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Applied Clay Science 162 (2018) 499–506
Contents lists available at ScienceDirect
Applied Clay Science
journal homepage: www.elsevier.com/locate/clay
Research paper
Interconnected silicon nanoparticles originated from halloysite nanotubes
through the magnesiothermic reduction: A high-performance anode
material for lithium-ion batteries
T
⁎
Wei Tanga, Xiaoxia Guoa, Xiaohe Liua, , Gen Chena, Haoji Wanga, Ning Zhanga, Jun Wangb,
⁎
Guanzhou Qiub, Renzhi Mac,
a
b
c
State Key Laboratory of Powder Metallurgy and School of Materials Science and Engineering, Central South University, Changsha, Hunan 410083, China
School of Minerals Processing and Bioengineering, Central South University, Changsha, Hunan 410083, PR China
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
A R T I C LE I N FO
A B S T R A C T
Keywords:
Silicon
Halloysite nanotube
Magnesiothermic reduction
Anode material
Lithium-ion battery
Silicon (Si) is a promising high-capacity anode material for the next-generation of rechargeable lithium ion
batteries (LIBs). Though there are formidable challenges from the large volumetric change during lithiation,
well-designed nanostructure and reduced size of Si can remarkably alleviate the negative effects. Herein we
apply a magnesiothermic reduction process to synthesize interconnected Si nanoparticles in large quantities.
Earth abundant clay of halloysite with tubular structure has been used as silica precursor after acid washing. A
high Si yield can be achieved upon pressing the precursor powder into a pallet before reduction. The obtained
interconnected Si nanoparticles exhibit a high specific capacity of 3752.4 mA h g−1 for the first cycle at1 A g−1
and 1469.0 mA h g−1 after 400th cycles at current density of 3.5 A g−1. Even tested at 5 A g−1 for 1000 cycles, a
high capacity of 735.1 mA h g−1 is obtained. The rate capability is also evaluated and a high capacity of
1050 mA h g−1 is achieved at 10 A g−1.
1. Introduction
Silicon (Si) based materials have attracted enormous attention due
to their important applications in many fields, such as solar energy
conversion, electronic devices, photovoltaics, optoelectronics, sensing,
and anodes for the rechargeable lithium-ion batteries (LIBs) (Lin et al.,
2015). There are many merits for Si as anode materials in LIBs. Compared to commercial graphite anode (372 mAh g−1), Si possesses high
gravimetric capacity upon lithiation to Li3.5Si (3579 mAh g−1)
(Chevrier et al., 2010). In addition, Si exhibits low lithiation/delithiation voltage (< 0.5 V vs. Li/Li+), (Liu et al., 2012a, 2012b; Xue et al.,
2013; Zhou et al., 2013) which can retain high open circuit voltage for
the full cell and avoid adverse lithium plating process. Low cost, nontoxicity, and elemental abundance in the earth also make it practical
and commercially available (Wu and Cui, 2012; Zuo et al., 2017). Although Si has attracted great attention as promising negative electrode
for LIBs, there are formidable challenges to replace the current commercial graphite anode due to serious capacity decay originating from
their poor electronic conductivity, (Pan et al., 2018) huge volume
change over 300% and gradually enhanced pulverization during the
charge-discharge processes, (Zhang, 2011) and continuous consumption of lithium ions during the formation-breaking-reformation process
of solid electrolyte interface (SEI) layer (Besenhard et al., 1997, Cho,
2010, Huggins, 1999, Scrosati and Garche, 2010, Szczech and Jin,
2011, Zhang et al., 2004, Zuo et al., 2017). Several strategies are
exploited to tackle the aforementioned critical issues, including combining Si with carbon or other materials, (Qu et al., 2012; Simon et al.,
2011; Wu et al., 2003) and utilizing nanostructured Si (nanowires,
nanotubes, nanoparticles, hollow materials), (Chan et al., 2009; Huang
et al., 2014; Lee et al., 2004; Li and Zhi, 2013; Liu et al., 2012a, 2012b;
Park et al., 2006; Ryu et al., 2016) to accommodate volume expansion
or relieve their inner stress (Choi and Kang, 2015; Jiang et al., 2017).
Recently, considerable effort has been devoted to the preparation of
Si based nanomaterials (Liang et al., 2014). In particular, silicon oxides
such as silica and silicates were also widely utilized to fabricate nanoscale Si via reduction processes. Lin and coworkers designed a molten
salt process to prepare Si nanoparticles through the reduction of silicon
zeolite by metallic Al (or Mg) in molten AlCl3 (Lin et al., 2015).
⁎
Corresponding author at: State Key Laboratory of Powder Metallurgy and School of Materials Science and Engineering, Central South University, Changsha,
Hunan 410083, China.
E-mail addresses: liuxh@csu.edu.cn (X. Liu), MA.Renzhi@nims.go.jp (R. Ma).
https://doi.org/10.1016/j.clay.2018.07.004
Received 22 April 2018; Received in revised form 26 May 2018; Accepted 2 July 2018
Available online 09 July 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
Applied Clay Science 162 (2018) 499–506
W. Tang et al.
mixtures were compacted into a pallet by an oil press under a pressure
of 20 MPa for 2 min. And then the wafer was transferred to a corundum
crucible. Next, this crucible was placed in a tube furnace fill with argon
atmosphere and heated up to 650 °C for 3 h. After the completion of Mg
reduction, the resulting powders were dissolved in 100 mL water under
mild stirring, 1 M HCl was dropping to this solution to remove residual
NaCl as well as Mg, and MgO byproducts and other possible impurities.
Finally, the Si was obtained by etching with diluted 2% HF.
However, once the reaction was triggered, the temperature of reactant
would rise sharply, and the severe heat accumulation was considered as
the main reason for collapsing and poor electrochemical performance.
To reduce heat accumulation, sodium chloride (NaCl) is usually introduced in chemical reduction process (Wang et al., 2015). The
melting point of NaCl is 801 °C, with a heat capacity of 517.1 J g−1,
which can effectively scavenge the heat released in reduction reaction
and prevent the reactants from overheating.
Halloysite is a naturally abundant clay mineral with tubular morphology. The external diameter and length is about 20–30 nm and
600 nm, respectively. The chemical composition of halloysite is
Al2Si2O5(OH)4·2H2O, (Abdullayev et al., 2012; Yah et al., 2012) which
is similar to kaolinite except for the presence of an additional water
monolayer between the adjacent clay layers. Halloysite nanotubes
consist of gibbsite octahedral sheet (Al-OH) groups on the internal
surface and siloxane groups (Si-O-Si) on the external surface. In particular, Zhang et al. has reported that gibbsite octahedral layer could be
etched, leaving silica nanotubes with porous structure (Zhang et al.,
2012). In addition, using halloysite nanotubes as Si source is not only
cost-efficient, but also favorable in structure and size. Very recently,
Zhou et al. demonstrated the halloysite clay could be converted into Si
nanoparticles through a magnesiothermic reduction process at a high
temperature of 700 °C for 6 h (Zhou et al., 2016). Thus, it is of great
significance to prepare nanoscale Si at a relatively mild condition.
Herein we demonstrated interconnected Si nanoparticles could be
synthesized in large quantities through the acid etching and subsequent
magnesiothermic reduction of silica nanotubes at 650 °C for 3 h. In
particular, after etching by hydrochloric acid, aluminum oxide can be
removed from the halloysite, leaving amorphous and porous silica
tubes. The mixed precursor could be pressed into a pallet to improve the
yield. The morphology evolution of different stage was monitored, exhibiting tubular morphology is difficult to retain. However, the porous
structure can be saved after chemical reduction with the addition of
NaCl, which can alleviate the volume expansion during lithiation. The
interconnected Si nanoparticles with large specific area exhibited a high
specific capacity, outstanding cycling stability and excellent rate capability.
The electrochemical properties of as-prepared Si were evaluated
through coin type cells (2025 R-type) which were assembled under an
argon-filled glove box (H2O, O2 < 1 ppm). Metallic Li sheet was used
as counter and reference electrode. 1 M LiPF6 in a mixture of ethylene
carbonate/dimethyl carbonate/diethyl carbonate (EC/DMC/EDC; 1: 1:
1 by volume) was served as the electrolyte. For preparing working
electrode, the slurry mixed with as-prepared active Si material, carbon
black and sodium alginate (SA) binder in a weight ratio of 6: 2: 2 in
water solvent were pasted onto a Cu foil. The foil at first dried in air at
60 °C and then dried in a vacuum oven at 100 °C overnight. The typical
loading mass of Si was approximately 0.8 mg cm−2. Galvanostatic
charge/discharge (GCD) measurements were conducted using a LANDCT2001A instrument at room temperature with a fixed voltage range of
0.005–1.5 V (vs. Li/Li+). Cyclic voltammetry (CV) was performed on
electrochemistry workstation (CHI660D), with a scanning rate of
0.1 mV s−1 at room temperature.
2. Materials and methods
3. Results and discussion
2.1. Materials
Fig. 1a exhibits the detailed schematic illustration of the different
stage, from raw clay powder to pure Si. Fig. 1b displays the corresponding digital photographs of products at different stage. First, prepurified clay minerals were prepared by HCl washing treatment. Halloysite comprises naturally occurring aluminosilicate nanotubes with a
1: 1 ratio of Al to Si and usually containing a small amount of other
metal element, such as Fe, Ti, K, which makes their color yellowishbrown as shown in Fig. 1b. All the metal elements can be removed
through inorganic acid etching. After the purified processing with
treatment by 3 M HCl at 120 °C, the light orange clay turns white, which
remains about 45% in weight. The acid treated halloysite could be totally dissolved in 1% HF, which implies the white powder is silica.
The detail of magnesiothermic reduction are illustrate in Fig. 1c.
First we mixed NaCl and pre-treated halloysite in water, and then dried
in oven. Next, we added Mg powder and ground in an agate mortar to
form a homogeneous mixture. The mixed powder was pressing into a
wafer at a pressure over 20 MPa for at least 2 min. The magnesiothermic reduction is actually a solid-phase reaction, thus compacting
the reagents can promote the reaction and boost the productivity. A
previous report has depict that by tableting treatment, the temperature
of the reaction could be reduced to under 500 °C,(Zhuang et al., 2017)
which is much lower than traditional condition of magnesiothermic
reduction.
The XRD pattern in Fig. 2a i) and ii) shows the transformation
process from typical halloysite to amorphous broad peak. Therefore, the
white power is mainly amorphous SiO2. Then SiO2, mixed with
2.4. Materials characterization
The crystallographic structures of the materials were determined by
a RIGAKU Rint-2000 X-ray diffractometer equipped with Cu − Kα radiation (λ = 1.54184 Å). Scanning electron microscopy (SEM) was
tested with a FEI Helios Nanolab 600i field emission scanning electron
microscope. Transmission electron microscopy (TEM), and high-resolution images (HRTEM) were obtained with an FEI Tecnai G2 F20
field emission transmission electron microscope operated at 200 kV.
2.5. Electrochemical characterization
The clay mineral used in this work was commercial yellowishbrown powder. Hydrochloric acid (HCl), NaCl, Mg powder and hydrofluoric acid (HF), all the chemicals of analytical grade were purchased from China National Pharmaceutical Group. They were used
without further purification. Milli-Q water was used throughout the
experiments.
2.2. Quantify SiO2 content in raw halloysite
10 g halloysite was dispersed in a beaker which contains 300 mL
3 M HCl. Then the mixture was continuous agitating and heating to
80 °C for 4 h. To obtain further purified SiO2, the white product was redispersed in 80 mL 3 mol/L HCl and then transferred to a 100 mL
Teflon-lined stainless-steel autoclave and kept in an electric oven at
120 °C for 12 h. The amorphous pure SiO2 was collected by centrifugation, washed several times with water, and dried at 120 °C.
2.3. Magnesiothermic reduction
Purified halloysite was mixed with Mg powder and NaCl at a weight
ratio of 1: 0.8: 1. First, purified halloysite was mixed with NaCl dispersed in water and stir for 1 h. Then the mixture was dried in 100 °C
oven and accumulated in a mortar. Then Mg powder was added in to
mortar and grind together to form a high dispersed mixture. The
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Fig. 1. The (a) diagram and (b) digital photographs of raw Halloysite clay, acid-etched clay, intermediate product, product after HCl treatment, final product of
silicon, (c) illustration of the preparation procedures of silicon in detail.
of Mg in certain area. The undesired Mg2Si and excessive MgO can be
simply removed by repeatedly washing with HCl. The XRD pattern of
product after HCl washing was shown in Fig. 2a iv), which shows a
range of peaks fitting the PDF card of silicon, but it still remains unreacted amorphous silica. The color was light brown. Then, after 1% HF
was added to remove residual SiO2, the color of product turns darker.
Pure silicon was acquired by washing with water and ethanol several
times, and dried in 80 °C oven for overnight. The corresponding XRD
pattern is shown in Fig. 2a v). The differences between Fig. 2a iv) and v)
are presented in Fig. 2b, which indicate the comparison between the
product before and after HF treatment. We can find a weak broad peak
at the same position as Fig. 2a ii), which can be ascribed to amorphous
SiO2. The broad peak of silica is almost undetectable, indicating the
high purity of Si. By contrast, the products without the pressing process
magnesium (Mg) powder as reducing agent, as well as sodium chloride
(NaCl), which was introduced as a safe, economical and efficient heat
scavenger, (Wang et al., 2017) which can effectively scavenge the heat
released in reaction and prevent the structure from collapsing. The
mixture was heated to 650 °C under argon atmosphere. The Si could be
formed as the following equation: 2Mg + SiO2 → 2MgO + Si. It is easy
to calculate that silicon dioxides could be reduced by Mg in a stoichiometric atom ratio of (SiO2/Mg = 1: 2), or weight ratio of (SiO2/
Mg = 1: 0.8). Unwanted byproduct magnesium silicide (Mg2Si) could
be result from excess Mg alloying with Si:4Mg + SiO2 → 2MgO + Mg2Si
and/or 2Mg + SiO2 → 2Mg2Si. The intermediates were washed by water
and dried. It is clearly seen that the intermediate is black from Fig. 1b.
The XRD pattern shown in Fig. 2a iii) depicts the mixture containing Si,
MgO, and Mg2Si. Small amount of Mg2Si can be detected due to excess
Fig. 2. (a) XRD patterns in different procedure of clay reduction: (i) raw clay of halloysite, (ii) acid-etched clay, (iii) intermediate, (iv) product after HCl treatment,
(v) final product of silicon. (b) magnified patterns in circled area form (a).
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Fig. 3. (a) SEM and (b) TEM of halloysite, (c)TEM and (d) magnified TEM images of the acid-etched clay.
present obvious broad peak in XRD pattern as shown in Fig. S1a. And
the color is yellowish white (Fig. S1b), implying small amount of unreacted silica. So the pressing process is beneficial to the formation of
silicon.
The morphology and structure of raw clay and evolution during the
HCl treatment process was ascertained by scanning electron microscope
(SEM) and transmission electron microscopy (TEM). Fig. 3a depicts the
SEM image of raw halloysite clay and indicate large quantity and good
uniformity halloysite nanotubes with a mean length of 600 nm and
external diameter of about 20–30 nm. Fig. 3b displays a typical TEM
image of raw halloysite nanotubes. The tubular structure with hollow
interiors could be observed clearly. Fig. 3c and d depict TEM and
magnified TEM images of acid-treated halloysite clay. Halloysite could
be totally etched aluminum oxide layer by acid treatment, and exuberant porous structure could be observed. The initial tubular morphology could still be maintained. Fig. S2a and b are separately EDS
spectrum before and after acid etching treatment. The aluminum and
silicon element content were nearly closed in halloysite raw clay as
shown in Fig. S2a. However, the peak of aluminum was almost disappeared after HCl washing (Fig. S2b), which further proved the
transformation of halloysite to amorphous silica.
Fig. 4a depicts the TEM image of intermediate product obtained via
magnesiothermic reduction of pre-treatment halloysite nanotubes and
subsequent washed by water. Bundle of nanotube after the reduction
could be found, and the surface was uneven, which illustrate the porous
structure was maintained. Then the product was washed by acid, as
shown in Fig. 4b. The tubular morphology was hardly to be seem,
which reveals the tubular structure is not inherited by acid treatment.
However, the porous structure could still be observed. Fig. 4c exhibits
the typical TEM image of final product after HF treatment, clearly indicating the porous structure of the Si nanoparticles. Fig. 4d is a magnified TEM image, revealing the interconnected feature of the porous Si
nanoparticles. The inset shows a selected area electron diffraction
(SAED) pattern of the Si nanoparticles. The diffraction rings could be
well indexed to (111), (220) and (311) planes, revealing a
polycrystalline nature of pure Si. The nanopores are simultaneously
formed upon the stacking of Si nanoparticles with specific area of
210.3 m2 g−1, as shown in Fig. S3a. The size of porous is analyzed in
Fig. S3b, which exhibits that the diameter mainly distributes in a range
of 2–10 nm. The NaCl additive plays an important role in the formation
of porous silicon, which prevents product from aggregation by absorbing heat released from reduction process. By contrast, the Si nanoparticles grow larger without NaCl, leaving less pores inside, as
shown in Fig. S4. A typical HRTEM image of Si nanoparticles shows in
Fig. 4e. The lattice spacing was measured to be 0.31 nm, which is
consistent with the (111) lattice plane of pure Si. SEM image of final
product is shown in Fig. 4f, confirming the homogeneous silicon nanoparticles.
Coin-type half-cells were assembled to evaluate the electrochemical
performance of as-prepared Si as anode active material. The cyclic
voltammetry (CV) curves of the first, second, and third cycles were
tested in 0.01–1.5 V voltage window at a scan rate of 0.1 mV s−1, as
shown in Fig. 5. During the first cycle, there is a peak not easy to observe at about 1.25 V, which is corresponding to the voltage of formation of SEI layer at the surface of silicon. And the discharge peak of first
cycle is lower than 0.1 V, according to the voltage-capacity profiles
shown in Fig. 5, relating to the discharge voltage of crystal silicon. It
disappeared from the second cycle, indicating the entire amorphization
of Si in the first cycle. The second and third cycle of discharge peaks rise
to around 0.19 V. Two distinct peaks at 0.38 and 0.52 V appeared in the
charge process, which could be attributed to the reaction between
amorphous LixSi and amorphous silicon. Peak current density and integrated area intensity were nearly unchanged in the subsequent discharge and charge cycles, indicating very small capacity losses during
cycling.
Fig. 6a shows the voltage-capacity profiles of Si electrodes after 1, 2
and 3 cycles at a current density of 1 A g−1. The cells were deep
charged and discharged between 0.005 V and 1.5 V. During the first
discharge process, the main potential plateau is located at around 0.1 V
(vs. Li+/Li), which agrees well with the lithiation process of crystallized
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Fig. 4. (a) TEM image of product after water washing, (b) TEM image of product after HCl etching, (c) TEM and (d) magnified TEM images of product after HCl and
HF etching, (e) HR-TEM and (f) SEM image of final product. The inset in (d) shows a select area electron diffraction (SAED) pattern of the Si nanoparticles.
Si.(Lin et al., 2014) In the second cycle, the discharge plateau moves to
a higher potential at around 0.2 V, which is accepted as the transformation of Si from crystalline to amorphous phase during the first cycle
(Zhang et al., 2014). The initial discharge and charge capacities of Si
are 3752.2 and 3040.1 mA h g−1 respectively, corresponding to the
initial Coulombic efficiency (CE) of 81.0%. Coulombic efficiency is a
critical factor to consider the reversibility of Si electrodes. The discharge irreversible capacity for the 1st charge is due to the formation of
the solid electrolyte interface (SEI) layer on the surface of electrodes,
and the irreversible reaction between Li+ and active materials, both of
which consume a great number of Li+ ions. The 2nd discharge and
charge capacities are respectively 3085.7 and 2976.9 mA h g−1, corresponding to the CE of 96.5%. The 3rd discharge and charge capacities
are 3040.1 and 2952.4 mA h g−1, respectively, corresponding to the CE
of 97.1%. After the SEI formation in the first cycle, the CE is higher than
95%, suggesting that Si electrode has an excellent reversibility. Fig. 6b
indicates the long-term cycling stability of as-preared Si at a current
density of 1.0 A g−1 with the first three cycles activated in a lower
current density to form a stable SEI layer. After 400 cycles, it still displays a relatively large capacity of 1469.0 mA h g−1 at a current density
of 3.5 A g−1.
Fig. 5. Cyclic voltammograms of first three cycles at a scan rate of 0.1 mVs−1.
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Fig. 6. Electrochemical characterizations of Si product. (a) Discharge-charge voltage curves at current density of 1 A g−1, (b) Cycling performance tested at 3.5 A g−1
and (c) at 5 A g−1, (d) The rate capability with current density ranging from 0.5 to 10 A g−1, (e) Cycling performances of porous silicon (red) and commercial silicon
tested at 0.5 A g−1, (f) Impedance measurements of silicon product before (black) and after (red) 50 cycles. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.)
density of 5 A g−1 at the 21th cycles, and 735.1 mA h g−1 after
1000 cycles. Especially, the CE of the Si electrode at a current density of
5 A g−1 is nearly 100% for each cycle. The remarkable performance at a
high current density may be attributed to the high specific area as
above mention. The Li+ diffusion pathway and large contact area with
The high-rate performance of Si nanoparticles was also evaluated, as
shown in Fig. 6c. Firstly, the cells are tested at a relative low current
density for first three cycles to activate the Si anode sufficiently, and
then change the current density to 3.5 A g−1 till the 20th cycles. The Si
electrode delivers a specific capacity of 1095.8 mA h g−1 at a current
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the electrolyte are more favorable for the fast kinetics.
In addition, Fig. 6d reveals the capability of the Si electrode at
different current densities ranging from 0.5 to 10 A g−1. The Si electrode delivers stable discharge capacities of 3025, 2716, 2316, 2047,
1723, 1544, 1353, 1319, 1202, 1143 and 1050 mA h g−1 at current
densities of 0.5, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, and 10.0 A g−1,
respectively. The specific capacity as high as 2447 mA h g−1 can be
restored when the current density decreases to 0.5 A g−1 after the highrate charge/discharge cycling of 10 A g−1, suggesting the composites
possess the high capacity stability and rate capability. Fig. 6e is the
cycling performance of our products (red) and commercial nanosized
silicon particles (black). The current density is 0.5 A g−1. After 200th
cycles, the capacity of commercial silicon has dropped from
3026.0 mA h g−1 to 274.8 mA h g−1, while porous silicon has declined
from 3586.4 mA h g−1 to1835.1 mA h g−1. It depicts that as-prepared
silicon nanoparticles has much more advantage than commercial silicon
nanoparticles.
The electrochemical impedance spectrum (EIS) is used to investigate the charge transport kinetics for the electrochemical properties of these electrodes. Fig. 6f shows the Nyquist plots of the AC impedance for Si electrodes before and after cycling. The equivalent
circuit diagram of AC impedance is shown in Fig. S5. The charge
transfer resistance (Rct) can be estimated by the diameter of the semicircle at the high frequency. The diameter of the semicircle at high
frequencies region remarkably decreases from 114.1 to 78.5 Ω, after
50 cycles, indicating that the electrode was gradually activated and the
conductivity was improved. The AC impedance curve displays small
quasi-semicircle within medium frequency region, which may be attributed to the formation of SEI layer. In addition to that, we can observe a decreased slope at low frequency region, reflecting the increase
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4. Conclusions
In summary, we described a facile synthetic method through the
acid etching and subsequent magnesiothermic reduction of natural
halloysite nanotubes at 650 °C for 3 h to prepare pure Si in large
quantities and high yield (over 70% of total Si element) for LIBs. The
obtained interconnected Si nanoparticles exhibited a high specific area
of 210.3 m2 g−1 and a high specific capacitance of 3752.2 mA h g−1 at
first the cycle and 1469.0 mA h g−1 after 400th cycles at current density
of 3.5 A g−1, and excellent rate capability of 735.1 mA h g−1 at current
density of 5 A g−1 after 1000th cycle and 1050 mA h g−1 at current
density of 10 A g−1. These results suggest the as-prepared Si derived
from halloysite clay is an excellent candidate as anode material for
next-generation LIBs.
Acknowledgements
W. Tang and X. Guo contributed equally to this work. This work was
supported by National Natural Science Foundation of China
(51372279), Hunan Provincial Natural Science Foundation of China
(13JJ1005). X. L. acknowledges support from Shenghua Scholar
Program of Central South University.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.clay.2018.07.004.
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