Nano Energy 78 (2020) 105341

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Nano Energy
journal homepage: http://www.elsevier.com/locate/nanoen

A sandwich-like silicon–carbon composite prepared by

surface-polymerization for rapid lithium-ion storage
Runsheng Gao a, b, Jie Tang a, b, *, Kun Zhang a, Kiyoshi Ozawa a, Lu-Chang Qin c
a
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan
b
Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-0006, Japan
c
Department of Physics and Astronomy, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3255, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Silicon-based materials are showing appealing potentials for electrical energy storage because of their unpar­
Surface-polymerization alleled theoretical energy density. In this work, a rapid and efficient surface-polymerization processing has been
Silicon-carbon composite developed to obtain a sandwich-like silicon-carbon composite structure for fast lithium storage. The anchored
Electrochemistry
silicon particles are connected with a low diffusion tortuosity in the designed structure that facilitates the
Lithium-ion battery
electron transport throughout the electrode and enhances the response rate under high current density. Elec­
trochemical measurements demonstrate that the silicon-carbon composite electrode exhibits a high capacity for
lithium storage. It shows a reversible capacity of 1990 mA h g− 1 at 0.5 C after 100 cycles and also has an
excellent capacity retention property (only − 0.062% capacity reduction per cycle) in long-term cycling at 1 C.
Furthermore, it can deliver a high reversible specific capacity of 1170 mA h g− 1 even at 4 C.

1. Introduction
Nowadays, portable electronic devices and electric vehicles are being
rapidly developed and they have brought great improvements to our
daily life. To meet the technological demands, energy storage systems
with both high power density and high energy density are capturing
more and more attention and ever-increasing interest in research. Sili­
con (Si), due to its ultrahigh theoretical energy density of 3579 mA h
g− 1, is regarded as one of the most promising candidate materials for the
next-generation rechargeable lithium (Li) ion batteries [1,2]. As the
second abundant element in the crust of the earth, it is also cost-effective
for large-scale production [3,4]. However, the practical utilization of Si
anode has been hampered by several issues. A major one is the
non-negligible volume change, caused by the alloying reactions of Li and
Si that usually result in an irreversible loss of active material and poor
cycling life [5]. Many efforts have been devoted to tackling this problem
and improving the lifespan of the electrode. For instance, techniques
using silver-assisted chemical etching, high-temperature magnesio­
thermic reduction, and highly elastic binder coating have been investi­
gated and reported for this purpose [6–8].
Among these strategies, carbon-coating has been a common and
effective approach to construct a high-performance Si-based composite
because of its great mechanical flexibility and excellent conductivity [9,
10]. Graphene oxide (GO), as a precursor of graphene, is a
two-dimensional structure of graphitic carbon featured with oxygenic
functional groups and it offers an alternative route for the integration of
carbon-based structures into versatile composites [11,12].
Inter-connected reduced GO (rGO) sheets have been used as a conduc­
tive network as well as an encapsulating shell to enhance the electro­
chemical performance of catalysts, supercapacitors, and batteries
[13–15]. It was also reported that GO could be used as a guest-material
to improve the electrochemical performance of Si-based electrodes [16,
17]. However, due to the stacked planar structure, graphene will have
good impermeability, though it was often overlooked that the tortuosity
could increase the ion diffusion paths because of the introduction of
graphene. Surface processing of GO offers an effective strategy for
constructing a composite electrode to achieve a high capacity in energy
storage and it can also reduce the restacking of the graphene sheets due
to van der Waals forces [18]. Conjugated polymers were broadly utilized
in various fields due to their conductivity and electronic properties [19].
Polyaniline (PANI) has not only great electrochemical activities and
controllable conductivity, but also excellent biocompatibility and easi­
ness in material preparation [20,21]. The doping level and electrical
conductivity of PANI can be controlled by the pH of the dopant acid

* Corresponding author. National Institute for Materials Science, 1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan.
E-mail address: tang.jie@nims.go.jp (J. Tang).

https://doi.org/10.1016/j.nanoen.2020.105341
Received 3 August 2020; Received in revised form 28 August 2020; Accepted 29 August 2020
Available online 15 September 2020
2211-2855/© 2020 Elsevier Ltd. All rights reserved.
R. Gao et al.
Fig. 1. (a) Schematic illustration for synthesis of p-Si@C (Route 1) and p-Si/C (Route 2) composite. (b) Photographs of material at various stages during processing.
solution. Moreover, a uniform coating of PANI onto the host material
surface can be easily accomplished by in situ polymerization. At present,
PANI has been employed extensively in electrodes for electrochemical
energy storage [22,23].
In this study, we applied a surface-polymerization approach to
coating the pre-adsorbed Si particles onto the GO sheets and combined
the excellent properties of these two materials to obtain our target
composite. The surface-aminated Si particles were pre-anchored first on
the GO sheets with the assistance of electrostatic interactions. The
surface-polymerization reaction was executed with small polymeric
molecules to enshroud and strengthen the interfacial contact between
the Si particle and GO sheet after the addition of aniline. This designed
composite structure was anticipated to extenuate the impermeability
originated from the planar graphene structure. Since high-temperature
treatment could promote the graphitization of GO and pyrolysis of
polymers and it is also beneficial for enhancing electronic conductivity
[24], we also annealed GO and PANI to generate polymer-derived car­
bon. With this structure, the Si particles were connected by an integra­
tive rGO conductive network, which can promote the electron transport
and thus boost the electrochemical activity of the active material. As an
electrode material, this polymer-derived carbon-coated silicon com­
posite (p-Si@C) showed an excellent capability in Li storage. It delivered
a high specific capacity of 3460 mA h g− 1 at 0.2 C (1 C = 1000 mA g− 1)
and also great rate performance. Furthermore, even at a current density
increased by 20 times to 4 C, this composite still showed a favorable
reversible capacity of 1170 mA h g− 1.
2. Experimental
2.1. Synthesis of p-Si@C composite material
Surface-amination was executed first to generate functionalized Si
particles. Typically, 250 ml of suspension with Si powders (~100 nm) in
an ethanol dispersion (1 mg ml− 1) was mixed with ammonia and water
and aminopropyltriethoxysilane (APTES) was then added into the mixed
solution under stirring for 3 h. The aminated Si was obtained by washing
several times and drying in vacuum for 12 h. Secondly, the as-obtained
aminated Si (120 mg) was dispersed in 20 ml of GO solution (5 mg ml− 1)
to obtain NH2–Si/GO. Due to the processing in amination, the Si parti­
cles with positively charged in the aqueous solution would be attracted
and anchored on the negatively charged GO sheets with the assistance of
electrostatic interactions. Thirdly, 0.9 ml of aniline monomers was
dispersed in 5 ml 1 M HCl and poured into the NH2–Si/GO solution. The
effective hetero-aggregations of NH2–Si@GO (modified with aniline)
were obtained after 30 s, while this process was extended by another 6 h
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Nano Energy 78 (2020) 105341
to further enhance polymerization. The filtered PANI@NH2–Si@GO was
dried in vacuum at 50 ◦ C overnight (Route 1). The final p-Si@C was
obtained by annealing at 600 ◦ C in argon atmosphere for 3 h with a
ramping rate of 5 ◦ C min− 1. The p-Si/C composite was prepared by
direct freeze-drying PANI/NH2–Si/GO and annealing (Route 2). The
active Si has a mass ratio of about 45 wt%.
2.2. Microstructural characterization
The zeta potential of NH2–Si and GO aqueous dispersion was
measured at pH = 9.9 and 5.2, respectively. The microstructure of the
composite was examined by scanning electron microscopy (SEM, JSM-
6500F, JEOL) and transmission electron microscopy (TEM, JEM-2100,
JEOL). The crystalline phases were also characterized by powder X-
ray diffraction (XRD, Rigaku SmartLab using Cu-Ka radiation with λ =
1.5418 Å). Raman spectroscopy (Nanophoton Raman Plus, λ = 532 nm)
was used to detect the structural features. X-ray photoelectron spec­
troscopy (XPS, ULVAC-PHI Quantera SXM) was employed to charac­
terize the surface states of the composite materials. Nitrogen adsorption-
desorption measurement (Quantachrome autosorb iQ) was used to
analyze the specific surface area and pore size distribution.
2.3. Electrochemical measurement
The electrode slurry was prepared by mixing the active material
(70%), conductive carbon black (15%), and styrene butadiene rubber
(7.5%)/CMC (7.5%) binder. This as-prepared homogeneous slurry was
coated onto a copper foil current collector and then vacuum-dried at
90 ◦ C for 10 h. Subsequently, coin cells were prepared in an argon-filled
glovebox using the coated electrodes as the working electrode with a
mass loading of about ~0.6 mg cm− 2, lithium foil as both the counter
electrode and the reference electrode, and a piece of Celgard 2400
polypropylene membrane was used as the separator. 1 M lithium hex­
afluorophosphate (LiPF6) in 1: 1 (v/v %) mixture of ethylene carbonate
(EC) and diethylcarbonate (DEC) was used as the electrolyte. The elec­
trochemical impedance spectroscopy (EIS) tests were carried out in a
frequency range of 100 mHz–200 kHz with a 10 mV ac amplitude, and
cyclic voltammetry (CV) curves were collected at a scan speed of 0.1 mV
s− 1in the voltage range of 0.005–1.5 V vs Li/Li+ using a VMP3 multi-
potentiostat/galvanostat (Biologic) system.
R. Gao et al.
Fig. 2. Zeta potential of NH2–Si, GO, and NH2–Si/GO.
3. Results and discussion
3.1. Material preparation and structural characterization
Fig. 1 shows a schematic of the synthesis route and the corresponding
photographs during material preparation at various stages. First, the
surface-aminated Si (NH2–Si) particles were dispersed homogeneously
into GO to obtain an NH2–Si/GO solution. The NH2–Si particles would
be pre-anchored on the GO sheets with the help of electrostatic in­
teractions due to the positively charged NH2–Si, generated during the
amination process, and the negatively charged GO in the solution. Zeta
potential measurement was carried out to confirm the chemical in­
teractions between NH2–Si and GO and the obtained results are shown in
Fig. 2. As we can see, a positively charged NH2–Si aqueous solution with
a zeta potential of about +38.8 mV was recorded. The GO solution
displays a negatively charged zeta potential of about − 38.7 mV.
Meanwhile, the zeta potential of the as-obtained NH2–Si/GO mixture
was weak and it moved to − 38.4 mV after mixing, indicating that the
electrostatic interactions induced combination of GO and NH2–Si. PANI
is a combination of aromatic carbon rings connected by nitrogen-
containing functional groups and it has a structure similar to graphite,
which would promote the incorporation of N from PANI into the
Fig. 3. Structural and morphological characterization of p-Si@C composite. (a–b) SEM images of sandwich-like structure at low magnifications. (c) Anchored Si
particles on both sides of graphene network. (d–e) TEM images of scattered Si particles on rGO network. (f) Polymer-derived carbon-coated Si particle.
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Nano Energy 78 (2020) 105341
partially graphitized carbon matrix during annealing [25]. In addition,
its good biocompatibility can facilitate to form a uniform composite
structure to enhance the electrochemical properties [26]. Thus, the
PANI/NH2–Si/GO clusters were obtained readily and rapidly by adding
aniline monomers as illustrated in Fig. 1b. It is mainly attributed to the
strong electrostatic interactions, hydrogen bonding, and π–π interactions
between the aniline monomer and GO [27]. These factors will promote
the formation of hetero-aggregations of different structures. Further­
more, the following polymerization of aniline would strengthen the
contact between the NH2–Si particles and the GO sheets. The
as-prepared composite (PANI@NH2–Si@GO) was constructed
layer-by-layer via filtration. Finally, the polymer-derived carbon-coated
silicon composite (p-Si@C) was obtained after annealing.
To understand the microstructure of the p-Si@C composite, scanning
electron microscopy (SEM) and transmission electron microscopy (TEM)
were applied for characterization and the results are shown in Fig. 3. The
SEM images revealed that p-Si@C has a uniform layer-by-layer stacking
in the composite structure (Fig. 3a). Different from the disorderly
packed structure of p-Si/C that was obtained by direct freeze-drying
(Fig. S3), the coated Si particles were sandwiched between adjacent
rGO layers, which would also relieve the tortuosity of ion diffusion paths
caused by the barriers in the graphene structure and boost the inter­
mixing at the interface between the anode and the current collector as
well. Besides, the initially isolated Si particles could be connected by the
conductive rGO network, thereby maximizing the Li storage in the active
material. As shown in Fig. 3c, the high-resolution SEM image further
demonstrated that most Si particles adhered on both sides of the rGO
sheets instead of being wrapped completely. The microstructure of p-
Si@C was also examined with TEM. As shown in Fig. 3d and e, the Si
particles were scattered quite uniformly on the entire rGO sheet and
they were therefore connected through the conductive rGO network.
The high-resolution TEM image (Fig. 3f) also revealed a seamless
polymer-derived carbon coating on the surface of the Si particle, which
is beneficial for the formation of favorable solid electrolyte interphase
(SEI) on the carbon layer and can thus maintain a good electrical contact
and long cycling life.
X-ray diffraction (XRD) was applied to analyze the crystalline phases
of the samples as shown in Fig. 4a. Pure GO showed a distinct peak at
R. Gao et al. Nano Energy 78 (2020) 105341

Fig. 4. Physical properties and characterization of as-prepared composite. (a) XRD patterns of p-Si@C, PANI@Si@GO, and GO. (b) Raman spectrum showing
characteristic peaks due to Si and graphitic structure. (c) Nitrogen adsorption/desorption isotherms with inset presenting pore size distribution. (d–f) XPS analysis of
p-Si@C with (e) N 1s and (f) Si 2p at high-resolution.

10.8◦ , corresponding to an average inter-layer spacing of 8.22 Å. It is utilized to evaluate the chemical contents and states on the surface of p-
attributed to the presence of water molecules and oxygenic functional Si@C. Due to the polymerization of aniline, N-related peaks were
groups [28,29]. With the addition of NH2–Si and aniline, the XRD observed in addition to C, O, and Si as shown in Fig. 4d. In the high-
pattern of PANI@NH2–Si@GO showed that the peak due to GO weak­ resolution N 1s spectrum given in Fig. 4e, there are two peaks: pyr­
ened and a broad peak between GO(001) and Si{111} appeared instead, idinic N (398.9 eV) and pyrrolic N (400.1 eV), which are due to the N
suggesting that partial aggregation of the GO sheets was relieved and atoms that were doped into carbon during the high-temperature
certain polymerization of aniline had occurred [30,31]. The other annealing. For electrode materials, N in a variety of states could serve
observed diffraction peaks of PANI@NH2–Si@GO at 28.4◦ , 47.3◦ , and as electron carriers as well as donors to increase the electrochemical
56.1◦ are derived from anchored Si particles, corresponding to the Bragg conductivity. In the high-resolution spectrum of Si 2p given in Fig. 4f,
reflections from the {111}, {220} and {311} lattice planes. After two XPS peaks were recorded at 99.3 and 103.6 eV, which are attributed
high-temperature annealing, the Bragg peaks due to the polymer and GO to the Si–Si and Si–O bonds.
disappeared and new peaks due to conductive carbon emerged in the
XRD pattern of p-Si@C, while the Bragg peaks due to Si remained. The
3.2. Electrochemical characterization in a half-cell system
newly formed C shells on the Si particles can improve the conductivity of
Si particles, which is also consistent with the TEM observations. Raman
The electrochemical properties for Li storage of the p-Si@C electrode
spectroscopy was also applied to investigate the samples. Fig. 4b shows
were evaluated in a half-cell configuration in which Li metal was used as
the Raman spectrum of p-Si@C, whose main peaks could be observed at
both the counter and the reference electrode. To understand the elec­
520, 945, 1357, and 1591 cm− 1. The Raman peaks located at 520 and
trochemical reactions, cyclic voltammetry (CV) measurement of the p-
945 cm− 1 are originated from the Si particles. On the right side of the Si
Si@C composite electrode was performed for the initial five cycles and
peaks, two distinct peaks at 1352 and 1587 cm− 1 are attributed to the D
the results are given in Fig. 5a. During the initial lithiation process, a
and G bands associated with structural defects that remained after the
broad cathodic peak at 0.75 V could be observed and it diminished in the
removal of oxygenic functional groups [32]. These defects could boost
second cycle, indicating an irreversible loss of capacity because of the
the permeating of electrolyte into the electrode and create more fast
formation of the SEI film on the surface of the electrode [10,33]. Two
diffusion paths for Li-ions. The graphitization of pyrolytic polymer also
peaks at 0.36 and 0.50 V were recorded in the anodic scan, which are
improved the electronic conductivity after high-temperature annealing.
attributed mainly to delithiation from LixSi to Si. In the meanwhile, due
Nitrogen adsorption-desorption measurement was conducted to
to continuous reactions between the active material and lithium, these
analyze the porous features of the as-prepared samples and the result is
characteristic peaks increased slightly in intensity over the first five
given in Fig. 4c. It exhibits a typical type IV isotherm according to the
cycles. This phenomenon of deep activation is also consistent with other
IUPAC classification and has a specific surface area of 29.5 m2 g− 1.
results on Si-based anodes [34], confirming that the designed structure
Moreover, the Barrett–Joyner–Halenda model was used to calculate the
promoted electrolyte penetration and electrochemical activity.
pore size distribution from the adsorption branch of the nitrogen
Galvanostatic charge/discharge profiles of the p-Si@C electrode
isotherm. The result (inset in Fig. 4c) shows that the diverse pores have
were obtained at various current densities and voltages ranging from
diameters ranging from 1 to 30 nm, which are good for promoting
0.005 to 1.5 V vs Li/Li+ (Fig. 5b). At a current density of 0.2 C (1 C =
electrolyte diffusion and reducing the transmission distance of Li-ions.
1000 mA g− 1), p-Si@C exhibited a high specific capacity of 3460 mA h
They are also helpful to improve the rate performance and Li storage
g− 1 at the first discharge based on the active Si material (Fig. S4) and the
in the active material. X-ray photoelectron spectroscopy (XPS) was
initial coulombic efficiency (ICE) was calculated by the galvanostatic

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R. Gao et al.
Fig. 5. Electrochemical characterization of as-synthesized electrodes. (a) CV curves of p-Si@C at scanning rate of 0.1 mV s− 1 between 0.01 and 1.5 V (vs Li/Li+). (b)
Charge/discharge curves of p-Si@C at various current densities. (c) Rate capability of p-Si@C and p-Si/C. (d) Comparison of rate performance with reported studies
in literature. (e) Cycling stability test at 0.5 C. (f) Representative lithiation/delithiation voltage profiles of p-Si@C at 0.5 C. (g) Cycling stability and coulombic
efficiency measurements of p-Si@C and p-Si/C electrode at 1 C.
charge/discharge cycle. When compared the ICE with a commercial Si
electrode (~30%), the p-Si@C electrode showed an increased ICE of
58%, attributed to the benefits from the uniform polymer-derived car­
bon layer coating, though the value should be further improved to
satisfy the requirements for engineering applications. Fortunately, the
pre-lithiation technology has been improved so that the ICE of Si-based
anode can be increased significantly for practical applications [35].
Anyway, the p-Si@C anode still demonstrated a high capacity of 2173
mA h g− 1 in the 2nd cycle with an improved CE of 95%. Benefiting from
rapid diffusion and penetrable structure, this electrode has an
outstanding response rate under high current density. With an increased
current density, the p-Si@C composite electrode remained to exhibit a
high specific capacity of 1170 mA h g− 1 even at 4 C. Fig. 5b also shows
that the main range of contributions to the specific capacity is less than
0.25 V during the discharge process, indicating that the excellent
capability in Li storage of the p-Si@C electrode is mainly contributed by
the active Si.
The rate capability was further examined to assess the electro­
chemical performance of p-Si@C and p-Si/C under various current
densities. Without the sandwich-like structure, the p-Si/C electrode
displayed a high specific capacity of 2067 mA h g− 1 at 0.2 C. However,
when the current density further increased, the p-Si/C composite elec­
trode showed a capacity decline, while it had a reversible specific ca­
pacity of 946 mA h g− 1 at 4 C. This result verified that the surface-
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Nano Energy 78 (2020) 105341
polymerization processing could improve significantly the perfor­
mance of the Si anode. On the other hand, the p-Si@C electrode
exhibited a better rate capability than that of p-Si/C, as shown in Fig. 5c,
and p-Si@C could deliver a specific capacity of 2173 mA h g− 1 at 0.2 C,
attributed to the presence of C coating and beneficial structure for
electrolyte penetration. Due to the designed sandwich-like structure,
this electrode maintained a higher reversible capacity of 1170 mA h g− 1
even at the increased current density of 4 C. When the current density
was returned to 0.2 C, the p-Si@C electrode recovered the reversible
capacity to 2068 mA h g− 1, which is very close to the initial capacity.
The comprehensive rate capability also outperforms the other reported
strategies for improving the Si anode as given in Fig. 5d [36–42]. These
results show that the electrode structure is sustainable during the lith­
iation and delithiation processes and they further indicate that p-Si@C
has improved electrochemical properties that led to fast electrochemical
responses even at high current densities. To investigate the superior
lithium storage properties of the as-prepared electrodes, electrochemical
impedance spectroscopy (EIS) was carried out and the Nyquist plots are
given in Fig. S7. The Nyquist plots showed typically a semicircle and a
sloped curve, representing the charge-transfer resistance of the interfa­
cial contact and a Warburg impedance in relation to the diffusion of Li
ions, respectively [43]. In the EIS result, the value of Rct (charge transfer
resistance) for p-Si@C was about 29 Ω, which is smaller than that for
p-Si/C (~42 Ω) in the high-frequency region, suggesting a lower
R. Gao et al.
Fig. 6. Kinetic analysis of p-Si@C composite electrode. (a) CV curves at different scan rates from 0.2 to 1.0 mV s− 1. (b) Determination of b value via relationship of
log(i) vs. log(ν). (c) Respective fraction of capacitive contribution at various scan rates. (d) Schematic for Li-ion transport in sandwich-like structure.
charge-transfer resistance caused by favorable intermixing at the inter­
face between the anode and the current collector. In the low-frequency
region, the sloped curve of p-Si@C is closer to a vertical line with a right
angle. This result indicates that it has a higher electrochemical activity
because of fast Li-ion diffusion, mainly attributed to anchored active
material structures and improved conductive network.
The cycling stabilities were evaluated at 0.5 C for 100 charge-
discharge cycles as shown in Fig. 5e. After 100 cycles, the p-Si@C
electrode still displayed a high reversible capacity of 1990 mA h g− 1,
giving rise to an excellent capacity retention of 93.6%. It also demon­
strates that p-Si@C has an outstanding capacity reversibility even at
deep lithiation/delithiation. Fig. 5f shows that the classic charge/
discharge profiles for the 20th, 50th, and 100th cycle are almost the
same, revealing the effectiveness of the p-Si@C electrode to maintain the
structural stability and improve the capacity retention. Furthermore,
this electrode presents a long cycling life. The extended stability test of
the p-Si@C and p-Si/C electrodes was executed in long-term cycling at 1
C and the results are shown in Fig. 5g. The p-Si@C electrode has a
reversible capacity of 1600 mA h g− 1 at 1 C after the initial activation
process at 0.2 C. Subsequently, it worked quite stable and was still able
to keep a reversibility capacity of 1301 mA h g− 1 even after 300 cycles at
1 C, corresponding to a retention 81.3% of the original capacity, which
is also superior to those of Si-based electrodes modified by the prevailing
methods (Table S1). The coulombic efficiency retained a high average of
99.3% throughout the cycling process. Under the same testing condi­
tions, p-Si/C showed a capacity decline and reached a reversible ca­
pacity of 868 mA h g− 1 after 300 cycles. The improved cycling
performance of the p-Si@C electrode is ascribed to the structural ben­
efits of the composite. Especially at high current densities, the sandwich-
like structure provided numerous fast channels for electrolyte penetra­
tion and ion transport to accelerate electrochemical activities. The cor­
responding and representative lithiation/delithiation voltage profiles
are also presented in Fig. S9, indicating that the p-Si@C electrode has an
excellent cycling stability.
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Nano Energy 78 (2020) 105341
To further investigate the behaviors in Li storage of the p-Si@C
electrode, the scan-rate-dependent CV tests were examined at different
scan rates to study the reaction kinetics, as shown in Fig. 6. In general,
the mechanism between the peak current (i) and scan rate (v) follows a
power-law relationship [44]:
i = avb (1)
where a and b are constants. When b = 0.5, it suggests that the elec­
trochemical behavior is mainly controlled by a solid-state process. On
the other hand, it usually indicates that the capacity is dominated by
surface-controlled reactions when b = 1.0. The b value of this electrode
is 0.77 according to the linear relationship between the log(i) and log(v)
given in Fig. 6b. This is attributed to the coexistence of both solid-state
diffusion and surface reactions in the process of Li storage. Furthermore,
each capacitive contribution could be determined by calculating the
capacitive contribution (k1 v) and the diffusion-controlled contribution
1
(k2 v2 ), respectively, according to the following equation [45]:
1
i = k1 v + k2 v2 (2)
where (k1 ) and (k2 ) are constants. The ratios of capacitive contribution
can be quantitatively determined through calculating the values of k1
and k2 as shown in Fig. S10. Fig. 6c displays the respective fraction of
capacitive contribution at the scan rate from 0.2 to 1 mV s− 1, showing
that the capacitive contribution increases with increasing scan speed. It
can deliver a greatest ratio of capacitive contribution up to 54% at the
scan rate of 1 mV s− 1, indicating that this structure could also enhance
the lithiation/delithiation process.
The two electrodes were also examined with SEM to measure the
changes in electrode thickness before lithiation and after 100 cycles at
0.5 C (Fig. 7). The starting thicknesses of p-Si@C and p-Si/C electrodes
before lithiation were measured as 48.1 μm and 50.3 μm, respectively.
After 100 cycles of lithiation/delithiation, the p-Si@C electrode showed
R. Gao et al.
Fig. 7. (a–d) Cross-sectional SEM images of p-Si@C and p-Si/C electrodes before (a, b) and after (c, d) completing 100 cycles at 0.5 C. Variation of electrode
thickness (e) before and after cycling and (f) corresponding fractional change.
an increase of thickness from 48.1 to 60.7 μm, corresponding to a
relatively small volume change of 26.2%. On the other hand, the
thickness change of p-Si/C is 17.9 μm, corresponding to a slightly
greater volume expansion (35.6%). Both of these measurements
confirmed that the surface-polymerization strategy could mitigate the
effect of volume expansion and preserve its good electrochemical ac­
tivity during the long cycling period.
4. Conclusions
We have developed an effective and efficient processing route to
prepare a Si–C (p-Si@C) composite that exhibits excellent properties in
lithium storage. The aminated Si particles were pre-anchored on the
surface of GO sheets. After adding aniline, the contact between NH2–Si
particles and GO sheets was further improved with the assistance of
various interactions including π–π interactions, electrostatic in­
teractions, and hydrogen bonding, to form a closely connected network
structure. With this designed structure, the electrolyte diffusion is
accelerated for penetration into the entire electrode to induce maximum
storage of lithium. When this composite was employed as an electrode, it
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Nano Energy 78 (2020) 105341
showed a high capacity up to 2173 mA h g− 1 at 0.2 C, while retaining a
high reversible capacity of 1170 mA h g− 1 even at 4 C. In addition, even
with high-rate electrochemical reactions, the cycling life of p-Si@C
remained high (only − 0.062% capacity loss per cycle) within 300 cycles
and gave rise to a reversible capacity of 1301 mA h g− 1.
CRediT authorship contribution statement
Runsheng Gao: Conceptualization, Methodology, Investigation,
Formal analysis, Visualization, Writing - original draft. Jie Tang:
Conceptualization, Formal analysis, Writing - review & editing, Super­
vision, Project administration. Kun Zhang: Visualization. Kiyoshi
Ozawa: Investigation, Writing - review & editing. Lu-Chang Qin:
Formal analysis, Visualization, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
R. Gao et al.
Acknowledgement
A part of this work was supported by NIMS Microstructural Char­
acterization Platform as a program of “Nanotechnology Platform” of the
Ministry of Education, Culture, Sports, Science and Technology (MEXT),
Japan.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.nanoen.2020.105341.
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Runsheng Gao received his M.S. degree from the College of
Chemistry and Chemical Engineering, Xiamen University, in
2017. He is now a junior researcher at the National Institute for
Materials Science and is pursuing his doctoral degree under the
supervision of Prof. Jie Tang in the Graduate School of Pure and
Applied Sciences at the University of Tsukuba, Japan. His main
research interest is the design and fabrication of nanostructured
materials for energy storage applications.
R. Gao et al.
Jie Tang is a senior research scientist and group leader of the
Advanced Low-Dimensional Materials Laboratory at the Na­
tional Institute for Materials Science and a joint professor at the
University of Tsukuba, Japan. She received her BEng degree in
materials science from Tsinghua University, China, and her PhD
degree in materials physics from the University of Osaka,
Japan. Her research interests include high-pressure physics,
electron emission materials, and graphene supercapacitors for
energy-storage applications. She has published more than 120
research papers and holds more than 30 patents in these areas.
Kun Zhang, received his Ph.D. degree in nanoscience and
nanotechnology from the University of Tokyo, Japan in 2008.
His current research aims at syntheses of two-dimensional (2D)
materials and 2D material/polymer composites as well as their
applications in various energy storage fields.
Nano Energy 78 (2020) 105341
Ozawa Kiyoshi is currently a Guest Researcher in the
Advanced Low-Dimensional Nanomaterials Group, National
Institute for Materials Science (NIMS), Japan. He received his
Ph.D. degree from Utsunomiya University, Japan in 2002. His
research focuses on the development and mechanism elucida­
tion of high-performance cathode and anode materials for
lithium-ion batteries and supercapacitors.
Lu-Chang Qin is a professor in the Department of Physics and
Astronomy at the University of North Carolina at Chapel Hill,
USA. He received his BS degree from the University of Science
and Technology of China, MS degree from Northwestern Uni­
versity, and ScD degree from the Massachusetts Institute of
Technology. His research interests include the development
and application of electron diffraction and microscopy methods
for materials characterization as well as nanostructured mate­
rials for electron emission and energy-storage applications.