Electrochimica Acta 56 (2011) 15121517

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A novel nanosized silicon-based composite as anode material for high

performance lithium ion batteries
Xiuyan Wang, Zhaoyin Wen , Yu Liu
CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050, PR China

a r t i c l e

i n f o

Article history:
Received 1 June 2010
Received in revised form 9 October 2010
Accepted 11 October 2010
Available online 16 October 2010
Keywords:
Silicon-based composite
Li-containing phases
Elastic matrices
High energy mechanical milling
Li-ion batteries

a b s t r a c t
A new kind of silicon-based composite anode with high initial coulombic efciency and good cycling
performance is synthesized by a wet high energy mechanical milling technique and characterized by Xray diffraction, transmission electron microscope and high resolution transmission electron microscope.
It is demonstrated that the in situ formed Si particles with size of 510 nm are uniformly distributed in the
elastic matrices consisting of the in situ formed Li-containing compounds, amorphous P2 O5 , SiP2 O7 , Ni,
SiNi alloys and conductive graphite. The elastic matrices can effectively alleviate the volume variations
of the active Si particles during long-term cycling. The as-prepared silicon-based composite electrode
reveals an initial discharge and charge capacity of 549 and 565.3 mAh g1 , respectively, with an initial
coulombic efciency of 103%. After 80 cycles, the reversible capacity of the composite electrode is up to
560.7 mAh g1 with a capacity retention rate of 99%.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
Currently, with the rapid development of portable electronic
devices, electric and hybrid vehicles, lithium ion-batteries with
high energy density and stable cycle life have been given high
demand. However, the development of Li-ion batteries is limited
due to the low theoretical capacity (372 mAh g1 ) of the commercialized carbon anode materials [1,2]. Therefore, great efforts to nd
alternative anode materials are underway. Silicon is of special interest because of its potentially large theoretical specic capacity (up
to 4.2 mole of Li per mole Si) as well as its satisfactory potential for
lithium insertion and extraction (<0.5 V vs. Li/Li+ ) [3]. The application of silicon anode, however, has been hindered by rapid capacity
fading upon charge/discharge cycling. The capacity loss was mainly
due to the expansion/contraction of the silicon particles during Li+
insertion/extraction [46].
Much attention has thus been paid on improving the cycling performance of Si-based systems [711]. To some extent, the severe
volume expansion could be alleviated by dispersing the active
silicon particles into one or two elastic matrices or some active
materials with low volume change to form a composite structure.
Yoshio et al. [7] synthesized a carbon-coated Si by a thermal vapor
decomposition (TVD) method with much better cyclability than
that of the pure Si. Takahiro et al. [8] reported carbon microspheres
containing Si and Zuo et al. [9] prepared a Si/C composite by pyrol-

Corresponding author. Tel.: +86 21 52411704; fax: +86 21 52413903.

E-mail addresses: zywen@mail.sic.ac.cn, wangxiuyan021@163.com (Z. Wen).
0013-4686/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.10.020

ysis. Such anodes have been proven to be very promising from both
a theoretical and experimental point of view. In particular, it was
shown that adding Si in a solgel graphite matrix allowed for capacities over 2000 mAh g1 [10], and as theory predicts by Aifantis et al.
[11], lower Si volume fractions would result in a better capacity
retention.
Unlike the above examples, another important way for preparing silicon-based materials is by in situ reduction methods using
silicon-containing compounds as the precursors of Si [1215]. Lee
and Lee [12] synthesized a kind of nano-Si dispersed oxides through
mechnochemical reduction of SiO by Al, followed by carbon coating.
The carbon-coated nano-Si dispersed oxides showed a reversible
capacity of over 600 mAh g1 . However, the initial capacity loss
is considerable. Kwon et al. [13] prepared a SnSi/C coreshell
nanoparticles using SiCl4 and SnCl4 as the precursors through
chemical reduction followed by annealing. This type of SiSn/C shell
nanoparticles exhibited an initial coulombic efciency of only 78%
and their long-term cycling performance was unsatisfactory. In
our previous work [14], a nanosized siliconnickelgraphite composite was prepared by high energy mechanical milling (HEMM)
followed by pyrolysis. The introduction of nickel and graphite
enhanced the electrical contact during cycling, and thus gave a
stable cycling performance, but the initial coulombic efciency
was only 66%. The initial capacity loss of the SiO-based anode
like SiO was partially resolved by obtaining the elemental Si
prior to the electrochemical charging/discharging through a solid
redox process between SiO and Li metal [15]. The obtained
composite demonstrated an improved initial efciency and
cyclability.

X. Wang et al. / Electrochimica Acta 56 (2011) 15121517

1513

Table 1
Composition of the as-prepared composites SL-56, SL-57, SL-58, SL-12, SL-58 + NPG and SL-12 + NPG.
Samples

Constituent

SL-56
SL-57
SL-58
SL-12
SL-58 + NPG
SL-12 + NPG

Mole ratio of SiO/Li (SL)

Ni (N) (wt. %)

P2 O5 (P) (wt. %)

Graphite (G) (wt. %)

5:6
5:7
5:8
1:2
5:8
1:2

2.5
2.5

2.5
2.5

5
5

However, some problems still remained to be resolved. For

example, the soft and ductile feature of Li metal led to serious
agglomeration of the composite during the HEMM process. Besides,
the long-term cyclability needs to be further improved.
In this work, a new kind of Si-based anode with improved electrochemical performances was synthesized using a two-step wet
HEMM process. In the rst milling step, an organic liquid was
employed as the milling medium, which could effectively prevent
the aggregation of the composite powder and lead to an amorphous structure. In the second milling step, nickel powder and an
amorphous oxide of P2 O5 were introduced into the amorphous
composite obtained from the rst milling step. The amorphous
oxide of P2 O5 can act as a buffer matrix and alleviate the volume
changes [16] while Ni metal is a good electronic conductor and it
can alloy with Si during the HEMM process, therefore, enhancing
the electrochemical properties of the composite [14].
2. Experimental
2.1. Synthesis of Si/Li-containing phases compositethe rst
milling step
Silicon monoxide (SiO, 99.99%, Sinopharm Chemical Reagent
Co., Ltd.) and lithium metal with four different mole ratios of 5:6,
5:7, 5:8 and 1:2, respectively, were rst transferred into 80 ml alumina vials, in an argon-lled glove box (KK-021AS, Korea Kiyon)
for high energy mechanical milling (HEMM). A certain amount of
dodecane was employed as the milling medium. The mechanical
milling was carried out in a Planetary Mono Mill P-5 at a rotation
rate of 766.5 rpm. After 10 h of milling, the as-milled powders were
heated at 100 C under vacuum for 24 h. The as-prepared samples
are marked as SL-56, SL-57, SL-58 and SL-12, respectively, which
are listed in Table 1.
2.2. Synthesis of Si-Ni/amorphous phases compositethe second
milling step
In view of high initial efciency and relatively good cyclability
as shown in Table 2, the samples of SL-58 and SL-12 were chosen
for further processing. The two samples were mixed with 2.5 wt.%
of Ni powder (coded as N), 2.5 wt.% of P2 O5 (coded as P) and 5 wt.%
of graphite (coded as G), respectively, and further milled for 5 h. The
nal product was obtained without any grinding and sieving. The
as-prepared samples are marked as SL-58 + NPG and SL-12 + NPG,
respectively, which are also listed in Table 1.

The sample was characterized by X-ray diffraction (XRD, Rigaku

RINT-2000) with Cu K radiation to identify the phases, transmission electron microscope (TEM, JEM-2010) and high resolution
transmission electron microscope (HRTEM) to observe the morphology and particle size of the synthesized composite materials.
Electrodes containing 60 wt.% active materials, 20 wt.%
polyvinylidene uoride (PVDF) binder and 20 wt.% acetylene
black were made by coating the slurry of the electrode ingredients
in N-methyl pyrrolidinone (NMP) onto nickel foam and dried at
100 C under vacuum for 10 h. The thickness of the electrodes was
about 28 m. The working electrodes were assembled in 2025
coin cells using Celgard 2400 as the separator and lithium foils
as the counter and reference electrodes. A solution of 1 M LiPF6
in EC: DMC (1:1 weight) was employed as the electrolyte. The
assembly of cells was processed in an argon lled glove box with
oxygen and water contents less than 1 ppm. The galvanostatic
charge/discharge tests were conducted on a LAND CT2001A battery
test system in a voltage range of 0.021.5 V (versus Li/Li+ ) at a current density of 0.1 mA cm2 . The cyclic voltammetry experiments
were performed on a CHI604C Electrochemical Workstation in
the potential window from 0 to 1.5 V (vs. Li+ /Li) at a scan rate of
0.05 mV s1 .

3. Results and discussion

3.1. Phase analysis and electrochemical behaviors
Fig. 1 shows the X-ray diffraction patterns of the samples
obtained by the rst milling step. As seen, traces of several weak
peaks corresponding to Si, Li4 SiO4 and Al2 O3 were observed,
demonstrating that the reaction 5SiO + 6Li 4Si + Li2 O + Li4 SiO4
occurred during the HEMM process [15]. However, the amorphous
or nanocrystallite feature of the samples was quite different from
the composite obtained from the dry HEMM process [15], which
should be ascribed to the presence of the dodecane which could
passivate lithium metal and effectively alleviate the agglomeration of the milling powder during HEMM process thus leading to a
nanocrystallite structure [17]. The peak intensity enhanced as the
ratio of Li to Si was decreased.
Table 2 shows the cycling performances of the as-prepared samples by the 1st milling step, named as SL-56, SL-57, SL-58 and SL-12,
respectively. As seen, all of the as-prepared electrodes showed
acceptable initial coulombic efciencies. Increasing the mole ratio
of Li to SiO is favorable to the initial efciency of the electrode. How-

Table 2
Cycling performance of the as-prepared composite electrodes.
Samples

1st Charge capacity (mAh g1 )

1st Discharge capacity (mAh g1 )

1st Efciency (%)

50th Charge capacity (mAh g1 )

R50/1
(%)

SL-56
SL-57
SL-58
SL-12

943.9
866.6
905.5
973.3

1133.8
978.3
972.1
926.8

83
89
93
105

290.3
330.9
661.6
677.8

31
38
73
70

R50/1
, reversible capacity retention rate for the 50th cycle compared with the 1st cycle.

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X. Wang et al. / Electrochimica Acta 56 (2011) 15121517

SiO:Li

Si/NiSi2; Ni/Ni17Si3;

SiP2O7 ;

5:8
5:7

5:6

10

Al2O3; #- Fe

Intensity / a.u.

Intensity / a.u.

1:2

(a)

Si; Li4SiO4; Al2O3

20

30

40

50

60

70

80

2 / degree

10

20

30

3.2. Morphological feature

Fig. 3(a) shows the TEM image of the as-prepared SL-58 + NPG
composite. Fig. 3(b) and (c) shows the HRTEM of the circled
areas 1 and 2 in Fig. 3(a), respectively. As seen in Fig. 3(b), the
nanosized Si particles with size of 510 nm were uniformly distributed in the amorphous matrices. Fig. 3(c) further conrmed
the existence of the nanosized Si and Ni particles, which was well
consistent with the XRD patterns in Fig. 2(a). From the above analysis, it was concluded that the nanosized Si particles formed in
the HEMM process were well dispersed in the amorphous matrices composed of lithium containing phases formed in the 1st
milling step, amorphous oxide, nickel, graphite and SiNi alloys
formed in the second milling step. These factors were highly
favorable for the cycling performance of the Si-based electrode
material.
3.3. Cyclic voltammograms
Fig. 4 compares the cyclic voltammograms of the as-prepared
SL-12 + NPG composite electrode and the pure SiO electrode. As
seen in Fig. 4(a), the pure SiO electrode experienced a sharp reduc-

(b)

50

60

70

80

Ni3Si; Ni/Ni17Si3;
SiP2O7 ;

Intensity / a.u.

ever, the long-term cycling performances rose at rst and lowered

afterwards. In view of the high initial efciency and the relatively
good cyclability, the samples of SL-58 and SL-12 were chosen for
further processing (the second milling step). The samples obtained
from the second milling step were marked as SL-58 + NPG and SL12 + NPG, respectively, which were listed in Table 1.
Fig. 2 shows the X-ray diffraction patterns of the two samples
obtained by the 2nd milling step. As shown in Fig. 2(a), the SL58 + NPG composite mainly consisted of Si, Ni, NiSi2 , Ni17 Si3 , and
SiP2 O7 . As impurities, Al2 O3 and Fe were also observed. In the SL12 + NPG composite, the peaks of Ni3 Si were observed instead of
Si and NiSi2 (Fig. 2(b)), which could be ascribed to the decrease of
Si content. The appearance of SiP2 O7 demonstrated that the amorphous oxide of P2 O5 could not only act as a dispersing matrix but
also bond with the active Si particles. This could effectively x Si and
buffer its volume change thus improved the cycling performances
of the composite.
By comparing with Fig. 1, it was seen that the peak intensity of
Al2 O3 and Fe impurities introduced by the HEMM process increased
because of the extended milling time. The contents of Al2 O3 and Fe
were 1.79 wt.% and 5.05 wt.%, respectively. Though as contaminations, they could act as buffering matrices and help alleviate the
volume variations of the Si particles upon cycling [12,18].

40

2/ degree

Fig. 1. X-ray diffraction patterns of the four as-prepared samples by the 1st milling
step with different mole ratios of SiO to Li.

Al2O3; #-Fe

10

20

30

40

50

60

70

80

2/ degree
Fig. 2. X-ray diffraction patterns of the as-prepared composite powder by the 2nd
milling step: (a) SL-58 + NPG and (b) SL-12 + NPG.

tion peak in the range of 0.250 V and a broad oxidation peak

between 0.2 and 0.7 V. The great area difference between the reduction and oxidation peaks in the rst cycle demonstrated a large
irreversible capacity, which should be mainly attributed to the
irreversible reaction from SiO to elemental Si in the rst lithium
insertion process [15]. Besides, it was noted that the current of
the reduction peak decreased with cycling while the oxidation
peak current rst increased then declined with cycling, which
indicated poor electrochemical and mechanical stabilities during
lithium insertion/extraction process. As shown in Fig. 4(b), the SL12 + NPG composite indicated one sharp reduction peak below 0.2 V
in the rst lithium insertion process, and accordingly the extraction
process occurred at 0.20.9 V with a broad shoulder. The peak in
the range of 0.60.9 V corresponding to the formation of the solid
electrolyte interface (SEI) lm was very weak. Besides, the area difference between the reduction peak and the oxidation peak of the
composite electrode is much smaller than that of the pure SiO electrode, indicating a much better reversibility. This might be due to
the excess lithium, which could react with the in situ formed Si
during the HEMM process and thus compensate for the capacity
loss during the rst lithium insertion process. During the subsequent scans, a slight difference from the rst scan was found. A
new reduction peak appeared at about 0.15 V and a new oxidation
peak at about 0.36 V, which were coincident with the lithiation and
delithiation of silicon [19].

X. Wang et al. / Electrochimica Acta 56 (2011) 15121517

1515

Fig. 3. TEM and HRTEM images of the as-prepared SL-58 + NPG composite powder.

In addition, the current of the redox reactions increased with

cycling, implying a possible activation process during the insertion/extraction process. Meanwhile, the voltage of the oxidation
peaks shifted negatively with cycling, indicating a possible decrease
in charge transfer resistance and polarization of the composite electrode [14], which might be considered as the result of the improved
structural stability.
3.4. Electrochemical performances
Table 3 gives the comparison of the electrochemical performances among the SL-58, SL-12, SL-58 + NPG and the SL-12 + NPG
composite electrodes. The SL-58 and SL-12 composite electrodes
delivered discharge (lithium insertion) capacities of 905.5 and

973.3 mAh g1 with initial coulombic efciencies of 93% and 105%,

respectively. The excellent efciency was mainly ascribed to the
pre-reduction of the SiO into elemental Si during the HEMM
process. Besides, the existence of the excess lithium nanocrystallite was also helpful to the increase of the efciency. But the
capacity retention rates of the two composites were still not satisfactory. When the above two composites were further combined
with the nickel powder and the amorphous oxide of P2 O5 (the
as-prepared composite named as SL-58 + NPG and SL-12 + NPG,
respectively), the cycling performances were greatly improved.
In addition, the initial coulombic efciencies of the SL-58 + NPG
and SL-12 + NPG composite electrodes still remained at 81%
and 103%, respectively, demonstrating favorable electrochemical
performances.

Table 3
Comparison of the cycling performance for the as-prepared composite electrodes: SL-58, SL-58 + NPG, SL-12 and SL-12 + NPG.
Samples

1st Charge capacity (mAh g1 )

1st Discharge capacity (mAh g1 )

1st Efciency (%)

80th Charge capacity (mAh g1 )

R80/1
(%)

SL-58
SL-58 + NPG
SL-12
SL-12 + NPG

905.5
499.4
973.3
565.3

972.1
614.3
926.8
549

93
81
105
103

494.9
458
497.2
560.7

55
92
51
99

R80/1
, reversible capacity retention rate for the 80th cycle compared with the 1st cycle.

1516

X. Wang et al. / Electrochimica Acta 56 (2011) 15121517

rd

(a) SiO

st

st

(a)

SiO
SL-12
SL-12+NPG

2.0

Current / mA

-1

2.5

1
rd
3
th
5

th

Potential vs. (Li/Li ) / V

-2

Charge
1.5

1.0

0.5

Discharge
0.0

3
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

500

1000

1500

Potential vs. (Li/Li ) / V

2000

2500

-1

Specific capacity / mAh g

-0.6

(b) SL-12+NPG

st

1
rd
3
th
5

1.6

(b)

Charge
st

1
nd
2
th
10
th
50

1.4

Potential vs. (Li/Li ) / V

-0.2

1.2

0.0
0.2
0.4
0.6
0.8
0.0

1.0
0.8
0.6
0.4
0.2

Discharge

0.0
0.3

0.6

0.9

1.2

1.5

-100

100

Potential vs. (Li/Li ) / V

400

500

600

700

Fig. 5. (a) The 1st discharge and charge curves for the as-prepared composite electrodes (SL-12 and SL-12 + BPG) and the pure SiO electrode; (b) the 1st, 2nd, 10th and
50th discharge and charge curves for SL-12 + NPG composite at a current density of
0.1 mA cm2 , in the potential window of 0.021.5 V.

the coulombic efciency remained above 99% during the subsequent cycles. While the reversible capacity of the SiO electrode was
only 116.1 mAh g1 at the 80th cycle with the capacity retention
rate of only 9.8%. The obviously improved cycling performances
of the composite could be ascribed to several factors. First, the
wet milling process could effectively prevent the aggregation of

105

Efficiency

1400

100
-1

Fig. 5(a) exhibits the discharge and charge curves of the asprepared composites SL-12 and SL-12 + NPG electrodes and the
pure SiO electrode. The rst cycle began with the discharging process, corresponding to the lithium insertion of the electrodes. From
the gure, we could see that the discharge curves of the as-prepared
composite electrodes were smoother than that of the SiO electrode, which might be related to the nanocrystallite structure of
the active particles in the composites. Fig. 5(b) shows the 1st, 2nd,
10th, and 50th discharge and charge curves of the as-prepared
SL-12 + NPG electrode. The composite electrode delivered a discharge and charge capacity of 549 and 565.3 mAh g1 with an initial
coulombic efciency of up to 103% (the excess lithium could further alloy with the in situ formed Si during the preparation process
and thus compensate for the capacity loss). The specic capacity
increased with cycling during the initial several cycles, indicating an activation process during the lithium insertion/extraction
process, which was coincident with the cyclic voltammogram.
The following discharge curves became almost overlapping, indicating a well kept conductive network between nano-silicon
particles and the matrices and a stable internal resistance
[15].
Fig. 6 demonstrates the cycling performances of the as-prepared
SL-12 + NPG composite electrode and the pure SiO electrode. It
was obvious that the cycling performance of the composite electrode was much better than the pure SiO electrode. After 80 cycles,
the SL-12 + NPG composite electrode delivered a discharge capacity of 560.7 mAh g1 with a capacity retention rate of 99% and

300

-1

Specific capacity / mAh g

Fig. 4. Cyclic voltammograms of (a) the pure SiO electrode; (b) the as-prepared SL12 + NPG composite electrode, in the potential window from 0 to 1.5 V (vs. Li+ /Li) at
the scan rate of 0.05 mV s1 .

200

Specific capacity / mAh g

1200
95
1000

SiO
SL-12+NPG

800

Charge capacity
600

90
85

400

80

200

75

0
0

10

20

30

40

50

60

70

Efficiency %

Current / mA

-0.4

70
80

Cycle number
Fig. 6. Comparison of the cycling performance between the as-prepared SL-12 + BPG
composite electrode and the pure SiO electrode.

X. Wang et al. / Electrochimica Acta 56 (2011) 15121517

the composite particles thus produced the nanosized and well

distributed Si particles, which was favorable for the stability of
the electrode. Second, the excess lithium could alloy with the in
situ formed Si during HEMM process, which could compensate for
the capacity loss during the initial cycles. Third, the introduction
of the amorphous oxide of P2 O5 could effectively buffer the volume changes of Si, since the P2 O5 not only acted as a dispersing
matrix but also bonded with the active Si particles. Fourth, the
formation of the SiNi alloys as well as the existence of the metallic nickel and graphite reinforced the electrode mechanically and
electronically.
4. Conclusions
A new kind of nanosized Si-based composite with favourable
electrochemical performances was synthesized by a two-step
wet HEMM process. By adjusting the ratio of SiO to Li, a composite with a favorable initial efciency could be obtained. It
was proved that adding the conductive agents of nickel and
graphite as well as the buffering matrix of amorphous P2 O5
effectively alleviated the volume variation and provided good electronic contact of the composite during cycling. The as-prepared
Si-based composite electrode delivered a discharge and charge
capacity of 549 and 565.3 mAh g1 with an initial coulombic
efciency of up to 103%. After 80 cycles, the as-prepared composite electrode revealed a reversible capacity of 560.7 mAh g1
with a capacity retention rate of 99%. The silicon-based composite could serve as a promising anode candidate for lithium ion
batteries.

1517

Acknowledgments
This work was nancially supported by NSFC Project No.
20333040 and 50672114, 863 Project of China No. 2006AA03Z232
and 973 Project of China No. 2007CB209700, as well as Research
Projects from the Science and Technology Commission of Shanghai
Municipality No. 08DZ2210900.
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