Journal of Power Sources 405 (2018) 61–69

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Journal of Power Sources

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Clay minerals derived nanostructured silicon with various morphology: T

Controlled synthesis, structural evolution, and enhanced lithium storage
properties
Qingze Chena,b, Shaohong Liuc, Runliang Zhua,∗, Dingcai Wuc, Haoyang Fua,b, Jianxi Zhua,
Hongping Hea,b
a
CAS Key Laboratory of Mineralogy and Metallogeny, Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou, 510640, China
b
University of Chinese Academy of Sciences, Beijing, 100049, China
c
Materials Science Institute, PCFM Lab and GDHPRC Lab, School of Chemistry, Sun Yat-sen University, Guangzhou, China

H I GH L IG H T S G R A P H I C A L A B S T R A C T

• Three Si nanostructures with various

morphology were successfully synthe-
sized.
• The morphology of nanostructured Si
greatly depended on nature of clay
minerals.
• 2D silicon from montmorillonite ex-
hibited the best electrochemical per-
formance.
• The structure-property relationship of
various Si nanostructures was estab-
lished.

A R T I C LE I N FO A B S T R A C T

Keywords: Nanostructuring is an effective strategy to enhance the structural and cycling stability of silicon anodes in li-
Nanostructured silicon thium-ion batteries. However, a controllable and cost-effective method for synthesizing nanostructured silicon
Clay minerals with various morphology is still a challenge. Herein, we synthesize zero-dimensional, two-dimensional, and
Controlled synthesis three-dimensional silicon nanostructures directly using low-cost and abundant clay minerals as precursors
Structural evolution
without any pretreatment and templates. Our results show that the morphology and microstructure of the re-
Lithium-ion battery anodes
sulting nanostructured silicon strongly depend on the architectural features of clay minerals, i.e., zero-dimen-
sional silicon from palygorskite, two-dimensional silicon from montmorillonite, and three-dimensional silicon
from halloysite. The silicon nanostructures show large specific surface area (over 80 m2 g−1) and hierarchical
pore structure. As anodes in lithium-ion batteries, two-dimensional nanostructured silicon from montmorillonite
exhibits the best electrochemical performance (i.e., 1369 mAh g−1 at 1.0 A g−1 with a capacity retention of 78%
over 200 cycles). This work provides a universal guideline from clay minerals to various silicon nanostructures
via an economical and scalable strategy, and reveals the fundamental structure-property relationship of different
silicon nanostructures synthesized under the same condition, which would contribute to the large-scale pro-
duction of high-performance and low-cost silicon-based anodes in lithium-ion batteries.

∗
Corresponding author.
E-mail address: zhurl@gig.ac.cn (R. Zhu).

https://doi.org/10.1016/j.jpowsour.2018.10.031
Received 25 July 2018; Received in revised form 18 September 2018; Accepted 9 October 2018
Available online 13 October 2018
0378-7753/ © 2018 Elsevier B.V. All rights reserved.
Q. Chen et al.
1. Introduction
Silicon is regarded as an attractive candidate for next-generation
anode of lithium-ion batteries (LIBs) owing to its exceptional theore-
tical capacity (∼4200 mAh g−1 with a Li22Si4 phase) and low discharge
potential (∼0.2 V vs. Li+/Li) compared with conventional graphite
anode materials [1–3]. However, the Si anode undergoes serious ca-
pacity fading because of its huge volume change during the lithiation/
delithiation process, which then causes the loss of electrical con-
ductivity and the increase of variable solid electrolyte interphase (SEI)
area [4–8]. Nanostructuring has been proven to be an effective strategy
for enhancing the structural and cycling stability of Si anodes [9,10].
Various Si nanostructures, including zero-dimensional (0D) nano-
particles [11,12], one-dimensional (1D) nanotubes and nanowires
[13,14], two-dimensional (2D) nanosheets [15,16], and three-dimen-
sional (3D) porous nanostructures [17–19], have been developed as the
anodes of LIBs and exhibited good electrochemical performance.
Despite these remarkable advances, the fabrication of nanos-
tructured Si with specific morphology always depends greatly on ex-
pensive silicon precursors, complicated procedures, and delicate
equipment, which severely hinder the practical application of Si an-
odes. For example, traditional methods, such as electroless or electro-
chemical etching of silicon wafers [20,21] and chemical vapor de-
position of silane [22,23], are controllable in designing Si
nanostructures but generally associated with low yield and high cost.
Due to the facile operation and low processing temperature, magne-
siothermic reduction of silica is a promising and scalable method to
synthesize nanostructured Si [24]. However, to control the morphology
of Si nanostructures, complex designs involving in additional templates
are usually introduced [25,26], which make the procedures energy-
intensive and time-consuming. As such, a facile, low-cost, and con-
trollable strategy for fabricating the nanostructured Si with different
morphology is of high significance.
With high silicon content, uniform nano-sized architectures, low
price, and natural abundance [27–29], clay mineral recently has been
regarded as one of the most attractive precursors for the synthesis of
nanostructured Si via magnesiothermic reduction [30–32]. As the metal
ions (especially Al) in clay minerals may easily react with other oxides
to form high temperature byproducts (e.g., spinel) during the heavily
exothermic reaction, previous studies always first transformed clay
minerals to amorphous SiO2 (to remove metal ions) by strong acid
etching [31,32]. Obviously, this method will severely destroy the ori-
ginal nanostructures of clay minerals and can hardly tailor the mor-
phology of nanostructured Si. Meanwhile, Adpakpang et al. also suc-
cessfully synthesized porous Si nanoplate without the generation of
high temperature phases by directly employing Al-free exfoliated clay
(Laponite) nanosheet as precursor [30].
However, considering the diverse structures and complex chemical
compositions of clay minerals, a universal guidance from clay minerals
to various Si nanostructures is of high necessity but remains a chal-
lenge. Theoretically, choosing the proper heat absorbent could lower
the system temperature and thus prevent the formation of the un-
favorable high temperature phases. As such, clay minerals with a
variety of special nanostructures wherein element Si is evenly dis-
tributed might be in situ converted to various Si nanostructures without
any pretreatment and templates. On the other hand, although various Si
nanostructures individually exhibited excellent electrochemical per-
formance, there have been very limited experimental studies on dis-
tinguishing the electrochemical performance of Si nanostructures with
various morphology synthesized under the same conditions (e.g., with
the same preparation method and from precursors with similar che-
mical compositions). By combining the abundant nanostructures of the
synthesized Si (from clay minerals) with their electrochemical perfor-
mance, one may reveal the essential structure-property relationship of
various Si nanostructures.
This work, for the first time, established the relationships among
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Journal of Power Sources 405 (2018) 61–69
natural clay minerals with different structure, nanostructured Si with
various morphology, and the corresponding electrochemical properties.
Si nanostructures with different morphology were synthesized directly
using three typical clay minerals (i.e., chain-layered palygorskite (Pal),
layered montmorillonite (Mt), and tubular halloysite (Hal)) without
pretreatment. The method involved in a modified magnesiothermic
reduction, in which a molten salt (i.e., NaCl) was employed as a heat
scavenger and a dispersing agent simultaneously. The molten salt might
provide a controllable high-temperature liquid environment for the
synthesis of nanoparticles by adsorbing the massive heat generated
from the exothermic reaction [33,34], consequently preventing the
formation of the unwanted byproducts. Our results indicated that the
microstructure and morphology of as-prepared nanostructured Si
highly depended on the microstructures of clay minerals. When used as
anodes in LIBs, the 2D nanostructured Si from Mt exhibited the best
electrochemical performance in terms of high specific capacity, good
rate capability, and stable cycling performance, which could be at-
tributed to the limited variable SEI area and efficient transport property
of 2D Si nanostructure.
2. Experimental section
2.1. Materials
Pal (purity > 93%, Anhui, China) and calcium-rich Mt (purity >
95%, Inner Mongolia, China) in this study were used as received
without further purification. Hal (Shanxi, China) was collected via
simple sedimentation (purity > 98%), and then dried overnight at
80 °C for the following experiments. Chemical compositions determined
by XRF results of the three clay minerals (wt.%) were listed (Table S1).
Magnesium (Mg, analytical grade) was purchased from Shanghai
Aladdin Chemical Reagent Co., Ltd and sodium chloride (NaCl, analy-
tical grade) from Shanghai RichJoint Chemical Reagents Co., Ltd. Both
hydrofluoric acid (HF, 40 wt.%) and hydrochloric acid (HCl, 37 wt.%)
were obtained from Guangzhou Chemical Reagent Factory.
2.2. Preparation of nanostructured silicon
The nanostructured Si was synthesized by a combination of mag-
nesiothermic reduction reaction and salt melt synthesis. According to
the results of preliminary experiments (Fig. S1), the mass ratio of 1: 0.8:
5 for clay: Mg: NaCl was selected. In a typical procedure, 1 g of clay
mineral (e.g., Mt), 0.8 g of Mg powders, and 5 g of NaCl were uniformly
mixed and then sealed into a stainless steel reactor in a glovebox filled
with Ar. This reactor was transferred to a corundum tube furnace and
heated with a heating ramp rate of 5° min−1 and maintained at 650 °C
for 5 h in a high-purity Ar flow. After cooling down naturally, the ob-
tained products were rinsed with distilled water to remove NaCl (which
could be easily recycled and reused by evaporating the supernatant).
Thereafter, the above products were further washed with 1 M HCl for
3 h to eliminate MgO and other impurities (e.g., Mg2Si), followed by
leaching with 1% HF. The resulting nanostructured Si was thoroughly
washed with distilled water and then vacuum-dried at 60 °C. For the
sake of convenience, the final Si product using Mt as precursor was
denoted as Si(Mt) and the others were denoted in the same way.
2.3. Characterization methods
Powder X-ray diffraction (XRD) patterns were collected on a Bruker
D8 ADVANCE X-ray diffractometer (Bruker AXS, Germany) at 40 kV
and 40 mA with Ni-filtered CuKα radiation (λ = 0.154 nm). Raman
spectra were recorded on a Renishaw 2000 confocal micro-Raman
Spectrometer (Renishaw, UK) with an Ar-ion laser (λ = 514.5 nm) and
an air-cooled CCD detector. X-ray photoelectron spectroscopy (XPS)
measurements were performed on a Thermo Fisher K-Alpha XPS in-
strument (Thermo Fisher Scientific, UK) with a monochromatic Al-Kα
Q. Chen et al.
X-ray source (1468.6 eV). Elemental components were determined by a
Rigaku ZSX 100e X-ray fluorescence spectrometer (XRF, Rigaku, Japan)
and a GVI IsoProbe multicollector inductively-coupled plasma mass
spectrometry (MC-ICPMS, GV Instruments, UK). N2 adsorption-deso-
rption isotherms were carried out at liquid nitrogen temperature
(−196 °C) on a Micromeritics ASAP 2020 system (Micromeritics, USA).
The samples were degassed at 200 °C under vacuum for 12 h before
measurement. The specific surface area (SBET) of the sample was cal-
culated via the multi-point Brunauer–Emmett–Teller (BET) equation,
and the pore size distribution (PSD) was evaluated by the Barrett-
Joyner-Halenda (BJH) method. Scanning electron microscopy (SEM)
and energy dispersive X-ray spectroscopy (EDS) were measured via an
SU-8010 cold field emission scanning electron microscope (Hitachi,
Japan). Transmission electron microscopy (TEM) and selected area
electronic diffraction (SAED) were recorded using an FEI Talos F200S
field-emission transmission electron microscope (FEI Co., USA) with
SAED attachments at an acceleration voltage of 200 kV.
2.4. Electrochemical measurements
The electrochemical performance of the resulting nanostructured Si
was evaluated in a coin-type cell (CR2032) assembled in an Ar-filled
glovebox (< 0.1 ppm of H2O and O2). The working electrode was
prepared by casting the well-mixed slurry on a clean cooper foil, and
then vacuum-dried at 60 °C for 12 h. The slurry consisted of 60% active
materials, 20% acetylene black (Super P), and 20% sodium alginate
(SA, analytical grade) binder by mass. The typical mass loading density
of the nanostructured Si was about 0.6–0.8 mg cm−2. Then, the elec-
trode sheet was cut into disks for coin-type cell fabrication. Lithium
foils were used as the counter and reference electrodes, and poly-
ethylene films (Celgard 2400) as separators. The electrolyte was com-
posed of 1 M LiPF6 solution in 1:1 v/v ethylene carbonate/dimethyl
carbonate (EC/DMC) and 10 wt.% fluorinated ethylene carbonate (FEC)
additives. Galvanostatic charge-discharge measurements were con-
ducted using a multichannel Battery Test System (LANHE, CT2001A) at
room temperature with a fixed voltage range of 0.001–1.5 V (vs. Li/
Li+). The cyclic voltammetry (CV) plots were performed on a CHI660D
electrochemical workstation at a scan rate of 0.1 mV s−1 in the voltage
range of 0.001–1.5 V (vs. Li/Li+). The electrochemical impedance
spectroscopy was conducted in the same equipment by using an alter-
nating current perturbation of 5 mV in the frequency range from 0.01 to
100 kHz. The specific capacity in this study was evaluated based on the
mass of active materials only. The cells after cycling were disassembled
in an Ar-filled glovebox, and the working electrodes were thoroughly
washed with acetonitrile to remove residual electrolytes, and then dried
for further measurements.
3. Results and discussion
3.1. Morphological and structural analysis of nanostructured silicon
As shown by the crystal structure diagrams (Figs. S2a, d, g), the clay
minerals in this work were phyllosilicates in which the individual layers
mainly consisted of a silicon-oxygen tetrahedral (T) sheet and an alu-
minum- or magnesium-oxygen/-hydroxide octahedral (O) sheet in ei-
ther a 1:1 (Hal) or 2:1 (Mt and Pal) proportion [27]. Accordingly, en-
tirely different morphologies were observed in the SEM and TEM
images (Fig. S2), i.e., nano-sized tubes for Hal, 2D layers for Mt, and
fibrous structures for Pal, respectively. These three clay minerals with
high purity (Fig. S3) were employed as the starting materials without
pretreatment.
The structure and composition of the resulting Si products were
summarized (Fig. 1). The sharp characteristic reflections of crystalline
Si appeared in the XRD patterns of all the resulting products (Fig. 1a)
[35,36]. Noticeably, the intensity of X-ray reflections gradually de-
creased in the order Si(Hal) > Si(Mt) > Si(Pal), which could be
63
Journal of Power Sources 405 (2018) 61–69
attributed to the decrease in crystal sizes of the obtained Si. According
to the Scherrer equation, the calculated crystal sizes of Si(Hal), Si(Mt),
and Si(Pal) were ∼90, 49, and 24 nm, respectively.
The Raman spectra of the resulting nanostructured Si showed the
Raman-scattering bands at ∼507 cm−1 (Fig. 1b) arising from the
scattering of the first-order optical phonon of Si [37]. Compared with
the intense Raman band (521 cm−1) of bulk crystalline Si (Fig. S4),
those of nanostructured Si shifted to a lower frequency and became
broad and asymmetric, which could be owing to the decrease of dia-
meters (i.e., the size-confinement effect as reported in previous studies)
[37–39]. Similarly, the successively weakened Raman-scattering bands
of Si(Hal), Si(Mt), and Si(Pal) implied the decrease in sizes of the na-
nostructured Si, as observed in the XRD results.
The high resolution Si 2p XPS spectra of the nanostructured Si can
be deconvolved into two primary peaks at ∼99.9 and ∼99.3 eV, which
could be assigned to Si 2p1/2 and Si 2p3/2 of elemental Si [40], re-
spectively (Fig. 1c). Several minor peaks at ∼100.5, ∼101.5, and
∼103.0 eV, corresponding to SiOx derivatives with different oxidation
states (Si+, Si2+, and Si3+, respectively) [30,41], may be attributed to
the post-oxidation of Si nanocrystals when exposed to the air. No trace
of SiO2 peak arising at ∼103.5 eV suggested the complete reduction of
the clay minerals.
The specific surface area and porosity of the nanostructured Si were
analyzed by N2 adsorption-desorption isotherms (Fig. 1d). All of the
nanostructured Si exhibited the same IV-type isotherms and H3-type
hysteresis loops which were indicative of slit-like mesopores of Si na-
noparticles based on the IUPAC classification [42]. In contrast to Si(Mt)
and Si(Hal), Si(Pal) had better N2 adsorption capacity in the high re-
lative pressure range, indicating the larger external surface area re-
sulting from the interspaces between agglomerated Si nanoparticles.
The SBET of Si(Hal), Si(Mt), and Si(Pal) were calculated to be ∼80, 83,
and 116 m2 g−1, respectively. Furthermore, the PSD curves manifested
that all of the Si samples displayed similar broad distribution of pore
size in the range of 2–100 nm centered at ∼25 nm, whereas the pore
volume increased in the order Si(Hal) < Si(Mt) < Si(Pal) (insert of
Fig. 1d).
The morphology and microstructure of the obtained Si were further
investigated by SEM and TEM images. Si(Mt) exhibited a lamellar and
porous structure (Fig. 2d), somewhat maintaining the original 2D
structure of Mt, while Si(Hal) and Si(Pal) showed a 3D interconnected
framework and a loose texture composed of 0D nanoparticles (Fig. 2a,
g), respectively, totally different from the original morphology of their
precursors. The corresponding EDS data and XPS survey spectra re-
vealed a high purity of the resulting nanostructured Si (the existence of
Si and O and the absence of metal elements) (Fig. S5), which was
confirmed by the elemental analysis results based on MC-ICPMS (Table
S2). The TEM images further indicated that the Si nanoparticles were
intrinsically interconnected by bridging or overlapping with each other,
forming abundant mesopores and macropores (Fig. 2b, e, and h), con-
sistent with the results of pore structure analysis. The SAED patterns
and the interplanar spacing values of ∼0.31 and 0.19 nm (well
matching with the (111) and (220) planes of polycrystalline Si) verified
the generation of high crystalline Si (Fig. 2c, f, i) [43,44]. Besides, the
HRTEM images demonstrated that the crystal sizes of the nanos-
tructured Si decreased in the order Si(Hal) > Si(Mt) > Si(Pal), which
was in good agreement with XRD and Raman results. These results
above clearly showed that the silicon precursors had a great influence
on the morphology and microstructure of the corresponding reduction
products.
3.2. Formation mechanism of nanostructured silicon with different
morphology
The ex situ XRD patterns of intermediates obtained from clay mi-
nerals showed that MgO, Mg2Si, and NaCl appeared simultaneously in
the intermediate at 500 °C (Fig. 3a and Fig. S6). The characteristic
Q. Chen et al.
Fig. 1. Characterization of nanostructured silicon samples from different clay minerals (i.e., Si(Pal), Si(Mt), and Si(Hal)). (a) XRD patterns, (b) Raman spectra, (c)
High resolution Si 2p XPS spectra, and (d) N2 adsorption-desorption isotherms (inset: the corresponding BJH pore size distributions).
reflection arising from Si became evident since 550 °C. With the tem-
perature further increasing, the peak intensity for MgO and Si gradually
increased, while that for Mg2Si decreased. These phenomena suggested
that Mg2Si acted as an intermediate phase during the reduction process,
which were further supported by the ex situ XRD patterns of the in-
termediates at 650 °C for different times (Fig. S7). Generally, Si was
formed via the direct magnesiothermic reduction reaction of SiO2
(s) + 2 Mg (s, l) → Si (s) + 2MgO (s). The above results implied an-
other way for the formation of Si, i.e., via the reactions of 4 Mg (s,
l) + SiO2 (s) → Mg2Si (s) + 2MgO (s) and Mg2Si (s) + SiO2 (s) → 2Si
(s) + 2MgO (s), which were thermodynamically possible [45,46]. The
similar phenomenon was also found in the synthesis of silicene flowers
[24]. Moreover, the SEM images and EDS analyses of intermediates
showed that the final Si products were fully covered by the byproducts
(e.g., MgO) and NaCl (Fig. 3b and Fig. S6), which was further supported
by the interlaced and/or overlapped lattice fringes of NaCl(111), Si
(111), and MgO(200) in the HRTEM images (Fig. 3d). After subsequent
selective etching, a high-purity nanostructured Si was obtained. When
the clay minerals were directly used as precursors via the magne-
siothermic reaction without introducing NaCl, the highly exothermic
process would easily lead to the formation of high temperature phases
(e.g., mullite and spinel) (Fig. S8), owing to the complex chemical
compositions of the clay minerals [27]. As such, the absence of any
impurity phases in the nanostructured Si synthesized in the case of NaCl
as heat absorbent convincingly verified the relatively low temperature
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Journal of Power Sources 405 (2018) 61–69
during the reduction process, which was attributed to the endothermic
effect via the fusion of NaCl [47]. Noticeably, the reflections of Al were
exclusively discernible in the XRD pattern of intermediate from Hal
(Fig. 3 and Fig. S6), arising from the reaction of Al2O3 (s) + 3 Mg (s, l)
→ 2Al (s, l) + 3MgO (s). However, element Al could be detected in all
of the EDS mapping of intermediates, which was ascribed to the
amorphous Al2O3 converted from the O sheets during the exothermic
reaction [48].
Based on above analyses, the reaction mechanism of nanostructured
Si with different structure could be deduced as follows: The magne-
siothermic reduction reaction between the external silicon-oxygen T
sheets and Mg was initiated at ∼550 °C. The released massive heat from
the exothermic reaction could be efficiently absorbed by the heat sca-
venger NaCl, consequently preventing the reaction system from being
overheated. Unlike those SiO2 precursors without any pores, the clay
minerals possessed a large amount of pores (e.g., the nanoscale lumens
of Hal, the interlayer spaces of Mt, and the structural channels of Pal),
and the molten salts and liquid Mg could easily enter into the interlayer
spaces and/or structural channels of clay minerals to ensure a complete
reaction (Fig. S9). For 1: 1 type Hal, the intercalated Mg could si-
multaneously react with both T and O sheets to produce Si and Al
(Fig. 3a), respectively, and the newly formed Al further reacted with
neighbor T sheet via the reaction of 4Al (s, l) + 3SiO2 (s) → 2Al2O3
(s) + 3Si (s) [49]. As a result, a 3D interconnected silicon framework
with large pores was obtained after eliminating the molten salts and
Q. Chen et al.
Fig. 2. Morphological characterization of nanostructured silicon samples from different clay minerals. SEM (left), TEM (middle), and HRTEM images (right) of Si
(Hal) (a–c), Si(Mt) (d–f), and Si(Pal) (g–i). The insets in the right panel represent the corresponding SAED patterns and magnified TEM images showing crystalline
structure.
byproducts (Fig. 4a), as observed in the SEM and TEM images (Fig. 2).
However, the interlamellar Mg could only contact with the adjacent T
sheets for 2: 1 type clay minerals. For Mt (Fig. 4b), the O sheets served
as isolation barriers to prevent the random bonding of the unsaturated
bonds on newly generated Si during the reduction reaction, conse-
quently maintaining a similar 2D structure as the original Mt. Com-
pared with layered Mt, chain-layered Pal lacks the 2D continuous O
sheets due to the periodically reversal of T sheets [27]. Therefore,
without available isolation barriers, Si(Pal) tended to form a loose
texture composed of 0D nanoparticles (Fig. 4c). Besides the direct
magnesiothermic reduction reaction, Si could be also synthesized via an
intermediate phase Mg2Si in all of the reaction systems above (Fig. 4).
The mechanism of magnesiothermic reduction from these three clay
minerals to nanostructured Si could also be extended to designing Si
nanostructure with specific morphology and structure from other clay
minerals.
3.3. Electrochemical performance of nanostructured silicon
The electrochemical performance of the resulting nanostructured Si
as anode material of LIBs was evaluated using CR2032 coin-type half
cells. Typical CV curves for the first five cycles of the Si(Mt) anode at a
scan rate of 0.1 mV s−1 were recorded to investigate the redox reactions
related to the charge and discharge processes (Fig. 5a). Two irreversible
peaks (i.e., a weak one at ∼1.26 V and a broad one at ∼0.80 V)
65
Journal of Power Sources 405 (2018) 61–69
occurred in the cathodic scan of first cycle but disappeared in sub-
sequent cycles, which could be ascribed to the decomposition of elec-
trolytes and the generation of the SEI membrane [50,51]. A sharp
cathodic peak at less than 0.1 V in the first and following scans corre-
sponded to the transformation of crystalline Si to an amorphous phase.
Meanwhile, a new reductive peak at ∼0.2 V emerged gradually, owing
to the lithiation process of amorphous Si formed from the initial cycle
[52]. In the first anodic scan, two distinct peaks centered at 0.37 and
0.51 V were observed, which were attributed to the extraction of li-
thium ions from LixSi alloy to generate amorphous Si [53,54]. The
enhanced intensities of both oxidative and reductive peaks over the first
few cycles indicated an activation process of nanostructured Si, which
was consistent with the previously reported Si-based anode materials
[55–57]. In addition, the CV patterns of Si(Hal) and Si(Pal) were quite
similar to those of Si(Mt) (Figs. S10a and c), suggesting the similar
fundamental lithiation and delithiation processes.
The galvanostatic discharge/charge curves of the Si(Mt) anode for
the first and second cycles at a current density of 0.2 A g−1 in the
voltage range of 0.001–1.5 V were depicted (Fig. 5b). All of the dis-
charge/charge voltage plateaus matched well with the reductive/oxi-
dative peaks in the CV curves. The first discharge curve exhibited a
sloping voltage plateau between 0.1 and 1.3 V and a long flat one at
∼0.1 V, generally associated with the formation of the stable SEI film
and the lithiation process of crystalline Si [58,59], respectively. The
later discharge plateau moved to a higher voltage (∼0.2 V) in the
Q. Chen et al. Journal of Power Sources 405 (2018) 61–69

Fig. 3. Characterization of intermediates obtained from Hal (without acid washing). (a) Ex situ XRD patterns of as-reduced Hal at different temperatures. (b) SEM
image and EDS mapping data, (c) TEM image, and (d) the corresponding HRTEM image of the intermediate synthesized at 650 °C.

Fig. 4. Schematic illustration showing the different reaction processes between the metallic reducing agent Mg and clay minerals (i.e., Hal (a), Mt (b), and Pal (c)).

second cycle, which was due to the phase transition from crystalline Si
to amorphous structure in the first cycle [60]. On the other hand, the
charge voltage plateaus of the first two cycles were ∼4.5 V, suggesting
the delithiation process of LixSi alloy. Moreover, the Si(Mt) anode dis-
played the initial specific discharge/charge capacities of 2853/2057
mAh g−1, corresponding to an initial Coulombic efficiency (CE) of
72.1%. The capacity loss was generally assigned to the irreversible
formation of SEI film and the side reactions between active materials
and electrolyte, which usually happened for most anode materials
[61–63]. Compared to Si(Mt), both Si(Hal) and Si(Pal) possessed the

66
Q. Chen et al.
Fig. 5. (a) CV curves of the Si(Mt) electrode at a scan rate of 0.1 mV s−1 in the voltage range of 0.001–1.5 V (vs. Li/Li+); (b) galvanostatic discharge/charge curves of
the Si(Mt) electrode at a current density of 0.2 A g−1 between 0.001 and 1.5 V (vs. Li/Li+); (c) rate capability of the Si(Mt) electrode at various current densities from
0.1 to 10 A g−1; (d) comparative cycling performance and the corresponding Coulombic efficiencies of the Si(Mt), Si(Pal), and Si(Hal) electrodes at current rates of
0.2 A g−1 for the initial three cycles and 1.0 A g−1 for the remaining cycles.
analogous discharge/charge feature, with the initial CEs of 74.1% and
66.3% (Figs. S10b and d), respectively. The lowest initial CE of Si(Pal)
may be due to its highest specific surface area, which could facilitate
the generation of SEI membrane.
The Si(Mt) anode delivered the reversible specific discharge capa-
cities of 2453, 2218, 1949, 1657, 1385, 1001, and 562 mAh g−1 at
current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, and 10 A g−1 (Fig. 5c),
respectively. Remarkably, the specific capacity retained 562 mAh g−1
even at 10 A g−1, which was still higher than the calculated capacity of
commercial graphite anode (372 mAh g−1). When the current density
was changed from 10 to 0.1 A g−1, the capacity could be almost fully
returned to the original value, implying an outstanding reversibility of
Si(Mt) anode. In addition, Si(Hal) and Si(Pal) also showed parallel rate
capacities to Si(Mt) (Fig. S11). The good rate performance of all the
nanostructured Si from clay minerals could be ascribed to well-crys-
tallized Si nanostructures with large SBET and pore volume, which could
alleviate the large strain resulting from the repeated lithiation and
delithiation processes. The hierarchical pore structures (the in-
corporation of macro-/mesopores) also contributed to improving the
electrode structure stability and electrochemical kinetics [56].
The cycling performance of the nanostructured Si was further ex-
amined (Fig. 5d). All of the electrodes were first activated at 0.2 A g−1
for the initial three cycles and then cycled at 1.0 A g−1 for the re-
maining cycles. With the similar initial specific capacity after the ki-
netic enhancement, the Si(Mt), Si(Pal), and Si(Hal) anodes exhibited
reversible capacities of 1369, 1163, and 928 mAh g−1 after 200 cycles,
corresponding to capacity retentions of 78%, 72%, and 56%, respec-
tively. The descending cycling performance of the above three Si an-
odes could be attributed to the distinct interfacial characteristic of
various Si nanostructures. Moreover, the Si(Mt) electrode showed a
67
Journal of Power Sources 405 (2018) 61–69
high CE over 99% after 40 cycles, while Si(Pal) and Si(Hal) required
near 70 and 90 cycles to reach such a level of CE, respectively (Fig. 5d).
The improved CE of Si(Mt) confirmed that 2D Si nanostructures could
restrain the irreversible depletion of lithium ions. Recently, the variable
SEI surface areas per unit mass of Si nanostructures with different
morphology during cycling were calculated theoretically to increase in
the order of 2D < 0D < 3D by the impressive work by Zhang et al.
[24]. In view of the large variable SEI surface areas during cycling, the
utilization of 0D Si(Pal) and 3D Si(Hal) inevitably needed additional
interfacial stabilization. By contrast, the 2D structure of Si(Mt) could
effectively accommodate the volume change of Si with introducing the
most limited variable SEI area, which consequently enhanced the sta-
bilization of the interface and Si nanostructures. On the other hand, in
spite of the smaller size and larger SBET and pore volume, 0D Si(Pal) still
showed poorer cycling performance than 2D Si(Mt). This results de-
monstrated that regulating the morphology had a stronger influence
than downscaling the particle size to improve the cycling stability of Si
nanostructures when the size was reduced to a certain extent (e.g., <
100 nm).
As shown by the TEM images of the nanostructured Si after cycling
(Fig. S12), all of the Si nanostructures exhibited the large volume
change and became amorphous. However, Si(Mt) did not break into
smaller particles and remained intact after cycling compared to Si(Hal)
and Si(Pal), suggesting the better structural and interfacial stability of
2D Si nanostructure during cycling. This character was further con-
firmed by the Nyquist plots based on electrochemical impedance
spectroscopy (Fig. S13). The charge transfer resistance at the surface of
anode and the interfacial resistance between electrolyte and electrode
could be estimated by the diameter of the high-frequency semicircle
[64–67]. The high-frequency semicircle diameter of the Si(Mt)
Q. Chen et al.
Fig. 6. Volume expansion tests of the electrodes. Cross-sectional SEM images of the Si(Mt) (a, b), Si(Pal) (c, d), and Si(Hal) (e, f) electrodes before electrochemical
test (a, c, e) and after 100 cycles at 1.0 A g−1 (b, d, f).
electrode showed the least variation from 5 to 100 cycles among the
three electrodes, indicating the minimum change of charge-transfer
characteristics of the Si(Mt) electrode. In addition, the cross-sectional
SEM images of the Si electrodes were measured to evaluate the volume
change in macroscopic view before and after 100 cycles at 1.0 A g−1
(Fig. 6). The Si(Mt) electrode exhibited a relatively minor volume ex-
pansion (∼54%) in comparison with Si(Hal) (> 103%) and Si(Pal)
(> 64%), which further manifested the enhanced interfacial stabiliza-
tion of 2D nanostructured Si.
Based on the above analysis, the high specific capacity, good rate
capability, and stable cycling performance of 2D Si(Mt) could be pri-
marily attributed to two aspects: First, compared with 0D Si(Pal) and
3D Si(Hal), more limited variable SEI area of 2D nanostructure could
enhance the stabilization of the interface and nanostructures, thus
minimizing volume variation and maintaining structural integrity
during cycling. Second, the intrinsically interconnected feature of
planar nanostructured Si contributed to robust and fast electron/ion
transport paths, which allowed Si(Mt) to stand relatively high current
density. Without the introduction of complicated preparation and sur-
face engineering strategies, the Si nanostructures in our work exhibited
good electrochemical performance for lithium storage in terms of
68
Journal of Power Sources 405 (2018) 61–69
practical viewpoints compared to other recently reported Si anodes
synthesized by other methods (Table S3). In future work, we will in-
troduce a second phase (e.g., carbon, metal, and conductive polymer)
on the surface of nanostructured Si. Such coating is expected to serve as
a soft media to buffer the stress derived from volume expansion and
improve the transport property, thus further enhancing the cycling
stability of nanostructured Si.
4. Conclusions
In summary, three Si nanostructures with various morphology were
successfully synthesized directly using clay minerals as precursors via a
molten salt-modified magnesiothermic reduction reaction. The mor-
phology and microstructure of the resulting nanostructured Si sig-
nificantly depended on the nature of clay minerals. Si(Mt) exhibited a
2D porous structure, maintaining the original morphology of Mt, while
Si(Hal) and Si(Pal) showed a 3D interconnected framework and a loose
texture composed of 0D nanoparticles, respectively, totally different
from their precursors. Without the introduction of sophisticated designs
and surface engineering strategies, all of the Si nanostructures exhibited
good electrochemical performance as the anodes of LIBs due to the
Q. Chen et al.
large SBET and hierarchical pore structure. Compared with Si(Hal) and
Si(Pal), Si(Mt) exhibited a more stable cycling performance (1369 mAh
g−1 at 1.0 A g−1 with an capacity retention of 78% over 200 cycles)
attributed to the limited variable SEI area of 2D nanostructure and
more efficient transport property. This work, for the first time, estab-
lished the relationships among natural clay minerals with different
structure, nanostructured Si with various morphology, and the corre-
sponding electrochemical properties. We disclosed the formation me-
chanism from clay minerals to nanostructured Si via magnesiothermic
reduction, which could be extended to designing Si nanostructure with
specific morphology using other clay minerals. Moreover, we revealed
the fundamental structure-property relationship of different Si nanos-
tructures synthesized under the same conditions, which would con-
tribute to the practical applications of nanostructured Si anodes in LIBs.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (41572031), grants from the National Program for
Support of Top-notch Young Professionals, Guangdong Provincial
Youth Top-notch Talent Support Program (2014TQ01Z249),
Guangdong Special Support Program, Team Project of Natural Science
Foundation of Guangdong Province, China (S2013030014241), Science
and Technology Planning Project of Guangdong Province, China
(2017B030314175), and the Foundation of Key Laboratory of Clay
Mineral Applied Research of Gansu Province, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences (CMAR-2017-01). The
authors also thank S. S. Wei from GIGCAS in Guangzhou for TEM
analysis. This is contribution No. IS-2596 from GIGCAS.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.jpowsour.2018.10.031.
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