Rare Met.
(2022) 41(2):438–447
https://doi.org/10.1007/s12598-020-01702-z
ORIGINAL ARTICLE
Electrolytic silicon/graphite composite from SiO2/graphite
porous electrode in molten salts as a negative electrode
material for lithium-ion batteries
Ning Wang, Yu-Yang Liu, Zhi-Xia Shi, Zhang-Long Yu, Hua-Ying Duan,
Sheng Fang, Juan-Yu Yang* , Xing-Ming Wang*
Received: 6 May 2020 / Revised: 27 September 2020 / Accepted: 29 December 2020 / Published online: 19 June 2021
! Youke Publishing Co., Ltd. 2021
Abstract Nano-silicon (nano-Si) and its composites have
been regarded as the most promising negative electrode
materials for producing the next-generation Li-ion batteries
(LIBs), due to their ultrahigh theoretical capacity. How-
ever, the commercial applications of nano Si-based nega-
tive electrode materials are constrained by the low cycling
stability and high costs. The molten salt electrolysis of
SiO2 is proven to be suitable to produce nano-Si with the
advantages of in-situ microstructure control possibilities,
cheap affordability and scale-up process capability.
Therefore, an economical approach for electrolysis, with a
SiO2/graphite porous electrode as cathode, is adopted to
produce nano-Si/graphite composite negative electrode
materials (SGNM) in this study. The electrolytic product of
the optimized porous electrode is taken as the negative
electrode materials for LIBs, and it offers a capacity of
733.2 mAh!g-1 and an initial coulombic efficiency of
86.8% in a coin-type cell. Moreover, the capacity of the
SGNM retained 74.1% of the initial discharging capacity
after 50 cycles at 0.2C, which is significantly higher than
that of the simple mixture of silicon and graphite obtained
from the formation of silicon carbide (SiC) between nano-
N. Wang, J.-Y. Yang*
GRIREM Advanced Materials Co., Ltd., China Automotive
Battery Research Institute Co. Ltd., General Research Institute
for Nonferrous Metals, Beijing 100088, China
e-mail: juanyuyang@163.com
Y.-Y. Liu, Z.-X. Shi, H.-Y. Duan, X.-M. Wang*
GRINM Resources and Environment Tech. Co. Ltd., General
Research Institute for Nonferrous Metals, Beijing 100088, China
e-mail: mansionwang010@163.com
Z.-L. Yu, S. Fang
China Automotive Battery Research Institute Co. Ltd., General
Research Institute for Nonferrous Metals, Beijing 100088, China
1
RARE METALS
Si and graphite particles. Notably, this new approach can
be applied to a large-scale production.
Keywords Li-ion battery; Negative electrode materials;
Molten salt electrolysis; Nano-silicon
1 Introduction
To date, the continued expansion of electric vehicles and
energy storage devices market has stimulated the demand
for high energy density Li-ion batteries (LIBs). The tradi-
tional graphite negative electrode materials, limited by its
low theoretical specific capacity of 372 mAh!g-1, cannot
meet that growing demand. In this circumstance, a novel
negative electrode material with a high capacity, long-term
stability and cheap affordability, is much needed [1]. Nano-
silicon (nano-Si) has been considered as the most promis-
ing alternative, due to its ultrahigh theoretical capacity of
4200 mAh!g-1, as forming Li22Si5 [2]. However, it is prone
to significant volume changes and the resulting fast
capacity declines during operation, which severely con-
strains the commercial application of nano Si-based nega-
tive electrode materials. To address this issue, there have
been various strategies proposed, which can be classed into
two categories [3]. One is designing an appropriate
microstructure such as nano-particles [4], nano-wires [5],
porous particles [6], hollow spheres [7] and core–shell [8].
The other is to synthesize nano Si-based composites with
carbon [9], graphite [10] and various metals [11]. Notably,
a tight bond between Si and other components is conducive
to improving cycling stability. For example, Iaboni and
Obrovac [12] have demonstrated that crystallographic
Li15Si4, which is considered to be circularly unstable, is not
Electrolytic silicon/graphite composite from SiO2/graphite porous
generated when Si-film was bonded to a substrate, which is
attributed to the compressive stress of a clamping effect. In
the research of Cui et al., Si nano-layer was chemically
vapor deposited (CVD) on the surface of graphite particles,
with the as-prepared negative electrode material producing
an excellent cycling performance [13].
Unfortunately, the materials involved in these strategies
are commonly prepared using various complex methods,
which increase the cost to a level that restricts their com-
mercial application. Thus, an approach that can reduce the
cost while ensuring the viability of large-scale production
is desired for the further progress in nano Si-based negative
electrode materials.
FFC Cambridge process, proposed by Chen, Fray and
Farthing in 2000 [14], is an electrolysis method that can
directly reduce solid oxides in molten salt without having
to reach high temperatures (below 900 "C). In 2003, it was
reported that pure silicon could be prepared by taking such
approach from SiO2 in molten calcium chloride (CaCl2)
[15, 16]. Subsequently, in 2009, the formation of Si nano-
wires (SiNWs) was demonstrated by the electrochemical
reduction of SiO2 pellets with a net-like microstructure in
the same electrolyte [17], while the relevant principles
were discussed in detail [18–21]. This study proves that
FFC Cambridge process can lead to the formation of spe-
cial microstructure while producing silicon, or in-situ
microstructure control. Moreover, in order to improve the
rate of reduction, the composite electrode containing both
silica and silicon was taken as the cathode [22], where
silicon was found to be effective in improving conductiv-
ity. The formation of Si / carbon hybrids during molten salt
electrolysis of SiO2/polydopamine was also demonstrated,
and silicon carbide (SiC) was observed to exist between
graphite and silicon particles, thus ensuring a strong bond
between them [23, 24]. However, a large amount of elec-
trochemical inert SiC, derived from a high reactivity of
amorphous carbon produced by pyrolysis, affected the
electrochemical performance of the electrolytic product.
More recently, it was demonstrated that, through a nano-Si
production line with an annual yield of 3 t as fabricated by
GLABAT, China, this method could be applied for com-
mercial purposes [25].
From the discussion above, it can be known that the
combination of Si-based negative electrode materials
engineering and molten salt electrolysis will be conducive
to extending the commercial application of both the
materials and the technology. In this article, the nano-
Si/graphite composites negative electrode material
(SGNM) intended for LIBs is prepared by electrochemi-
cally reducing a SiO2/graphite porous electrode (SGPE) in
molten CaCl2.
In the course of electrolysis, SiO2 is reduced, and
SiNWs are grown in-situ on the surface of graphite. SiC is
Rare Met. (2022) 41(2):438–447
439
supposed to develop on the surface of nano-Si and graphite,
thus resulting in a tight bond between them. Such a
microstructure can improve the cyclic stability of the
materials due to three reasons. (1) The formation of crys-
talline Li15Si4 and the resulting drastic volume varies
during cycling is suppressed, to avoid damage to the
electrode structure. (2) Nano-Si is prevented from
agglomeration. (3) Conductivity is improved by the nano-
Si fixed on conductive graphite, which makes it capable to
maintain conductive connections at the time of volume
expansion and contraction.
To obtain the above-mentioned microstructure, the
nano-SiO2 present in the composite SGPE should be dis-
persed on the graphite surface uniformly, and developing a
net-like structure attached to the surface of graphite parti-
cles. This is crucial to producing the SGNM with a tight
bond between nano-Si and graphite. Hence, the preparation
process of SGPEs was surveyed experimentally, based on
which its effects on the properties and microstructure of
SGPEs were revealed. Subsequently, the preparation of the
SGNM was demonstrated through the molten salt elec-
trolysis with an optimized SGPE as cathode, further with
which the electrochemistry of the electrolytic SGNM was
analyzed.
2 Experimental
The nano-SiO2 with a purity of 99.8% and a median par-
ticle diameter of 30 nm was taken as the raw material.
Besides, three varieties of graphite were selected to study
the effect on SGPEs, including the natural graphite nega-
tive electrode material with a median particle size of
17–23 lm (labeled as NG), the synthetic graphite negative
electrode material with a median particle size of 18–22 lm
(labeled as SG) and the conductive additive graphite for
LIBs with most particle size less than 6 lm (labeled as
CG), respectively. The nano-Si prepared using vapor phase
method with a purity of 99.9% and a particle size of 30 nm
was used to prepare the comparison material.
SGPEs were obtained from a mixture of nano-SiO2 and
various graphite under hot-pressed molding.
Firstly, the nano-SiO2 and graphite powders were dis-
persed in deionized water, before being dried at 120 "C for
48 h to obtain the mixture. Then, the mixture was crushed
to 50 meshes, and molded into SGPEs, with a size of
50 mm 9 50 mm 9 5 mm, by means of hot-pressed
molding performed in an inert atmosphere with a molding
pressure of 12 MPa and varying temperatures, which are
1000, 1100 and 1200 "C, respectively.
SGNM was synthesized via molten salt electrolysis with
an optimized SGPE as cathode. The electrolysis was
operated in a sealed stainless steel reactor at 850 "C,
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440
purged with argon gas on a continued basis, with molten
CaCl2 as electrolyte. SGPEs were assembled with stainless
steel current collectors for the purpose of electric connec-
tion. First, pre-electrolysis was conducted to remove any
impurities from the molten salt at 2.5 V for 1 h between
two graphite blocks used as both anode and cathode. Then,
a constant voltage (1.5 V) was applied for the electro-
chemical reduction between graphite blocks anode and
SGPE cathode until the electric quantity reached the the-
oretical value required for the complete reduction of SiO2.
The electrolyzed SGPE was washed using deionized water
and hydrochloric acid vigorously to remove the attached
CaCl2. The powders collected from the reacted electrodes
were dried in vacuum, and then labeled as SGNM, for later
analysis.
By contrast, a material (labeled as CS) was prepared by
simply mixing nano-Si and CG powders in a mortar. It was
designed to reach nearly the same specific capacity as the
electrolytic SGNM.
With regard to material characterization, the
microstructure, particularly pore structure, of the SGPEs
and SGNM was characterized via a combination of field-
emission scanning electron microscope (FESEM), trans-
mission electron microscope (TEM) and mercury intrusion
porosimeter (MIP). Additionally, the bulk density of the
SGPEs was also tested by MIP. The measurement of
specific surface area and tap density of the raw materials
was performed using the Brunauer Emmett and Teller
(BET) method and fixed-funnel method, respectively. The
resistivities of SGPEs were examined using a four-point
probe method while that of raw powders was verified by a
powder resistivity test instrument. The composition of raw
graphite and electrolytic SGNM was studied using X-ray
diffractometer (XRD) and X-ray energy dispersive spec-
trometer (EDS).
In respect of electrochemistry measurements, both
SGNM obtained from an optimized SGPE and CS were
taken as active material for comparison. The active mate-
rial, conductive agent (Super-P/vapor-grown carbon fibers,
VGCF) and binder (car-cboxymethyl cellulose, CMC/
polyacrylic acid, polyacrylic acid (PAA)/styrene butadiene
rubber, SBR) were dispersed in deionized water with active
materials: super-P: VGCF: CMC: PAA: SBR at a ratio of
86:5:1:3.2:0.4:4.4. Then, the mixture was dispersed by a
Fragugo shear dispersion emulsifier machine for 30 min.
Subsequently, the mixed slurry was coated on 8 lm of
copper foil with the thickness of 70 lm, before being dried
at ambient temperature. Then, the coated copper foil was
punched into disks with a diameter of 14 mm, before being
dried in vacuum at 100 "C for 12 h. Then, the electrode
was used to perform electrochemistry measurements.
CR2032 coin-type cells were assembled with copper foil
coated electrode, Li-metal counter electrode,
1 Rare Met. (2022) 41(2):438–447
N. Wang et al.
polypropylene microporous films separator (Celgard 2300)
and a conventional electrolyte (1.0 mol!L-1 LiPF6/ethyl
cellulose ether (EC): diethyl carbonate (DEC): methyl
ethyl carbonate (EMC) = 1:1:1, in volume ratio), in a glove
box. Electrochemistry was tested using the following
method on a LAND battery tester. Coin-type cells were
constantly current discharged to 0.005 V with a specific
current of 0.1C. Then, the current was set to 0.01C, and the
cells were held until the voltage reached 0.005 V again.
Subsequently, charging was carried out within the voltage
range of 0.005–2.000 V at 0.2C (1C = 750 mA!g-1).
3 Results and discussion
Figure 1 illustrates the preparation process for SGNM.
Firstly, nano-SiO2 and graphite are mixed uniformly and
molded via hot-pressed molding into SGPE with net-like
SiO2. The reason for hot-pressed molding to be adopted is
that the volume of SiO2 clusters decreases when the net-
like structure develops at the time of heat treatment, thus
causing the gap to arise between graphite and SiO2 in the
SGPE. While hot-pressed molding could close the gap
promptly due to the pressure applied during the heat
treatment, that can help maintain the compactness of the
electrode structure. Then, the SGPEs are electrolyzed, and
the products are washed repeatedly to obtain the SGNM,
which is intended for the later experiments and electro-
chemical characterization.
The morphology of nano-SiO2 used as raw material is
shown in Fig. 2a. It can be seen from this figure that there
is an aggregate of spherical particles with a diameter
varying from 20 to 70 nm, and the median particle diam-
eter is roughly 30 nm. Besides, the FESEM images of the
three varieties of graphite used in this study are shown in
Fig. 2b–d. NG, as shown in Fig. 2b, is a high-end natural
graphite negative electrode material which contains a
similar ellipsoidal particle with a relatively uniform parti-
cle size varying from 10 to 35 lm, with the typical
diameter being 20 lm approximately. Additionally, NG
particles are comprised of smaller lamellar graphite, but
they have a smooth surface, which is probably due to its
carbon coating layer according to introduction information.
The negative electrode material SG, as shown in Fig. 2c, is
introduced as a synthetic graphite. Compared with NG, it
has a similar median particle size of 20 lm, but a more
significant variation from 5 to 50 lm. Apart from that, a
more irregular particle shape with sharp protrusions can be
observed on most SG particles. It’s different from these
two varieties of negative electrode materials that CG, as
shown in Fig. 2d, is a commonly used conductive additive
graphite for LIBs. It shows a flake particle with a diameter
smaller than 10 lm, and the typical diameter is * 3 lm,
Electrolytic silicon/graphite composite from SiO2/graphite porous 441

Fig. 1 Schematic diagram of SGNM preparation process

Fig. 2 FESEM images and (insets) higher-resolution images of raw materials for SGPE: a nano-SiO2, b natural graphite (NG)
electrode material, c synthetic graphite (SG) negative electrode material, and d conductive additive graphite (CG) for LIBs; e XRD
patterns and f resistivity—pressure profile of three types of graphite powders used as raw materials

which is closer to the size of nano-SiO2 than that of NG respectively. In comparison, the SSA of nano-SiO2 is
and SG. Moreover, the specific surface area (SSA) of NG, 207 m2!g-1, and the tap density is 0.05 g!cm-1. In this
SG and CG is 3.6, 4.1 and 20.0 m2!g-1, respectively, while respect, CG is considered more suitable as the raw material
the tap density of them is 0.86, 0.85 and 0.20 g!cm-1, used to produce SGPEs, which is because its approximate

Rare Met. (2022) 41(2):438–447 1

442 N. Wang et al.

SSA and lower tap density can provide more space for
nano-SiO2 and increase the chance of contact between
nano-SiO2 and graphite.
Figure 2e shows XRD patterns of three varieties of
graphite. They are all characterized by four diffraction
peaks, centering on * 26.5", 44.5", 54.5" and 77.4", which
are corresponding to the (002), (101), (004) and (110)
crystal planes of typical graphite, respectively. In the
meantime, no peak of other phases is observed. However,
the diffraction peaks differ in intensity, especially those
corresponding to the lattice plane (002) of graphite located
at * 26.5". The diffraction peaks of SG are the highest in
intensity, while that of CG is the lowest. It is generally
believed that the intensity of the diffraction peak is related
qualitatively to the crystallinity of the materials, when the
measurement is performed on the same XRD equipment.
Besides, the graphite with a low crystallinity is more
chemically active. Therefore, it can be judged that SG is
the most crystalline and the least chemically active. Con-
versely, CG is the least crystalline and most chemically
active.
Figure 2f shows the resistivity—pressure relationships Fig. 3 FESEM images of a-c composite mixture and d-f SGPEs
for three varieties of graphite. When the powders are containing varying graphite: a, d SGPE containing NG negative
pressured under 12 MPa, the resistivity of all varieties of electrode material; b, e SGPE containing SG negative electrode
material; c, f SGPE containing CG for LIBs (inset in f being
graphite decreases rapidly with the pressure. While the enlarged image showing details of CG with a very small particle
pressure increases above 12 MPa, the resistivity continues size)
to decrease, but the absolute of the slope decreases.
Therefore, the hot-pressed molding is determined to be
carried out at 12 MPa to minimize the resistivity of the that there are nano-SiO2 clusters and bare graphite particles
SGPEs, which is beneficial to improve the current effi- in the mixture of nano-SiO2 and NG, indicating that these
ciency in electrolysis. Furthermore, the conductivity of CG two components are completely separated. While in the
is superior to that of the other two varieties of negative mixture of nano-SiO2 and SG as well as nano-SiO2 and
electrode graphite regardless of the pressure, while it is CG, there are more nano-SiO2 covered graphite particles
5.3 mX!cm for NG, 6.7 mX!cm for SG and 3.1 mX!cm for that can be observed, which is because their irregular shape
CG at 12 MPa, respectively. is easier for nano-SiO2 to bond to, as analyzed above.
From above, it is expected that CG is more suitable as Subsequently, the mixtures were molded into SGPEs by
a raw material for SGPE due to five reasons. Firstly, its hot-pressed molding at a pressure of 12 MPa and a tem-
low tap density provides more space for nano-SiO2. perature of 1100 "C. The cross-sections of these SGPEs
Secondly, small particles and large SSA increase the were observed by FESEM, as shown in Fig. 3d–e. The
possibility of contact between nano-SiO2 and graphite. morphology of SGPEs containing NG and SG is semblable
Thirdly, irregular shape facilitates the bonding of nano- and is a heterogeneous structure where the graphite, black
SiO2. Fourthly, low crystallinity and high chemical particles 10–35 lm in diameter, are clustered and separated
activity facilitate the formation of tight bond between by nano-SiO2, which is the gray band that is * 1–10 lm
electrolytic Si and graphite, which is supposed to improve wide consists of small particles with a diameter of dozens
the cycling stability of the SGNM. Lastly, high conduc- of nanometers. Since SiO2 is insulating, such microstruc-
tivity is beneficial to electrolysis. To confirm this infer- ture is adverse to improving electrode conductivity. On the
ence, each variety of graphite was mixed with nano-SiO2 contrary, the SGPE with CG shows a greater homogeneity
at a mass ratio of 2:3, and the mixture was molded into than the others. Gathering into gray bands with a width of a
SGPEs at a pressure of 12 MPa and a temperature of few microns, nano-SiO2 is uniformly distributed among
1100 "C. Then, the properties of as-prepared SGPEs were CG particles, with the black flaky particles sized * 3 lm.
characterized. Besides, most flaky graphite particles are connected to each
The mixture of graphite and nano-SiO2 is observed by other to build a conductive network, which is attributed to
FESEM, as shown in Fig. 3a–c. It can be seen from Fig. 3a the fact that the small particle and large SSA of CG

1 Rare Met. (2022) 41(2):438–447

Electrolytic silicon/graphite composite from SiO2/graphite porous
increase the possibility of contact between graphite as well
as between graphite and nano-SiO2.
The resistivity and bulk density of the SGPEs were
measured to further characterize the microstructure, with
the results shown in Table 1. The resistivity of CG-SGPE,
which is 46 mX!cm, is significantly lower than that of NG
and SG-SGPEs, which are 73 and 80 mX!cm, respectively,
due to the higher conductivity of CG and the homogeneous
microstructure of CG-SGPE as described previously.
While the bulk density barely changes for all the three
specimens, which is 1.31, 1.45 and 1.41 g!cm-1 for the
SGPEs containing NG, SG and CG, respectively. It is thus
suggested that nano-SiO2 fills most of the space between
graphite, which means that the main difference in electrode
microstructure depends on the distribution of the two
components.
According to previous reports, the reduction of SiO2 into
Si occurs at the three-phase interlines, which are positioned
between the electron conductor, electrolyte and reactant
SiO2 [17, 26]. Hence, low resistivity improves the electri-
cal conductivity of electrons, low bulk density allows the
electrolyte to infiltrate the electrode rapidly, and homoge-
neous microstructure increases the contact between con-
ductive graphite and nano-SiO2, which is beneficial to the
course of electrolysis. Therefore, the SGPE containing CG
is deemed more suitable for electrolysis due to its lower
resistivity, density and greater homogeneity.
In order to further optimize the microstructure of SGPE,
the mixture of CG and nano-SiO2 was hot-press molded at
1000, 1100 and 1200 "C, with the pressure reaching
12 MPa, to determine the impact of molding temperature
on the microstructure. CG is selected since it is more
suitable for the electrode used in molten salt electrolysis
than the other graphite as analyzed above. Subsequently,
the microstructure and electrolysis process of CG-SGPE
prepared at different temperatures were characterized and
studied comparatively.
FESEM images of CG-SGPEs are shown in Fig. 4a–c,
with the elemental distributions tested by EDS mapping
displayed alongside the images to help distinguish between
graphite and SiO2 particles as marked in the FESEM
images. The morphology of CG, flake particles with sev-
eral microns in diameter in Fig. 4a, does not change, due to
its stability in such temperature range. While nano-SiO2
Table 1 Physical properties of SGPEs with different graphite
Graphite Bulk density/(g!cm-1) Resistivity/(mX!cm)
NG 1.31 73
SG 1.45 80
CG 1.41 46
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443
shows a net-like morphology, which is similar to that
reported in Ref. [11]. The original morphology of SiO2,
spherical particles with a diameter of * 30 nm, barely
changes. The microstructure of SGPE prepared via
1100 "C, as shown in Fig. 4b, is similar to that at 1000 "C.
In addition to a spot of sintered SiO2 particles, the particles
with an undulating surface and a diameter of hundreds of
nanometers are observed. As shown in Fig. 4c, when the
preparation temperature rises to 1200 "C, the net-like
morphology of the nano-SiO2 almost vanishes, and it is
transformed into a glass-like dense particle with a diameter
of a few microns, while the graphite particles remain
unchanged. Although the melting point of SiO2 is *
1650 "C, nano-SiO2 can melt at lower temperatures due to
the nano-size effect [27]. Therefore, it is believed that
nano-SiO2 particles sinter as the hot-press molding tem-
perature increases.
As a consequence, when the hot-pressed molding tem-
perature surges from 1000 to 1200 "C, the bulk density of
the SGPEs increases from 1.14 to 1.78 g!cm-3, while
resistivity and porosity decline from 71 to 33 mX!cm and
from 54.2% to 28.5%, respectively, which is attributed to
nano-SiO2 sintering that depletes the pores and improves
the contact between graphite particles. The physical prop-
erties of the SGPEs prepared at different temperatures are
shown in Table 2. Similar results can be obtained by
analyzing the pore size distribution profiles of CG-SGPEs
prepare at different temperatures, as shown in Fig. 4d.
There are two peaks that can be observed in the profiles of
1000 and 1100 "C SGPEs, which center on 20 nm and
500–1000 nm, respectively. The peak located at 20 nm is
associated with the pores between nano-SiO2 particles,
while the other, located at 500–1000 nm, is associated with
the pores between graphite particles. When the temperature
at which the specimens are treated is elevated to 1200 "C,
the peak at 20 nm fades away, while the other barely
changes, which is consistent with the morphology change
of nano-SiO2 and graphite particles. This suggests that the
microstructure of the SGPE is reflected mainly by SiO2,
which sinters with the hot-press molding temperature, and
it changes rapidly at * 1100 "C. As the molding temper-
ature rises above 1100 "C, SGPE gradually loses its nano-
microstructure. For the nano-microstructure, it is necessary
to obtain nano-Si in electrolytic product, which means the
molding temperature of SGPE is limited to below 1100 "C.
In order to further determine the effect of hot-press
temperature on SGPEs, the molten salt electrolysis with
SGPEs molded at different temperatures as cathode was
carried out, as introduced in the experimental section. The
current density and time profile of these electrolysis are
shown in Fig. 4e, by which the average current density of
the electrolysis was calculated, as shown in Table 2.
1
444 N. Wang et al.

Fig. 4 FESEM images and element distributions tested by EDS mapping of SGPEs molded at different temperatures by hot-pressed
process: a 1000 "C, b 1100 "C, c 1200 "C; d pore size distribution profiles of SGPEs; e current density—time profiles of electrolysis
used CG-SGPEs which are hot-press molded at 1000, 1100 and 1200 "C as cathode

Table 2 Physical properties and electrolytic process data of SGPEs prepared via hot pressing at different temperatures
T/"C Bulk density /(g!cm-1) Resistivity/(mX!cm) Porosity/% Current density/(A!cm-2) Thickness expansivity/%

1000 1.14 71 54.2 2.6 0

1100 1.41 46 42.7 3.0 125
1200 1.78 40 28.5 1.8 200

The average density of electrolysis current for electrol-
ysis at 1000 and 1100 "C SGPEs is basically the same,
reaching 2.6 and 3.0 A!m-2, respectively. Besides, it drops
to 1.8 A!m-2 when the SGPE molded at 1200 "C is taken
as cathode. It can also be considered that the current den-
sity decreases as the porosity of SGPEs increases, as does
resistivity. According to the general electrochemical
principles, the average current density, which represents
the rate of electrolysis qualitatively, is related positively to
porosity, which is due to less resistance of ions transport,
and is negatively associated with resistivity, which is
attributed to the declining rate of electron transfer. There-
fore, in our research, the rate of electrolysis is largely
affected by porosity rather than resistivity. Presumably,

1 Rare Met. (2022) 41(2):438–447

Electrolytic silicon/graphite composite from SiO2/graphite porous
this is ascribed to the excellent electrical conductivity of
graphite, which makes the resistivity of electrodes not as
different as required to produce significant effects.
Another notable phenomenon is that the thickness of the
SGPEs increased after electrolysis, as shown in Table 2.
The thickness of SGPE molded at 1000 "C barely changed
before and after electrolysis, while the thickness of the one
prepared at 1100 and 1200 "C increased by 125% and
200%, respectively. The thickness increase of the electrode
during electrolysis is related to the force caused by the ions
diffusing through the electrode, which increases evidently
with the rise of electrode forming temperature, or with the
loss of porosity. The vanishing porosity leads to the
increased resistance to ion diffusion, which increases the
expansion of the electrode accordingly. The excessive
volume expansion causes the instability or even destruction
of electrode during the electrolysis process, which proves
that CG is preferable to meet the requirements of SGPE.
Considering the need for net-like structure SiO2 to
produce SiNWs [17], SGPE should be prepared at 1100 "C,
so as to form a net-like microstructure while maintaining
high porosity and low resistivity, which is conducive to
electrolysis. Therefore, the SGPE containing nano-SiO2
and CG at a mass ratio of 2:3, was prepared at 1100 "C by
hot-press molding, and was electrolyzed. While the elec-
trolytic product, SGNM, was measured by coin-type cells.
In contrast, a material (labeled as CS) as-prepared by
simply mixing silicon nano-particles and CG was tested in
the same way.
Fig. 5 a–c FESEM images, d TEM image, e line-scanning elemental profile and f XRD patterns of CG-SGPE and electrolytic product
of CG-SGPE which hot-pressed molded at 1100 "C
Rare Met. (2022) 41(2):438–447
445
FESEM images of SGNM are shown in Fig. 5a–c. The
morphology of the electrolytic material is consistent with
the schematic in Fig. 1. It can be observed that plenty of
nano-wires with the fairly uniform diameters of * 50 nm
and a length of 1 lm intertwine with each other and bond
to the surface of graphite. The flaky particles are
sized * 5 lm, and originate from the net-like SiO2 in the
SGPE.
Figure 5d shows TEM image of the nano-wires
obtained. The diameters of the nano-wires are less than
50 nm as shown in the image, which can protect the
nano-wires from damage due to the significant volume
changes during lithium/delithium and produce an excel-
lent cyclic performance. The element distribution across
a nano-wire was measured by line-scanning elemental
profile, as illustrated in Fig. 5e, which reveals that the
most important element in the radial direction is Si. In
addition, a small amount of O element is present in the
nano-wire, which is considered to be obtained from the
natural oxidation layer of the electrolytic Si. These
results indicate that the obtained SGNM consists of
SiNWs and graphite, in which SiNWs are adhered to the
graphite particles.
XRD patterns of the CG-SGPE and electrolytic SGNM,
as shown in Fig. 5f, further confirm this result, which is
because the wide peak according to amorphous SiO2
located at * 21.5" in the XRD pattern of CG-SGPE is
replaced with the peaks of (111) and (220) crystal plane of
Si located at * 28.5" and 47.3" in the XRD pattern of
1
446
Fig. 6 a, b Voltage—capacity profiles of SGNM and a simple mixture of nano-Si and CG powders (CS); c cycling performance profile
of SGNM and CS
SGNM. While the characteristic diffraction peaks located
at * 26.5", 44.5" and 54.5", corresponding to the (002),
(101) and (004) crystal planes of graphite, respectively, can
be observed in XRD patterns of both CG-SGPE and
SGNM, indicating that the CG failed to react during the
electrolysis process. It is noteworthy that the diffraction
peak of SiC (111) crystal planes, located at 35.6", can also
be sought out in XRD pattern of SGNM, thus confirming
its presence. According to previous reports, it is assumed
that SiC forms at the interface between SiO2 and graphite
particles, indicating a tight chemical bond between Si and
graphite [28]. Such tight binding resulting from the for-
mation of SiC is conducive to improving the cyclic per-
formance of SGNM for three reasons as follows. Firstly,
the formation of crystalline Li15Si4 resulting from the
significant volume changes during cycling is suppressed, to
avoid damaging the electrode structure. Secondly, nano-Si
is prevented from agglomeration. Lastly, conductivity is
improved by fixing nano-Si on conductive graphite, which
is effective in maintaining conductive connections during
volume expansion and contraction. Unfortunately, there is
still no firm evidence obtained to suggest such tight
binding.
To demonstrate the electrochemistry of SGNM, it was
assembled into a coin-type cell for testing. For comparison
1 Rare Met. (2022) 41(2):438–447
N. Wang et al.
purpose, a simple mixture of CG and nano-Si (label as CS)
was tested in the same way.
Figure 6a, b shows voltage-capacity profiles of the first
cycle of SGNM and CS, which was tested between 0.005
and 2.000 V. During the first-time delithiation, the SGNM
offers a specific capacity of 733.2 mAh!g-1, corresponding
to an initial coulombic efficiency of 86.8%. While the CS
shows a capacity of 731.6 mAh!g-1 and initial coulombic
efficiency of 85.1%, which conforms to the design. Fig-
ure 6c shows the cycling performance as well as coulombic
efficiency of SGNM and CS, respectively. After 50 cycles,
the reversible capacities retained for SGNM and CS are
74.1% and 9.8% of the first discharging capacity, respec-
tively. It can be seen from such result that the cycling
performance of SGNM is more excellent compared to CG,
as previously analyzed. This is speculated to result from
the formation of SiC between nano-Si and graphite, as
reflected in the XRD pattern shown in Fig. 5f, and the
source of this advantage has been discussed above.
4 Conclusion
In this study, nano-Si/graphite composite negative elec-
trode materials (SGNM) were prepared by molten salt
Electrolytic silicon/graphite composite from SiO2/graphite porous
electrolysis with SiO2/graphite porous electrode (SGPE) as
cathode. According to the result, SGPE should be molded
below 1100 "C by hot-press molding, so as to obtain a
microstructure of net-like SiO2 attached to graphite parti-
cles, which is necessary to form a tight bond between nano-
Si and graphite via electrolysis. The TEM and XRD results
confirmed that the electrolytic SGNM is mainly comprised
of graphite particles, Si nano-wires with a diameter of less
than 50 nm. Compared to the contrast sample (CS) which
is a direct mixture of graphite and vapor phase method
prepared nano-Si, electrochemical contrast study demon-
strated that electrolytic SGNM can produce a better cycling
performance, with 74.1% of the first discharging capacity
retained after 50 cycles.
More importantly, the method proposed in this paper
can be applied to a large-scale production at low cost.
Moreover, it can be commonly used for the commercial-
ized production of silicon-based negative electrode mate-
rials, despite future research being needed.
Acknowledgements This work was financially supported by the
National Key Research and Development Program of China (No.
2016YFB0301305) and the Talent Plan Project of Beijing (No.
2018000097607G378) and the National Natural Science Foundation
of China (U166420031).
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