Crystal structure analysis and first principles (006) and (102), (108) and (110) doublet peaks in the
aks in the all
calculation on Lix(Ni,Mn)O2-based cathode active
material for Li-ion battery
Oki Sekizawa, Takuya Hasegawa, Naoto Kitamura,
Yasushi Idemoto
Department of Pure and Applied Chemistry,
Faculty of Science and Technology,
Tokyo University of Science,
2641 Yamazaki, Noda, Chiba 278-8510, Japan
INTRODUCTION
Many transition metal oxides, such as LiCoO2
and LiNiO2, have been developed as cathode materials for
the lithium ion battery1). LiCoO2 is the most widely used
cathode material, but it suffers from the high cost and the
relatively high toxicity of the Co. As an alternative
cathode, this study focused on the Į-NaFeO2 type
LiMn0.5Ni0.5O2, which exhibits high and stable reversible
capacity2). For this materials, we previously investigated
thermodynamic stability, crystal and electronic structures
and cathode performances by using difference synthesis
method and changing Li content3). In the average structure
analysis, influence of Li/Ni cation mixing and Ni/Mn 3b
site ordering on electronic structure was not clear. From
such background, in this work, we investigated the cation
mixing and 3b ordering by first principle calculations and
structure analysis on neutron and synchrotron X-ray
diffractions, and then we discussed the relationship
between electronic structures and cathode performances
in LixMn0.5Ni0.5O2.
EXPERIMENTAL
The LixMn0.5Ni0.5O2 samples were prepared by
solid-state method using LiOH㨯H2O, MnO2 and Ni(OH)2
as starting materials. The mixture was ground in an agate
mortar for 24h. This mixture was heated at 650℃ for 24h
in air, and then calcined at 950℃ for 15h in air. For the
cell performance test, the cathode was prepared by mixing
the LixMn0.5Ni0.5O2 powder, acetylene black and PVdF at
a weight ratio of 85:10:5, and the electrolyte was 1M
LiPF6 in EC/DEC(vol. 1:1) solution. The crystal structure
of LixMn0.5Ni0.5O2 was determined by powder neutron
diffraction using HERMES(JRR-3), and synchrotron X-
ray diffraction using BL19B2(SPring-8). The data was
refined using the RIETAN-FP. The nuclear and electron
densities were determined by powder neutron diffraction
and synchrotron XRD, respectively, based on the
maximum entropy method (MEM) using the PRIMA
program. In first principle calculation, we used VASP-
code, WIEN2k-code and DV-XĮ, and constructed the
structure model based on structure analysis result of
neutron diffraction data. We optimized atomic positions
and lattice parameters in the structures with various 3b
ordering and Li/Ni cation mixing by VASP-code. We
used GGA and set k-point as 20(5×4×1), cut-off energy as
500eV and convergence parameter as 2.0×10-3eV/Å-1. In
DV-XĮ, we used cluster with 6Å radius in which Ni at Li
site, i.e. cation mixing Ni, was centered, and then
calculated ionisity and bond overlap population with
Madelung potential. For FLAPW calculation, we use
WIEN2k-code. We set k-point as 60 (6×5×2), Rkmax as
7.0, convergence parameter as 1.0×10-5Ry and calculated
for electron density and density of state.
RESULTS AND DISCUSSION
From XRD patterns, it was found that all the
samples synthesized in this work had the Į-NaFeO2 type
structure (S.G.: R-3m). There is a clear splitting of the
compounds. The metal composition of the samples
determined by ICP was almost the same as the nominal
composition. The samples with x=1.03 showed good
cycle performance, i.e. high capacity in first cycle and
high capacity retention. In order to investigate the crystal
structure in detail, we performed Rietveld analysis. The
analysis on neutron diffraction indicated that cation
mixing were about 10% in each sample. Fig.1 shows
electron density calculated from synchrotron XRD data
by MEM. As a result, it was found that 3b-6c bond was
the strongest in the sample with x=1.03.
As a theoretical approach, we carried out
structure optimization on different 3b ordering model at
first, and then found that ‘zigzag’ structure4) was the most
stable structure. From the calculation about Li/Ni cation
mixing position, it was indicated that crystal structure was
stabilized by the mixing. Li and Ni ionisities whose
positions were near mixing atom were higher than normal
position. By comparison with LiNiO2, Ni-O bonding of
Lix(Ni,Mn)O2 was weaker. However, Mn-O bonding was
considerably high and thus total bonding of 3b-6c became
high by Mn substitution. This is one of the reasons why
Lix(Ni,Mn)O2 shows good thermal stability. Fig.2 shows
electron density at a saddle of 3b-6c in Lix(Ni,Mn)O2
calculated by WIEN2k. As shown in this figure, the
sample with x=1.03 shows the maximum interaction of
3b-6c. This result was coincident with experimental data.
Because the sample with x=1.03 showed good cycle
performance, it can be concluded that strong 3b-6c
bonding, in other word, host structure stability resulted in
better cycle performance.
(i) (ii)
6c 6c
3b 3b
(iii) Contour line
F(N)=1×6N/step N:-1~1, step:10
6c
(i) x=1.00
3b (ii) x=1.03
(iii) x=1.08
Fig.1 Electron density of Lix(Ni,Mn)O2
[(110) plane] (MEM).
0.085
Ɣ:Mn-O
Electron density / e㨯Έ-3
Ŷ:Ni-O
0.084
0.083
0.082
1.00 1.05 1.10
Li content
Fig. 2 Electron density at a saddle of 3b-6c
in Lix(Ni,Mn)O2 (WIEN2k).
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Mater. Chem., 17, 3167 (2007).