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Facile Spray‐Drying Synthesis of Dual‐Shell Structure

Si@SiOx@Graphite/Graphene as Stable Anode for Li‐Ion Batteries

Article · May 2019

DOI: 10.1002/ente.201900464

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Facile Spray-Drying Synthesis of Dual-Shell Structure

Si@SiOx@Graphite/Graphene as Stable Anode for Li-Ion
Batteries
Jianbin Li, Wenjing Liu, Qi Wan,* Fangming Liu, Xuan Li, Yingjun Qiao, Meizhen Qu,
and Gongchang Peng*

grid.[1] Indeed, the commercial graphite

A dual-shell structure Si@SiOx@graphite/graphene (SGGr) is prepared by large- anodes (372 mAh g
1) cannot meet the
scale spray-drying. In this composite, Si nanoparticles act as the core, SiOx energy demand, whereas silicon (Si) with
and graphite/graphene serve as the shell. Transmission electron microscopy high theoretical capacity (4200 mAh g
1)
is regarded as the next-generation anode
(TEM) studies show that Si nanoparticles are coated with a 1–2 nm SiOx layer and
material.[2] Except the ultra-high capacity,
embedded into the sheets of graphite/graphene. Amorphous SiOx and graphite/ Si has other advantages such as low
graphene as the production layer can prevent Si directly connecting with the lithiation/delithiation potential (<0.5 V vs
electrolyte and improve the entire structural stability. In addition, nitrogen Liþ/Li), abundant reserves, and environ-
adsorption–desorption measurements indicate that the prepared SGGr has a mental friendliness.[3] However, the practi-
higher Brunauer–Emmett–Teller (BET) surface area (48.4 m2 g
1) than pure cal applications for Si anode are still
2
1 hampered by several problems: 1) the huge
Si (36.2 m g ) due to the existence of mesopores and macropores, which can
volume expansion (300%) over repeated
shorten the lithium-ion transport pathway and provide enough void space for
Liþ insertion/extraction processes inevita-
accommodating the volume expansion. The prepared SGGr exhibits a high bly induces the pulverization of active
reversible specific capacity of 1089.3 mAh g
1 after 400 cycles (0.16% decay per material and continuous growth of solid
cycle), indicating that SGGr has the great potential for industrial application for electrolyte interphase (SEI) layer on Si
lithium-ion batteries. and 2) the low intrinsic electronic conduc-
tivity and slow Liþ diffusion speed for Si
causes a poor rate performance.[2a,4] All
these factors lead to a rapid capacity fading
1. Introduction and a bad cycling stability.
To solve these problems, various morphologies of Si were
Rechargeable lithium-ion batteries (LIBs) have been widely used designed, including Si nanoparticles,[5] nanowires,[6] nano-
in portable and wearable devices, electric vehicles (EVs), and smart tubes,[7] nanofilms,[8] porous structure,[9] and so on. In addition,
combining Si with other buffer matrixes, such as carbon[10] and
metal oxide, is an efficient way to alleviate these problems.
Dr. J. Li, Dr. W. Liu, Dr. X. Li, Dr. Y. Qiao, Prof. M. Qu, Prof. G. Peng Among a number of buffer matrixes, carbonaceous material
Chengdu Institute of Organic Chemistry
can not only serve as the buffer matrix to accommodate the huge
Chinese Academy of Sciences
Chengdu, Sichuan 610041, P. R. China volume expansion of Si but also act as the conductive material to
E-mail: pgc0102@cioc.ac.cn improve electronic conductivity and Liþ diffusion rate.[1b,3,11]
Dr. J. Li, Dr. X. Li, Dr. Y. Qiao In addition to the pure Si, SiOx also has received increasing
Group of Chemistry and Chemical Engineering attention for its high capacity and less volume expansion. A suit-
University of Chinese Academy of Sciences able amount of SiOx is beneficial to enhance the cycling perform-
No. 19 (A) Yuquan Road, Beijing 100039, P. R. China
ance.[8b] Thus, many efforts have been made to combine Si with
Prof. Q. Wan SiOx and carbonaceous material. For example, Chen et al.[12]
School of Materials Science and Engineering
Southwest University of Science and Technology prepared multi-walled carbon nanotubes (MWCNTs)@Si/
Mianyang 621010, P. R. China SiOx@C through magnesiothermic reduction, carbon coating,
E-mail: wanqi@swust.edu.cn and subsequent acid treatment. Tang and co-workers[13] synthesized
Dr. F. Liu hollow nanospheres of Si/SiOx@C through tetraethyl orthosilicate
Institute of Materials (TEOS) hydrolyzing, polymer coating, preoxidation, carbonization,
China Academy of Engineering Physics and magnesiothermic reduction. As we can see, combining Si,
Jiangyou 621908, P. R. China
SiOx with carbon material can effectively improve the cycling stabil-
The ORCID identification number(s) for the author(s) of this article ity. However, the preparation process for some work is complicated.
can be found under https://doi.org/10.1002/ente.201900464. Herein, we first prepared Si@SiOx@graphite/graphene
DOI: 10.1002/ente.201900464 (SGGr) through one-step and scalable spray-drying. During this

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process, Si was oxidized by hot air and a thin SiOx film was
formed. In addition, the unique dual-shell structure was
designed, where Si nanoparticles act as core coated with a
double-layer SiOx and graphite/graphene. Graphite/graphene
as the carbon framework and amorphous SiOx can accommodate
the volume change and guarantee the structural stability. In
addition, graphite/graphene can also enhance the dispersibility
of Si/SiOx nanoparticles and improve the conductivity of
SGGr. As a consequence, the dual-shell SGGr microspheres
deliver high energy density and long cycling life in LIBs.
2. Results and Discussion
The entire preparation of SGGr is shown in Figure 1. First, Si
nanoparticles, graphite sheets, and graphene oxide (GO) were
homogeneously mixed in deionized water. Here, graphite and
graphene can help disperse the Si nanoparticles. In addition,
GO can act as the binder to stabilize the suspension. After stir-
ring and sonication, the obtained suspension was spray-dried by
hot air to form the precursor Si@SiOx@graphite/graphene
oxide (SGGO). During this process, the SiOx was produced on
the surface of Si nanoparticles and Si@SiOx was embedded into
the sheets between graphite and graphene. Then, the as-prepared
sample SGGr was calcinated at 850  C for 3 h under Ar atmosphere.
X-ray powder diffractometer (XRD) is used to investigate
the crystal phase of SGGr. As shown in Figure 2a, the sharp
and intensive peaks at 28.4 , 47.3 , 56.1 , 69.1 , and 76.4 belong
Figure 1. Schematic illustration showing the preparation process of SGGr.
Figure 2. a) XRD pattern of SGGr. b) Raman spectrums of SGGr, silicon, graphite, and graphene.
Energy Technol. 2019, 1900464 1900464 (2 of 8)
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to (111), (220), (311), (400), and (331) planes (PDF No. 27-1402)
of crystalline Si. In addition, the peak at 26.4 can also be
observed in SGGr, which results from the graphite and gra-
phene. Raman spectroscopy is used to further characterize the
structure of SGGr. As can be seen in Figure 2b, the peaks of
SGGr at 513.5 and 941.2 cm
1 are attributed to the crystal Si,
which is consistent with the XRD result. Compared with pure
Si, the characteristic peaks of silicon shift to higher frequencies
(blue-shift) in SGGr and decline in intensity, which indicates the
masking effect resulting from graphite/graphene and amor-
phous SiOx on the surface of the Si nanoparticles.[14] Except
for the peaks of silicon, peaks at 1349.7 and 1591.9 cm
1 corre-
spond to D-band originated from the disordered structure in
carbon material and G-band corresponding to the ordered
sp2 phase, respectively. The intensity ratio of ID/IG in SGGr is
1.25, which is lower than graphene (ID/IG ¼ 1.3) due to the
introduction of graphite. The lower ID/IG value represents the
higher graphitization degree and better electrical conductivity.
The surface chemical compositions and chemical states of
pure Si and SGGr are investigated by X-ray photoelectron
spectroscopy (XPS). From the wide-scan spectrum shown in
Figure 3a,c, the peaks located at 531.8, 284.6, 149.4, and
97.9 eV correspond to the O 1s, C 1s, Si 2s, and Si 2p, respec-
tively. The result indicates that no other elements are introduced,
except Si, O, and C in SGGr, which is in good agreement with the
results of XRD. In addition, the Si 2p and Si 2s peaks of pure Si
are much higher than SGGr because of the coating of graphite
and graphene. The high-resolution Si 2p spectrums of pure Si
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Figure 3. a) XPS wide-scan spectrum of pure Si. b) High-resolution XPS spectrum of Si 2p for pure Si. c) XPS wide-scan spectrum of SGGr. d) High-
resolution XPS spectrum of Si 2p for SGGr.
and SGGr are presented in Figure 3b,d. The Si 2p peak located
at 99 eV belongs to crystal Si, and another peak located
at 102.2 eV (pure Si) or 103.2 eV (SGGr) belongs to silicon
oxide (SiOx). After spray-drying, the content of SiOx increases
from 9.1% to 39.8%. Compared with bare Si, SiOx suffers less
volume expansion and delivers a better cycling performance.[15]
The morphology and structure of SGGr were observed by scan-
ning electron microscopy (SEM). As shown in Figure 4a, the pure
Si nanoparticles have an agglomerating morphology that consists
of balls of different sizes, from 30 to 100 nm. After the spray-
drying process, graphite, graphene, and Si@SiOx nanoparticles
aggregate into irregular balls (3–10 μm) with abundant voids
(Figure 4b). Moreover, when in contact with hot air, Si nanopar-
ticles partly oxidizes into SiOx and thus turn into Si@SiOx par-
ticles. As we can see in Figure 4c, there are a few graphene
and graphite sheets exposed on the surface of the spherical
particles, indicating that graphene and graphite supply a unique
carbon framework inside. The unique carbon framework can not
only increase the electrical conductivity but also provide enough
volume for the expansion during the lithiation process. As
revealed by the energy-dispersive X-ray spectroscopy (EDS) in
Figure 4d–f, the Si, O, and C elements in SGGr are homo-
geneously distributed. The O element mainly comes from SiOx
layer, which is in accord with the XPS result.
To further confirm the structure and morphology of SGGr,
transmission electron microscopy (TEM) and high-resolution
transmission electron microscopy (HRTEM) testing are performed.
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As shown in Figure 4g, the Si@SiOx nanoparticles embed into
graphite and graphene uniformly, in connection with the EDS map-
ping results. Here, graphite and graphene supply a supporting
framework that can load Si@SiOx and prevent them from aggregat-
ing. Figure 4h shows that during spray-drying, Si@SiOx, graphite,
and graphene connect together and produce a porous structure,
which can accommodate the volume change of SGGr during the
lithiation/delithiation process. The Si nanoparticles are coated
with a uniform and thin (1–2 nm) SiOx layer, as clearly shown in
Figure 4i. The SiOx layer is amorphous, whereas the nano-Si has
a nice crystallization. In addition, the distinct lattice fringes of
0.34 and 0.31 nm belonging to (002) plane of the ordered graphene
sheets and (111) plane of crystalline silicon can be observed, which
is consistent with the XRD results.
The N2 adsorption/desorption measurement is used to calcu-
late the surface area of SGGr. As shown in Figure 5a, a hysteresis
loop at the pressure 0.45–0.98 in SGGr can be seen, which refers
to the existence of mesopores and macropores. Figure 5b shows a
type-II curve, which indicates there is no pore structure in pure
Si. In addition, the calculated BET surface area and pore volume
for SGGr are 48.4 m2 g
1 and 0.163 cc g
1, respectively, which
are higher than that of pure Si (36.2 m2 g
1 and 0.087 cc g
1).
The improvement in the surface area mainly comes from the
piled pore between the graphite and the graphene sheets, which
can effectively relieve the volumetric expansion of Si/SiOx during
cycling and allow active material to have a better contact with the
electrolyte. Therefore, the special porous structure can shorten
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Figure 4. SEM images of a) pure Si and b,c) SGGr. d–f) EDS mapping of Si, O, and C for SGGr. g,h) TEM and i) HRTEM images of SGGr.

Figure 5. Nitrogen adsorption–desorption isotherms of a) SGGr and b) pure Si.

the lithium-ion transmission pathway and accelerate the electro-
chemical reaction.
To investigate the lithium-ion storage in SGGr, cyclic voltam-
metry is conducted for the first five cycles at a scan rate
of 0.1 mV s
1. As shown in Figure 6a, two broad peaks at
1.56–1.7 V and 0.37–0.58 V occur in the first cathodic sweep
but disappear in the subsequent cycles, which is attributed to
the decomposition of the electrolyte additive fluoroethylene
carbonate (FEC) and the formation of SEI, respectively.[11a,16]
For the following cycles, the reduction peak at 0.18 V is attributed
to the lithium-ion insertion into graphite/graphene, and the
sharp reduction peak <0.1 V corresponds to the transformation
from crystalline Si to amorphous Si (Si ! LixSi).[11b,17] Also,
there are two anodic peaks at 0.35 and 0.53 V, indicating a

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Figure 6. a) Cyclic voltammetry curves of SGGr for the first five cycles at a scan rate of 0.1 mV s
1. b) The first charge/discharge curves of SG, SGr, and
SGGr at 0.1 A g
1. c) Cycling performance comparison of pure Si, SG, SGr, and SGGr at 0.2 A g
1. d) Rate performance of SG, SGr, and SGGr at various
current densities. e) Long-term cycling performance of SGGr at 1 A g
1.

two-step delithiation process, from LixSi to amorphous Si.[3a]
Obviously, the intensity of these characteristic peaks grows
with the cycling process due to the gradual activation and
electrolyte penetration of the SGGr electrode.[18] Moreover,
the good repeatability of the peaks indicates an excellent cycling
stability of SGGr anode during the repeated charge/discharge
process.[11b]
The initial galvanostatic charge/discharge curves of Si@
SiOx@graphite (SG), Si@SiOx@graphene (SGr), and SGGr at
0.1 A g
1 are shown in Figure 6b. For the first cycle, the charge/
discharge capacities are 1170.9/1551.9 mAh g
1 for SG, 2236.3/
2934.9 mAh g
1 for SGr, and 2325.2/2997.8 mAh g
1 for SGGr.
Obviously, SG displays a much lower capacity than SGr and
SGGr due to the lacking of GO during spray-drying process. In
addition, their initial coulombic efficient (ICE) are 75.5%, 76.2%,
and 77.6%, respectively. It is noted that the reason for the low
ICE is mainly resulting from the irreversible loss of Liþ which will
form the SEI film on the surface of SGGr.
The cycling performance of SG, SGr, and SGGr is compared
at a current density of 0.2 A g
1, as shown in Figure 6c. As we can
see, all the composites prepared by spray-drying deliver an
improving cycling performance compared with the pure Si.
The rapid capacity decay implies that not all the Si nanoparticles
participate in the electrochemical reaction due to the lacking of
the protection of the SiOx layer and graphite/graphene. During
the repeated lithiation/delithiation process, bare Si undergo
severe volume expansion and lose connection with the current
collector. Among SG, SGr, and SGGr, SGGr plays a superior

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cycling stability than the others. After 100 cycles, SGGr still has a
higher capacity (1549.1 mAh g
1) and a better capacity retention
(66.6%), whereas the capacity for SG is 695.7 mAh g
1 (capacity
retention: 57.9%) and the capacity for SGr is 1246.4 mAh g
1
(capacity retention: 64.2%). The significant improvement in
cycling performance is due to the synergistic effect between
the graphite and the graphene. Here, graphite has a perfect
crystallization to provide a stable cycling property and graphene
can not only improve the dispersibility during the spray-drying
but also serve as a flexibility-coating layer to ease the volume
expansion stress.
Figure 6d shows the rate capability of SGGr, SGr, and SG at
different current densities, ranging from 0.1 to 2 A g
1. Under
the corresponding charge/discharge current densities at 0.1,
0.5, 1, and 2 A g
1, SGGr delivers the average charge capacities
of 2372.1, 1972.7, 1606.0, and 1394.1 mAh g
1, respectively.
When the charge/discharge current density returns back to
0.1 A g
1, the charge capacity recovers to 1954.2 mAh g
1.
Similar to the other two samples, the charge capacities decrease
with the increase in current density, which results from the
polarization at the high current density. However, SGGr can still
maintain a high capacity and continue to be steady at 2 A g
1.
The huge improvement mainly results from the graphite and
graphene, which will improve the electrical contact during Liþ
transfer and therefore reduce the polarization.
The long-term cycling stability of SGGr is also tested at a cur-
rent density of 0.1 A g
1 for the first two cycles and 1 A g
1 for
the subsequent cycles. As shown in Figure 6e, SGGr still plays a
high reversible specific capacity of 1089.3 mAh g
1 after 400
cycles corresponding to 0.16% decay per cycle. Especially after
60 cycles, SGGr becomes absolutely active and forms a stable
SEI film, only 1 mAh g
1 loss per cycle. Compared with pure
Si, huge improvement in the long-term cycling stability for SGGr
is achieved with the help of dual-shell structure composing SiOx
and graphite/graphene. Here, SiOx will react with Liþ and form
amorphous silicon, Li2O, and a series of lithium silicate, in which
the latter two can alleviate the volume expansion effect.[19] In
addition, acting as the coating layer, SiOx, and graphite/graphene
can protect bare Si from exposing to the electrolyte directly,
minimize the side effects, and thus enhance the electrochemical
performance of SGGr.
To illustrate the superior electrochemical performance of our
study, Table 1 compares the cycling performance of Si@SiOx
anode with similar reports. Obviously, the prepared SGGr
exhibits an outstanding cyclability. In addition to the high
capacity, SGGr is simple to prepare and suitable for large-scale
Table 1. Cycling performance comparison of Si@SiOx anode for LIBs in
similar reports.
Reversible specific Current
Anode material capacity [mAh g
1] density [A g
1]
Coaxial CNTs@Si/SiOx@C 450 (500th) 0.4
Core-shell Si@SiOx/C 760 (100th) 0.1
Dual Core-shell Si@SiOx@C 1030 (500th) 1 [21]
Hollow Si@SiOx/@C 940 (100th) 1 [13]
Si@SiOx@graphite/graphene 1089 (400th) 1 This work
Energy Technol. 2019, 1900464
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production through facile spray-drying method. Compared with
the other preparing method, spray-drying is a continuous pro-
cess, which can efficiently obtain production. In addition, water
is used as a solvent, leading to an economical and environment-
friendly result.
To better understand the role of SiOx and graphite/graphene
dual-shell structure, electrochemical impedance spectrometry
(EIS) measurements are carried out. Figure 7a exhibits the exper-
imental and fitted Nyquist plots of SGGr and pure Si before
cycling together with the corresponding equivalent circuit. For
both SGGr and pure Si, the Nyquist curves consist of a depressed
semicircle in the high–medium frequency region, associated
with the charge-transfer resistance (Rct) and an oblique line at
low-frequency region connected to the lithium-ion diffusion
impedance in the active materials (Zw).[5,22] Obviously, the calcu-
lated Rct of SGGr (47.6 Ω) is much lower than the pure Si
(148.2 Ω), which means the graphite/graphene can provide a
better electronic conductivity and enhance the connection
between the active materials after spray-drying.
The diffusion coefficient of Liþ (D) for SGGr and pure Si are
also calculated according to the following equations[23]
D ¼ 0.5ðRTÞ2 =ðn2 F 2 Aσ w CÞ2 (1)
0
Z ¼ Rs þ Rct þ RSEI þ σ w ω
0.5 (2)
In the equation, R, T, n, F, A, σw, and C are the gas constant,
the absolute temperature, the electron number of reaction trans-
fer, the Faraday constant, the area of electrode surface, the
Warburg impedance coefficient, and the molar concentration
of lithium-ion, respectively.
Figure 7b shows the relationship between the real impedance
(Z 0 ) and the reciprocal root square of the lower angular frequency
(ω
0.5). Based on the aforementioned Equation (2), the slopes of
the curves represent the Warburg impedance coefficient (σw).
The σw of Si is calculated to be 21 328, which is ten times higher
than that of SGGr (2038). According to Equation (1), the diffu-
sion coefficient of Liþ (D) for SGGr is more than 100 times than
pure Si, indicating that the unique dual-shell structure can sig-
nificantly improve the Liþ diffusion coefficient with the help of
SiOx and graphite/graphene.
To observe the volume change of SGGr and pure Si during
cycling, the morphologies of anodes before cycling and after
200 cycles at 1 A g
1 are tested using SEM. As shown in
Figure 8a,c, there is no obvious crack on the surface of both
SGGr and pure Si electrode before cycling. After 200 cycles,
the SGGr electrode (Figure 8b) still remains intact and smooth,
but pure Si electrode (Figure 8d) suffers severe fracture and
dehisces into small pieces. Similar to SGGr, SG and SGr
(Figure S1, Supporting Information) also maintain integrity.
The difference mainly results from the unique dual-shell struc-
ture, in which the inner-layer SiOx and the outer-layer graphite/
Reference
graphene can provide a good protection for the Si nanoparticles.
[12] All the aforementioned characteristic results show that after
[20] the spray-drying process, Si, graphite, and graphene form a
unique dual-shell structure, in which SiOx acts tightly as the
inner shell coating on Si and graphite/graphene acts as the outer
shell containing Si/SiOx nanoparticles. As the buffer material,
graphite/graphene can construct pores for accommodating the
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Figure 7. a) EIS spectra of SGGr and pure Si electrodes before cycling. b) The relationship between Z 0 and ω
0.5 at low frequency for SGGr and pure Si.
Figure 8. SEM images of prepared SGGr electrode: a) after 1 cycle, b) after
200 cycles, c) pure Si electrode after 1 cycle, d) after 200 cycles.
volume change during the repeated charge/discharge process.
Meanwhile, graphite/graphene can also serve as the conductive
framework, which can promote the transmission of electrons
and significantly improve the electrochemical performance. In
addition, the contents of SiOx on the surface of Si and the
proportion of graphite, graphene, and Si nanoparticles will be
studied in our next work.
3. Conclusions
SGGr with dual-shell structure is successfully prepared through
spray-drying process and the following calcining process. As
Li-ion anode, SGGr delivers a high reversible capacity
(1089.3 mAh g
1) and a remarkable cycling stability (0.16% loss
per cycle) after 400 cycles at 1 Ag
1. Even cycling under 2 A g
1,
SGGr still continues to be steady with an average specific capacity
of 1394.1 mAh g
1. In this study, spray-drying is used, which is
Energy Technol. 2019, 1900464
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considered as a facile and economical method for large-scale
production. Therefore, SGGr has a great industrial potential
in composite anode material for high-performance lithium-ion
batteries. Importantly, this fabrication method could also be used
in other electrochemical energy-storage materials.
4. Experimental Section
Preparation of SGGr: The SGGr composite was fabricated by spray-drying
method with graphite, GO, and Si nanoparticles as precursor suspension.
The specific experimental procedure was as follows: Si nanoparticles (7 g)
(30–50 nm, Guangzhou Hongwu Material Technology Co., Ltd), 2 g artifi-
cial graphite (d50: 15 μm, flake, analytical grade, Chengdu Kelong
Chemical Reagent Co., Ltd.), and 1 g GO (3–10 layers) prepared using
modified Hummers’ method were dispersed in 90 mL of deionized water
and 10 mL of absolute ethyl alcohol. The suspension was stirred and son-
icated for 2 h. After mixing, the homogeneous suspension was spray-dried
by hot air. The specific spray-drying condition was followed: the inlet gas
temperature was 200  C, the outlet gas temperature was 100  C, and the
flow rate of suspension was 20 mL min
1. After spray-drying, the SGGO
power was obtained and heat treated at 850  C for 3 h under Ar atmosphere.
For comparison, the Si@SiOx@graphite (SG) and Si@SiOx@graphene
(SGr) were also prepared through spray-drying method and heat
treatment.
Material Characterization: The morphology and structure of samples
were observed using the JEOL JSM-7500F SEM and the Tecnai G2 F20
S-TWIN TEM. Element distribution was conducted with EDS attached
to the SEM. The structural properties of these samples were characterized
using the Bruker D8 ADVANCE A25X XRD (Cu Kα source, λ ¼ 1.5406 A).
XPS was performed on Escalab 250Xi. Raman measurements were con-
ducted under a wavelength of 632.8 nm on LabRAM HR. The BET-specific
surface area of the samples was measured on Kubo-X1000 in a static
measurement mode.
Electrochemical Measurement: The electrochemical performance of the
electrode was tested by using CR2032 coin cells assembled in an argon-
filled glove box. First, the anode was fabricated by mixing 80% active mate-
rial SGGr, 10% conductive SP, and 10% binder carboxymethylcellulose
(CMC) into a homogenous slurry. Then the slurry was coated on a copper
foil and punched into pieces with the diameter of 12 mm after drying over-
night. Lithium metal was used as the counter electrode. LiPF6 (1 m) in
ethylene carbonate (EC) and diethyl carbonate (DEC) (v/v ¼ 1:1) with
5% FEC was used as the electrolyte. The charge and discharge tests were
performed on the Neware 4000s battery test system. The galvanostatic
charge–discharge was first performed at 0.1 A g
1 for two cycles to active
anode and then cycled at different current densities in the voltage ranging
from 0.01 to 2 V. Cyclic voltammograms (CV) and EIS were measured on
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the electrochemical workstation (Multi Autolab M204, Metrohm). CV test
was performed with a voltage region of 0.001–3 V and a scan rate
of 0.1 mV s
1. For EIS measurement, the frequency ranges from
10 mHz to 100 kHz with an amplitude of 5 mV.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
This work was financially supported by the Collaborative Innovation
Project of Industrial Cluster of Chengdu, Sichuan (2017-XT00-00001-GX).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
graphene, lithium-ion batteries, silicon, silicon oxide, spray-drying
Received: April 23, 2019
Revised: May 17, 2019
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