Journal of The Electrochemical Society, 159 (5) A525-A531 (2012) A525

0013-4651/2012/159(5)/A525/7/$28.00 © The Electrochemical Society

Structural Analysis during Charge-Discharge Process of Li2 FeSiO4

Synthesized by Molten Carbonate Flux Method
Akira Kojima,a,z Toshikatsu Kojima,b and Tetsuo Sakaib,∗,z
a Graduate School of Chemical Science and Engineering, Kobe University, Kobe City, Hyogo 657-8501, Japan
b Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology
(AIST), Ikeda City, Osaka 563-8577, Japan

A Li2 FeSiO4 cathode material for lithium-ion batteries was synthesized by a molten carbonate flux method at 500◦ C. The Li2 FeSiO4
showed reversible capacity of 160 mAh g−1 at the 0.07 C rate in the voltage range of 1.5 – 4.2 V. Crystal structural change
during charge–discharge process for the Li2 FeSiO4 was investigated using high-resolution synchrotron X-ray diffraction in order to
understand charge-discharge performance. It was found that crystal structure of the Li2 FeSiO4 transformed to a new structure of a
charged phase and a discharged one during the first charge-discharge. Crystal structure of the charged phase and the discharged one
was supposed to have a monoclinic system with space group P21 /n based on models of cations disordering of Li+ , Fe2+ and Fe3+ .
© 2012 The Electrochemical Society. [DOI: 10.1149/2.jes112828] All rights reserved.

Manuscript submitted September 30, 2011; revised manuscript received January 30, 2012. Published February 16, 2012.

Since the 1950s, a class of the polyanionic materials such as
Li2 MSiO4 (M=Mg, Zn, Ca, Co, Fe, Mn) have been studied intensively
as a glass-ceramics materials for traditional ceramics industry.1–9
Among the materials, Li2 FeSiO4 , Li2 MnSiO4 and Li2 CoSiO4 were
highlighted as cathode materials for large-scale lithium-ion batter-
ies nowadays.10–13 The Li2 FeSiO4 and Li2 MnSiO4 consist of abun-
dant elements (Si, Fe and Mn) and have several advantages such
as high safety, less toxicity and high theoretical capacity of around
330 mAh g−1 . Although both materials have similar theoretical ca-
pacity, many research works have been done for the Li2 FeSiO4 be-
cause it shows more stable charge-discharge performance than the
Li2 MnSiO4 .10, 14–22 Crystal structure change during charge-discharge
process plays an important role in understanding charge-discharge
performance of cathode materials. However, crystal structure of
the Li2 FeSiO4 during charge-discharge process has not been fully
clarified.
The Li2 FeSiO4 synthesized by a solid-state reaction method has
crystal structure of orthorhombic system (space group Pmn21 ).10
Charged phase (LiFeSiO4 ) and discharged one (Li2 FeSiO4 ) were
reported to show isostructural with initial one and their crystallo-
graphic parameters were found to show agreement with the calcu-
lated ones.14, 23–25 The Li2 FeSiO4 synthesized at different tempera-
tures shows two new kinds of polymorphs with monoclinic system
(P21 /n)26 and orthorhombic one (Pmnb).27 According to recent re-
search works, crystal structure of the Li2 FeSiO4 could be classified
as follows; orthorhombic system (Pmn21 ) at 150 – 400◦ C,28, 29 mon-
oclinic system (P21 /n) at 700 – 800◦ C,23, 26, 30 orthorhombic system
(Pmnb) at 900◦ C.27, 28, 30
We have reported that a high purity Li2 FeSiO4 with monoclinic
system (P21 /n) was successfully synthesized at 500◦ C by molten car-
bonate flux method and showed stable cycling performance.31 In this
study, crystal structural change during charge-discharge process for
the Li2 FeSiO4 with monoclinic system (P21 /n) has been examined
using high-resolution synchrotron XRD and X-ray absorption fine
structure (XAFS) analysis.
Experimental
A Li2 FeSiO4 was prepared by molten carbonate flux method as
described in our previous report.31 A molten carbonate flux with a
nominal composition of (Li0.435 Na0.315 K0.25 )2 CO3 was obtained by
calcination of a mixture consisting of Li2 CO3 (Kishida Chemical,
99.99%), Na2 CO3 (Nacalai Tesque, 99.5%) and K2 CO3 (Nacalai
Tesque, 99.5%) in molar ratio of 0.435: 0.315: 0.250, respectively,
at 700◦ C for 1 h under CO2 atmosphere. After cooling, the solidified
∗ Electrochemical Society Active Member.
z
E-mail: akira.kojima@aist.go.jp; sakai-tetsuo@aist.go.jp
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flux was ground to powder. The obtained flux powder was mixed with
a iron oxalate dihydrate (Aldrich, 99%) and a Li2 SiO3 (Kishida Chem-
ical, 99.5%) in molar ratio of 1.2: 1: 1, respectively, and heat-treated
at 500◦ C for 13 h under atmospheres of mixed gas of CO2 /H2 (100/3
vol./vol.). The obtained sample was ground and then washed by dis-
tilled water in order to remove residual carbonates. In a preliminary
study, it was found that the least expensive Fe powder can be used as
iron source for synthesis of the Li2 FeSiO4 at 500◦ C and about 1kg
of the material was successfully obtained. It was confirmed that the
residual carbonates can be collected by vaporizing water and they can
reused for the synthesis.
The Li2 FeSiO4 sample was ball-milled with acetylene black (AB)
in weight ratio of 5 : 4, and then the obtained mixture was heat-treated
at 700◦ C for 2 h under CO2 /H2 (100/3 vol./vol.) atmosphere to obtain
Li2 FeSiO4 /carbon composite. The Li2 FeSiO4 /carbon composite was
mixed with AB and polytetrafluoroethylene in weight ratio of 80: 13:
7, respectively. The mixture was attached on an aluminum mesh to
obtain a Li2 FeSiO4 cathode. The cathode was tested in a 2032 type
coin cell assembled using a lithium foil (Honjo Metal Co., Ltd.) anode,
a separator (Celgard 2400) and an electrolyte (1M LiPF6 in EC/DEC
(1:1 vol./vol.)).
Galvanostatic charge-discharge tests were performed at 60◦ C with
a current density of the 0.07 C rate (10 mA g−1 ) in the voltage range
of 1.5 – 4.2 V using battery testing system (BLS series, Keisokuki
Center Co. Ltd.).
Crystal structure of as-prepared Li2 FeSiO4 , a charged one and a
discharged one was characterized using a high-resolution synchrotron
X-ray diffraction (XRD) (BL19B2 beam line, SPring8, Japan). The
Li2 FeSiO4 cathode was charged and discharged at various states in
a 2032 type coin cell, then taken out from the cell and rinsed for
several times using dimethyl carbonate, followed by drying in vacuum
overnight. The charged and the discharged sample were obtained by
scraping out the cathode surface.
The obtained samples were filled into glass capillary with outer
diameter of 0.3 mm for XRD measurement. The XRD data was col-
lected using a large Debye–Scherrer camera with an imaging plate.
The diffraction patterns were recorded in the 2θ range of 5.00–78.00◦
with a step size of 0.01◦ . The wavelength of the X-ray was cali-
brated to λ = 0.7003 Å using CeO2 as a standard. The measure-
ment time of the X-ray was 5 minutes for as-prepared sample and
30 minutes for the charged and the discharged one. The crystal struc-
ture was refined by the Rietveld method with the program RIETAN-
2000.32
Shape and size of the as-prepared Li2 FeSiO4 powder were ob-
served using scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). SEM images were taken on a JEOL
JSM-6390 microscope at an accelerating voltage of 30 kV. TEM im-
ages were taken on a JEOL JEM-2010 microscope at an accelerating
 A526 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012)

20000

15000 + observed
calculated
10000 Bragg position
Intensity

5000

0 Li2FeSiO4
Li2SiO3
Fe3O4

difference

5 10 15 20 25 30 35 40 45 50 55 60 65 70
2θ / degree

Figure 1. (Color online) The XRD pattern, calculated one and their difference based on the Rietveld refinements of the Li2 FeSiO4 synthesized at 500◦ C.

voltage of 200 kV. Electron diffraction (ED) was observed for the
as-prepared Li2 FeSiO4 powder to confirm crystal structure.
The as-prepared Li2 FeSiO4 , the charged and the discharged sam-
ple were mixed with the boron nitride powders in order to make
into pellets of 10 mm in diameter for the extended X-ray absorp-
tion fine structure (EXAFS) measurement. The EXAFS measurement
was conducted using the BL14B2 beam line at SPring-8, Japan. The
measurement was conducted using the transmission detection modes
at room temperature. The Fe K-edge EXAFS spectra were recorded
in the energy range of 6897–8211 eV. The measurement time of the
EXAFS spectra was 90 seconds. The exact values of each shell for
these samples were calibrated using the program REX2000.33

Results and Discussion

Figure 1 compares high-resolution synchrotron XRD patterns and
calculated ones on the basis of the Rietveld refinements for the
as-prepared Li2 FeSiO4 with a monoclinic system in space group
P21 /n.26, 30 Reliable factor (Rwp ) and crystallographic parameters de-
rived from the refinement are summarized in Table I. The observed
and calculated patterns match very well, and the Rwp for the sample are
small (about 6%) enough to indicate high reliability. The as-prepared Figure 2. SEM image of the Li2 FeSiO4 powder synthesized at 500◦ C.
sample shows Li2 FeSiO4 (93 wt%) with some impurities such as
Li2 SiO3 (4 wt%) and Fe3 O4 (3 wt%).
Figure 2 shows morphology of the as-prepared Li2 FeSiO4 observed
by SEM. Flake like particles with size range of 0.2–1 μm are formed
at 500◦ C. The particles size was smaller than that synthesized by the

Table I. Crystallographic parameters obtained through Rietveld refinements for as-prepared Li2 FeSiO4 , the charged and discharged cathode
materials.

Lattice constants Reliable factors

Space Volume
Sample Phase group a (Å) b (Å) c (Å) β (deg) (Å3 ) Rwp Re S

Sample-A As-prepared Li2 FeSiO4 P21 /n 8.2256(4) 5.01441(9) 8.2303(4) 99.143(2) 335.16 6.33 3.59 1.77
Sample-E Charged phase (LiFeSiO4 ) P21 /n 8.3811(6) 5.0258(2) 8.3564(3) 103.459(6) 342.33 6.93 2.11 3.29
Sample-D Discharged phase (Li2 FeSiO4 ) P21 /n 8.3089(2) 5.0378(1) 8.276(1) 98.01(1) 343.06 6.84 2.10 3.25

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 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012) A527

4.5
C E
(a) 4.0

3.5 B 1st

Voltage / V
2nd
3.0
5th
2.5

2.0

1.5 D
1.0
0 50 100 150 200

Capacity / mAh g-1

Figure 4. Charge-discharge curves of the Li2 FeSiO4 with the 0.07 C rate in
the voltage range of 1.5–4.2 V at 60◦ C. Notation shows 3.1 V at the first charge
(Sample-B), 4.2 V at the first charge (Sample-C), 1.5 V at the first discharge
(Sample-D) and 4.2 V at the second charge (Sample-E).

(b)
In order to evaluate charge-discharge performance, the as-prepared
Li2 FeSiO4 sample was ball-milled with acetylene black (AB) and then
the obtained mixture was heat-treated to obtain Li2 FeSiO4 /carbon
200 composite. In a preliminary experiment, the XRD peaks of the ball-
milled sample became broader than that of the as-prepared one, how-
100 ever, those peaks were regenerated by heat-treatment. The ball-milled
sample showed large polarization and no plateau voltage at 3.1 V and
020 010 010 020 2.8 V in its charge-discharged curves. Thus, the heat-treated sample
was selected for investigating structural change of the Li2 FeSiO4 dur-
100 ing charge-discharge process. Figure 4 shows charge-discharge curves
of the Li2 FeSiO4 tested with the 0.07 C rate in the voltage range of
200 a* 1.5 – 4.2 V at 60◦ C. The Li2 FeSiO4 shows initial charge capacity
of 120 mAh g−1 , initial discharge one of 178 mAh g−1 and stable
charge-discharge capacity of about 160 mAh g−1 after the second cy-
[001] cles. Only initial discharge capacity of the Li2 FeSiO4 was higher than
b* half of the theoretical capacity (166 mAh/g), which might be ascribed
to some irreversible reaction. The capacity of 160 mAh g−1 corre-
Figure 3. TEM image (a) and electron diffraction patterns from [001] zone sponds about one mole of lithium per formula unit of the Li2 FeSiO4 .
axis (b) for the as-prepared Li2 FeSiO4 synthesized at 500◦ C.
Plateau voltage at the first charge curve for the Li2 FeSiO4 was
3.1 V, and shifted to 2.8 V at the first discharge, then kept at 2.8
V after the second cycles. XRD measurement has been done for sam-
same method at 700◦ C (about 5 μm) as reported previously.31 A ples at various states of charge and discharge such as 3.1 V at the first
tendency toward agglomeration of individual particles was observed. charge (Sample-B), 4.2 V at the first charge (Sample-C), 1.5 V at the
Figure 3 shows TEM image and electron diffraction (ED) patterns first discharge (Sample-D) and 4.2 V at the second charge (Sample-E)
for the as-prepared Li2 FeSiO4 . The TEM image confirmed that the as shown in Fig. 4.
shape and size of particles were agreed with those observed by SEM Figure 5 shows the XRD patterns of the Li2 FeSiO4 sample at
(Fig. 3a). The ED patterns can be indexed on the basis of a monoclinic various states of as-prepared (Sample-A), 3.1 V at the first charge
unit cell with space group P21 /n (Fig. 3b). (Sample-B), 4.2 V at the first charge (Sample-C), 1.5 V at the first

4.2V E
Intensity / Arb. unit

1.5V D Figure 5. The XRD patterns of the Li2 FeSiO4

at various states of as-prepared Li2 FeSiO4
(Sample-A), 3.1 V at the first charge (Sample-
4.2V C B), 4.2 V at the first charge (Sample-C), 1.5 V at
the first discharge (Sample-D) and 4.2 V at the
second charge (Sample-E).
3.1V B

as-prepared A

5 10 15 20 25 30 35 40 14.0 14.5 15.0 15.5 16.0

2θ / degree

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 A528 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012)

25000
+ observed
20000
calculated
15000 Bragg position

10000
Intensity

5000

0 Charged phase (LiFeSiO4)

Li2SiO3
Fe3O4
Carbon

difference

5 10 15 20 25 30 35 40 45 50 55 60 65 70
2θ / degree

Figure 6. (Color online) The XRD pattern, calculated one and their difference based on the Rietveld refinements of the Li2 FeSiO4 at 4.2 V at the second charge
(Sample-E).

discharge (Sample-D) and 4.2 V at the second charge (Sample-E).
When the Li2 FeSiO4 (Sample-A) was charged to 3.1 V (Sample-B),
new patterns appeared, and to 4.2 V (Sample-C) the patterns com-
pletely changed as shown in enlarged view with 2θ from 14 to 16
degree. A new pattern was obtained when the sample was discharged
to 1.5 V (Sample-D), which is different from that of Sample-C. The
sample charged to 4.2 V at the second charge (Sample-E) showed
the same patterns as that of Sample-C. It is clear that crystal struc-
tures of the Li2 FeSiO4 transforms to the new charged phase (Sample-
C and Sample-E) and the new discharged one (Sample-D) during
charge-discharge process. The chemical formulas of the charged and
discharged phase were represented as LiFeSiO4 and Li2 FeSiO4 , re-
spectively in the following parts.
Previously, Setoguchi et al. determined the crystal structure of
lithium zinc silicate (Li2 ZnSiO4 ) to have monoclinic system (P21 /n)
using single crystal and found that cation-site disordering of Li+
and Zn2+ was occurred.8, 9 Nytén et al. reported that crystal struc-
ture of charged phase and discharged one for Li2 FeSiO4 showed
isostructural with as-prepared Li2 FeSiO4 which possessed orthorhom-
bic system (Pmn21 ).14 They pointed out that there were cation-
site disordering between Li and Fe ions in their charged and dis-
charged phases. We have adapted a model of cations disordering
for structural analysis of the charged phase. For identifying changes
in crystallographic sites, chemical formula in the model was de-
scried as [Li1-x Fex ]4e1 [Li1-y Fey ]4e2 [Li1-z Fez ]4e3 SiO4 based on initial
crystal structure of the Li2 FeSiO4 ([Li]4e1 [Li]4e2 [Fe]4e3 SiO4 ) with a
monoclinic system in space group P21 /n for structural analysis of
the charged phase. There are two crystallographic 4e sites (4e1 , 4e2 )
for Li+ and one 4e site (4e3 ) for Fe2+ in crystal structure of the as-
prepared Li2 FeSiO4 . To find out the best fitting model, we carried out
the Rietveld refinements using a structure model generated by varying
occupancy of Fe occupied the sites of 4e1 , 4e2 and 4e3 . As the result,
only the observed occupancy of Fe (z) at the 4e3 site showed negative
value (−0.20), indicating that occupation of the 4e3 site by Fe was
unacceptable. Thus, the whole Fe has applied to occupy the 4e1 and
4e2 sites. Note that site occupancy of Li was calculated by subtracting
occupancy of Fe from unity because lithium is a very weak scatter
and almost invisible by XRD when heavy elements are present.
Figure 6 shows the best Rietveld refinements result for the Sample-
E. Reliable factor (Rwp ) and crystallographic parameters are summa-
rized in Table I. The observed XRD patterns are fitted with patterns
calculated from the model of the charged phase (LiFeSiO4 ) and impu-
rity phases such as Li2 SiO3 (0.23 wt%), Fe3 O4 (1.10 wt%) and carbon
(50.87 wt%) added to the cathode. The Rwp for the sample are small
enough to indicate high reliability. The charged phase (LiFeSiO4 )
was proposed to be the same monoclinic system (P21 /n) as that of
the as-prepared Li2 FeSiO4 . The cell parameters for the charged phase
(LiFeSiO4 ) are larger than those of the as-prepared one as shown in
Table I. The charged phase (LiFeSiO4 ) has larger unit cell volume than
the as-prepared one by 2.1%. The refined structural parameters and se-
lected bond length for the charged phase (LiFeSiO4 ) are summarized
in Table IIa and Table IIIa, respectively.

Table II. The structural parameters for (a) the charged phase (Sample-E) and (b) discharged phase (Sample-D) derived from the Rietveld
refinements. g = site occupancy, B = overall isotropic atomic displacement parameter.

(a) the charged phase (LiFeSiO4 ) (b) the discharged phase (Li2 FeSiO4 )

Atom Site g x y z B(Å2 ) Atom Site g x y z B(Å2 )

Fe1/Li1 4e1 0.491(4)/0.509* 0.6452(7) 0.831(1) 0.6299(7) 0.76(6) Fe1/Li1 4e1 0.528(4)/0.472* 0.6600(9) 0.784(1) 0.675(1) 0.80(6)
Fe2/Li2 4e2 0.509/0.491* 0.5876(6) 0.188(1) 0.0647(7) 0.54(6) Fe2/Li2 4e2 0.472/0.528* 0.5957(9) 0.167(1) 0.1063(9) 0.52(5)
Si 4e 1 0.025(1) 0.792(1) 0.790(1) 0.42(5) Li3 4e3 1 0.286(5) 0.797(6) 0.544(5) 1.0
O1 4e 1 0.8619(9) 0.694(2) 0.823(1) 0.2(2) Si 4e 1 0.0342(9) 0.814(1) 0.801(1) 0.20(4)
O2 4e 1 0.434(1) 0.233(2) 0.885(1) =O1 O1 4e 1 0.861(1) 0.694(2) 0.822(1) 0.2(2)
O3 4e 1 0.691(1) 0.768(2) 0.414(1) =O1 O2 4e 1 0.425(2) 0.220(2) 0.879(2) =O1
O4 4e 1 0.974(1) 0.888(1) 0.228(1) =O1 O3 4e 1 0.675(2) 0.793(3) 0.432(2) =O1
O4 4e 1 0.953(2) 0.868(2) 0.219(2) =O1

Note: Site occupancy for each atom was fixed to unity except for Li1, Li2, Fe1 and Fe2. Site occupancy for Li1 and Li2 is calculated value and indicated
with asterisk. B value of Li3 for the discharged phase was fixed to unity.

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 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012) A529

Table III. Selected bond length (Å) for (a) the charged phase (Sample-E) and (b) discharged phase (Sample-D).

(a) the charged phase (LiFeSiO4 ) (b) the discharged phase (Li2 FeSiO4 )

Fe1/Li1 −O1 1.8698 Si −O1 1.5368 Fe1/Li1 −O1 2.0743 Li3 −O1 2.0230
−O1 2.2388 −O2 1.6116 −O1 1.9552 −O2 1.9958
−O3 1.9532 −O3 1.5642 −O3 2.0893 −O3 2.0858
−O4 2.1189 −O4 1.6107 −O4 1.9183 −O4 2.0580
Mean 2.0452 Mean 1.5808 Mean 2.0093 Mean 2.0407
Fe2/Li2 −O2 2.1770 Fe2/Li2 −O2 1.9671 Si −O1 1.5819
−O2 1.7500 −O2 2.1971 −O2 1.6499
−O3 1.8607 −O3 2.0806 −O3 1.5806
−O4 2.1634 −O4 1.8569 −O4 1.6117
Mean 1.9878 Mean 2.0254 Mean 1.6060

A model of cations disordering has been applied for structural 10

analysis of the discharged phase (Li2 FeSiO4 ). For identifying changes
in crystallographic sites, chemical formula in the model was descried
as [Li1-u Feu ]4e1 [Li1-v Fev ]4e2 [Li1-w Few ]4e3 SiO4 based on initial crystal
8
structure of the Li2 FeSiO4 with a monoclinic system in space group Fe-O
P21 /n for the structural analysis. To find out the best fitting model, we As-prepared
carried out the Rietveld refinements using a structure model generated Li2FeSiO4
by varying occupancy of Fe occupied the sites of 4e1 , 4e2 and 4e3 . 6
As the result, only the observed occupancy of Fe (w) at the 4e3 site FT Fe-Si
showed negative value (−0.07), indicating that the 4e3 site was not be Charged
occupied by Fe. Thus, the whole Fe has applied to occupy the 4e1 and 4 sample
4e2 sites. Note that site occupancy of Li was calculated by subtracting
occupancy of Fe from unity. The 4e3 site would be occupied by Li
because one mole of lithium per formula unit was returned to crystal Discharged
2 sample
structure of the charged phase (LiFeSiO4 ) in the discharge process
(Fig. 4 Sample-D).
Figure 7 shows the best Rietveld refinements result for the Sample-
D. Reliable factor (Rwp ) and crystallographic parameters are summa- 0
rized in Table I. The observed XRD patterns are fitted with patterns 0 1 2 3 4 5
calculated from the model of discharged phase (Li2 FeSiO4 ) and impu- R/Å
rity phases such as Li2 SiO3 (0.19 wt%), Fe3 O4 (0.31 wt%) and carbon
(57.93 wt%) added to the cathode. The analysis gives a reliable refine- Figure 8. Fe K edge EXAFS spectra for as-prepared Li2 FeSiO4 , the charged
ment results, supporting validity of the new structural model. Crystal and discharged cathode materials.
structure of the discharged phase (Li2 FeSiO4 ) shows the same mon-
oclinic system (P21 /n) as that of as-prepared one and the charged
one. The discharged phase (Li2 FeSiO4 ) shows larger unit cell vol- Figure 8 shows the Fourier transforms of the Fe K-edge EXAFS
ume than the charged one by 0.2%. The refined structural parameters spectra for as-prepared Li2 FeSiO4 , the charged and discharged cath-
and selected bond length for the discharged phase (Li2 FeSiO4 ) are ode materials (Sample-E and D). The fitting parameters for these sam-
summarized in Table IIb and Table IIIb, respectively. ples are summarized in Table IV. The peaks observed at the shorter

20000
+ observed
15000 calculated
Bragg position
10000
Intensity

5000

0 Discharged phase (Li2FeSiO4)

Li2SiO3
Fe3O4
Carbon

difference

5 10 15 20 25 30 35 40 45 50 55 60 65 70
2θ / degree

Figure 7. (Color online) The XRD pattern, calculated one and their difference based on the Rietveld refinements of the Li2 FeSiO4 at 1.5 V at the first discharge
(Sample-D).

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 A530 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012)

Table IV. Fitting parameters in Fe K-edge EXAFS analysis for as-prepared Li2 FeSiO4 , the charged and discharged cathode materials.

Sample Phase Shell Coordination number (N) Distance (Å) Debye-Waller factor (Å2 )

Sample-A As-prepared Li2 FeSiO4 Fe-O 4 2.01(2) 0.06(4)

Sample-E Charged phase (LiFeSiO4 ) Fe-O 4 1.96(3) 0.09(2)
Sample-D Discharged phase (Li2 FeSiO4 ) Fe-O 4 1.96(3) 0.08(7)

distance side would be ascribed to the first shell of the Fe–O bonds,
and the ones at the longer distance side would be ascribed to the second
shell of the Fe–Si bonds. The observed values of the Fe–O distances
were 2.01(2) Å for the as-prepared, 1.96(3) Å for both the charged
and discharged sample, respectively. The values of the charged and
discharged sample were consistent with mean values of Fe-O refined
by the Rietveld method as shown in Table III, supporting that the
obtained atomic position for the charged and discharged phase would
be reasonable.
Crystal structures of (a) the as-prepared Li2 FeSiO4 , (b) the charge
one and (c) the discharged one are illustrated using the computer
program VESTA 34 as shown in Figure 9. When the as-prepared
Li2 FeSiO4 was charged, lithium ion released and cation-site dis-
ordering of Li+ and Fe2+ /Fe3+ was occurred to transform to the
charged phase. When the charged phase was discharged, lithium
ion returned to occupy vacant site, and then the discharged phase
was formed. New two-phases (the charged phase; LiFeSiO4 and the
discharged one; Li2 FeSiO4 ) were repeated during charge-discharge
process. Very small volume change (0.2%) was observed for the
Li2 FeSiO4 during charge-discharge process as compared to that (7%)
for LiFePO4 ,35 which would contribute to stable cycling stability of the
Li2 FeSiO4 .
Conclusions
The Li2 FeSiO4 with monoclinic system (P21 /n) was prepared by
molten carbonate flux method at 500◦ C. The Li2 FeSiO4 showed re-
versible capacity of 160 mAh g−1 at the 0.07 C rate. Crystal struc-
ture of the as-prepared Li2 FeSiO4 transformed to new structure of the
charged phase at the first charge and the discharged one at the first dis-
charge. Crystal structure of both the phases were supposed to belong
to monoclinic system (P21 /n) based on models of cations disordering
of Li+ , Fe2+ and Fe3+ . Volume change of the unit cell was only 0.2%

(a) As-prepared Li2FeSiO4 (P21/n)

1st Charge

(b) Charged phase LiFeSiO4 (P21/n) Discharge (c) Discharged phase Li2FeSiO4 (P21/n)

Charge

Figure 9. (Color online) Crystal structures of (a) as-prepared Li2 FeSiO4 , (b) charged phase and (c) discharged one. SiO4 tetrahedra; blue, LiO4 tetrahedra; green,
FeO4 tetrahedra; brown, (Fe1/Li1)O4 /(Fe2/Li2)O4 tetrahedra; light blue.

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 Journal of The Electrochemical Society, 159 (5) A525-A531 (2012) A531

between both the phases, which would contribute to stable cycling 15. Z. L. Gong, Y. X. Li, G. N. He, J. Li, and Y. Yang, Electrochem. Solid-State Lett., 11,
stability of the Li2 FeSiO4 . A60 (2008).
16. L. M. Li, H. J. Guo, X. H. Li, Z. X. Wang, W. J. Peng, K. X. Xiang, and X. Cao, J.
Power Sources, 189, 45 (2009).
17. S. Zhang, C. Deng, and S. Yang, Electrochem. Solid-State Lett., 12, A136 (2009).
Acknowledgments 18. X. B. Huanga, X. Li, H. Y. Wang, Z. L. Pan, M. Z. Qu, and Z. L. Yu, Electrochim.
Acta, 55, 7362 (2010).
The authors appreciate J. Niwa, H. Murase, K. Kawasumi, 19. T. Muraliganth, K. R. Stroukoff, and A. Manthiram, Chem. Mater., 22, 5754 (2010).
M. Murase and T. Shimo for helpful advice. Dr. M. Tabuchi, Dr. 20. X. Y. Fan, Y. Li, J. J. Wang, L. Gou, P. Zhao, D. L. Li, L. Huang, and S. G. Sun, J.
M. Morishita, Dr. R. Kataoka and T. Miyuki (AIST) are thanked for Alloy Comp., 493, 77 (2010).
21. C. Deng, S. Zhang, B. L. Fu, S. Y. Yang, and L. Ma, Mater. Chem. Phys., 120, 14
fruitful discussions on electrochemical performance and structural (2010).
analysis. Dr. Y. Kitano and T. Uchida are thanked for the TEM obser- 22. H. Guo, X. Cao, X. Li, L. Li, X. Li, Z. Wang, W. Peng, and Q. Li, Electrochimica
vations and those analyzes. Acta, 55, 8036 (2010).
23. A. R. Armstrong, N. Kuganathan, M. S. Islam, and P. G. Bruce, J. Am. Chem. Soc.,
133, 13031 (2011).
References 24. M. E. Arroyo-de Dompablo, M. Armand, J. M. Tarascon, and U. Amador, Elec-
trochem. Commun., 8, 1292 (2006).
1. M. K. Murthy and F. A. Hummel, J. Am. Ceram. Soc., 38, 55 (1955). 25. P. Larsson, R. Ahuja, A. Nytén, and J. O. Thomas, Electrochem. Commun., 8, 797
2. I. M. Stewart and G. J. P. Buchi, Trans. Brit. Ceram. Soc., 61, 615 (1962). (2006).
3. P. Tarte and R. Cahay, C. R. Acad. Sci. Paris, 139C, 777 (1970). 26. S. Nishimura, S. Hayase, R. Kanno, M. Yashima, N. Nakayama, and A. Yamada,
4. A. R. West and F. P. Glasser, J. Solid State Chem., 4, 20 (1972). J. Am. Chem. Soc., 130, 13212 (2008).
5. M. Setoguchi and C. Sakamoto, J. Crystal Growth, 24–25, 674 (1974). 27. C. Sirisopanaporn, A. Boulineau, D. Hanzel, R. Dominko, B. Budic, A. R. Armstrong,
6. M. Setoguchi, Y. Kobayashi, H. Yamaguchi, C. Sakamoto, and K. Akatsuka, P. G. Bruce, and C. Masquelier, Inorg. Chem., 49, 7446 (2010).
OsakaKyoikuDaigakuKiyou, 28, 1 (1979). 28. C. Sirisopanaporn, C. Masquelier, P. G. Bruce, A. R. Armstrong, and R. Dominko,
7. H. Yamaguchi, K. Akatsuka, M. Setoguchi, and Y. Takaki, Acta Cryst., B35, 2680 J. Am. Chem. Soc., 133, 1263 (2011).
(1979). 29. N. Yabuuchi, Y. Yamakawa, K. Yoshii, and S. Komaba, Dalton Trans., 40, 1846
8. M. Setoguchi, Yogyo-Kyokai-Shi, 87, 51 (1979). (2011).
9. M. Setoguchi, Osaka Kogyo Gijutsu Shikensho Hokoku, 374, 1 (1988). 30. A. Boulineau, C. Sirisopanaporn, R. Dominko, A. R. Armstrong, P. G. Bruce,
10. A. Nytén, A. Abouimrane, M. Armand, T. Gustafsson, and J. O. Thomas, Electrochem. and C. Masquelier, Dalton Trans., 39, 6310 (2010).
Comm., 7, 156 (2005). 31. T. Kojima, A. Kojima, T. Miyuki, Y. Okuyama, and T. Sakai, J. Electrochem. Soc.,
11. R. Dominko, M. Bele, M. Gaberšček, A. Meden, M. Remškar, and J. Jamnik, 158, A1340 (2011).
Electrochem. Commun., 8, 217 (2006). 32. F. Izumi and T. Ikeda, Mater. Sci. Forum, 321–324, 198 (2000).
12. Z. L. Gong, Y. X. Li, and Y. Yang, J. Power Sources, 174, 524 (2007). 33. T. Taguchi, T. Ozawa, and H. Yashiro, Phys. Scripta, T115, 205 (2005).
13. C. Lyness, B. Delobel, R. Armstrong, and P. G. Bruce, Chem. Comm., 4890 (2007). 34. K. Momma and F. Izumi, J. Appl. Crystallogr., 41, 653 (2008).
14. A. Nytén, S. Kamali, L. Haggstrom, T. Gustafsson, and J. O. Thomas, J. Mater. 35. A. S. Andersson, B. Kalska, L. Häggström, and J. O. Thomas, Solid State Ionics,
Chem., 16, 2266 (2006). 130, 41 (2000).

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