Materials Science and Engineering B 131 (2006) 173176

A nanosized silicon thin film as high capacity anode

material for Li-ion rechargeable batteries
Hong Guo, Hailei Zhao , Chaoli Yin, Weihua Qiu
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, PR China
Received 22 December 2005; received in revised form 30 March 2006; accepted 14 April 2006

Abstract
deposited on rough Cu foil by a radio frequency magnetron sputtering is used as anode
Silicon thin film with thickness in range 10005300 A
materials for Li-ion rechargeable batteries. The SEM, XRD and TEM analysis reveals that the Si thin film has a floccular nano-sized multi-crystalline
structure. Li ions insertion/extraction evaluation is performed mainly with constant current charge/discharge cycling and cyclic voltammetry (CV)
at room temperature. The cycleability and reversible discharge capacity are found to depend on the film thickness, and thinner films give larger
Si film provides a reversible specific capacity over 3500 mA hg1 with excellent cycleability under 0.5 C
accommodation capacity. A 3120 A
charge/discharge rate.
2006 Elsevier B.V. All rights reserved.
Keywords: Silicon thin film; Anode materials; Li-ion batteries; Radio-frequency magnetron sputtering

1. Introduction
The constant strong demand for lithium rechargeable batteries as a power supply for portable electronic devices, electric vehicles and military special devices has accelerated the
research and development of new electrode materials having
higher energy density and better cycle stability [13].
In order to improve the electrochemical performance of
anode, the currently used carbonous active materials, having a
specific capacity of about 372 mA hg1 , should be replaced by
some new materials [47]. Intensive studies have been focused
on silicon anode materials due to its extremely high lithium storage (Li22 Si5 :4200 mA hg1 ), however, its cyclic performance is
poor due to the large volume change associated with Li ion
insertion/extraction [810]. For enhancement of electrochemical performance, modification of the electrode structure seems
to be a vital factor [11]. Recently, the introduction of nano-sized
materials in batteries has been suggested to be a possibility since
the physical, electrical and chemical properties of nano-sized are
very different from those of their bulk counterparts. For example, Song et al. [12] investigated the film thickness dependence
of the electrochemical behaviour of nano-crystalline Mg2 Si thin

Corresponding author. Tel.: +86 10 62334863; fax: +86 10 62332570.

E-mail address: hlzhao@mater.ustb.edu.cn (H. Zhao).

0921-5107/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2006.04.008

film electrodes, and the results showed that the nano-structural

characteristic of the anodes is important for improving the electrochemical performance of Li rechargeable batteries. Sayama
et al. [13] deposited Si thin film having thickness over 6 m. S.
Ohara et al. [14] have found that the Si film vacuum deposited on
a Ni foil revealed a specific energy density over 1000 mA hg1 ,
however, the cycleability was still insufficient for practical use.
In the present work, application of a radio-frequency (rf) magnetron sputtering system, nano-sized multi-crystalline silicon
film electrode was fabricated, and its electrochemical performance was investigated. In an attempt to overcome the mechanical disintegration of electrode due to its large volume change
during Li insertion/extraction, a rough Cu foil mechanical filed
with sandpaper was used as a substance. Increasing the contact area between the deposited film and substrate may help the
active silicon film to accommodate large volume change without
pulverizing.
2. Experimental
A piece of polished n-type silicon wafer (pure >99.9999%)
with diameter of 2.54 cm and thickness of 5 cm was loaded as a
target. The chamber was evacuated down to 3.4 104 Pa as a
base pressure and a working pressure of 0.15 Pa was maintained
with Ar gas. Silicon films were deposited by rf magnetron sputtering onto a 50 m thick Cu foil roughened with 700 mesh-grain

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H. Guo et al. / Materials Science and Engineering B 131 (2006) 173176

sandpaper to give several thicknesses in the range 10005300 A.

The film thickness was controlled by monitoring the deposited
film with a quartz vibrating microbalance mounted near the substrate in the vacuum chamber. The amount of silicon deposited
was calculated assuming a density of 2.33 g cm3 for the silicon
thin film.
X-ray diffraction (XRD) was carried out over the 2 range
from 10 to 110 using a Rigaku D/max-A diffractometer with
Cu K radiation. The surface morphologies of the deposited
silicon thin film were observed with a Hitachi S-3500 N scanning electron microscope (SEM), and the microcosmic particle
morphology of Si film was observed by transmission electron
microscope (TEM, JEM-100CXII) and the corresponding lattice structure was identified by selected area electron diffraction
(SAED) technique. TEM sample were dispersed in ethanol and
collected on a holey micro grid supported on a copper mesh. For
electrochemical performance evaluation, half-cell studies were
performed. The obtained film was cut into the round electrode
with diameter of 0.85 cm, then it was pressed and dried at 120 C
under vacuum for 24 h. The cells were assembled in argon filled
glove-box. Metallic lithium foil was used as counter electrode.
The electrolyte was 1 M LiPF6 (Merck, battery grade) in a mixture of ethyl carbonate (EC) and dimethyl carbonate (DMC) (1:1
in vol. ratio). Celgard 2400 polyethylene was used as the separator. Cycling tests were carried out at the charge and discharge
current density of 0.5 C in the voltage range of 0.011.5 V
versus Li/Li+ by LAND BT-10 tester (Wuhan, China). Cyclic
voltammetry was performed between 0.01 and 1.6 V with scan
rate of 0.05 mV s1 .
3. Results and discussion
No reflections except those of the Cu substrate were detected
by XRD on the film deposited by rf magnetron sputtering, as
shown in Fig. 1. This suggests that the deposited Si film has
a nanostructure, where its grain size is smaller than the X-ray
coherence length, which may be difficult to be identified by XRD
technique.
thick) prepared
The SEM image of a silicon thin film (3120 A
by rf magnetron sputtering is shown in Fig. 2. Spherical large

on a rough Cu
Fig. 1. XRD pattern of a Si thin film with thickness of 3120 A
foil.

prepared by rf
Fig. 2. SEM image of a Si thin film with thickness of 3120 A
magnetron sputtering.

particles with a average size of 2 m were observed. Combined

with the XRD result that no peaks due to Si were identified, it
is reasonable to state that the spherical particles should have a
multi-crystalline structure, and the grain size inside this large
particle should be in nano-scaled. The thin film presents loose
microstructure with obvious small opening hole among different
particles. It can not only be helpful to buffering the volume
changes of Si film electrode during electrochemical reaction, but
also provide with effective pathways for Li ions transportation
and consequently contributing to higher energy density and good
cycle stability of Si film.
Fig. 3 shows the TEM image of a silicon thin film prepared
by rf magnetron sputtering. It reveals a floccules structure, no
clear grains can be observed. SAED analysis indicates that the
film is a multi-crystalline, as evidenced by the clear loops of
diffraction inserted in Fig. 3. The large particles observed by
SEM are practically aggregates of nano-sized Si grains.
The inset is the selected area electron diffraction of Si film,
showing the multi-crystalline Si characteristic.

Fig. 3. TEM micrograph of silicon film prepared by rf magnetron sputtering.

H. Guo et al. / Materials Science and Engineering B 131 (2006) 173176

Fig. 4. Cycling performance profiles of silicon film electrodes with different

thicknesses.

The cycling performance profiles of three silicon film electrodes with different thicknesses are shown in Fig. 4. All the Si
films with different thicknesses exhibit a very high capacity, suggesting that the incorporation of nanostructure electrodes into
batteries can enhance the electrochemical performance [15,16].
However, it decreases with the increase in Si film thickness,
which is in good agreement with the results that the capacity is dependent on the film thickness previously reported by

other groups [17,18]. The cycle stability of Si film with 5120 A

thickness degrades rapidly with the increasing cycle number,
suggesting that thick film is not favourable to the improvement
of capacity properties of Si film. The relatively low electrical
conductivity of Si and the relatively long diffusion distance of
Li ions in thick film should be responsible for this phenomenon.
Elucidation of this phenomenon in detail remains to be studied
in future.
Si thin film exhibits very high discharge
Though the 1210 A
capacity over 4000 mA hg1 , it shows capacity fluctuation in the
processing of electrochemical reaction. The main reason is prob Si thin film compared to other samples has
ably that the 1210 A
relatively larger surface area, thus more easily being oxidized in
the course of operation. Impurity comes into being, thus affect
the performance of electrode. It is interesting to note that the
Si film displays a high reversible specific capacity of
3120 A
3500 mA hg1 and an excellent cycling stability, the capacity
is still as high as 3150 after 25 cycles. It reveals that each silicon atom reacted with about 3.6 Li atoms, which is higher than
most of the reported results. This phenomenon is attributable
to the high roughness of Cu substance, which expands the contact area between Si film and Cu substance, leading to a much
stable electrode structure during the expansion and contraction
process of electrode caused by lithium insertion and extraction
from Si film. The loose microstructural characteristic of Si film
as revealed in Fig. 2 is certainly favorable to the diminution
of volume change, thus to the improvement of the cycling stability. Moreover, the loose structure of Si film provides more
pathways for Li ions transportation, which is also beneficial to
the cycleability of electrode. It is noticed that the first discharge
capacities of these three electrodes are over the theoretical value

175

thickness.
Fig. 5. Charge/discharge curves of Si film with 3120 A

of Si, around 4200 mA hg1 . The possible oxide existing on the

surface of Si particles should be responsible for the unconventionality. Due to the large specific surface area of Si film, it is
readily to be contaminated by oxygen during the preparation
process. In the first lithiation phase, the oxides will be reduced
to yield Li2 O resulting in the irreversible capacity, as Li cannot extract from Li2 O during the electrochemistry reaction [14].
Moreover, the formation of SEI film on the electrode surface
may also make contribution to the high initial capacity of Si
film [19].
thickness
The charge/discharge curves of Si film with 3120 A
are shown in Fig. 5. Lithium ions insert into and extract from
Si film electrode are defined as discharge and charge processes,
respectively. In the initial discharge, the potential drops rapidly
to a plateau of 0.4 V, and then decreases to 0.01 V gradually.
However, since the second cycle, this potential plateau increases
from 0.4 V to ca. 0.45 V. This voltage fluctuation may be due to
the inactive features of Si against the electrochemical reactions.
During the discharge process, Si film electrode undergoes
three-step reactions, marked A, B and C in Fig. 5. For lithiation
process, SEI film will form firstly on the particle surface before
step A during the first cycle. Step A around 0.4 V corresponds to
the formation of LiSi according to the specific capacity of lithiation. The plateau below 0.2 V (step B to C) corresponds to the
process of Li insertion into LiSi to form Li3.6 Si. For delithiation
process, these insertion processes are reversed. Li will first be
extracted from Li3.6 Si (C and B ), then from the LiSi alloy (A )
gently instead of obvious plateaus. The Si film will be reformed
when the cell is recharged to 0.8 V. However, the formation of the
SEI film is irreversible. The charge and discharge curves become
almost overlapping for the following 23 cycles, suggesting the
excellent cycleability of Si film electrode. After several cycles,
the discharge plateaus can also be observed obviously, indicating
the stable multi-crystalline structure of Si film.
Si film electrode are
Cyclic voltammetry plots of 3120 A
shown in Fig. 6. The CV plots show 3 cathodic peaks
and 2 anodic peaks, corresponding to potential plateaus in
charge/discharge curves. The peaks obtained are attributed to
the potential dependent formation and decomposition of Li-Si
alloys of different compositions [20]. The voltage only with a

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H. Guo et al. / Materials Science and Engineering B 131 (2006) 173176

ion micro-battery. Several interesting works shown in this paper

remains to be ongoing in detail in our lab.
Acknowledgement
This work was supported by National Natural Science Foundation of China (No.50371007).
References

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Fig. 6. Plots of cyclic voltammetry of Si film with 3120 A

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improvement.
4. Conclusions
Si thin film on rough Cu foil fabricated by rf magnetron sputtering shows a high reversible specific capacity and an excellent
for this expericycleability at a appropriate thickness of 3000 A
ment. Excessively thick film is apparently unfavorable not only
for the delivery capacity but also for the cycle stability. Loose
microstructure of prepared Si film is helpful to buffering the
large volume change caused by the lithiation and delithiation
of Si film and thus beneficial to the improvement of electrode
stability. Si thin film is apparently a promising anode for lithium-

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