J Mater Sci (2016) 51:64526463

Phase relations of Li2OFeOSiO2 ternary system

and electrochemical properties of LixSiyOz compounds
Danlin Yan1, Xiaofeng Geng1, Yanming Zhao2,3,*, Xinghao Lin1, and Xudong Liu1
1

School of Material Science and Engineering, South China University of Technology, Guangzhou, Peoples Republic of China
School of Physics, South China University of Technology, Guangzhou 510640, Peoples Republic of China
3
State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, Peoples
Republic of China
2

Received: 6 January 2016

ABSTRACT

Accepted: 29 March 2016

Phase equilibria in the ternary Li2OFeOSiO2 system have been studied by

means of X-ray powder diffraction. The experimental results show that no new
lithium ferrous silicate compounds can be found in our experimental condition
which may be a candidate cathode material for LIBs. The Li2OFeOSiO2 system
can be characterized by the existence of 9 three-phase regions. In Li2OSiO2
binary system, Li2SiO3 and Li4SiO4 are purely synthesized by solid-state reactions; other new information includes the electrochemical properties of Li2SiO3
and Li4SiO4 compounds, where the electrochemical test indicated that initial
discharge-specific capacities can reach to 136 and 129 mAhg-1, respectively.
Enhanced performance was exhibited after carbon coating. The initial dischargespecific capacities of carbon-coated Li2SiO3 and carbon-coated Li4SiO4 compound can reach to 230 and 220 mAhg-1 respectively. Our results show that
Li2SiO3 and Li4SiO4 samples have better capacity retention except for the first
discharge. No significant change can be seen in ex situ XRD patterns for Li2
SiO3/C, while the lithium-ion insertion/extraction reaction may exist in Li4SiO4
as forming solid solutions (nominated Li4?xSiO4).

Published online:
7 April 2016

Springer Science+Business

Media New York 2016

Introduction
Rechargeable lithium-ion batteries (LIB) have been
popularly accepted in a wide variety of applications,
and great efforts have been made in last two decades to
design new electrode materials and electrolytes to
improve the energy density, safety, and efficiency of
LIBs. For this purpose, silicon-based materials have
been studied widely due to their high capacities and

Address correspondence to E-mail: zhaoym@scut.edu.cn

high energy efficiency. Besides of its low-cost, nontoxicity, and environment friendly, the theoretical
specific capacity of silicon is 10 times more than graphite and its voltage is of about 0.5 V higher than the
corresponding graphite materials [1, 2]. However, severe capacity fading hinders the commercial application
of Si due to particle pulverization, severe electrolyte
degradation, and formation of unstable solid electrolyte
interface (SEI) during repeated charge/discharge cycles

6453

J Mater Sci (2016) 51:64526463

[35]. Therefore, numerous studies for Si-based anode

materials have been carried out to improve their electrochemical performances in LIBs. Most of the recent
works are focused on nanocrystallization of the Si particles [68] and dispersing them in inactive SiOx buffer
matrices and/or conductive carbons [9, 10].
Since the demonstration of reversible lithium insertion and extraction for LiFePO4 in 1997 [11], lithium
transition metal phosphates with olivine-type structures, LiMPO4 (M = Co, Ni, Mn, Fe) have received
extensive attention as promising novel cathode materials for rechargeable lithium batteries, where the
excellent character is mainly afforded by such a 3D
framework structure. In addition, it has been shown
that polyanions enable low transition metal redox
energies through the inductive effective effect, thereby
allowing some sort tuning of such energies [12].
Structures containing silicon polyoxanion (silicates)
provide an attractive area of investigation. It is well
known that silicon atom can be coordinated by oxygen
atoms to form a fourfold co-ordination environment,
affording greater variety in redox potential adjustment. Considering this, recent works tend to give a
preliminary evaluation of the inductive effect of the
SiO4 group, and Li2FeSiO4 is expected to be a promising new cathode material for lithium-ion batteries [13].
Li2FeSiO4 was reported as lithium-ion battery cathode
materials for the first time by Nyten et al. [14], and then
by Y. Yang et al. using solgel method [15].
The emergence of Li2FeSiO4 compound as promising candidate cathode materials for LIBs encourages
us to further investigate the Li2OFeOSiO2 system to
explore whether there exists other new lithium ferrous silicon polyoxanion which may be as a candidate
cathode material. To our knowledge, no phase diagram of the Li2OFeOSiO2 system is available yet.
Exploring the Li2OFeOSiO2 phase diagram by
experimental method is an effect way to learn more
about the phase relations of the Li2OFeOSiO2 ternary system and also can provide a reference for their
application of the corresponding materials in the
future. In addition, Li2SiO3 and Li4SiO4 in Li2OSiO2
binary system were studied as glass system, molten
salt systems, high-temperature ceramic glaze, etc. [16,
17]. It should be noted that these two compounds are
the intermediate products during the silicon-based
anode materials chargedischarge process, where
Li4SiO4 can act as a migration path for lithium ions
[18]. However, no data on electrochemical properties
have been reported when using Li2SiO3 and Li4SiO4 as

anode materials directly for LIB. Here, the charge/

discharge capacities as well as the cycle performances
were investigated for the first time, and the results
should be a clue to understand the electrochemical
process for the Si-based anode materials.
In our paper, the phase relation of Li2OFeOSiO2
ternary system under the 95 % Ar ? 5 % H2-reducing atmosphere has been systematically investigated
by means of X-ray diffraction (XRD) and new data on
electrochemical properties of Li2SiO3 and Li4SiO4 as
anode materials for LIB were also reported in this
paper for the first time. Our measurement results
show that, although no new compound was found in
binary and ternary system under such circumstances,
pure-phase Li2SiO3 and Li4SiO4 were obtained for the
first time using solid-state method. Besides, the initial
specific capacities of 68 and 83 mAhg-1 at the discharge current density of 20 mA/g can be obtained
for Li2SiO3 and Li4SiO4, respectively. After carbon
coating, higher discharge capacities of 200 and 141
mAhg-1 were obtained and a better cycle performance can be exhibited except for the first cycle.

Experimental section
All the samples studied in our paper were prepared
by high-temperature solid-state reactions in the same
experimental atmosphere. The starting materials were
analytically pure Li2CO3, FeC2O4
2H2O, and H2SiO3
powder reagents. The appropriate amounts of starting
materials were mixed by grounding in an agate
mortar for 30 min. Then the mixtures were preheated
in a porcelain crucible at 350 C for 10 h in Ar atmosphere in order to decompose the oxalate and eliminate the water. The specimens were reground again,
pressed into pellets of 10 mm in diameter and
12 mm in thickness, and sintered at temperature
range of 700750 C for 12 h under a stream of a
mixture of 95 % Ar ? 5 % H2 gas to prevent formation of trivalent iron. The process was repeated until
its diffraction pattern had no further changes. The
pure Li2SiO3 and Li4SiO4 samples were synthesized
with the same procedures mentioned above, while
5 wt% glucose as carbon source was added to starting
materials to prepare the carbon-coated samples. The
phase identification of the product was carried out by
XRD using a D/Max-2400 (Rigaku) diffractometer
with Cu Ka radiation. A graphite monochromator
was used for diffracted beams. Scanning electron

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J Mater Sci (2016) 51:64526463

microscopy (SEM) was performed with a JEOL JSM5610 and FEI StrataTM DB235 SEM/FIB microscope.
The electrochemical characterization of Li2SiO3 and
Li4SiO4 powders as anode of the two-electrode electrochemical cells were measured using an automatic
battery tester system (Land, China). The anode of the
two-electrode cells were fabricated by blending the
Table 1 List of phase
identications for various
specimens in the system Li2O
FeOSiO2

prepared powder with acetylene black and polyvinylidene fluoride (PVDF) binder in a weight ratio of
80:10:10 in N-methyl-2-pyrrolidone (NMP). The
obtained slurry was coated on Cu foil, dried at 50 C
for 24 h, and pressed (5 MPa), respectively. The electrodes fabricated were dried again at 90 C for 12 h in
vacuum and cut into 0.8 9 0.8 cm2 in size. Two-

No.

LiO0.5 (at%)

FeO (at%)

SiO2 (at%)

Phase identication

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43

30
45
50
70
40
33.33
40
44.44
50
57.14
66.67
70.59
75
77.78
80
85.71
88.89
90.91
0
0
0
0
0
60
70
50
60
80
80
70
60
40
20
40
46.67
50
40
20
20
20
45
60
50

70
55
50
30
60
0
0
0
0
0
0
0
0
0
0
0
0
0
20
50
57.14
66.67
80
20
10
20
10
10
5
5
5
20
50
40
40
33.33
10
30
60
70
50
30
25

0
0
0
0
0
66.67
60
55.56
50
42.86
33.33
29.41
25
22.22
20
14.29
11.11
9.09
80
50
42.86
33.33
20
20
20
30
30
10
15
25
35
40
30
20
13.33
16.67
50
50
20
10
5
10
25

Li2Fe3O4 ? FeO
Li2Fe3O4 ? LiFeO2
LiFeO2
LiFeO2 ? Li2O
Li2Fe3O4
SiO2 ? Li2SiO3
SiO2 ? Li2SiO3 ? Li2Si2O5
SiO2 ? Li2SiO3
SiO2 ? Li2SiO3 ? Li2Si2O5
SiO2 ? Li2SiO3 ? Li4SiO4
Li2SiO3
Li2SiO3 ? Li4SiO4
Li2SiO3 ? Li4SiO4
Li2SiO3 ? Li4SiO4
Li4SiO4
Li2CO3 ? Li4SiO4
Li2CO3 ? Li4SiO4
Li2CO3 ? Li4SiO4
Fe2SiO4 ? SiO2
Fe2SiO4 ? SiO2
Fe2SiO4 ? SiO2
Fe2SiO4
Fe2SiO4 ? FeO
Li2FeSiO4 ? LiFeO2 ? Li4SiO4
Li2FeSiO4 ? LiFeO2 ? Li4SiO4
Li2FeSiO4 ? Li2SiO3
Li2FeSiO4 ? Li2Si2O5 ? Li2SiO3
Li2CO3 ? LiFeO2 ? Li4SiO4
Li2CO3 ? LiFeO2 ? Li4SiO4
Li2FeSiO4 ? Li2SiO3 ? Li4SiO4
Li2FeSiO4 ? Li2Si2O5 ? Li2SiO3
Li2FeSiO4 ? Li2Si2O5
Li2FeSiO4 ? Fe2SiO4
Li2FeSiO4 ? Fe2O3
Li2FeSiO4 ? Li2Fe3O4
Li2FeSiO4 ? Li2FeO2
Li2FeSiO4 ? Li2Si2O5 ? SiO2
Li2FeSiO4 ? Fe2SiO4 ? SiO2
Li2FeSiO4 ? Fe2SiO4 ? FeO
Li2FeSiO4 ? FeO
Li2FeSiO4 ? Li2Fe3O4 ? LiFeO2
Li2FeSiO4 ? LiFeO2 ? Li4SiO4
Li2FeSiO4

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J Mater Sci (2016) 51:64526463

electrode cells were assembled in a Mikrouna glove

box filled with high-purity argon, where the lithium
metal foil was used as anode, Celgard 2320 as separator, and 1M LiPF6 in EC:DMC (1:1 vol.%) was used as
an electrolyte. The electrochemical capacity measurements were performed in the voltage range between
0.01 and 3 V, and the electrochemical capacity of
samples was evaluated on the active materials.
Electrochemical impedance spectroscopy (EIS) was
carried out on an AUTOLAB PGSTAT100-type electrochemical workstation (Metrohm AG company).
EIS measurements were carried out in the frequency
range from 0. 1 Hz to 100 kHz.

[30], Li4SiO4 [31], Li8SiO6 [32]. Only three compounds,

Li2Si2O5, Li2SiO3, and Li4SiO4 were found to exist in our
binary and ternary compounds sintered at 750 C.
FeOSiO2
In the FeOSiO2 system, four compounds: FeSiO3 [33,
34], Fe2SiO4 [35, 36], Fe5Si3O12 [37], and Fe7SiO10 [38,
39], have been reported. In our experimental conditions, we did not obtain FeSiO3, Fe5Si3O12, and
Fe7SiO10. Here, we obtained an olivine-type silicate
Fe2SiO4 with the space group Pbnm (ICSD#10410).
That only Fe2SiO4 was detected may be attributed to
the using of H2 as a reducing agent and the H2SiO3 as
starting material in our experiment.

Results and discussion

Ternary Li2OFeOSiO2 system
In Li2OFeOSiO2 system, a total of 43 specimens
with different compositions were prepared under a
stream of a mixture of 95 % Ar ? 5 % H2 gas. The
compositions and their phase identifications in the
system Li2OFeOSiO2 are listed in Table 1.

Binary systems
Li2OFeO
In Li2OFeO binary system, eight lithium ferrites, Li2Fe3O4 (ICDD-PDF 37-1432), LiFeO2 [19], LiFe5O8 [20],
Li5FeO4 [21], Li2Fe2O4 [22], Li3Fe5O8 [23], Li2Fe3O5
(ICDD-PDF 41-0971), and Li5Fe5O8 (ICDD-PDF
40-0943) have been reported. LiFe5O8 was reported by
Berbenni et al. synthesized using Li2CO3 and FeC2O4

2H2O as starting materials with solid-state method at
600 C under nitrogen flow [24]. However, with the
same starting materials in our reducing hydrogen
atmosphere conditions, only Li2Fe3O4 and LiFeO2 were
obtained. It should be noted that in the two compounds obtained in our experiment in the Li2OFeO
system, LiFeO2 contains trivalent iron. In fact, the same
result has been verified by our group under the same
experimental condition [25, 26]. Furthermore, in Berbennis work, it was mentioned that Fe2O3 can form
even when divalent iron compound FeC2O4
2H2O is
decomposed under a protective atmosphere [24].
Li2OSiO2
Six compounds have been reported in the Li2OSiO2
system: Li2Si3O7 [27], Li2Si2O5 [28], Li2SiO3 [29], Li6Si2O7

No experimental work has been reported about ternary Li2OFeOSiO2 phase diagram. Furthermore, it
has only one compound Li2FeSiO4 reported in the
Li2OFeOSiO2 system. Here, our objective is to
explore whether there exist other new lithium ferrous
silicates which may be a candidate cathode material
for LIBs. However, our experimental results show that
no new compounds can be found at 750 C under a
stream of a mixture of 95 % Ar ? 5 % H2 gas. The
phase relations in the ternary Li2OFeOSiO2 system
are shown in Table 2. Figure 1 shows the subsolidus
phase relations constructed from powder XRD data of
43 specimens, which consists of 9 three-phase regions.

The electrochemical study about Li2SiO3

and Li4SiO4
In Li2OFeOSiO2 system, besides the attracting of
Li2FeSiO4, Li2SiO3, and Li4SiO4 in Li2OSiO2 binary

Table 2 List of 9 three-phase region

No.

Phase identication

1
2
3
4
5
6
7
8
9

Li2CO3 ? LiFeO2 ? Li4SiO4

Li2FeSiO4 ? LiFeO2 ? Li4SiO4
Li2FeSiO4 ? Li2SiO3 ? Li4SiO4
Li2FeSiO4 ? Li2Si2O5 ? Li2SiO3
Li2FeSiO4 ? Li2Si2O5 ? SiO2
Li2FeSiO4 ? Fe2SiO4 ? SiO2
Li2FeSiO4 ? Fe2SiO4 ? FeO
Li2FeSiO4 ? Li2Fe3O4 ? FeO
Li2FeSiO4 ? Li2Fe3O4 ? LiFeO2

6456
system also appeal our attention. They are the most
common intermediate products during the charge
discharge cycling in silicon-based materials, especially in SiO/C composite [4044]. The accurate roles
of Li2SiO3 and Li4SiO4 in Si-based anode materials

J Mater Sci (2016) 51:64526463

are still controversial. Takami et al. [45] observed

both of them in XRD patterns, and considered them
as irreversible products appearing in the cycling of
nano Si clusterSiOxC composite material. However,
Liu et al. reported that Li2SiO3 can reversibly form
and disappear during the charge/discharge process
in SiOC composite, but Li4SiO4 remained unchanged during the cycle process [46]. No experimental
work has been reported about the electrochemical
properties Li2SiO3 and Li4SiO4. Here, we have presented their electrochemical performance firstly.
The electrochemical properties of Li2SiO3

Figure 1 Subsolidus phase relation of the system Li2OFeO

SiO2 (dots single phase; square two phases; triangle three phases).

Figure 2a shows the XRD patterns of pure Li2SiO3 and

carbon-coated Li2SiO3 compounds. All diffraction
peaks of two compounds can be indexed based on an
orthorhombic structure with space group Cmc2/1
successfully, using the program Dicvol [47]. The stepscanned XRD data of the Li2SiO3/C composite were
refined by the GSAS program; the results are shown in
Fig. 2b. The weighted factor Rwp is 8.69 %, suggesting
that single-phase Li2SiO3 can be obtained under our
experimental condition; and no impurities were

Figure 2 a X-ray diffraction patterns of Li2SiO3 and Li2SiO3/C, b XRD renement results of Li2SiO3/C, c the SEM images of the
Li2SiO3 sample, d the SEM images of the Li2SiO3/C sample, e shows the crystal structure of Li2SiO3.

J Mater Sci (2016) 51:64526463

6457

Figure 3 The galvanostatic charge/discharge proles of the carbon-free Li2SiO3 (a) and carbon-coated Li2SiO3 (c) for the rst three
cycles and 50th cycles. The cycle performances of the carbon-free Li2SiO3 (b) and carbon-coated Li2SiO3 (d).

detected under the resolution of X-ray diffractometer.

, b = 5.400(4) A
,
The cell parameters of a = 9.394(5) A

c = 4.654(0) A obtained from the refinement results

are in good agreement with the values reported by
Hesse [29]. The framework of Li2SiO3 based on the
obtained crystal structure parameters is shown in the
inset of Fig. 2e. In this orthorhombic structure, Si
atoms occupy within the SiO4 tetrahedra, and each
SiO4 tetrahedron shares two edges with adjacent
tetrahedra to form zigzag SiO4 tetrahedra chains,
extending along c direction. And Li ions locate in the
interspaces of SiO4 tetrahedra chains.
Figure 2c, d present the SEM images of the Li2SiO3
and Li2SiO3/C samples. Both of the two samples are
sphere-like particles with the particle size of *1 lm.
Figure 3a, c show the typical chargedischarge
curves of Li2SiO3 and Li2SiO3/C obtained in our

experiments during the first three cycles in 0.013.0 V

range versus Li at current density of 5 mA/g. As seen
in Fig. 3, the first discharge curves for carbon-coated
and carbon-free samples are similar in shape, especially the small sloping potential region (1.501.35 V),
which disappeared in the subsequent cycles. The
existence of small platform in the first discharge
profile may be attributed to the side reactions like
formation of SEI film on the surface of electrode. As
shown in Fig. 3a, c the initial discharge and recharge
capacities of carbon-coated Li2SiO3 are 230 and 115
mAhg-1, while the corresponding of carbon-free
Li2SiO3 are 136 and 54 mAhg-1. Furthermore, the
initial coulombic efficiency (CE) of Li2SiO3/C is
*50 %, while that carbon-frees is only 40 %; and
both of them increased quickly in the following cycles
and remain nearly 100 % thereafter (Fig. 3b, d). The

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Figure 4 a X-ray diffraction patterns of Li4SiO4 and Li4SiO4/C, b XRD renement results of Li4SiO4/C, c the SEM images of the
Li4SiO4 sample, d the SEM images of the Li4SiO4/C sample, e shows the crystal structure of Li4SiO4.

relatively low initial coulombic efficiency may be

attributed to the irreversible capacity loss, including
side reactions such as formation of solid electrolyte
interface (SEI) film and decomposition of electrolyte.
The cycle performances of the Li2SiO3 and Li2SiO3/
C at different current density are shown in Fig. 3b and
d, respectively. Li2SiO3/C shows relatively higher
initial discharge capacity of 200 mAhg-1, while carbon-free ones is 68 mAhg-1 at the current density of
20 mA/g. At the current density of 20 mA/g, after 50
cycles a reversible capacity of 60 mAhg-1 is maintained for Li2SiO3/C composite. And 20 mAhg-1 can
be held for the carbon-free sample. Although the
charge/discharge capacity of this material is not high,
it exhibits high charge/discharge reversibility except
for the first cycle.
The electrochemical properties of Li4SiO4
Figure 4a shows the XRD patterns of carbon-free Li4
SiO4 and carbon-coated Li4SiO4, respectively. Both of
them can be successfully indexed based on a monoclinic structure (ICSD Card No. 8222) with the program

Dicvol [46]. Figure 4b presents the Rietveld refinement

results of the Li4SiO4/C compound, and a space group
of P21/m was chosen as the structural refinement
model. The reasonable small weighted factor Rwp
(11.19 %) suggests that single-phase Li4SiO4 was
obtained in our experimental process with
, b = 6.102(9) A
, c = 16.740(6) A
,
a = 11.557(6) A
b = 99.047(3), and Z = 14. The cell parameters
obtained from the refinement results are in good
agreement with the values reported previously [48].
The Li4SiO4 has a typical orthosilicate structure, where
Si ions are tetrahedrally coordinated with oxygen and
form isolate (SiO4)4- groups. And lithium ions occupy
7 crystallographical sites with 4-, 5-, and 6- co-ordination to oxygen ions Fig. 4e. Figure 4c, d show SEM
micrographs of Li4SiO4 and Li4SiO4/C samples. The
particles in both samples were agglomerated severely
with the particle size of 12 lm.
Galvanostatic charge/discharge cycling was performed in the voltage range between 0.01 and 3 V
versus Li. Figure 5a, c present the 1st, 2nd, 3rd, and
50th charge/discharge curves of carbon-free Li4SiO4
and carbon-coated Li4SiO4, respectively at the current

J Mater Sci (2016) 51:64526463

6459

Figure 5 The charge/discharge proles of the carbon-free Li4SiO4 (a) and carbon-coated Li4SiO4 (c) for the rst three cycles and 50th
cycles. The cycle performances of the carbon-free Li4SiO4 (b) and carbon-coated Li4SiO4 (d).

density of 5 mA/g. As expected, the electrochemical

performance of the carbon-coated Li4SiO4 was better
than that of the carbon-free Li4SiO4. The initial discharge capacity of carbon-free is 129 mAhg-1; it
increases to 220 mAhg-1 for the carbon-coated sample. Figure 5b, d show the variations in the dischargecharge capacity versus the cycle number at
different current densities. The reversible capacity
after 50 cycles of carbon-coated Li4SiO4 (91 mAhg-1)
electrode at 5 mA/g was higher than that of the
carbon-free Li4SiO4 electrode (40 mAhg-1). Li4SiO4
also exhibits better cycle performance except for the
first cycle. Especially carbon-coated sample, at the
current density of 20 mA/g, 93 % of the discharge
capacity of second cycle is still maintained after 50
cycles. We also observed that carbon-coated Li4SiO4

shows better rate performance at high current density

compared to the carbon-free Li4SiO4.
Here, we attributed poor electrochemical performance of the carbon-free samples to its low electronic
conductivity whose order of magnitude is *10-9.
Carbon coating applied here introduces amorphous
carbon to improve the electronic conductivity as well
as to enhance the electrochemical performance. Electrochemical impedance spectroscopy (EIS) measurements were carried out to evaluate the charge-transfer
resistances of the carbon-free samples and carboncoated samples, as shown in Fig. 6. The Nyquist plots
were fitted via an equivalent circuit (Fig. 6c), and
charge-transfer resistances (Rct) of the electrodes were
obtained from the fitting results (inset Fig. 6a, b). As
seen, the charge-transfer resistances decreased

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J Mater Sci (2016) 51:64526463

Figure 6 a The Nyquist plots of Li2SiO3 and Li2SiO3/C, b the Nyquist plots of Li4SiO4 and Li4SiO4/C, c equivalent circuit for Nyquist
plots.

Figure 7 Ex situ XRD patterns of Li2SiO3/C (a) and Li4SiO4/C (b).

significantly after carbon coating, suggesting higher

electronic conductivities of the carbon-coated samples.
Figure 7 shows ex situ XRD patterns of Li2SiO3/C
and Li4SiO4/C electrodes. It should be noted that the
electrochemical process of Li2SiO3/C and Li4SiO4/C
reported here disagrees with Takami et al. [45] and
Liu et al. [46] in nano Si clusterSiOxC composite
material or in SiOC composite. As shown in Fig. 7,
all main diffraction peaks can be preferably maintained when discharged to 0.01 V and recharged to

3 V for Li2SiO3/C electrodes from their ex situ XRD

results. And no significant change can be seen in its
ex situ XRD patterns for Li2SiO3/C. It would be easy
to understand taking its low capacity into consideration. While for the Li4SiO4/C sample, the obvious
disappearance of the peaks or appearance of new
peaks are not observed. It can be seen that the two
peaks of Li4SiO4/C sample (P21/m symmetry) with
the indexes of (-113) and (211) (ICSD Card No. 8222)
in the selected regions in Fig. 7b amalgamate to

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J Mater Sci (2016) 51:64526463

become one broadening peak under the resolution of

XRD pattern when discharged to 0.01 V, and they
reversibly separated again when recharged to 3 V.
This indicates that the lithium-ion insertion/extraction reaction may exist in Li4SiO4/C as forming solid
solutions (nominated Li4?xSiO4).

[4]

[5]

[6]

Conclusions
In this study, the isothermal section of the Li2OFeO
SiO2 system was determined at 750 C under the
95 %Ar ? 5 % H2 reducing atmosphere and have
been systematically investigated by means of XRD.
There are 6 compounds in the Li2OFeO, FeOSiO2,
and Li2OSiO2 binary systems and one exist in the
Li2OFeOSiO2 ternary system. Our experimental
results show that no other new lithium ferrous silicates exist under our experimental condition.
According to our experimental results, the Li2O
FeOSiO2 system can be characterized by the existence of 9 three-phase regions. The electrochemical
study was performed on Li2SiO3 and Li4SiO4 with
carbon-free and carbon-coated, and the results show
that the performance can be improved after carbon
coating. No significant change can be seen in ex situ
XRD patterns for Li2SiO3/C, while the lithium-ion
insertion/extraction reaction may exist in Li4SiO4/C
as forming solid solutions (nominated Li4?xSiO4).

Acknowledgements
This work was funded by NSFC Grant supported
through NSFC Committee of China (Nos. 51172077 &
51372089), the Foundation supported through the
Science and Technology Bureau of Guangdong
Government (No. S2011020000521).

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

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