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Electrochimica Acta
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a r t i c l e
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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-
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.
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
Ni (N) (wt. %)
P2 O5 (P) (wt. %)
5:6
5:7
5:8
1:2
5:8
1:2
2.5
2.5
2.5
2.5
5
5
Table 2
Cycling performance of the as-prepared composite electrodes.
Samples
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.
1514
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)
20
30
40
50
60
70
80
2 / degree
10
20
30
(b)
50
60
70
80
Ni3Si; Ni/Ni17Si3;
SiP2O7 ;
Intensity / a.u.
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.
1515
Fig. 3. TEM and HRTEM images of the as-prepared SL-58 + NPG composite powder.
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
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
(a) SiO
st
st
(a)
SiO
SL-12
SL-12+NPG
2.0
Current / mA
-1
2.5
1
rd
3
th
5
th
-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
2000
2500
-1
-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
-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
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
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
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.
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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