Journal of Electroanalytical Chemistry 884 (2021) 115074

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Journal of Electroanalytical Chemistry

journal homepage: www.elsevier.com/locate/jelechem

A facile fabrication of micro/nano-sized silicon/carbon composite with a

honeycomb structure as high-stability anodes for lithium-ion batteries
Qinxing Xie a,⇑,1, Shipeng Qu a, Peng Zhao b
a
Tianjin Key Laboratory of Advanced Fibers and Energy Storage, School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
b
Department of Chemistry, Nankai University, Tianjin 300017, China

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

Keywords: Silicon based anodes for lithium ion batteries have attracted great interests because of a high theoretical capac-
Lithium ion battery ity of 4200 mAh g−1. To achieve high performance and low cost silicon anodes by overcoming their inherent
Silicon anode drawbacks, a facile route was carried out to successfully encapsulate the micro/nano-sized silicon particles into
Yolk-shell structure a nitrogen-enriched porous carbon matrix using CaCO3 as the structural template, polyacrylonitrile (PAN) as
Composite
the carbon and nitrogen source. The resultant porous composite (Si/PC) exhibits dramatically enhanced cycling
Porous carbon
stability and excellent rate performance, about 830 mAh g−1 can be achieved after discharged/charged at
200 mA g−1 for 200 cycles with a high retention of 81.5% based on the second reversible capacity, further-
more, 230 mAh g−1 can still be maintained even at a high current density of up to 3200 mA g−1. The enhanced
performance is ascribed to the unique porous structure that can accommodate the volume variation of silicon
during the lithiation/delithiation process, and the increased conductivity due to the enriched nitrogen species
in the carbon network.

1. Introduction Nowadays, the most common anodes are graphite materials, and
the graphite has a low theoretical capacity of 372 mAh g−1
Lithium ion batteries (LiBs) are a kind of electrochemically [4,18,19]. In recent years, silicon materials have attracted great atten-
rechargeable energy storage systems, in which the lithium ions travel tion as anodes for LiBs because of a high theoretical capacity of
between the cathode and anode through an electrolyte during 3590 mA g−1 based on the alloyed form of Li15Si4 achievable at room
charge/discharge process. Due to a number of advantages such as temperature and of 4200 mAh g−1 according to the fully lithiated Li22-
high energy density, memory-free effect and long cyclic life, LiBs Si5 at high temperature, which is more than ten times that of graphite,
have been dramatically developed and widely applied in small elec- as well as low lithiation potential (0–0.4 V vs. Li/Li+), high natural
tronic devices such as smart phones, laptops, digital cameras and abundance and other advantages [20–23]. It has to be noted that sili-
potable tools, as well as in the large application fields including pub- con anodes suffer from a huge volume expansion of up to about 400%
lic transportation, aerospace engineering, national defense and med- if fully lithiated into Li22Si5, which induces a giant internal strain,
ical systems [1,2]. To satisfy the global growing demand for new resulting in severe pulverizing and flaking off from the electrode, con-
and clean energy with the development of human society, more sequently accounting for huge capacity degradation and poor cycling
advanced LiBs with high energy density and high power density performance. Additionally, due to the constant volume expansion
are required, which has stimulated an intensive research of new elec- and contraction of silicon, the solid-electrolyte interphase (SEI) film
trode materials of low-cost, high capacity and good environmental becomes very unstable and easily undergoes continual formation,
benignity. In the aspect of anodes, the research mainly focuses on which irreversibly consumes extra amount of electrolyte and lithium
the carbonaceous materials including graphite-based carbon [3–5], ions, resulting in dramatically decreased capacity, low Coulombic effi-
hard carbon [6–8], carbon nanotubes [9,10] and graphenes ciency (CE) and reduced electronic conductivity, as well as the
[11–13], as well as non-carbonaceous materials such as transition increased ionic transport resistance in the electrodes [24,25].
metal oxides/sulfides [14–16], alloys [17] and so on. Therefore, to realize a practical application of high performance

⇑ Corresponding author.
E-mail address: [email protected] (Q. Xie).
1
ORCID iD: 0000-0002-8953-5276

https://doi.org/10.1016/j.jelechem.2021.115074
Received 24 December 2020; Received in revised form 21 January 2021; Accepted 9 February 2021
Available online 18 February 2021
1572-6657/© 2021 Elsevier B.V. All rights reserved.
Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

silicon-based anodes, the key is how to prevent the electrode pulver- and ultrasonicated for 3 h, and then the dispersion was added drop-
ization and maintain a stable SEI film. It seems that this issue could wise into the CaCl2 solution under stirring. After that, the mixture
be addressed to some extent by reducing the particle sizes from micro- was further stirred for 10 min and filtered to obtain Si@CaCO3. The
to nano-scale, and a critical particle diameter of ca. 150 nm was product was rinsed with water for several times, and then with ethanol
reported by Huang [26]. According to the previous investigation, sili- and dimethylformamide (DMF). Finally, Si@CaCO3 was dispersed in
con particles with smaller sizes than this value did not show obvious 1–2 mL of DMF, and then a certain amount (0.24 and 0.30 g, respec-
crack or fracture due to the enhanced ability to accommodate internal tively) of PAN was dissolved. The solution was stirred for 1 h to get
strain during lithiation/delithiation process. Hence, more and more a uniform mixture, and dried at 60 °C under vacuum to obtain
efforts have been devoted to designing and fabricating various nanos- Si@CaCO3/PAN precursor. The precursor was pre-oxidized at 280 °C
tructured morphologies, such as one-dimensional (1D) silicon nano- for 4 h in air, and washed by the diluted hydrochloric acid and water
wires [27,28] and nanotubes [29,30], two-dimensional (2D) silicon to remove the template. The purified precursor was carbonized at
nanosheets/nanofilms [31] and other three-dimensional (3D) nano- 650 °C for 6 h in nitrogen atmosphere, and the product was designated
porous architectures [32,33]. Furthermore, the nano-engineered parti- as Si/PC24 and Si/PC30 based on the mass of PAN, respectively. For
cles are able to provide more active sites for lithium ion storage, and comparison, 0.1 g of silicon particles was directly dispersed in
shorten the ion diffusion distance because of the increased contact 1–2 mL of DMF, and then 0.24 g PAN was dissolved. The mixture
area with the electrolyte. was uniformly stirred for 1 h and dried in vacuum as well to obtain
It has to be noted that the electrode volume variation is generally the Si/PAN precursor. Si/PAN was pre-oxidized, purified and car-
too severe to be completely alleviated although the nano-sized archi- bonized using the same procedure, and the product was designated
tectures can withstand the stress and limit cracking of silicon, the pul- as Si/C24.
verization and detachment from current collector can still occur during
a long-term charge/discharge cycling. Therefore, in order to more
effectively improve electrochemical performance of the silicon anodes,
further efforts have been made to have silicon nanoparticles encapsu- 2.2. Structure characterization
lated into another phases such as various carbonaceous materials
[34–37] and conductive polymers [38]. Among these matrix candi- The particle sizes of the sand-milled silicon powers were analyzed
dates, carbon materials such as amorphous carbon, graphite, carbon by using a Winner2308A automatic laser particle size analyzer using
nanotubes and graphene have attracted great attention because of pure water as the dispersant. The surface morphology and interior
their unique structure, high conductivity, strong mechanical strength microstructure of the as-prepared composites were investigated by
and excellent chemical stability, which can not only adapt volume field-emission scanning electron microscopy (FESEM) performed on
variation but also improve the conductivity of the silicon anodes, a Hitachi S-4800 microscope, and transmission electron microscopy
accounting for enhanced cycling stability and rate capability. Up to (TEM) carried out on a Tecnai G2 F20 microscope, respectively. The
now, a large number of nano-sized/porous silicon based Si/C compos- crystal structure and phase purity of the samples were evaluated by
ites have been prepared via chemical vapor deposition (CVD) [39], the X-ray powder diffraction (XRD) patterns that were measured on
spray drying/pyrolysis [40] and high energy ball-milling [41] meth- a Rigaku D/MAX-2500 diffractometer (Cu Kα). The thermo-gravimet-
ods. However, the manufacturing processes of the nano-sized silicon ric analyses (TGA) were performed in air within a temperature range
and porous silicon are generally complicated and expensive. of 25–800 °C at a heating rate of 10 °C min−1 on a NETZSCH
In this work, we tried to use the micro-sized silicon (ca. 5–10 μm) TG209F3 thermal analyzer. The surface features of the materials were
as the starting material to fabricate the micro/nano-sized silicon/car- investigated by X-ray photoelectron spectroscopy (XPS) that was
bon composite of high performance but with a low manufacture cost. recorded on a Thermo scientific K-Alpha spectrometer with an Al Kα
The original silicon was first sand-milled to get the micro/nano-sized irradiation source. The nitrogen sorption isotherm measurements were
particles, and then the particles were encapsulated into the porous car- carried out at 77 K on a V-Sorb 2800P sorptometer to determine the
bon to form a mixed yolk-shell and granadilla-like architecture by specific surface area and pore sizes of the materials.
using CaCO3 as the structural template, polyacrylonitrile (PAN) as
the carbon and nitrogen source. The doping of nitrogen in carbon
structure was intended to improve the conductivity of the material.
As expected, the porous (Si/PC) composite exhibits significantly 2.3. Electrochemical measurements
improved electrochemical performance compared to the convention-
ally fabricated Si/C composites due to the unique porous structure. The electrochemical tests for all materials were performed at room
Additionally, the facile fabrication strategy could enable further appli- temperature using CR2430-type coin cells. The working electrodes
cation of the silicon-based composites as high performance anodes for were fabricated using the conventional casting method, and each elec-
LiBs. trode consists of 70 wt% active materials, 15 wt% Super-P as the con-
ducting agent and 15 wt% sodium alginate (SA) as the binder that
were casted on the copper foil as the current collector. The cells were
2. Experimental
assembled in an argon-filled glove box, the lithium disk was used as
the counter electrode, Celgard 2300 as the separator, and 1 M LiPF6
All chemicals were analytical grade and used without further
in a mixed solvent of ethylene carbonate (EC)/diethyl carbonate
purification. The micro-sized silicon powders (around 5–10 μm) were
(DEC) (V:V = 1:1) with 5 wt% fluoroethylene carbonate (FEC) as
sand-milled for 4 h using a HCX-2L type miller prior to the experiment.
the electrolyte. The galvanostatic charge/discharge (GCD) tests of
To alleviate surface oxidation and pollution, no water and other sol-
the assembled cells were conducted on a Kino LAND2001A-type
vents were used as the milling reagents.
multi-channel battery tester. The applied potential window was
5 mV − 3.0 V (vs. Li/Li+), and the current densities and specific
2.1. Materials preparation capacities were determined based on the mass of the composites on
each electrode. The cyclic voltammetry (CV) within 5 mV − 3 V
2.12 g of Na2CO3 (0.02 mol) and 2.22 g CaCl2 (0.02 mol) were sep- and electrochemical impedance spectroscopy (EIS) in a frequency
arately dissolved in 100 mL of distilled water. 0.1 g of silicon powders range from 100 kHz to 0.01 Hz were recorded on a CHI660E electro-
were dispersed in the Na2CO3 solution, and stirred dramatically for 1 h chemical system.

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

3. Results and discussion with the CaCO3 layer, the other two structure units such as Si@C and
Sin@C without hollow space between the Si core and carbon shell
3.1. Structure of the materials could also be present in the product.
Fig. 3 shows the SEM images for the samples. The conventional Si/
The sizes of the sand-milled silicon particles were analyzed, and the C24 composite prepared without CaCO3 template exhibits the irregu-
resultant volume-based size distribution curve is shown in Fig. 1a. It lar shaped particles with diverse sizes and relatively smooth surface,
can be seen that the trimodal distribution exhibits three peaks repre- as shown in Fig. 3a. On the contrary, the composites including Si/
senting three different size ranges. The strongest peak centered around PC24 and Si/PC30 are highly porous with a honeycomb structure, as
170 nm indicates that a majority of the particles have the sizes dis- shown in Fig. 3b-f. The formation of the porosity can be attributed
tributed below 380 nm, which accounts for an accumulated volume to the removed template (refer to Fig. 2). For both Si/PC24 and Si/
of about 80%. The other two peaks represent a small amount of parti- PC030, the microsized yolk-shell structure can be observed. As shown
cles that have a size range of 0.8–5.1 um and 5.1–17.6 um, which may in Fig. 3c, the “shell” is a thin carbon layer forming a 3D porous carbon
be attributed to the incompletely grinded original particles and the network, and the “yolk” is an irregular shaped small particle. Another
agglomerated secondary nanoparticles that were not well dispersed type of “yolk” particle can also be observed in Fig. 3f, it is a secondary
during the measurement. According to the analysis, the D10, D50 porous unit that consists of a large number of small primary particles
and D90 values were determined to be 101, 198 and 2329 nm, respec- with a similar morphology to that of sand-milled silicon. As we dis-
tively. SEM image (inset of Fig. 1a) clearly reveals that the silicon par- cussed above, the formation of the secondary “yolk” particles of silicon
ticles have nearly spherical morphology, and the sizes are in could be ascribed to the stick effect of the precipitated calcium carbon-
accordance with the particle size measurement. Additionally, the ate. Additionally, this agglomerated spheres can be well maintained
XRD pattern of the sample matches well with the theoretical diffrac- after the carbonization and purification because of the carbon derived
tions of Si in a cubic structure (JCPDS no. 27–1402), indicating the from PAN filled in the voids of the precursor. The special porous car-
high purity of the milled silicon powders. bon framework can not only increase the conductivity of the compos-
Fig. 2 illustrates the formation scheme and the proposed porous ites, but also provide a large quantity of cavities that can be used as
structure of the Si/PC composite. The intermediate of Si@CaCO3 electrolyte reservoirs and ion transport channels, furthermore, the hol-
was first prepared via a co-precipitation method. Typically, the sand- low space can accommodate volume expansion of silicon during the
milled silicon particles were dispersed into Na2CO3 solution, and then charge/discharge process. Hence, an improved cycling stability can
added dropwise into CaCl2 solution under stirring. In this process, be expected. To gain a further understanding, the interior microstruc-
CaCO3 can be precipitated on the surface of silicon particles, forming ture of Si/PC30 was further analyzed by TEM measurements. The TEM
a core–shell structure. Possibly there could be three types of particle images (Fig. 3g,h) show that the polycrystalline silicon particles are
units including the isolated and agglomerated Si@CaCO3, as well as encapsulated in the highly porous carbon matrix with cavities formed
the bare CaCO3 particles. The agglomerated particles could be formed between them. The high resolution TEM (HRTEM) images of the
due to the in-situ generated CaCO3 that sticks the primary particles selected areas clearly exhibit the lattice fringes of the cubic silicon
together. The purified Si@CaCO3 powders were then well dispersed nanocrystals including (2 2 0) plane with d = 0.19 nm and (1 1 1) plane
in DMF, and mixed with a certain amount of PAN to get a homoge- with d = 0.31 nm.
neous mixture. In this process, a second layer of PAN was coated on The phase composition and crystal structure of the samples were
the surface of the above mentioned three particle units. For the analyzed by the XRD measurements. As shown in Fig. 4a, all samples
agglomerated secondary particles, PAN could penetrate into the voids exhibit nearly identical XRD patterns. The sharp peaks at about 28.4,
between the adjacent primary particles. After being dried in a petri 47.2, 56.1, 69.1, and 76.3° (2θ) can be indexed to (1 1 1), (2 2 0),
dish for a quick evaporation of the solvent, the mixture underwent a (3 1 1), (4 0 0) and (3 3 1) planes of the cubic silicon (JCPDS no.
two-step thermal treatment. After the initial pre-oxidization process, 27–1402). Additionally, a weak broad peak observed at around 24.0°
the CaCO3 layer was washed off by using the diluted hydrochloride can be assigned to the amorphous carbon in the composites. The car-
acid so as to achieve the porous structure units. Ideally, the final bon component was formed by the pyrolysis of PAN, which can
Si@PC porous composite may be composed of all three structure units improve the conductivity and restrict the volume variation of silicon
including two yolk-shell structured Si@void/C and Sin@void/C (gran- during the lithiation/delithiation process. There are no other diffrac-
adilla-like) and porous carbon (PC) (refer to Fig. 2). Meanwhile, if the tion peaks that can be assigned to CaCO3 or other impurities, indicat-
isolated silicon or agglomerated silicon particles were not well coated ing the composites have been well purified.

Fig. 1. (a) Particle size distribution and SEM image (inset), as well as (b) the XRD pattern for the sand-milled silicon.

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Fig. 2. Fabrication scheme and the proposed structure units of the Si/PC composite.

Fig. 3. SEM images for (a) Si/C24, (b,c) Si/PC24, (d-f) Si/PC30; (g,h) HRTEM images for Si/PC30.

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Fig. 4. (a) XRD patterns, (b) TGA curves, (c) nitrogen isotherm and (d) pore size distributions for the samples.

Table 1
BET specific surface area (SBET) and pore structure parameters for the samples (mi and me represent the micropores and mesopores, Dave represents the average pore
diameter, and Vt means the total pore volume, respectively).

SBET (m2 g−1) Smi (m2 g−1) Sme (m2 g−1) Dave (nm) Vmi (cm3 g−1) Vt (cm3 g−1)

Si/C24 5.3 0 5.3 10.0 0 0.013

Si/PC24 30.3 7.9 22.4 2.9 0.004 0.044
Si/PC30 42.0 9.8 32.2 2.9 0.005 0.062

To analyze the content of silicon and carbon species in the compos- with a distinct hysteresis loop located in a relative pressure (P/P0)
ites, TGA measurements were performed in air from room temperature ranges of 0.45–1.0, implying that the mesopores have been developed
to 800 °C at a heating rate of 10 °C/min. As shown in Fig. 4b, the TGA in the structure, as shown in Fig. 4c. According to the Brunauer-
curves exhibit a very small weight loss of ca. 2.9% for Si/PC24 and Emmett-Teller (BET) method, the specific surface area was calculated
3.5% for Si/PC30 below 160 °C, respectively, which can be attributed and summarized in Table 1. Compared to the conventional Si/C24, the
to the surface removal of the physically adsorbed water molecules. As porous composites including Si/PC24 and Si/PC30 exhibit signifi-
the temperature increases up to 300 °C, the other dramatic weight loss cantly increased surface area, which can be ascribed to the well-devel-
can be observed, which is attributed to the combustion of carbon oped porosity. The pore-size distribution curves based on the Barrett-
(C + O2 → CO2). There is no more weight loss detectable above Joyner-Halenda (BJH) model (Fig. 4d) exhibit that most pores in Si/
800 °C. Therefore, the final residues are determined to be 37.5% and P24 are mainly smaller than 10 nm, whereas those in Si/PC24 and
33.3% of the initial mass for Si/PC24 and Si/PC30, respectively. So Si/PC30 are smaller than 100 nm, indicating a much broader pore-size
the silicon content is about 38.6% for Si/PC24, and about 34.5% for range. These meso- and macropores in Si/PC should be originated from
Si/PC30 after the deduction of the adsorbed water. It has to be noted the large vacancy generated due to the removal of the CaCO3 template.
that the onset temperature of carbon pyrolysis for Si/PC24 is about This unique porous structure is beneficial for the enhancement of elec-
45 °C higher than that for Si/PC30. For Si/PC24, probably some silicon trochemical performance of the materials as anodes for LiBs due to a
particles are not completely encapsulated by the carbon layer due to a couple of advantages. Generally, the meso- and macropores are able
lower carbon content, and may be distributed on the outer surface of to accommodate the electrolyte and facilitate lithium ion diffusion,
the carbon, which could exert a shielding effect that accounts for a meanwhile effectively buffer volume variation of the active compo-
higher onset temperature for the carbon pyrolysis. nents during the charge/discharge process.
N2 adsorption/desorption measurements were carried out at 77 K To characterize the surface features of the composites, XPS mea-
to investigate the specific surface area and porous nature of the mate- surements were carried out for Si/PC30. The resultant survey spectrum
rials. All samples demonstrate the type-IV sorption isotherm curves reveals several distinct signals including C1s, N1s, O1s, Si2s and Si2p,

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Fig. 5. (a) The survey XPS spectrum, and the fitted high resolution (b) C1s, (c) N1s and (d) Si2p.

indicating that the material surface is composed of C, N, O and Si ele- (Fig. 1) does not reveal any diffractions of the oxides, it is very likely
ments with an atomic ratio of 74.8/16.0/6.8/2.5, as shown in Fig. 5a. that their amount is extremely small. The slight oxidation could occur
Therefore, the mass percentage of silicon on the surface can be esti- during the sand-milling process of silicon and thermal treatment pro-
mated to be around 1.0% only, indicating that silicon particles have cess of the precursor.
been well encapsulated into the carbo matrix. The high resolution
C1s spectrum was fitted into five major constitutes including CAC/ 3.2. Electrochemical performance of the materials
C@C at 284.6 eV, CAN at 285.1 eV, CAO at 285.8 eV, C@O at
286.9 eV and O@C-O at 288.7 eV [14,42], respectively, as shown in CV tests were conducted at a scan rate of 0.1 mV s−1 in the poten-
Fig. 5b. The N1s spectrum was fitted into four groups including N-6 tial range of 0.01–3.0 V (vs. Li/Li+) to investigate the electrochemical
(pyridinic-N) at 398.3 eV, N5 (pyrrolic-N) at 399.7 eV, N-Q (quater- behavior, and the initial three cycles for all samples are shown in
nary-N) at 400.8 eV and N-X (oxidized-N) at 403.4 eV [19,42], respec- Fig. 6a-c. A very weak broad peak at around 1.23 V can be observed
tively, as shown in Fig. 5c. The doped nitrogen atoms are originated for all samples in the first cathodic scan, but it becomes invisible after-
from the –CN groups of PAN. The polar oxygenic groups and the pyri- wards, which is generally ascribed to the preliminary electrolyte
dinic-N and N-X species could enhance the wettability of materials to decomposition. Additionally, there is a pronounced cathodic peak
the hydrophilic electrolytes, hence facilitating the diffusion of lithium close to 0 V, which corresponds to the intercalation of lithium ions
ions [43]. Furthermore, the pyridinic and pyrrolic-N species and the in the carbon layers, and the lithiation of crystalline silicon into the
induced defects around them are able to offer extra storage sites for amorphous LixSi phases (Eqs. (2),(3)) [8,44,46,47]. During the subse-
lithium ions [43,44]. Meanwhile, the graphitic-N is beneficial for the quent anodic sweep, two peaks at ca. 0.37 V and 0.54 V are observed,
improvement of local charge density of carbon network, so a higher which can be attributed to a two-step reversible delithiation process of
percentage of this kind of nitrogen could effectively enhance the elec- LixSi to amorphous silicon, including the low-voltage delithiation (Eq.
tronic conductivity of the materials, which accounts for a better high- (4)), and the high-voltage delithiation process (Eq. (5)) [48]. Further-
rate performance. The high-resolution Si2p spectrum in Fig. 5d con- more, both Si/PC24 and Si/PC30 initially exhibit an intense broad
sists of Si-Si and Si-O signals, the former was deconvoluted into two peak at around 0.67 V that has disappeared upon cycling, which is
peaks, including 99.6 eV for Si-Si2p3/2, 100.2 eV for Si-Si2p1/2, and very likely ascribed to the formation of the SEI layer and the occur-
the latter can be fitted into three peaks including 102.1 (Si2+), rence of other irreversible reactions (Eq. (1)) [44], accounting for an
103.5 (Si3+), 104.5 eV (Si4+) for Si-O [34,45], indicating the forma- irreversible capacity loss in the first cycle. The subsequent cathodic
tion of SiOx on the surface of Si particles. As the XRD pattern scan reveals an additional peak at ca. 0.21 V, which is probably attrib-

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Fig. 6. (a-c) CV curves and (d-f) GCD profiles for the samples.

uted to the higher voltage lithiation of Si and the formation of amor- C24, 1767/1450 mAh g−1 for Si/PC24, and 1585/1244 mAh g−1
phous LixSi (Eq. (6)) [48]. The peak at ca. 0.37 V becomes stronger for Si/PC30, corresponding to an efficiency of 73.0, 82.1 and 78.5%,
after the first two cycles, which indicates the improved Li+ extraction respectively. The irreversible capacity loss in the first cycle, i.e. 372
kinetics [44]. Additionally, the peak intensities observed in both mAh g−1 for Si/C24, 317 mAh g−1 for Si/PC24 and 341 mAh g−1
cathodic and anodic processes exhibit an increasing tendency upon for Si/PC30 can be attributed to the irreversible formation of SEI lay-
cycling, implying the gradual activation process. ers. The efficiency rapidly increases up to around 95.0% for Si/C24,
and around 98.0% for Si/PC24 and Si/PC30 for the second and fifth
Liþ + e + electrolyte ! SEI (Li) ð1Þ
cycles, respectively. Therefore, the porous Si/PC24 and Si/PC30 com-
posites demonstrate much better electrochemical performance than
C + xLiþ + xe $ LiCx ð2Þ the conventional Si/C24 anode. Additionally, Si/C24 exhibits much
more rapid capacity fading, and the remaining discharge/charge
Si (crystalline) + xLiþ + xe ! Lix Si (amorphous) ð3Þ capacities are only 367/356 mAh g−1 (CE = 97.0%) after 50 cycles,
whereas Si/PC24 and Si/PC30 can still maintain 937/926 mAh g−1
Lix Si (amorphous) $ Lixy Si (amorphous) + yLi + ye ð4Þ (CE = 98.8%) and 1008/998 mAh g−1 (CE = 99.0%), respectively.
The rapidly decreased capacity over cycling and lower CE for Si/C24
Lixy Si (amorphous) $ Si (amorphous)+ (x-y)Liþ + (x-y)e ð5Þ can be ascribed to the shortcomings of the solid interior structure in
which the Si particles intimately contact the carbon matrix without
Si (amorphous) + xLiþ + xe $ Lix Si (amorphous) ð6Þ any voids formed between them to accommodate the volume expan-
sion of silicon during the lithiation process, hence the carbon layer
The discharge/charge profiles at a current density of 200 mA g−1 could crack and consequently lose protective effect due to the
for all samples and the pristine Si anode for comparison are presented expanded LixSi alloys, resulting in an unstable SEI film and a poor
in Fig. 6d-g. The first discharge/lithiation curve displays a long flat cycling stability. On the contrary, as discussed above, Si/PC24 and
plateau below 0.25 V due to the irreversible formation of the typical Si/PC30 have unique porous architecture around the silicon particles
SEI layer (refer to Eq. (1)), the lithium intercalation process into the that can effectively buffer the volume variation and prevent them from
carbon to form LiCx (Eq. (2)) and alloying process of crystalline Si to the direct contact with the electrolyte, which accounts for the
form amorphous LixSi phase (Eq. (3)). The initial discharge/charge improved lithium storage performance. Moreover, it can be seen that
specific capacities of the first cycle are 1379/1007 mAh g−1 for Si/

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Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Si/PC24 and Si/PC30 exhibit the remarkable charge capacity in the cated Si/C24 composite, the porous samples including Si/PC24 and
potential range of 1.5–3.0 V compared to the pristine silicon and Si/ Si/PC30 exhibit significantly improved cycling performance. The
C24 anodes (Fig. 6d-h), which could be attributed to an extra contribu- enhanced electrochemical stability can be attributed to their unique
tion of the porous carbon component in the samples, as the porous porous structure that can accommodate the volume variation of Si dur-
structure can provide more lithium ion storage sites. To highlight this ing the lithiation/delithiation process. Meanwhile, Si/PC30 demon-
impact on the total lithium storage capability of the composites, the strates a much higher stability than Si/PC24. Initially, Si/PC24
charge capacity percentage (CCP) above 1.5 V for the 5th and 50th demonstrates higher specific capacities for the first few cycles due to
cycles with relation to the specific surface area (SBET) and total pore its higher silicon content, but the capacity gradually decreases over
volume (Vt) of the samples is plotted in Fig. 6i. Clearly, the CCP above cycling and become lower than that for Si/PC30 after about 40 cycles.
1.5 V increases with the increased SBET and Vt. Therefore, Si/PC30 After 200 cycles, Si/PC30 can still maintain 830 mAh g−1, accounting
exhibits the highest CCP among all of the composites, ca. 22% for for a high retention of 81.5% based on the reversible capacity of the
the 5th cycle and ca. 28% for the 50th cycle can be achieved, respec- second cycle, whereas Si/PC24 can retain 453 mAh g−1 with a reten-
tively. Furthermore, the increased CCP upon cycling may be ascribed tion of only 33.2%. This observation could be because of the higher
to the activated porous structure during the lithiation/delithiation carbon content of Si/PC30 that can provide more effective protection
process. for silicon particles than Si/PC24. Furthermore, Si/PC30 demonstrates
Fig. 7a shows a long term cycling stability of the samples at a cur- much better electrochemical stability than other Si/C composites
rent density of 200 mA g−1. Compared to the conventionally fabri- reported previously, as summarized in Table 2.

Fig. 7. (a) Long-term cycling stability at a current density of 200 mA g−1, (b) rate performance at various current densities, and (c) the average capacity at current
densities from 50 to 3200 mA g−1 for two-time consecutive tests for the samples, as well as d) the cycling stability at 400 mA g−1 after the rate test for Si/PC30.

8
Q. Xie et al. Journal of Electroanalytical Chemistry 884 (2021) 115074

Table 2 Declaration of Competing Interest

A performance comparison of the Si/C composites.

Composite Current density (mA Reversible Ref. The authors declare that they have no known competing financial
g−1) capacity interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Porous Si/graphite/ 100 675.5 (100 [49]
CNTs@C cycles)
Cobalt-doped silicon- 50 610 (50 cycles) [50]
graphite Acknowledgements
Silicon@carbon/graphene 200 780 (100 [51]
cycles) This study was funded by Tianjin Key Projects of New Materials
Core-shell Si/C composite 200 ca.800 (200 [52] Science and Technology (17ZXCLGX00050).
cycles)
Sub-micron Si/C@graphite 100 428.1 (100 [53]
cycles)
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