures. The effect of the calcina-
tion temperature on the morphologies of the LiMn1.5Ni0.5O4
powders is shown in Figure 1. The LiMn1.5Ni0.5O4 powders
calcined at 700 oC exhibited nano-rod morphologies and
aggregation of the powders, whereas powders calcined at
800 oC exhibited a well-faced crystallized spinel phase instead
of a rod shape. As the calcination temperature increased, the
particle size increased and the particle shape and distribution
became more uniform. However, the particles calcined at
1000 oC had a larger size of several microns with aggregated
morphologies between the particles. As a result, the
LiMn1.5Ni0.5O4 powders calcined at temperature ranges of Figure 2. XRD patterns of LiMn1.5Ni0.5O4 powders prepared at
different calcination temperatures.
800 to 900 oC are well-distributed crystalloids with little
agglomeration.
Figure 2 shows the XRD patterns of the LiMn1.5Ni0.5O4 where λ is the wavelength of the X-ray used, θB is the Bragg
cathode powders calcined at different temperatures. The angle of the diffraction peak considered, and B is the width
crystalline phase of all the powders can be identified to be a at an intensity equal to half of the maximum intensity.22
spinel structure indexed by cubic Fd3m in which lithium When the calcination temperature was increased from 700 to
ions occupy the tetragonal (8a) sites, transition metals (Mn 1000 oC , the mean crystallite size of the cathode powders
and Ni) are located at the octahedral (16d) sites, and oxygen increased from 28 to 35 nm. By increasing the calcination
atoms reside in 32e sites.21 This indicates that the Mn site temperature, the peak widths of the LiMn1.5Ni0.5O4 powders
in the LiMn2O4 is partially substituted by Ni. Scherrer’s become narrower and the relative intensities of the charac-
formula given in Eq. (1) was used to determine the mean teristic peaks gradually increase, indicating that a better
crystallite size (t) of the powder: crystalline structure of LiMn1.5Ni0.5O4 was obtained. How-
ever, some very tiny peaks are observed around 37.5, 43.7
t = (0.94 λ)/(B cos θB) (1)
and 63.6o, which correspond to the weak impurity phases
of LixNi1-xO.23,24 According to the previous reports,25
LiMn1.5Ni0.5O4 can loss oxygen and disproportionate to a
mixture of a spinel phase and a secondary phase LixNi1-xO
because of partial reduction of Mn4+ to Mn3+ at elevated
temperature. Thus, the formation of the LixNi1-xO phase may
result in a decrease of the Ni content and the Mn valence in
the spinel phase. This result indicates that heat treatment at
higher temperature results in more oxygen deficiency,

Figure 1. SEM images of LiMn1.5Ni0.5O4 powders obtained at Figure 3. EDS spectrum of LiMn1.5Ni0.5O4 powders calcined at 850
o
different calcination temperatures. (a) 700, (b) 800, (c) 850, (d) C, and dot mappings for the Mn and Ni atoms in the corresponding
900, (e) 950 and (f) 1000 oC. LiMn1.5Ni0.5O4 powders.
Structure and Electrochemical Performance of LiMn1.5Ni0.5O4 Materials Bull. Korean Chem. Soc. 2013, Vol. 34, No. 1 61

Figure 4. Initial charge and discharge curves of LiMn1.5Ni0.5O4 Figure 5. Discharge capacities of LiMn1.5Ni0.5O4 cathode materials
cathode materials obtained at different calcination temperatures as a function of cycle number (0.5C rate, cut-off voltage: 3.0-4.9 V).
(0.5C rate, cut-off voltage: 3.0-4.9 V).

formation of Mn3+ and the occurrence of a secondary phase.

Figure 3 shows the EDS spectrum and dot mapping
images of the LiMn1.5Ni0.5O4 cathode powders calcined at
850 oC. In the dot mapping, the Mn and Ni components were
observed to be well-dispersed inside the submicron-sized
LiMn1.5Ni0.5O4 powders. From the EDS spectrum shown in
figure, the atomic ratio of manganese and nickel was calcu-
lated to be about 3.01:1, which is consistent with the
chemical composition of the LiMn1.5Ni0.5O4 powders.
Figure 4 shows the initial charge and discharge curves of
LiMn1.5Ni0.5O4 cathode materials calcined at different temper-
atures. The Li/LiMn1.5Ni0.5O4 cells were subjected to charge
and discharge cycling in the voltage range of 3.0-4.9 V at a
constant current rate of 0.5C. The initial discharge capacities Figure 6. Discharge curves of the LiMn1.5Ni0.5O4 cathode materials
prepared at 850 oC, as a function of the C rate. The charging
of LiMn1.5Ni0.5O4 active materials ranged from 122 to 126
current rate was 0.1C with a 4.9 V cut-off.
mAh g−1, depending on the calcination temperature. The
highest discharge capacity (126 mAh g−1) was delivered by
LiMn1.5Ni0.5O4 powders calcined at 850 oC. Discharge below 850 oC, the LiMn1.5Ni0.5O4 cathode materials have
capacities vs cycle number of the LiMn1.5Ni0.5O4 cathode smaller particle size and larger specific surface area, thus
materials between 3.0 and 4.9 V are shown in Figure 5. higher dissolution of transition metals and electrolyte oxida-
LiMn1.5Ni0.5O4 cathode material obtained at 850 oC exhibit- tion rate on its surface can be expected during cycling.
ed high discharge capacity and good capacity retention (93% Accordingly, the capacity retention behaviors of LiMn1.5Ni0.5O4
of initial discharge capacity after 100 cycles). As explained cathode materials obtained at 700 and 800 oC are not as good
earlier, high calcination temperature may result in oxygen as that of LiMn1.5Ni0.5O4 obtained at 850 oC. As a result, the
loss, Ni deficiency of LiMn1.5Ni0.5O4 and formation of LiMn1.5Ni0.5O4 cathode materials calcined at 850 oC exhibit-
LixNi1-xO impurities,24 which decrease the discharge capa- ed the best electrochemical performance in consideration of
city and deteriorate the cycling stability of the spinel discharge capacity and capacity retention.
LiMn1.5Ni0.5O4 materials calcined at temperature higher than We evaluated the rate capability of the LiMn1.5Ni0.5O4
850 oC. On the other hand, the integrated crystalline phase cathode materials obtained at different temperatures. The Li/
for structural stability is not well formed when the calcina- LiMn1.5Ni0.5O4 cells were charged to 4.9 V at a constant
tion temperature is below 850 oC. As a result, the discharge current rate of 0.1C and discharged at different current rates
capacities are low in the LiMn1.5Ni0.5O4 materials calcined at ranging from 0.1 to 2.0C. The discharge curves of the
temperature lower than 850 oC. It is well known that the LiMn1.5Ni0.5O4 cathode materials obtained at 850 oC are
dissolution of transition metals suffering from unavoidable shown in Figure 6. Both voltage and discharge capacity
HF in electrolyte and the formation of LiF on the surface of decreased gradually as current rate increased. At 2.0C rate,
cathode materials due to the electrolyte decomposition are the cell delivered a relatively high discharge capacity of 112
mainly responsible for the capacity loss of electrode materials mAh g−1. Figure 7 compares the relative discharge capacities
during cycling.25-28 When the calcination temperature is of LiMn1.5Ni0.5O4 cathode materials obtained at different
62 Bull. Korean Chem. Soc. 2013, Vol. 34, No. 1 Seo Hee Ju and Dong-Won Kim

Acknowledgments. This work was supported by the

National Research Foundation of Korea Grant funded by
the Korean government (MEST) (NRF-2009-0092780 and
NRF-2009-C1AAA001-0093307) and the Human Resources
Development of KETEP Grant funded by the Korea govern-
ment Ministry of Knowledge Economy (No. 20104010100560).

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