Materials Chemistry and Physics 121 (2010) 519–522

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Materials Chemistry and Physics

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Silicon nanowire array films as advanced anode materials for lithium-ion

batteries
Rui Huang, Jing Zhu ∗
Beijing National Center for Electron Microscopy, The State Key Laboratory of New Ceramics and Fine Processing, Laboratory of Advanced Materials, Department of Materials Science
and Engineering, Tsinghua University, Beijing 100084, People’s Republic of China

a r t i c l e i n f o a b s t r a c t

Article history: Silicon nanowire array films were prepared by metal catalytic etching method and applied as anode mate-
Received 7 October 2009 rials for rechargeable lithium-ion batteries. The films completely consisted of silicon nanowires that were
Received in revised form 23 January 2010 single crystals. Aluminum films were plated on the backs of the silicon nanowire films and then annealed
Accepted 9 February 2010
in an argon atmosphere to improve electronic contact and conduction. In addition to easy preparation and
low cost, the silicon nanowire film electrodes exhibited large lithium storage capacity and good cycling
Keywords:
performance. The first discharge and charge capacities were 3653 mAh g−1 and 2409 mAh g−1 , respec-
Nanostructures
tively, at a rate of 150 mA g−1 between 2 and 0.02 V. A stable reversible capacity of about 1000 mAh g−1
Etching
Electrochemical techniques
was maintained after 30 cycles. The good properties were ascribed to the silicon nanowires which better
Electrochemical properties accommodated the large volume change during lithium-ion intercalation and de-intercalation.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction However, some untransformed silicon wafer substrate with several

hundred micrometers in thickness remained and so contributed to
Rechargeable lithium-ion batteries are important devices for the capacity of the anode [5]. In this article, silicon nanowire (SiNW)
today’s information-based mobile society. They have been applied array films with Si–Al alloy layers on the backsides were prepared
in portable electronic devices, electric vehicles and implantable and applied for rechargeable lithium-ion battery anodes. The sili-
medical devices. One of the major challenges for designing elec- con wafer substrates were completely transformed into SiNWs, so
trode materials is to combine both high lithium storage capacity the anode capacities were solely from the SiNWs. The SiNW array
and good cycling properties. Graphite commercially used in films showed much better cycling performance than that of sili-
lithium-ion batteries has good cycling performance but a rather con nanocrystals [15]. The SiNW films fabricated by us have several
low specific capacity of 372 mAh g−1 . Silicon-based negative elec- advantages as anode materials for lithium-ion batteries: first, small
trodes for lithium-ion batteries have attracted great attention due SiNW diameter better accommodates the large volume change dur-
to their high theoretical specific capacity of 4200 mAh g−1 [1–12]. ing the lithium-ion intercalation and de-intercalation processes;
However, silicon experiences a large volume change (>300%) dur- second, Si–Al alloy layers improve electronic contact and conduc-
ing lithium-ion insertion and extraction processes, which leads to tion; third, as the SiNWs form a film, the electrode does not need
structural pulverization and electrical disconnection from the cur- conducting additives or binders that will add extra weight; fourth,
rent collector. The electrical disconnection results in the rapid fade the SiNW films can be easily prepared by using metal catalytic
of the cell’s capacity. A few strategies have been brought forward etching method. The fabrication procedure is simple, cheap and
to improve the cycling stability, for example, decreasing the struc- industrially oriented.
tures to nanosize [13] or using the elemental thin films or alloys
[14]. Nanosized silicon-based anodes have shown an improved 2. Experimental details

cycle lifetime because nano-silicon can accommodate the large vol- The SiNW array films of 10 mm × 10 mm × 90 ␮m were prepared by using metal
ume change and maintain the structural integrity of the electrode catalytic etching of single-crystal p-type Si (1 0 0) wafers [16–21]. The detailed
during the lithiation/de-lithiation process [3,15]. preparation procedure is shown in Fig. 1. We first deposited silver-nanoparticle
Silicon nanowires (SiNWs) fabricated by metal catalytic etch- (AgNP) films on a silicon wafer using a mixture of HF and AgNO3 . And then the
silver-nanoparticle-covered silicon wafer was etched using a HF aqueous solution
ing of silicon wafers were used for lithium-ion battery anodes [5].
in a sealed Teflon autoclave at 50 ◦ C for 90 min. The above two steps were per-
formed twice to completely transform the silicon wafer into SiNWs. After that, the
silver nanoparticles were removed from the SiNW film using a HNO3 aqueous solu-
tion. Finally, an aluminum film with 300 nm thickness was plated on the back of the
∗ Corresponding author. Tel.: +86 10 62794026; fax: +86 10 62771160. SiNW film using thermal evaporation under vacuum (10−4 Pa) and alloyed with the
E-mail address: jzhu@[Link] (J. Zhu). SiNWs, aiming at forming a layer of good electronic conductor on the back of the

0254-0584/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/[Link].2010.02.017
520 R. Huang, J. Zhu / Materials Chemistry and Physics 121 (2010) 519–522

Fig. 1. Schematic diagram of the preparation procedure of the SiNW film electrode.

SiNW film: firstly, a thin Al2 O3 layer was formed on the surface of the aluminum
film in an O2 atmosphere at 600 ◦ C for 10 min to prevent the evaporation of the alu-
minum at such a high temperature; then, the SiNW film was annealed in an argon
atmosphere at 600 ◦ C for 1 h to form Si–Al alloy layers. The Si–Al alloy layers sig-
nificantly improved electronic contact and conduction. The mass of the SiNW film Fig. 2. Representative XRD spectrum of the SiNW film.
electrode, i.e., the SiNW film with the Si–Al alloy layers on the back, was measured
by an electronic analytical balance. The typical active mass was 6.50 mg. CR2032
coin cells were assembled in an argon-filled glove-box using the SiNW films as the Ref. [22], which indicates the axes direction of the silicon nanowires
working electrodes and lithium metal foils as the counter electrodes. The electrolyte has a preferred orientation of [1 0 0]. The result is further supported
was 1 M LiPF6 dissolved in a 1:1 (volume ratio) mixture of ethylene carbonate and
diethyl carbonate. The as-prepared samples were characterized by X-ray diffraction
by the following SEM and TEM analysis. Note that no SiO2 phase
(XRD) with Cu K˛ radiation, a scanning electron microscope (SEM) (Hitachi S-5500) and other impurities were detected, indicating the high purity of
with energy-dispersive X-ray spectroscopy (EDS) (Oxford Instrument) and a trans- the as-prepared samples.
mission electron microscope (TEM) (JEOL JEM-2010F, 200 kV). Cyclic voltammetry Fig. 3 shows SEM images of the SiNW film electrode. The diame-
was performed on a CHI660C potentiostat/galvanostat analyzer (CH Instruments,
ters of the SiNWs are in the range of 20–300 nm. It can be seen from
Inc.) at a scanning rate of 1 mV s−1 in the voltage range of 2–0.02 V. Galvanos-
tatic discharge–charge cycling was carried out on a CT2001A charge–discharge unit Fig. 3(a) and (b) that the back of the SiNW film is different from the
(LAND Inc.) in the potential range of 2–0.02 V (vs. Li/Li+ ) at current densities of front because the aluminum is plated on the back. The thickness of
150 mA g−1 and 300 mA g−1 . the SiNW film is about 90 ␮m, as measured from the cross-section
image shown in Fig. 3(c). The axes direction of the nanowires is
3. Results and discussion [1 0 0] direction which is normal to the original silicon wafer. An
EDS spectrum (Fig. 3(d)), corresponding to Fig. 3(b), confirms that
Fig. 2 shows the typical XRD pattern of the SiNW film. It can be the aluminum is distributed on the backside of the SiNW film.
seen that the peaks at 32.96◦ and 69.13◦ can be completely indexed TEM images of the SiNW shown in Fig. 4 indicate that the
as (2 0 0) and (4 0 0) of the standard cubic phase silicon, according to prepared SiNWs are single crystals and the axes direction of the

Fig. 3. Top-view SEM images of: (a) the front and (b) the back of the SiNW film electrode. (c) Cross-section SEM image of the SiNW film electrode. (d) EDS spectrum of (b).
 R. Huang, J. Zhu / Materials Chemistry and Physics 121 (2010) 519–522 521

Fig. 4. TEM images of the SiNW: (a) bright-field image and (b) HRTEM image. The
inset in (a) shows the corresponding SAED pattern.

nanowires is the [1 0 0] direction of crystalline silicon. The plane

spacings in the high resolution TEM (HRTEM) image shown in
Fig. 4(b) were measured to be 3.1 Å and 2.7 Å and the lattice planes
−
were completely indexed as (1 1 1) and (0 0 2) of silicon, respec-
tively, which is consistent with the index of the selected area
electron diffraction (SAED) pattern.
The electrochemical properties of the SiNW film electrodes were
systematically investigated. A cyclic voltammogram of the SiNW
film electrode is shown in Fig. 5(a). As both silicon and aluminum
are lithium-alloying elements, the reaction of lithium ion with the
Si–Al alloy may take place. According to the Si–Al phase diagram,
the eutectic Si–Al alloy, Al87.8 Si12.2 , is expected to form after the
SiNW film electrode was annealed at 600 ◦ C for 1 h. The mass of
the Al87.8 Si12.2 alloy, about 0.09 mg, which was calculated based
on the mass of the plated aluminum film with 300 nm in thick-
ness, is much less than that of the SiNWs, about 6.41 mg. Moreover,
the theoretical specific capacity of Al87.8 Si12.2 , about 1309 mAh g−1
[23], is much lower than that of silicon, 4200 mAh g−1 . Therefore,
the Si–Al alloy has little effect on the electrochemical performance
of the SiNW film electrode. The neglectable influence of the Si–Al
alloy is also supported by the current–potential characteristics of
the cyclic voltammogram that are the same as previous experi-
ments on silicon anodes [3] and different from experiments on Si–Al Fig. 5. (a) Cyclic voltammogram for the SiNW film electrode from 2.0 to 0.02 V at
alloy anodes [23]. A cathodic peak at 20 mV is associated with the a scan rate of 1 mV s−1 . (b) Galvanostatic discharge/charge curves of the SiNW film
insertion of lithium ion into the SiNWs. An anodic peak, located at electrode cycled at a current density of 150 mA g−1 between 2 and 0.02 V. (c) Cycling
about 620 mV, corresponds to the extraction of lithium ion from behavior and Coulombic efficiency of the cell with the SiNW film. The data for the
theoretical capacity of lithiated graphite (dashed line) are shown as a comparison
the SiNWs. The redox peaks should be owing to the reaction of sili-
to display the improvement when using the SiNW film electrode.
con and lithium forming Lix Si alloys. The magnitude of the current
peaks increases with cycling because more material is activated to
react to lithium with each scan [9]. The discharge–charge cycling than 30 cycles, which is much higher than the capacity of the sili-
properties were evaluated between 2 and 0.02 V up to 31 cycles con nanocrystals after 31 cycles that is 650 mAh g−1 [15]. The high
as shown in Fig. 5(b) and (c). Fig. 5(b) shows the 1st, 5th, 10th, capacity and long cycle lifetime of the SiNW film electrode demon-
15th, 25th and 30th discharge–charge cycle curves of the SiNW strates the advantages of our SiNW anode design: first, the Si–Al
film electrode at a current rate of 150 mA g−1 between 2 and 0.02 V. alloy layers act as good electronic conductors; second, the small
The first discharge and charge capacities of the SiNW film elec- SiNW diameter better accommodates the large volume change dur-
trode are 3653 mAh g−1 and 2409 mAh g−1 , respectively, indicating ing lithium-ion insertion/extraction process [3]. The same cell was
a Coulombic efficiency of 66% and an initial ratio of the irreversible further evaluated for rate capability, which is shown in Fig. 5(c).
capacity of 34%. The initial irreversible capacity loss should mainly When the current rate is increased to 300 mA g−1 , a stable capacity
originate from irreversible trapping of inserted lithium ions by the of about 800 mAh g−1 can be achieved. When the current density is
host materials and/or formation of a solid/electrolyte interface (SEI) reduced back to 150 mA g−1 , a stable high capacity of 1000 mAh g−1
layer on the surface of the active material. The initial irreversible can be resumed.
capacity loss (more than 1000 mAh g−1 ) is a little high, which Fig. 6 shows TEM images of the SiNW after 31 cycles (after charg-
should be reduced by some methods such as coating carbon [4] ing to 2 V). The cycled nanowires are constituted of amorphous
before the SiNW film electrode can be used in commercial batter- and crystalline phases, indicating that original crystalline struc-
ies. Coulombic efficiency is above 90% after the first cycle (Fig. 5(c)). ture is mostly collapsed. A similar phenomenon was observed in
In addition, the SiNW film electrode exhibits good cycling stabil- SiNWs after 10 cycles [3]. Compared to the pristine sample, some
ity as shown in Fig. 5(c). While the capacity decays gradually over SiNWs are broken into aggregated nanoparticles probably due to
the first 15 cycles, it stabilizes to around 1000 mAh g−1 for more nonuniform volume changes among nanowires.
522 R. Huang, J. Zhu / Materials Chemistry and Physics 121 (2010) 519–522

Acknowledgement

This work is financially supported by National 973 Project of

China, Chinese National Nature Science Foundation.

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