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Amorphous Si/SiOx/SiO2 nanocomposites via facile scalable synthesis as

anode materials for Li-ion batteries with long cycling life{
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Published on 23 October 2012 on http://pubs.rsc.org | doi:10.1039/C2RA22187J

Fang Dai, Ran Yi, Mikhail L. Gordin, Shuru Chen and Donghai Wang*
Received 17th September 2012, Accepted 22nd October 2012
DOI: 10.1039/c2ra22187j

Novel Si/SiOx/SiO2 nanocomposites were prepared via a facile

and scalable wet synthesis. The amorphous structure, nanoscale
particle size, and composition of the Si/SiOx/SiO2 material were
characterized and its electrochemical performance as an anode for
Li-ion batteries was evaluated. The material shows a stable
cycling capacity of y600 mA h g21 over 350 cycles with high
coulombic efficiency of .99%.
High-energy-density lithium ion batteries with long cycling lives have
been regarded as promising energy storage devices for plug-in hybrid
and electric vehicles.1 The development of high energy Li-ion
batteries requires new anode materials with higher energy density
than that of conventional graphite-based materials. Silicon has been
considered as a promising high-energy anode because of its
abundance and high theoretical capacity (.3500 mA h g21).2 In
spite of these advantages, the practical use of Si has thus far been
hindered by significant capacity decay mainly due to the large
volume changes (y300%) and unstable solid electrolyte interphase
(SEI) during the charging and discharging processes.3
Many attempts to improve the cycling stability of Si anodes have
been made, such as designing porous structures,4 nanocrystalline
particles,5 nanowires,6 hollow structures and core-shell structures.7
Besides metallic Si, Si alloys and Si-containing composites have also
been investigated. Among those, SiOx-based composites are one of
the most attractive candidates8 because of their excellent cycling
performance.8j,9 During the lithiation process of SiOx, lithium oxide
and lithium silicates are irreversibly formed and act as a buffer layer
to tolerate the large volume change of the Si and facilitate formation
of stable SEI layers.8f,h,9a,10 Previous studies also show that nanosized SiOx materials are less susceptible to pulverization due to
mechanical fracture by volume change during the charge and
discharge processes, and thus have superior cycling stability to larger
particles.11 For example, Chen et al. prepared an SiOx nanotube
material which shows a reversible capacity of 940 mA h g21.12 Park
et al. reported a reversible capacity of 1280 mA h g21 for a carbon
coated Si/SiO/SiO2 composite.8k Yamamoto et al. showed a SiO/
carbon nanofiber composite with a reversible capacity of 890 mA h
g21.13 However, only limited cycling performance (,100 cycles) has
Department of Mechanical and Nuclear Engineering, The Pennsylvania
State University, University Park, Pennsylvania 16802, United States.
E-mail: dwang@psu.edu
{ Electronic supplementary information (ESI) available. See DOI: 10.1039/
c2ra22187j

12710 | RSC Adv., 2012, 2, 1271012713

been reported for SiOx-based anode materials, except for the SiO/C
composite reported by Osaka et al. (842 mA h g21 after 7200
cycles).8l
To date, most synthesis routes of SiOx materials are through either
oxidation of silicon or reduction of SiO2.8e,g,j Preparation of nanosized SiOx in these manners is difficult because it requires nano-sized
precursors that are themselves difficult to generate. This is especially
true for the oxidation method, as preparation of the nano-sized Si
precursor is usually performed by vapour deposition techniques and
is thus hard to scale up, which has hindered the application of the
corresponding SiOx materials in Li-ion batteries.14 In addition,
carbon coating is indispensable for most SiOx materials in order to
achieve good cycling performance, thus making the preparation
process more complicated.8b,c,gj
Here we report a new Si/SiOx/SiO2 anode material prepared via a
facile and scalable route. Introducing SiCl4 as the Si source, the
synthesis includes the formation of chloride-capped Si precursor by
reduction of the SiCl4 in solution, followed by oxidation of the
precursor. The characterization results suggest formation of
amorphous Si/SiOx/SiO2 composite with nanoscale particle sizes.
Without further surface or structural modification, the material
shows an initial charge capacity of 610 mA h g21, good cycling
stability (maintained at .600 mA h g21 after 350 cycles), and
excellent coulombic efficiency after the initial cycles (average .99%).
The preparation of the Si/SiOx/SiO2 nanocomposite was carried
out in a glovebox filled with Ar. The synthesis route (see ESI{) is
shown in Scheme 1. Sodium potassium alloy (NaK) was slowly
added to a toluene solution of SiCl4 via a syringe. The reaction
mixture was then heated under reflux for four hours. Fine black
particles were formed during the reflux process. After treatment with
diethyl ether solution of hydrogen chloride, the color of the particles
changed to brown. These final products were removed from the
glove box, washed with excess de-ionized water, and collected by
filtration. The as-prepared material was annealed at 500 uC in Ar
before use.

Scheme 1 Synthesis route of the Si/SiOx/SiO2 nanocomposite.

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Unlike other reducing reagents such as sodium naphthanide,

which are used to obtain nanocrystalline Si,15 the NaK reducing
reagent helps form an amorphous Si structure. The reduction of
SiCl4 by NaK first forms chloride-terminated silicon particles. The
terminal chloride ligands then react with H2O to form a terminal
hydroxide structure (eqn (1)).15c Some hydrogen-terminated particles,
which may be generated under the acidic conditions, also react with
H2O to form terminal hydroxide structure (eqn (2)). H2O penetrates
into the particle structure and the oxygen inserts into SiSi bonds to
form silicon oxide (eqn (3)). This Si oxidation process is similar to
oxidation of a porous Si surface.16
SiCl + H2O A SiOH + HCl

(1)

SiH + H2O A SiOH + H2

(2)

(SiSi)SiOH + 2H2O A (SiOSiO)SiOH + 2H2

(3)

The oxygen content of the Si/SiOx/SiO2 nanocomposite was

determined to be 42 wt% by thermogravimetric analysis (TGA) (Fig.
S1{). Thus the material as a whole is identified as SiO1.3. The particle
size and morphology were examined by transmission electron
microscopy (TEM). The TEM images clearly show that the Si/
SiOx/SiO2 takes the form of irregular aggregated particles with an
average primary particle size of about 10 nm (Fig. 1A and Fig. S2{).
In addition, no ordered lattice fringes are observed in the highresolution TEM image, which shows the particles are amorphous
(Fig. 1B). The X-ray powder diffraction (XRD) pattern of the
nanocomposite after calcination is shown in Fig. 2A. It shows two
broad peaks located at about 2h = 28u and 50u, which are similar to
those of SiO.8a,h,17 No obvious Si peaks are observed. Brunauer
EmmettTeller (BET) surface area analysis indicates that the
nanocomposite has a surface area of 257.5 m2 g21. The isothermal
sorption profile suggests that the material contains mesopores with
BarrettJoynerHalenda (BJH) pore diameter of about 10 nm,
which are the voids between aggregated nanoparticles (Fig. S3{). The
energy-dispersive X-ray (EDS) spectrum confirms the presence of
both silicon and oxygen (Fig. S4{). The X-ray photoelectron
spectroscopy (XPS) of the nanocomposite shows a strong peak at
about 103 eV with a broad shoulder, suggesting formation of SiOx
and SiO2 (Fig. 2B).4a,5,7c,18 The other small peak at about 100 eV
indicates a small amount of Si present in the particle.4a,5,7c,18 The
appearance of the Si signal could be attributed to the Si remaining
inside the particle without oxygen insertion. However, according to

Fig. 1 (A) TEM image of Si/SiOx/SiO2 nanocomposite. (B) HRTEM

image of the Si/SiOx/SiO2 nanoparticle in the composite.

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Fig. 2 Characterization of the Si/SiOx/SiO2 nanocomposite: (A) XRD

pattern and (B) XPS spectrum.

the HRTEM and XRD studies, even this remaining Si is amorphous

(Fig. 1B). The integration of the peaks revealed that the ratio of
metallic Si and silicon oxides was 1 : 5. It is impossible to give the
exact ratio between SiOx and SiO2 due to the unknown x number of
the SiOx.
The structure of the Si/SiOx/SiO2 nanocomposite was further
investigated by FT-IR spectroscopy (Fig. 3). The spectrum shows a
peak at 1082 cm21, which is assigned to the vibrational stretch of Si
OSi belonging to silicon oxides (SiOx and SiO2).16c,19 The peak at
2260 cm21 suggests the appearance of OySiHx, which arises from
the oxidation of the surface silicon hydride structure. The broad peak
around 3700 cm21 is ascribed to SiOH vibrational stretch.16c,19
According to the XPS and FT-IR results, the particle structure could
be described as a mixture of Si and silicon oxides which is terminated
by oxide (O), hydroxide (OH), and hydride (H) groups. The
appearance of the vibrational stretches of SiOSi, OySiHx, and
SiOH is evidence that the formation of the SiOx is due to the
reaction of the functional group-terminated Si surface with H2O (eqn
(3)). The appearance of the terminal oxide group (O) suggests the
formation of the SiO2 from the full oxidation of the Si.19 The exact
ratio of SiOx and SiO2 is not clear yet due to the unknown number x
of SiOx.
The electrochemical performance of the Si/SiOx/SiO2 material as
an anode for Li-ion batteries was tested using CR2016 coin-type
half-cells. The dischargecharge profiles of electrodes during the 1st,
2nd, 100th, and 350th cycles at 200 mA g21 between 0.02 V and 1.5
V are shown in Fig. 4A. The first discharge capacity is 2190 mA h
g21, and the capacity stabilizes at y650 mA h g21 for the cycles
thereafter. The dischargecharge profiles show little change from the
2nd cycle to the 350th cycle. The low first cycle coulombic efficiency
(y30%) may be attributed to the formation of an SEI layer and

Fig. 3 FT-IR spectrum of the Si/SiOx/SiO2 nanocomposite.

RSC Adv., 2012, 2, 1271012713 | 12711

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area and thus better electrical contact with the conductive additive
than is the case for larger particles. In addition, fracture can be
avoided because the tension generated in nanoparticles can be easily
relaxed due to their small size.11 The silicon oxides also act as buffer
layers for the large volume change of the Si during the dischargingcharging process.8f,8h,9a,10a,b Finally, the amorphous structure of the
composite could prevent pulverization due to the isotropic expansion
during lithium insertion, as compared to the highly anisotropic
expansion of crystalline Si. The capacity loss of the material is mainly
due to the irreversible formation of lithium oxides and lithium
silicates during lithiation of the SiOx.8j,9a,20 However, although the
use of SiOx rather than metallic Si requires sacrificing some capacity,
this formation of buffer layers grants the material excellent volume
change tolerance.8e,8g,8l,9b,10a
In conclusion, we synthesized a novel amorphous Si/SiOx/SiO2
composite with nanoscale particle size. The solution-based synthesis
under mild reaction conditions is easy to scale up. Electrochemical
characterization reveals that the material has a very stable capacity
and solid rate performance. The silicon oxide-containing amorphous
structure of the Si/SiOx/SiO2 nanocomposite can effectively accommodate the volume change of Si during the dischargingcharging
process. The relationship between the content of silicon oxides in the
composite and the anode performance, such as the first cycle
coulombic efficiency and cycling stability, is under further investigation.
This work was supported by the Assistant Secretary for Energy
Efficiency and Renewable Energy, Office of Vehicle Technologies of
the U.S. Department of Energy under Contract No. DE-AC0205CH11231, Subcontract NO. 6951378 under the Batteries for
Advanced Transportation Technologies (BATT) Program.
Fig. 4 Electrochemical performance of the Si/SiOx/SiO2 nanocomposite.
(A) Dischargecharge profiles obtained after 1st, 2nd, 100th and 350th
cycles. (B) Charge capacity and coulombic efficiency of 350 cycles between
0.021.5 V. (C) Charge capacity at various rates from 0.4 A g21 to 8 A g21.

irreversible formation of lithium oxides and lithium silicates within

the nanocomposites.8j,9a,20
The nanocomposite shows good cycling stability. The cycling
performance at 200 mA g21 between 0.02 V and 1.5 V is shown in
Fig. 4B. After the initial cycle, the capacity increases until it peaks at
650 mA h g21 after about 30 cycles. This increase is attributed to the
slow activation of the Si/SiOx-containing material. The material then
shows good capacity retention after 100 cycles (.99%) and after 350
cycles (.95%) compared with the peak capacity. The coulombic
efficiencies reach 99.5% after around 30 cycles and remain at
.99.5%.
The rate performance of the nanocomposite anode was also tested
at current densities of 0.4 A g21, 0.8 A g21, 2 A g21, 4 A g21, and 8
A g21. The results are shown in Fig. 4C. The anode shows good
coulombic efficiency (.99%) even at a current density of 8 A g21.
The capacity at this current density is still 375 mA h g21, which is
comparable to the theoretical capacity of graphite. A capacity of
.630 mA h g21 is again observed when the current density is reset to
0.4 mA g21 after 60 cycles, showing that the electrode was not
damaged by the high rate test.
The excellent cycling stability of the Si/SiOx/SiO2 nanocomposite is
attributed to its nanoscale particle size and the amorphous SiOxcontaining structure. The small particle size leads to higher surface
12712 | RSC Adv., 2012, 2, 1271012713

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