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org Research Article

Scalable Synthesis of Pore-Rich Si/C@C Core−Shell-Structured

Microspheres for Practical Long-Life Lithium-Ion Battery Anodes
Weili An,⊥ Peng He,⊥ Zongzhou Che, Chengmao Xiao, Eming Guo, Chunlei Pang, Xueqin He,
Jianguo Ren,* Guohui Yuan,* Ning Du, Deren Yang, Dong-Liang Peng, and Qiaobao Zhang*
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ABSTRACT: Silicon/carbon (Si/C) composites have rightfully

earned the attention as anode candidates for high-energy-density
lithium-ion batteries (LIBs) owing to their advantageous capacity
Downloaded via TEL AVIV UNIV on May 8, 2023 at 19:30:10 (UTC).

and superior cycling stability, yet their practical application remains

a significant challenge. In this study, we report the large-scale
synthesis of an intriguing micro/nanostructured pore-rich Si/C
microsphere consisting of Si nanoparticles tightly immobilized onto
a micron-sized cross-linked C matrix that is coated by a thin C
layer (denoted P-Si/C@C) using a low-cost spray-drying approach
and a chemical vapor deposition process with inorganic salts as
pore-forming agents. The as-obtained P-Si/C@C composite has
high porosity that provides sufficient inner voids to alleviate the
huge volume expansion of Si. The outer smooth and robust C
shells strengthen the stability of the entire structure and the solid−electrolyte interphase. Si nanoparticles embedded in a microsized
cross-linked C matrix show excellent electrical conductivity and superior structural stability. By virtue of structural advantages, the as-
fabricated P-Si/C@C anode displays a high initial Coulombic efficiency of 89.8%, a high reversible capacity of 1269.6 mAh g−1 at
100 mA g−1, and excellent cycle performance with a capacity of 708.6 mAh g−1 and 87.1% capacity retention after 820 cycles at 1000
mA g−1, outperforming the reported results of Si/C composite anodes. Furthermore, a low electrode swelling of 18.1% at a high areal
capacity of 3.8 mAh cm−2 can be obtained. When assembled into a practical 3.2 Ah cylindrical cell, extraordinary long cycling life
with a capacity retention of 81.4% even after 1200 cycles at 1C (3.2 A) and excellent rate performance are achieved, indicating
significant advantages for long-life power batteries in electric vehicles.
KEYWORDS: Si anode materials, core−shell structure, microspheres, porous structure, lithium-ion batteries

1. INTRODUCTION high specific surface area of nanostructured electrodes causes

Lithium-ion batteries (LIBs) are important energy storage consumption of more electrolyte, resulting in a low initial
devices with high energy density.1 Silicon (Si) has been Coulombic efficiency (ICE). On the other hand, a lower
volume energy density caused by the lower tap is detrimental
considered to be a feasible alternative for next-generation high-
to practical applications of Si anode materials.16−18 As an
energy-density LIB anodes, due to its high specific capacity of
alternative, microsized Si-based materials present a high tap
above 3500 mAh g−1, abundance, and environmentally friendly
density and a high volumetric capacity compared to their
nature.2,3 Nevertheless, applications of Si anode materials are
nanosized counterparts. However, microscaled Si particles are
hindered by a huge volume expansion (>300%) during
more likely to undergo serious structural pulverization and
repeated charge and discharge processes, which results in the
poor ion/electron transport efficiency during the cycling
structural pulverization of electrode materials and rapid
process, leading to rapid capacity fading. Considering these
capacity degradation.4−6 In addition, Si anode materials have
trade-offs, it is confirmed that developing microscale Si/C
poor electronic/ionic conductivity, which results in poor rate
composites consisting of nanoscale units can effectively solve
capability.7,8
Introducing highly conductive components to construct
composite materials, such as Si/C composites and Si alloys, Received: November 22, 2021
can effectively overcome poor electronic conductivity.9,10 Accepted: February 2, 2022
Designing nanostructured Si materials can buffer the huge Published: February 17, 2022
volume change of Si and improve the cycle life.11−13
Unfortunately, additional difficulties and challenges faced by
nanostructured electrodes must still be overcome.3,14,15 The

© 2022 American Chemical Society https://doi.org/10.1021/acsami.1c22656

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Figure 1. Schematic illustration of the preparation process of P-Si/C@C microspheres.
this contradictory problem.13,19−23 In such a micro/nano-
structured material, individual Si nanoparticles are tightly
connected with carbonaceous materials, and they are
interconnected with each other in a three-dimensional (3D)
conductive network. This unique architecture enhances the
conductivity of active materials, reduces the side reactions of Si
with the electrolyte during cycling, and increases the tap
density of Si-based materials, providing improved cycling
performance with high volumetric energy density. Pomegran-
ate-like microspheres,13 nano/microstructured Si/C compo-
sites,24 and microsized Si−C composites with interconnected
nanoscale building blocks25 have significantly extended the
cycle life of Si. However, fabricating these microsized Si/C
composites usually involves toxic reagents, complex reactions,
and low yields, which are difficult to scale up to the industrial
level. Alternatively, the spray-drying method, which presents
the advantages of large-scale preparation, low cost, and
environmental friendliness, is often used to synthesize micro/
nanostructured Si/C composites with Si nanoparticles and
organic precursors or other carbonaceous materials as raw
materials, such as watermelon-inspired Si/C microspheres,26
Si/nitrogen-doped C/CNT hierarchical-structured spheres,27
hierarchical 3D Si/CNT composite,28 and others. However,
microsized Si/C composites prepared by spray drying do not
have sufficient internal space to effectively alleviate the
tremendous volume expansion of Si when increasing the Si
content in the composites, owing to the tight accumulation of
nanoparticles and the filling of the organic carbon source. This
results in large electrode film swelling, which impedes the
practical application of microsized Si/C composites.3,29
Designing and large-scale preparation of microsized Si/C
composites with high initial Coulombic efficiency (ICE), good
electrical conductivity, excellent cycling performance, and low
electrode swelling properties are therefore highly desirable but
still very challenging.
Hence, we present a scalable method for fabrication of an
intriguing micro/nanostructured pore-rich Si/C microsphere
with Si nanoparticles tightly immobilized onto the micron-
sized cross-linked C matrix that is coated by a thin C layer
(denoted P-Si/C@C) using a spray-drying method and a
chemical vapor deposition (CVD) process with inorganic salts
(NaCl) as pore-forming agents. This architectural design
integrates nanostructured Si nanoparticles and the microsized
cross-linked C matrix with the outer robust C shell and shows
several attractive features favoring enhanced performance.
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Specifically, the as-synthesized P-Si/C@C possesses abundant
internal pores, providing enough interspace to relieve the huge
volume expansion of Si and accelerating the kinetic process of
Li+ diffusion in the electrode. Si nanoparticles embedded in a
cross-linked C matrix (P-Si/C) improve the conductivity of Si
and avoid electrochemical agglomeration. A smooth C shell on
the surface of P-Si/C further increases structural stability,
inhibits the outward expansion, and stabilizes the solid
electrolyte interphase (SEI) film. Benefiting from its structural
advantages, the as-fabricated P-Si/C@C electrode delivers a
high ICE of 89.8%, superior reversible capacity (1269.6 mAh
g−1 at 100 mA g−1), outstanding cycling stability (708.6 mAh
g−1 with 87.1% capacity retention after 820 cycles at 1000 mA
g−1), outperforming several Si/C composite anodes in previous
reports. Further, the P-Si/C@C microspheres exhibit a low
electrode swelling of 18.1% at a high areal capacity of 3.8 mAh
cm−2. Impressively, after assembly in a 3.2 Ah cylindrical cell
with an NCA cathode, extraordinary long-life cyclability with a
capacity retention of 81.4% even after 1200 cycles at 1C (3.2
A) and excellent rate performance with a capacity retention of
93.4% from 0.2 to 3C are achieved. Our findings provide
valuable guidance for the purposeful design of porous micro/
nanostructures of Si/C composite anodes toward practical
high-energy-density LIBs with long-term cycling stability.
2. EXPERIMENTAL SECTION
2.1. Material Synthesis. First, 500 g of Si nanoparticles, 360 g of
NaCl, 150 g of poly(vinylpyrrolidone) (PVP), and 150 g of citric acid
were dispersed in a 2 kg of ethanol/0.5 kg of deionized water mixed
solution via ultrasonic treatment for 0.5 h to form a well-distributed
suspension solution at 25 °C. Then, the solution was spray-dried
using a spray-drying machine at an inlet temperature of 140 °C to
obtain Si/PVP/citric acid/NaCl microspheres. The as-collected
microspheres were annealed at 900 °C for 1 h in an Ar atmosphere
to obtain Si/C/NaCl microspheres. After that, C2H2 gas was
introduced at a flow rate of 1 L min−1 at 0.1 MPa for 4 h to obtain
Si/C@C/NaCl microspheres. After washing away NaCl in hot water,
P-Si/C@C microspheres were obtained. For comparison, Si/C@C
microspheres were prepared by the same method as the P-Si/C@C
except without addition of NaCl as a pore-making agent.
2.2. Material Characterization. The crystal structure and
component of products were characterized using a D8 DISCOVER
X-ray diffractometer (XRD) (Bruker) equipped with Cu Kα radiation
and Raman scattering (HB RamLab). The morphology was
characterized using a Hitachi S-4800 field emission scanning electrical
microscope (FE-SEM), an ion milling system (Hitachi E-3500), and
an FEI Tecnai G2 F20 transmission electrical microscope (TEM).
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Figure 2. (a) SEM image and (b) magnified SEM image of P-Si/C@C; (c, d) transverse section SEM image of P-Si/C@C; and (e) the
corresponding elemental mapping images.
Energy-dispersive X-ray spectroscopy (EDS) element mapping images
were recorded by FIB-SEM (Crossbeam 340/5, Zeiss). Thermogravi-
metric analysis (TGA) was performed using a TA Instruments Q60.
The tap density of the samples was measured with a Quantachrome
DTA-6-220 tap machine and the distribution of partial size was
obtained using a Mastersizer 3000 laser particle size analyzer.
2.3. Electrochemical Assessment. The electrochemical proper-
ties of electrode materials were tested after being assembled into
CR2025 coin cells. 70% of active materials, 15% of super P, and 15%
of the CMC binder were mixed with deionized water to form a
homogeneous slurry. The slurry was uniformly coated onto a Cu foil
and then vacuum-dried for 5 h at 90 °C. The active material loading
was controlled at about 3.5 mg cm−2. The coin-type cells were
assembled in an Ar-filled glovebox with a Celgard 2400 as the
separator and a solution of 1 M LiPF6 in ethylene carbonate and
diethyl carbonate (1:1, v/v). Cyclic voltammetry (CV) was conducted
on a CHI 760e electrochemical workstation at a scan rate of 0.5 mV
s−1. Galvanostatic charge/discharge (GCD) tests were carried out on
a Land CT2001A battery testing system. The specific capacities of P-
Si/C@C and Si/C@C anodes were calculated based on the whole
mass of Si and C. The electrode swelling of anodes was monitored
and recorded in real time via an in situ electrode thickness change
(TEC) testing system. A two-electrode flat cell (2E-CELL-ETC,
Eager Corporation, Japan) was assembled with excess NCA as a
cathode and tested on a battery tester for 20 cycles. After mixing P-Si/
C@C with a graphite anode to form a composite anode with a
capacity of 550 mAh g−1, an 18 650-type cylindrical cell with a cell
capacity of 3.2 Ah was assembled and then evaluated using a battery
tester in a potential range from 2.7 to 4.2 V at room temperature.
3. RESULTS AND DISCUSSION
In this work, Si nanoparticles (Figure S1a−c) as the precursor,
poly(vinylpyrrolidone) (PVP), and citric acid as the carbon
resources were used to prepare Si/PVP/citric acid composites
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via a spray-drying method. The schematic of the synthesis
strategy of P-Si/C@C is depicted in Figure 1. First, Si
nanoparticles, moderate salt (NaCl), citric acid, and PVP were
dispersed and dissolved in an ethanol/water solution to form a
uniform slurry. Si/C/NaCl microspheres were then obtained
using a spray-drying process followed by high-temperature
treatment, where PVP and citric acid acted as a binder and a
cross-linked carbon matrix to connect and embed Si nano-
particles, respectively, and NaCl acted as a pore-making agent
during the processes of dissolution, precipitation, melting, and
solidification. Finally, an amorphous C layer was further
embedded in and coated on the Si/C/NaCl microspheres to
obtain Si/C@C/NaCl microspheres by a CVD process. After
washing away NaCl in Si/C@C/NaCl, P-Si/C@C core−shell-
structured microspheres with a high porosity of 38.2% were
obtained. Porosity can be changed by choosing the type of salt
and adjusting solubility at different temperatures.
The SEM images of the Si/PVP/citric acid/NaCl
composites in Figure S2a show that most of the composites
have a uniform spherical structure. The SEM image (Figure
S2b) reveals that Si/PVP/citric acid/NaCl spheres show a
rough and porous surface, indicating that the spheres comprise
smaller Si nanoparticles and NaCl particles. In the spray-drying
process, NaCl is precipitated from the solution and dispersed
uniformly in the Si/PVP/citric acid/NaCl composite, acting as
a pore-forming agent. PVP and citric acid act as the cross-
linked carbon matrix in which Si nanoparticles are uniformly
embedded and dispersed. NaCl melts at high temperatures to
fill nanopores to avoid the collapse and clogging of nanopores
during the annealing process, leaving a sufficient number of
pores when washed away by water. After the CVD process, the
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Figure 3. (a) XRD pattern, (b) Raman spectra, (c) TG curve, (d) particle distribution, (e) nitrogen adsorption/desorption isotherms, and (f)
Barrett−Joyner−Halenda (BJH) pore size distribution of P-Si/C@C.
obtained Si/C@C/NaCl microspheres retain the spherical
morphology of Si/C/NaCl microspheres (Figure S2c). A
magnified SEM image of a microsphere (Figure S2d) shows
that its surface exhibits a compact and smooth morphology.
Transverse section SEM images of the Si/C@C/NaCl
microspheres are provided in Figure S2e, showing their
interior structure. The nanopores in the Si/C@C/NaCl
microspheres are successfully filled with C through the CVD
process, and the C shell is closely encapsulated on the surface
of the microspheres, which decreases the specific surface area
for improving the ICE. The EDS mapping (Figure S2f) of Si/
C@C/NaCl microspheres was conducted on a cross section of
the microspheres, which shows that the Si, C, and Na are
evenly distributed over the entire cross section of the particles.
Even after the complete removal of NaCl by water, P-Si/C@C
microspheres were obtained.
SEM images in Figure 2a,b show that P-Si/C@C maintains a
spherical morphology with no significant structural change or
damage and has a smooth and dense surface. FIB-SEM is used
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to analyze the inner structure. The cross-sectional view in
Figure 2c,d clearly shows that a large number of pores are
present in P-Si/C@C and are uniformly distributed in the
cross-linked C matrix. The large interstitial space from the
pores left by washing away NaCl can relieve the huge volume
expansion of Si and reduce electrode swelling, enhancing the
electrochemical performance and improving the battery safety.
The continuous C matrix can provide a superior 3D
conductive network for Si nanoparticles to improve the rate
performance and avoid electrochemical agglomeration after
uniformly embedding Si in this C matrix. Si/C@C micro-
spheres prepared by the same method, but without the
addition of NaCl as a pore-making agent, have a relatively
dense internal structure, leaving insufficient voids to relieve the
volume expansion of Si (Figure S3). The EDS mapping of P-
Si/C@C (Figure 2e) shows the uniform distribution of Si and
C elements and no residual Na element in P-Si/C@C after
washing with water. The TEM image in Figure S4a clearly
shows that the obtained microsphere has a porous structure.
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Figure 4. (a) CV curves of P-Si/C@C, (b) GCD profiles of P-Si/C@C measured at 100 mA g−1 from 0.01 to 2 V; (c) cycling test of P-Si/C@C
and Si/C@C at 100 mA g−1; (d) rate performance; and (e) long-term cycling test at 1000 mA g−1 for P-Si/C@C and Si/C@C.
The corresponding TEM image in Figure S4b displays a crystal
lattice fringe with an interlayer spacing of the (111) plane of
crystalline Si and demonstrates the amorphous nature of the
outer C shell.
The XRD patterns of the as-prepared Si/C@C/NaCl
microspheres and P-Si/C@C microspheres are shown in
Figures S5 and3a. Remarkably, three intense diffraction peaks
correspond to the (111), (220), and (311) crystal planes of Si
according to PDF card no. 005−0565. A broad peak centered
at 25° is observed for Si/C@C microspheres, demonstrating
an increase in the amorphous carbon content of the
composite.9,30,31 Compared with the XRD pattern (Figure
S5) of Si/C@C/NaCl, no NaCl diffraction peaks are observed
for P-Si/C@C, indicating that NaCl in P-Si/C@C can be
completely removed by washing with water. The peak at 513
cm−1 in the Raman spectra of P-Si/C@C (Figure 3b) is
attributed to Si and the peaks at 1341.9 and 1589.3 cm−1 are
assigned to the D and G bands of C, respectively. In the P-Si/
C@C microspheres, the relatively low intensity of the band at
515 cm−1 could be related to the masking effect of the C
shell.32,33 The ratio of the D/G band is almost 1.12, confirming
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an amorphous C structure.34,35 The TG analysis results show
that the percentage of amorphous C in P-Si/C@C micro-
spheres is 53.8% by weight (Figure 3c), suggesting that about
46.2 wt % Si can be introduced to P-Si/C@C by the spay-
drying process. The size distribution of P-Si/C@C is from 1.4
to 23 μm, with an average diameter (D50) of ∼5.7 μm (Figure
3d). According to the adsorption isotherm shown in Figure
3e,f, P-Si/C@C has a low specific surface area of 12.2 m2 g−1
and shows a wide size distribution from 30 to 150 nm and is
centered at 94 nm. The symmetric normal pore size
distribution and low specific surface area of the particles are
beneficial for preparing dense electrodes and improving
volumetric energy density. Compared with P-Si/C@C, Si/
C@C presents a higher specific surface area of 245 m2 g−1
(Figure S6a) and a C content of 62.3 wt % (Figure S6b), which
results in low ICE and specific capacity.
The electrochemical performances of the P-Si/C@C and Si/
C@C microspheres were evaluated using coin-type cells. The
mass loading of the anodes was approximately 3.5 mg cm−2.
The CV curves of the P-Si/C@C microsphere electrode from
0.01 to 2.0 V are shown in Figure 4a. In the first cathodic cycle,
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Figure 5. (a, b) SEM images of P-Si/C@C after 100 cycles; (c) the corresponding transverse section SEM image of P-Si/C@C after 100 cycles;
cross section SEM images of (d) P-Si/C@C and (e) Si/C@C electrode films; and schematic illustration showing the structural evolution of (f) P-
Si/C@C and (g) Si/C@C during cycling.
peaks at 0.19 and below 0.1 V correspond to the formation of
amorphous LixSi. Two anodic peaks at 0.32 and 0.53 V
correspond to the process of delithiation, which is consistent
with previous reports.36,37 Figure 4b shows the 1st, 2nd, and 5th
GCD profiles of P-Si/C@C microspheres measured at 100 mA
g−1. The first discharging and charging capacities are 1413.7
and 1269.6 mAh g−1, respectively, corresponding to an ICE of
89.8%, which is higher than those Si anodes reported in the
literature studies.14,25,38,39 The improved ICE could be
attributed to the low specific surface area and the compact C
shell of P-Si/C@C microspheres, which reduces side reactions
on the Si surface and prevents the electrolyte from permeating
through the entire P-Si/C@C. From the 2nd to the 5th cycles,
the shape of the charge/discharge profiles shows a trend to
overlap, indicating good cycling stability. The cycling perform-
ance of the P-Si/C@C microspheres was investigated at 100
mA g−1. The discharge capacity (Figure 4c) of P-Si/C@C is
maintained at 1003 mAh g−1 after 100 cycles, corresponding to
a capacity retention of ∼86% from the third cycle onward. For
comparison, Si/C@C exhibits a much faster capacity fade, and
a capacity of only around 764.6 mAh g−1 is retained after 100
cycles. To evaluate rate capability, the P-Si/C@C micro-
spheres were cycled at various current densities (Figure 4d).
The P-Si/C@C microspheres exhibit superior rate perform-
ance, with much higher capacities of 1174.3, 1056.5, 940,
813.1, and 606.5 mAh g−1 at current densities of 0.1, 0.2, 0.5,
1.0, and 2.0 A g−1, respectively, than that of Si/C@C
microspheres, due to the enhancement of electric conductivity
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caused by structural stability and integrity. Remarkably, when
the current density returns to 100 mA g−1 after 40 cycles, a
stable high charge capacity of 1146.1 mAh g−1 is recovered for
the P-Si/C@C microspheres. To highlight the advantages of
the pore-rich structure of P-Si/C@C, long cycling performance
was tested at a higher current density of 1000 mA g−1 (Figure
4e). Si/C@C microspheres show a discharge capacity of 471.8
mAh g−1 (1.65 mAh cm−2) after 820 cycles with a capacity
retention of 63.6%. By contrast, the P-Si/C@C microspheres
can still deliver a stable discharge capacity of approximately
708.6 mAh g−1 (about 2.5 mAh cm−1) after 820 cycles,
showing a high capacity retention of 87.1%, which is more
competitive than Si/C@C microspheres and reported Si/C
composites (Table S1). In this work, P-Si/C@C microspheres
have a high tap density of 0.92 g cm−3, which is also higher
than that of most reported porous C−Si nanocompo-
sites.3,13,26,27,40−44 The volumetric capacity of the electrode
was calculated to be 1168 mAh cm−3 at 100 mA g−1, which is
near 5 times higher than Si nanoparticles16 and 2.5 times
higher than graphite anodes.45 Electrochemical impedance
spectroscopy (EIS) tests were performed to evaluate the
resistance of the P-Si/C@C and Si/C@C electrodes during
charge/discharge cycling. As shown in Figure S7a, the Nyquist
plots of the Si/C@C microsphere electrodes have two
semicircles in the high-frequency region and a sloped line in
the low-frequency region. As depicted in the corresponding
equivalent circuit (inset in Figure S7), the semicircle in the
high-frequency range represents charge transfer between the
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Figure 6. Cross section SEM images of (a, b) P-Si/C@C and (c, d) Si/C@C electrode films (a, c) before cycling and (b, d) after five cycles. (e)
Thickness changes versus time curves of P-Si/C@C and Si/C@C from in situ ETC tests.
electrolyte and SEI (RSEI), and the charge transfer (Rct)
occurring at the surface of the electrode.46−48 Comparing the
EIS obtained on the cells after 100 cycles, the smaller
semicircles of RSEI and Rct of P-Si/C@C compared to Si/C@C
further verify a more stable SEI film formed on the P-Si/C@C
microsphere surface because of a more stable structure upon
cycling and higher conductivity than those of Si/C@C. The
powder conductivity curves in Figure S7b show that P-Si/C@
C has a much higher conductivity than Si/C@C even at a high
pressure of 64 MPa, promoting improved rate performance.
The morphology of the P-Si/C@C microspheres obtained
by SEM after 100 cycles was further examined to evaluate the
excellent structural stability of P-Si/C@C microspheres
(Figure 5). As shown in Figure 5a,b, the P-Si/C@C electrode
can still maintain a good spherical structure without an obvious
change in particle size and observable cracks after 100 cycles at
100 mA g−1, indicating rather high structural stability. The
cross section SEM image of the P-Si/C@C electrode (Figure
5c) clearly shows that no crack or fracture is observed inside
the P-Si/C@C microspheres and that the cross-linked C
matrix maintains its integrity and shows structural stability
after full lithiation. In addition, most of the interpores are
squeezed and reduced after full lithiation, illustrating that pore-
rich P-Si/C@C can provide sufficient inner voids to buffer the
volume expansion of Si and then exhibit low electrode swelling.
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The cross section SEM image (Figure 5d) of the P-Si/C@C
electrode film further demonstrates that the electrode is still in
compact contact with the Cu foil after the 100th cycle,
presenting no obvious cracking and a dense structure, and the
spherical structure of P-Si/C@C remains without rupture,
leading to excellent cycling stability. However, the Si/C@C
electrode film is clearly cracked, the spherical structure of Si/
C@C is destroyed, and serious pulverization is clearly
indicated in Figure 5e, resulting in rapid capacity decay. This
damage to the entire structure results in poor cycle
performance, low ICE, inferior rate performance, and large
electrode swelling, hindering the practical application of Si/
C@C in LIBs. For a microsized Si/C composite anode,
sufficient internal space plays a crucial role in alleviating the
large volume expansion to improve electrochemical perform-
ance. Figure 5f,g show a schematic illustration of the structural
evolution of P-Si/C@C and Si/C@C during cycling. P-Si/C@
C microspheres can maintain structural stability and integrity,
even after many cycles, and exhibit no obvious particle level
toward expansion because the pore-rich internal structure can
provide enough void space to accommodate the huge volume
expansion of Si. For comparison, Si/C@C microspheres that
lack sufficient porosity suffer from serious cracks and ruptures,
resulting in more significant electrode swelling and poor
electrochemical properties.
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Figure 7. (a) GCD profiles of P-Si/C@C//NCA in the cylindrical cell; (b) CE of first 110 cycles; (c, d) the rate performance of P-Si/C@C//NCA
cylindrical cell; and (e) its correspoding cycling test.
For practical applications, the large electrode film swelling of
Si anodes must be urgently addressed, although this is still
extremely challenging. As shown in Figure 6a,b, the cross
section SEM images of the P-Si/C@C electrode film show an
average thickness of 30.2 μm before the cycle and 34.5 μm
after full lithiation, exhibiting a thickness swelling of 14.2%. At
the same areal capacity (3.8 mAh cm−2), the thickness of a Si/
C@C electrode film is 31.4 μm before the cycle and 42.2 μm
after five cycles (Figure 6c,d), corresponding to an electrode
film expansion of 34.4%. The P-Si/C@C electrode therefore
exhibits significantly reduced electrode film swelling compared
to reported Si-based anodes.25,38−42 To further evaluate the
electrode film thickness change of the P-Si/C@C anode in a
full cell, in situ ETC tests were applied for real-time
monitoring of electrode thickness changes of the P-Si/C@C
anode in a two-electrode cell (Figure S8).49 Figure 6e shows
the electrode film thickness change of the two anodes during
the first 20 cycles (the cycling processes took approximately
five days). Si/C@C shows an electrode swelling of 28.4% at
100% SOC and 13.5% at 0% SOC in the first cycle. P-Si/C@C
has a low electrode swelling of 15.2% at 100% SOC and 6.6%
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at 0% SOC in the first cycle, thus showing a lower thickness
change than Si/C@C. After 20 cycles, the electrode swelling
stabilizes at approximately 18.1% at 100% SOC and 12.7% at
0% SOC. The smaller electrode film expansion of P-Si/C@C
ensures long cycling stability and promotes the safety and
stability of LIBs that use Si-based anodes, profiting the
industrialized application of Si anodes.
To evaluate battery performance in commercial LIBs,
18650-type cylindrical cells (P-Si/C@C//NCA) with 3.2 Ah
were assembled using P-Si/C@C blending graphite as an
anode and N8-L NCA (Figure S9a-c) as a cathode and tested
in the potential between 2.7 and 4.2 V. N8-L NCA shows a
high capacity of 203.5 mAh g−1 and an ICE of 89.3% (Figure
S9d). The energy density of cylindrical cells can reach
approximately 256 Wh Kg−1 based on a 3.5 V platform
voltage and an average battery weight of 43.8 g. The GCD
curves (Figure 7a) of the P-Si/C@C//NCA cylindrical cell
show a discharge capacity of 3180 mAh and a charging
capacity of 3548 mAh, together with an ICE of 89.6%. In
addition, the P-Si/C@C//NCA cylindrical cell maintains a
high CE (Figure 7b) over 99.8% after only 10 cycles, ensuring
https://doi.org/10.1021/acsami.1c22656
ACS Appl. Mater. Interfaces 2022, 14, 10308−10318
ACS Applied Materials & Interfaces
the high reversible capacity and superior cycling stability of the
cylindrical cell.
Moreover, the cylindrical cell shows high-rate capacities of
3205.4 and 2993.4 mAh at 0.2C and 3C, respectively,
demonstrating a high capacity retention of approximately
93.4% and outstanding rate performance (Figure 7c,d). The
long-term cycling performance of the cylindrical cell described
in Figure 7e shows impressive cycle stability with capacity
retentions of 84.9 and 81.4% after 1000 and 1200 cycles at 1C,
respectively, which is better than those reported Si anodes
(Table S1) and meets the main demand for long-term cycling
LIBs in EVs.
The excellent Li storage properties of the P-Si/C@C
microsphere are probably related to its well-designed structure.
In particular, the compact C shell prevents the electrolyte from
permeating through the entire P-Si/C@C microsphere and
reduces side reactions, leading to a superior ICE. The Si
nanoparticles embedded in the 3D continuous C matrix as the
core of the microspheres can enhance the conductivity of the
composites and prevent the agglomeration of Si nanoparticles
during charge/discharge cycling, resulting in enhanced cycling
stability. The enormous number of internal pores in the
microspheres effectively buffers the volume changes of Si,
enhancing the structural integrity of P-Si/C@C and restricting
electrode swelling. This method by in situ pore-forming agents
to control the porosity of electrode materials can be extended
to other high-volume-expansion electrode materials. However,
how to find the best balance between porosity, compaction
density, and compaction density still needs to be systematically
studied.
4. CONCLUSIONS
In summary, we demonstrated a scalable approach to produce
intriguing core−shell-structured P-Si/C@C microspheres
through spray-drying and CVD processes with inorganic salts
as the pore-forming agents. This architectural design of the
micro/nanostructured P-Si/C@C composite offers the excep-
tional advantages of nanosized Si, microsized cross-linked C
matrix, and outer C nanocoating for boosting its electro-
chemical performance. With prominent merits in the structure,
the as-fabricated P-Si/C@C electrodes display extraordinary
electrochemical performance, namely, a high ICE of 89.8%,
superior reversible capacity, and excellent cycling performance
with 87.1% capacity retention after 820 cycles at 1000 mA g−1.
Impressively, a low electrode swelling of 18.1% at a high areal
capacity of 3.8 mAh cm−2 can be obtained. Remarkably, when
coupled with a commercial NCM cathode into a 3.2 Ah 18650-
type cylindrical cell, the full cell exhibits superior cycling
performance with a high capacity retention of 81.4% after 1200
cycles at 1C and exceptional rate performance with a capacity
retention of 93.4% from 0.2 to 3C, demonstrating significant
potential for practical applications. Our findings in this work
clearly indicate that the P-Si/C@C microspheres with a high
tap density (0.92 g cm−3) show great potential as alternatives
for substituting current commercialized graphitic anodes for
next-generation high-energy-density LIBs and offer important
insights into designing high-performance alloy anodes.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c22656.
10316
www.acsami.org Research Article
SEM images; TEM images; XRD patterns; nitrogen
adsorption/desorption isotherms; Nyquist plots; TG
curve; GCD profiles; table for the comparison of the
electrochemical characteristics and other important
features of P-Si/C@C; and other reported Si/C
composites (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Jianguo Ren − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China; Email: renjianguo@btrchina.com
Guohui Yuan − MIIT Key Laboratory of Critical Materials
Technology for New Energy Conversion and Storage, School
of Chemistry and Chemical Engineering, Harbin Institute of
Technology, Harbin 150001, P. R. China; Email: ygh@
hit.edu.cn
Qiaobao Zhang − Department of Materials Science and
Engineering, College of Materials, Xiamen University, Xiamen
361005 Fujian, P. R. China; orcid.org/0000-0002-3584-
5201; Email: zhangqiaobao@xmu.edu.cn
Authors
Weili An − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China; MIIT Key Laboratory of Critical
Materials Technology for New Energy Conversion and
Storage, School of Chemistry and Chemical Engineering,
Harbin Institute of Technology, Harbin 150001, P. R. China
Peng He − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China
Zongzhou Che − BTR New Material Group Co., Ltd.,
Shenzhen 518107, P. R. China
Chengmao Xiao − BTR New Material Group Co., Ltd.,
Shenzhen 518107, P. R. China
Eming Guo − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China
Chunlei Pang − BTR New Material Group Co., Ltd.,
Shenzhen 518107, P. R. China
Xueqin He − BTR New Material Group Co., Ltd., Shenzhen
518107, P. R. China
Ning Du − State Key Laboratory of Silicon Materials and
School of Materials Science and Engineering, Zhejiang
University, Hangzhou 310027, P. R. China
Deren Yang − State Key Laboratory of Silicon Materials and
School of Materials Science and Engineering, Zhejiang
University, Hangzhou 310027, P. R. China
Dong-Liang Peng − Department of Materials Science and
Engineering, College of Materials, Xiamen University, Xiamen
361005 Fujian, P. R. China; orcid.org/0000-0003-4155-
4766
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.1c22656
Author Contributions
⊥
W.A. and P.H. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the China Postdoctoral
Science Foundation (2020M672827), the National Natural
Science Foundation of China (Grants Nos. 52072323,
52122211, and 51872098), and the “Double-First Class”
https://doi.org/10.1021/acsami.1c22656
ACS Appl. Mater. Interfaces 2022, 14, 10308−10318
ACS Applied Materials & Interfaces
Foundation of Materials and Intelligent Manufacturing
Discipline of Xiamen University.
■
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