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Scalable synthesis of silicon nanosheets from sand


as an anode for Li-ion batteries†
Cite this: Nanoscale, 2014, 6, 4297
Won-Sik Kim, Yoon Hwa, Jung-Hoo Shin, Myung Yang, Hun-Joon Sohn
and Seong-Hyeon Hong*

The silicon nanostructure is a promising candidate for an anode of Li-ion batteries due to its high theoretical
capacity. In this work, we have demonstrated the scalable synthesis of Si nanosheets from natural sand by
magnesiothermic reduction, and suggested a new formation mechanism for Si nanosheets. In the
suggested mechanism, an Mg2Si intermediate phase was formed at an early stage of the reduction
process, which leads to the two-dimensional Si nanostructure. The synthesized Si nanosheets have a
leaf-like sheet morphology ranging from several ten to several hundred nanometers, and show
Received 8th October 2013
Accepted 26th January 2014
comparable electrochemical properties to the commercial Si nanopowder as an anode for lithium ion
batteries. For the improved electrochemical performance, Si nanosheets are encapsulated with reduced
DOI: 10.1039/c3nr05354g
graphene oxide (RGO), and the RGO-encapsulated Si nanosheet electrode exhibits high-reversible
www.rsc.org/nanoscale capacity and excellent rate capability.

yields 3-dimensional macroporous or mesoporous Si. Recently,


Introduction free-standing ultrathin Si nanosheets were prepared by mag-
The demand for high-energy, high-power density, and high rate- nesiothermic reduction, but graphene oxide (GO) was used as a
capability lithium ion batteries (LIBs) has increased for use in sacricial template, and the synthesis was a rather complicated
hybrid electric vehicles (HEVs), back-up electricity storage units, and high-cost process.11
and light-weight and portable electric devices.1 Carbon-based In this study, Si nanosheets are successfully prepared by
materials have been the most common anode materials in magnesiothermic reduction using commercial sand as a
commercial LIBs, but their specic capacity is relatively low precursor and a template. This is the rst attempt and low-cost
(372 mA h g1) with a poor rate capability.2–4 Silicon (Si) is a scalable process for the preparation of Si nanostructures
promising alternative, because it has the highest theoretical (2-dimensional silicon nanostructures) without any specic
capacity (Li15Si4, 3579 mA h g1 at room temperature) and low template. A new formation mechanism of Si nanosheets during
operating voltage (0.1 V vs. Li/Li+).5–8 However, silicon-based magnesiothermic reduction is also proposed. In addition, Si
electrodes undergo a large volume change during cycling, which nanosheets are encapsulated with reduced graphene oxide
causes pulverization and loss of electrical connectivity leading (RGO) to enhance the electrochemical properties. The RGO
to poor cycle performance. To overcome this problem, various Si encapsulation is expected to increase the electrical conductivity
nanostructures have been fabricated including nanoparticles, and prevent the pulverization of Si nanosheets resulting from
nanowires, nanosheets, nanohollows, and nano-core–shells.9–13 the large volume expansion during lithium insertion/extraction.
These Si nanostructures show relatively excellent electro-
chemical properties, but the fabrication of nanostructured Si
commonly requires complicated routes with toxic precursors or Results and discussion
high-cost techniques such as CVD (chemical vapor deposi-
The synthesis procedure of RGO-encapsulated Si nanosheets is
tion).9,10,14–16 The magnesiothermic reduction of SiO2 is an
schematically presented in Fig. 1. Commercially available sand
attractive and cost-effective method to obtain nanostructured
was crushed by planetary ball milling, and then mixed with
Si.11,12,17–20 It requires a lower processing temperature and a
magnesium (Mg) powder as a reducing agent. The magnesio-
shorter reaction time, compared to the other reduction
thermic reduction was carried out at 700  C, which yielded the
processes.21–23 The magnesiothermic reduction of SiO2 generally
multi-layered nanosheets. The recovery of Si nanosheets was
achieved by two-stage leaching using HCl and HF solutions. The
Department of Materials Science and Engineering and Research Institute of Advanced
magnesium-containing compounds (MgO and Mg2Si) were
Materials, Seoul National University, Seoul 151-744, Republic of Korea. E-mail:
shhong@snu.ac.kr removed by HCl, and the unreacted SiO2 was etched out by HF.
† Electronic supplementary information (ESI) available. See DOI: Finally, RGO was uniformly coated onto Si nanosheets by the
10.1039/c3nr05354g APTES modied process.24

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conrms the 2-dimensional sheet morphology (Fig. 2b). The


spots and rings in the selected area diffraction (SAED) pattern
are indexed to be Si (ICDD #27–1402). Consequently, well-crys-
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tallized Si sheets are synthesized from the commercial sand


using a facile magnesiothermic reduction reaction. The high-
magnication TEM image indicates that the Si sheets are
composed of several nanosheets (Fig. 2d). The lattice fringes are
clearly seen in the high-resolution TEM image of the individual
nanosheet revealing that the Si nanosheet is a single crystal
(Fig. 2e). The determined interplanar spacing of 0.314 nm
corresponds well with the (111) plane of the Si diamond struc-
ture. The magnesiothermic reduction of silica (SiO2) generally
Fig. 1 Schematic illustration of the synthesis of RGO-encapsulated Si
nanosheets. yields 3-dimensional macroporous or mesoporous silicon.17–20
Thus, the Si nanosheets obtained in this study appear to be
formed with a different mechanisim or route from that of the
The commercial sand comprises irregularly shaped particles conventional magnesiothermic reduction.
with a rough surface, and the particle size is 200 mm (see the The phase developments during magnesiothermic reduction
ESI, Fig. S1a†). The particle fracture occurred during the plan- and acid leaching were investigated by X-ray diffraction (XRD),
etary ball milling, and the particle size was signicantly and the patterns for milled sand, as-reduced, HCl-etched, and
reduced. The milled powder exhibits a fractured morphology HF-etched specimens are shown in Fig. 3. The milled sand is a
with a wide size distribution (Fig. S1b†). Flat cleavage-like crystalline quartz and no phase change is observed aer plan-
surfaces are discernible in the micron-sized particles. Without etary ball milling (Fig. 3a). The XRD pattern reveals that the as-
the ball milling process, similar Si nanosheets were obtained, reduced specimen is composed of Si, MgO, and unreacted SiO2
but the amount of obtained Si nanosheets was small. Thus, we (Fig. 3b). A stoichiometric weight ratio of SiO2 : Mg ¼ 1 : 0.8 (or
have employed the ball milling to crush the sand and produce a 1 : 2 molar ratio) based on the following reaction SiO2 + 2Mg ¼
more at surface, which increases the production of Si nano- Si + 2MgO is used, but unreacted SiO2 is still present. The
sheets. Fig. 2a shows a representative scanning electron volatilization of gaseous Mg and/or the formation of interme-
microscopy (SEM) image of as-synthesized Si. The obtained Si diate phases (magnesium silicide, Mg2Si) have been attributed
has a leaf-like sheet morphology, and the size ranges from to the presence of unreacted SiO2 in the magnesiothermic
several ten to several hundred nanometers. The silicon sheets reduction reaction.25 The peak broadening is observed in the
appear to be exible and very thin although the exact thickness diffraction patterns for Si and MgO, which can be attributed to
cannot be estimated from the SEM image. The specic surface the formation of nano-crystallites. MgO is completely dissolved
area determined from the nitrogen absorption–desorption in HCl solution (Fig. 3c), and unreacted SiO2 is removed by HF
isotherm is 55.8 m2 g1, which is larger than that of commercial solution, which results in the crystalline Si (Fig. 3d).
Si nanopowder (33.7 m2 g1) (Fig. S2†). The low-magnication To nd out the formation mechanism of Si nanosheets
transmission electron microscopy (TEM) image further during magnesiothermic reduction, the mixture of milled sand
and magnesium was heat-treated at different temperatures, and
the corresponding XRD patterns are presented in Fig. 4a. At

Fig. 2 (a) FESEM, (b) low-magnification TEM, (c) selected area electron
diffraction (SAED) pattern, (d) high-magnification TEM, and (e) high- Fig. 3 XRD patterns of (a) ball-milled, (b) as-reduced, (c) HCl-etched,
resolution TEM images of as-synthesized Si nanosheets. and (d) HF-etched samples.

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Fig. 4 (a) Ex situ XRD patterns of as-reduced sand at different temperatures. (b–d) TEM images of HCl-etched products (reduced at 700  C for 4
h). (e) Schematic illustration of the formation of Si nanosheets.

500  C, the as-reduced specimen was composed of Mg2Si, MgO, (reduced at 700  C) was examined by TEM to reveal the micro-
and unreacted SiO2. Surprisingly, Mg2Si was found, and Si was structure of the reduction products (Fig. 4b). The low-magni-
not detected. The peak for Si appeared at 550  C. Upon cation TEM image showed that HCl-etched powder had either a
increasing the reduction temperature, the peak intensity for Si hollow or yolk/shell-like structure. The high-magnication
and MgO increased while the intensity for Mg2Si and SiO2 image indicated that the yolk/shell structure consisted of three
decreased. At 650  C, the Mg2Si phase completely disappeared, parts: a dense shell, a porous middle layer, and a dense core
and no further phase change occurred at higher temperatures. (Fig. 4c). The core was the unreacted SiO2, implying that the
The obtained results indicate that Mg2Si is formed as an yolk/shell-like powder was the on-going reduction product. The
intermediate phase at an early stage of the reduction process, outer shell was identied as crystalline Si with planar defects,
and Si is produced by consuming Mg2Si and SiO2. Generally, the and the middle layer was composed of 5 nm Si nanoparticles
magnesiothermic reduction of SiO2 is expressed as follows: (Fig. 4d). The distinctive microstructure of Si suggests that two
layers were formed in the different routes. Assuming the tran-
SiO2 + 2Mg / Si + 2MgO (1) sient presence of Mg2Si during the magnesiothermic reduction,
the following formation mechanism of Si nanosheets is
proposed (Fig. 4e). Initially, Mg2Si is formed between Mg and
For the complete reduction of SiO2, an Mg/SiO2 molar ratio SiO2 through reaction (3). The excess Si in Mg2Si is precipitated
of 2.0 is required. Recently, it was reported that Mg2Si is formed as a Si layer, while Mg2Si reduces SiO2 into Si through reaction
as an intermediate phase even below the stoichiometric ratio (2) forming the Si/MgO nanocomposite. The unreated Mg and
(1.5),25 and Mg2Si is further reduced into Si through the MgO (or Mg2Si) are dissolved with HCl, which results in the
following reaction: dense-Si/porous-Si/unreacted SiO2 core–shell structure. Finally,
Si with a nanosheet morphology is obtained by removing the
Mg2Si + SiO2 / 2Si + 2MgO (2)
unreacted SiO2 and nanoparticle Si with HF solution. The
Based on the previous report and the results obtained in this precipitation of Si from Al–Mg–Si alloys with an excess of Si has
study, the following overall reactions are proposed for the been reported previously.26,27 The reduction of SiO2 by Mg2Si
magnesiothermic reduction of SiO2: and the synthesis of Si with the nanosheet morphology are
under investigation. For further evidence, as-reduced speci-
4Mg + SiO2 / Mg2Si + 2MgO (3) mens at 550 and 600  C were examined by TEM. The cross-
sectional TEM specimens were prepared by ultra-microtome.
Mg2Si + SiO2 / 2Si + 2MgO (4) The presence of Mg2Si, MgO, and Si was conrmed by SAED
patterns, but the individual layers could not be distinguished
These two reactions are thermodynamically possible (see the TEM images of microtomed samples, Fig. S4†).
(Fig. S3†) and reaction (3) has more negative Gibbs free energy To enhance the electrochemical properties, Si nanosheets
at the reduction temperatures. Thus, it is suggested that the are encapsulated with RGO by the APTES modied process. The
magnesiothermic reduction of SiO2 can occur via an interme- SEM micrograph shows that RGO-encapsulated Si maintains
diate Mg2Si phase and the formation of Mg2Si might result in the sheet-like morphology (Fig. 5a). The individual nanosheets
the nanosheet morphology of Si. The HCl-etched specimen are well separated with increased thickness, indicating that the

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Fig. 5 (a) FESEM, (b) low-magnification TEM, (c) selected area electron
diffraction (SAED) pattern, (d) high-magnification TEM, and (e) high-
resolution TEM images of RGO-encapsulated Si nanosheets.

Si nanosheets are thoroughly covered with RGO. The high-


magnication TEM image further conrms the sheet
morphology (Fig. 5b). The SAED pattern corresponds to that of
Si (Fig. 5c), but the high-resolution TEM image clearly shows
that the crystalline Si was well coated with the layered RGO of
5–10 nm thickness (Fig. 5d). In addition, the Raman spectrum
of RGO-encapsulated Si nanosheets displays two broad peaks
(D band at 1367 cm1 and G band at 1582 cm1) revealing the
presence of RGO in the sheet-like morphology (see the ESI,
Fig. S5†).
The discharge/charge voltage proles of the Si nanosheet
and RGO-encapsulated Si nanosheet electrodes are shown in
Fig. 6a. The cycling experiments are conducted in the voltage
Fig. 6 (a) Voltage profiles of Si nanosheet and RGO-encapsulated Si
range between 0.0 and 2.0 V (vs. Li/Li+) at a current density of nanosheet electrodes after 1, 2, 10, 30, and 50 cycles at 200 mA g1
200 mA g1. The shape of the voltage proles is similar to that of between 0.0 and 2.0 V, (b) cyclability of commercial Si nanopowder, Si
a typical Si electrode.12,19,20,28 The initial discharge and charge nanosheet, and RGO-encapsulated Si nanosheet electrodes, and (c)
capacities of the Si nanosheets are 3563 and 2431 mA h g1, rate capability of RGO-encapsulated Si nanosheet electrode between
0.01 and 2.0 V.
respectively. The RGO-encapsulated Si nanosheets shows
slightly higher capacities (3769 and 2625 mA h g1, respec-
tively). The coulombic efficiency of the rst cycle was 70% for
both electrodes. The observed values for RGO-encapsulated Si reported graphene/nano-sized Si composites,31 the RGO
nanosheets are higher than those for the previously reported encapsulation effect was more signicant, and the improved
nano-sized Si/RGO composite.29 The lower capacities of the cycle retention in this study can be attributed to the better
nano-sized Si/RGO composite can be attributed to the existence encapsulation of Si with RGO due to the nanosheet morphology.
of SiOx due to a high reaction activity of 5 nm Si. As a reference, However, the capacity degradation was still observed in the
the cyclic performance of commercial Si nanopowder was per- RGO-encapsulated Si nanosheet electrode and further surface
formed (Fig. 6b) and the obtained results are similar to the treatment is required to improve the cycle performance. The
previous studies.30 The fabricated Si nanosheet electrode rate capability of the RGO-encapsulated Si nanosheet electrode
exhibits the comparable reversible capacity to the commercial is promising and it exhibited a capacity of 1113 mA h g1 even at
Si nanopowder (Fig. 6b), even though it was synthesized from a high current density of 3 A g1 (Fig. 6c).
sand. As expected, the RGO-encapsulated Si nanosheets showed
the improved cycle retention. The cycle performance of the Experimental procedures
RGO-encapsulated Si nanosheet electrode at a high rate (500 mA
g1) exhibited the similar tendency with slightly lower capacity Synthesis of silicon nanosheets
(see the ESI, Fig. S6†). The average capacity of ve cells was 1 g of commercial sand (Ficher Scientic) was crushed by
1762 mA h g1 aer 25 cycles and the standard deviation was planetary ball milling for 4 h. The crushed sand was washed
87 mA h g1. Thus, the electrochemical data were quite with D.I. water, dried, and calcined at 600  C for 1 h to remove
consistent and reproducible. Compared to the previously the organic impurities. Then, 0.4 g of calcined sand and 0.32 g

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of magnesium (325 mesh, Stream) were hand-mixed. The active material within the voltage range between 0.0 V and 2.0 V
mixture was heat-treated at 700  C for 4 h under a 5 vol.% H2/N2 (vs. Li/Li+).
atmosphere. The obtained brown products were washed with
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hydrochloric acid and hydrouoric acid solution (10 wt%).


Conclusions
Synthesis of graphene oxide (GO) In summary, we facilely synthesized the Si nanosheets from
natural sand by magnesiothermic reduction. The thin Si
GO was synthesized through Hummers' method by reacting
nanosheets were precipitated from an intermediate Mg2Si
commercially available graphite akes (Sigma Aldrich) in a
phase to make the composition balance of Mg2Si. The synthe-
mixture of H2SO4, NaNO3, and KMnO4.31 Aer completion of the
sized Si nanosheets were well crystallized and showed compa-
reaction, H2O2 was added to the reaction vessel. The brown GO
rable electrochemical properties to commercial Si nanopowder
was obtained by ltering, washing with 1 M HCl and D.I. water
as an anode for lithium rechargeable batteries, and further
twice, and drying.
enhancement was achieved by RGO encapsulation. The RGO-
encapsulated Si nanosheets showed excellent rate capability. In
RGO encapsulation this work, we have demonstrated the facile synthesis of an Si
0.1 g of prepared silicon nanosheets was dispersed in 100 mL of nanostructure from natural sand with improved electro-
absolute ethanol, and 2 mL of APTES was added.24 Aer stirring chemical properties, and suggested a new formation mecha-
for 4 h, the solution was washed and centrifuged. Then, 0.15 g nism for Si nanosheets.
of synthesized GO was dispersed in 80 mL of water by tip-
sonication, and 20 mL of silicon nanosheet ethanol solution
was added to the prepared GO solution. Aer stirring for 4 h, the
Acknowledgements
solution was washed, centrifuged, and dried. The obtained This work was supported by the National Research Foundation
composite powder was reduced at 400  C for 6 h under a 5 vol.% of Korea (NRF) grant funded by the Korea Government (MSIP)
H2/N2 atmosphere. (NRF-2012R1A2A4A01008226).

Characterization
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