Journal of Alloys and Compounds xxx (xxxx) xxx

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

One-step synthesis of nanoporous silicon @ graphitized carbon

composite and its superior lithium storage properties
Zhiguo Wang , Biao Zheng , Hui Liu , Chun Zhang , Fangfang Wu , Huayun Luo , Peng Yu *
School of Chemistry and Materials Science, Hunan Agricultural University, Changsha, 410128, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Nanoporous silicon @ graphitized carbon (NPSi@C) composites have been reasonably designed and
Received 1 May 2020 synthesized via one-step magnesiothermic co-reduction using rice husks as the silicon source and CO2 as
Received in revised form the carbon source. In the self-assembly process, the nano-silicon prepared from rice husk-derived SiO2 is
6 November 2020
made into a porous structure and uniformly recombined with graphitized carbon formed by CO2
Accepted 15 November 2020
reduction at low temperature (680
C). The nanoporous structure has contributed to accommodate the
Available online xxx
large volume effect of activated silicon and provides sufficient channels for the transfer of lithium ions.
Furthermore, the graphitized carbon layers effectively enhance the electrical conductivity and coulombic
Keywords:
Lithium ion batteries
efficiency of the composites, which is conducive to the improvement of electrochemical performance.
Anode materials The optimized NPSi@C composite exhibits superior lithium storage properties with the initial coulombic
Silicon/carbon composites efficiency of 41.0% and the reversible specific capacity of 681.8 mA h g1 after 100 cycles at 0.2 A g1. This
Graphitized carbon study suggests a simple, low-cost, and scalable strategy, which maximizes the advantages of traditional
Magnesiothermic reduction magnesiothermic reduction, to the preparation of Si/C composites as the most promising alternative
anode materials for lithium ion batteries.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction commercial application of silicon-based materials for LIBs. On the

one hand, during the lithiation/delithiation processes, the fearful
Lithium ion batteries (LIBs) are regarded as the dominating volume expansion (>300%) of silicon particles leads to repetitive
power sources for portable electronic devices, electric vehicles and cracking and regeneration of solid electrolyte interphase (SEI) layer
renewable energy storage systems, and the field has been awarded and electrode pulverization, resulting in drastically decay of the
the Nobel Prize. However, higher energy density and superior capacity and cycle performance. On the other hand, the low elec-
cycling stability requirements for practical applications demand trical conductivity leads to an inferior rate capability [18,19].
further improvements of the present LIBs [1,2]. Apparently, the Therefore, many strategies such as silicon particle nano-
limited theoretical capacity (372 mA h g1) places a restriction on crystallization [20,21], alloying [14,22], adopting porous structure
the development of commercial graphite anode materials, which is [23,24] and conductive layer (including graphite, amorphous car-
difficult to meet the demands for high-performance LIBs [3,4]. In bon, graphene and other materials) coating [25e27] have been
recent years, plenty of studies have been carried out to explore proposed to overcome the above-mentioned problems. Moreover,
various anode materials such as lithium metal [5e7], metal oxide the combination of two or more approaches can effectively
[8e10], lithium titanate [11e13] and silicon-based materials improve lithium storage properties of silicon-based materials.
[14e16]. Among the possible candidates, silicon-based materials Generally, each approach is implemented individually, which leads
have broad application prospects because of the ultra-high theo- to complex processes, increased costs, and difficulties in
retical specific capacity (3579 mA h g1 for Li3$75Si), moderate industrialization.
lithiation potential (around 0.4 V vs. Liþ/Li) and abundant silicon Since carbon materials have high electrical conductivity and
resources [17]. Nevertheless, two major challenges exist in the flexibility, which can effectively buffer the volume changes of sili-
con, Si/C composites have been deemed as the most practical
silicon-based anode materials for LIBs. The ultra-high capacity of
silicon and the special advantages of carbon can be fully utilized for
* Corresponding author. Si/C composites [21,28]. The silicon materials in the composites are
E-mail address: [email protected] (P. Yu).

https://doi.org/10.1016/j.jallcom.2020.157955
0925-8388/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Z. Wang, B. Zheng, H. Liu et al., One-step synthesis of nanoporous silicon @ graphitized carbon composite and its
superior lithium storage properties, Journal of Alloys and Compounds, https://doi.org/10.1016/j.jallcom.2020.157955
Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

almost nano-silicon, which can be obtained by many synthetic the CO2 atmosphere (purity: 99.5%, flow rate: 200 mL min1), and
methods such as magnesiothermic reduction [29,30], carbothermal the heating rate was 5
C min1. Afterwards, the resulting powder
reduction (above 2000
C) [31] and ball-milling [32]. Magnesio- was immersed into 1 M HCl solution for 6 h to completely remove
thermic reduction method has attracted much attention because it MgO and Mg2Si, and then immersed into 5 wt% HF solution for
can prepare silicon from SiO2 reduction at low temperature (below 20 min with stirring to remove residual SiO2. Finally, the targeted
700
C). However, the thermal effect generated during the mag- NPSi@C composites were obtained after washing with deionized
nesiothermic reduction process can cause the local temperature to water to neutrality and drying at 60
C in a vacuum condition for
be very high, which needs to be addressed [18,33]. The carbon 12 h. The final samples were labelled as NPSi@C-1, NPSi@C-2 and
materials in the composites are usually derived from the pyrolysis NPSi@C-3 representing the SiO2-to-Mg mass ratio of 1:1.5, 1:2 and
of organic compounds in situ [34] and external addition of graphite 1:3, respectively. For comparison, nano-silicon particles (RH-Si)
[35], hard carbon [28] or soft carbon [16], which can be achieved by were prepared from rice husk-derived silica under the same pro-
a variety of methods, including physical mixing [26], chemical va- cess but some different conditions at the SiO2-to-Mg mass ratio of
por deposition (CVD) [19] and hydrothermal treatment [27]. 1:1 in argon atmosphere. The pure carbon layer (M-carbon) was
Compared with hard carbon and soft carbon, graphite has a higher prepared by flowing CO2 through an open corundum reactor con-
initial coulombic efficiency and is the most ideal and practical taining 1 g Mg powder under the same sintering conditions.
carbon material for Si/C composites at present. Normally, organic
compounds used as a carbon source are expensive and release 2.2. Physical characterization
irritant gas during the pyrolysis process, which is environmental
unfriendliness. The prepared carbon materials added later are un- The crystallographic phase of the materials was characterized by
evenly distributed and not tightly enough bound to the silicon X-ray diffraction (XRD), which was conducted on a Shimadzu X-ray
materials. However, the in-situ graphitization of carbon materials diffractometer (XRD-6000) with a 2q ranging from 10
to 80
and a
in Si/C composites requires a high temperature above 2500
C, scanning rate of 2
min1 using Cu-Ka radiation (l ¼ 1.54178 Å).
which inevitably leads to the agglomeration of nano-silicon parti- Specific surface area and pore diameter distribution were deter-
cles and the formation of SiC [36]. Consequently, it is crucial to mined through nitrogen adsorption/desorption isotherms using a
develop the technologies for graphitization of carbon materials at QuadraSorb SI instrument. The determination of carbon content in
low temperature. the NPSi@C composites was performed using a thermogravimetric
In addition, special structures such as hollow and porous analyzer (TGA2, Mettler Toledo, Switzerland) at a ramp rate of 10
C
structures have been designed to further improve the lithium min1 in the air flowing from room temperature to 800
C. The
storage properties of Si/C composites. Porous silicon with the ad- morphology and element distribution were observed by the scan-
vantages of effectively releasing the stress created by the volume ning electron microscopy (SEM, TESCAN MIRA3) equipped with the
changes of silicon also triggers a lot of research [37]. It is note- energy dispersive X-ray spectrometer (EDS). Transmission electron
worthy that the agricultural waste rice husks contain about 20% microscopy (TEM, Tecnai G2 F20) and high-resolution TEM
silica by mass, which can be used as a low-cost renewable silicon (HRTEM) were applied to explore the microstructure of the mate-
source. The natural biomass structure in rice husks is inherited by rials. The elements on the surface were analyzed by X-ray photo-
the final silicon material, which is beneficial for electrochemical electron spectroscopy (XPS, Thermo Fischer ESCALAB Xiþ). Raman
performances [38,39]. spectra were measured using the Renishaw inVia with an Ar ion
Herein, we propose an attractive method for preparing nano- laser source at 532 nm.
porous silicon @ graphitized carbon (NPSi@C) composites by one-
step magnesiothermic co-reduction. In this way, rice husks, a 2.3. Electrochemical measurements
kind of agricultural wastes, are used to provide interlinked silica
nanoparticles based on the simple acid etching and sintering pro- To prepare the working electrodes, the as-prepared materials,
cesses. CO2 is used as a protective gas and creatively introduced as a LiPPA and super P with the mass ratio of 7:2:1 were mixed with
new carbon source. Nano-silicon materials uniformly coated with water to produce aqueous slurry, which was coated on a copper foil
graphitized carbon are obtained by magnesiothermic co-reduction by scraping and then dried at 120
C for 12 h. The surface density of
in CO2 atmosphere at low temperature, following an acid etching the electrode foils was 1.0 mg cm2. CR2032-type coin cell was
process to fabricate NPSi@C composites with superior structure and composed of the working electrode, a counter electrode (lithium
lithium storage properties. Moreover, this strategy is also applicable metal foils), separator (polypropylene membrane, Celgard 2325)
to the existing magnesiothermic reduction systems and provides an and electrolyte (1 M LiPF6 solution) in a mixture of ethylene car-
idea for the high-value utilization of agricultural wastes. bonate/dimethyl carbonate/fluoroethylene carbonate (EC/DEC/FEC,
3:6:1 v/v/v), which was assembled in an Ar-filled glovebox. The
2. Experimental galvanostatic tests of the cells were performed on a battery test
system (LAND CT-2001A) over the voltage window of 0.005e1.5 V
2.1. Materials preparation (vs. Liþ/Li) at 25
C. Cyclic voltammetry (CV) and electrochemical
impedance spectroscopy (EIS) measurements were carried out
Rice husks were immersed into 10 wt% HCl reflux solution at using an electrochemical analyzer (IVIUM Vertex.C.EIS). The CV was
80
C for 2 h. The leached rice husks were filtered and collected, tested between 0.005 and 3.0 V (vs. Liþ/Li) at a scan rate of
washed to neutrality with deionized water, dried at 120
C for 12 h, 0.1 mV s1. The EIS was tested with an amplitude voltage of 5 mV,
and then sintered at 700
C in the air atmosphere for 2 h to produce and the frequency range was from 100 kHz to 0.01 Hz at room
silica nanoparticles (RH-SiO2). temperature.
Subsequently, NPSi@C samples were prepared via one-step
magnesiothermic co-reduction as follow: Firstly, the obtained RH- 3. Results and discussion
SiO2 and Mg powder (200 mesh, purity: 99%) were evenly mixed at
the SiO2-to-Mg mass ratio of 1:1.5, 1:2 and 1:3, respectively. Then, Fig. 1 displays the XRD patterns of the products obtained in each
the mixtures were tiled on the bottom of corundum reactor and process flow. As shown in Fig. 1(a), the diffraction peak appears to
placed in a tube furnace, followed by calcining at 680
C for 3 h in be broad and less crystalline, indicating that RH-SiO2 is essentially
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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 1. XRD patterns of RH-SiO2 (a), RH-Si and NPSi@C composite materials before HF solution etching (b), RH-Si and NPSi@C composite materials (c), M-carbon (d) and Enlarging
pattern of NPSi@C-1 sample at red areas (e). (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

composed of amorphous SiO2. All the XRD patterns of RH-Si and temperature, which leads to the formation of SiC. Therefore, SiC is
NPSi@C composite materials after etching with HCl solution, not HF more or less present in NPSi@C composites. Fig. 1(e) display the
solution (Fig. 1(b)) display the distinct diffraction peaks of the enlarging pattern of NPSi@C-1 sample at red areas. The SiC in
crystal Si phase (JCPDS 27e1402) and a gimmicky broad charac- NPSi@C-1 sample mainly exists in the form of cubic b-SiC phase
teristic peak of SiO2 near 21.9
. In particular, the remarkable (SiCe3C, JCPDS 74e2307), while the form of SiC in NPSi@C-3
diffraction peaks of SiC are observed in the XRD pattern of NPSi@C- sample is the mainly hexagonal a-SiC phase (SiCe2H, JCPDS
1 sample. Due to the adverse impacts of SiO2 on the lithium storage 89e1396). It is known that the temperature required for the syn-
properties of the Si-based composites, it is necessary to remove thesis of SiCe2H is higher than that of SiCe3C. With the increase of
unreacted SiO2 in the subsequent process. The XRD patterns of RH- Mg powder, the most heat accumulation from magnesiothermic
Si and NPSi@C composite materials are displayed in Fig. 1(c). It is reduction reaction in the preparation of NPSi@C-3 sample leads to
found that the broad diffraction peak of SiO2 disappears obviously the production of SiCe2H [45].
by HF solution etching, which means that SiO2 has been effectively In order to further confirm the properties of the NPSi@C com-
removed. Moreover, the carbon peaks of NPSi@C-2 and NPSi@C-3 posites, the Raman spectroscopy is performed. As can been seen
samples are visible. This intensive carbon peak indicates that car- from the Raman spectra in Fig. 2(a), the intense peaks situated at
bon crystallinity is relatively high. Since most of the carbon in about 510 cm1 represent silicon in the NPSi@C composites, the
NPSi@C-1 sample is converted to SiC, there are no obvious carbon distinct peaks located at around 1327 and 1591 cm1 correspond to
peaks on the XRD pattern. The pure carbon layer has been syn- the D band induced by carbon disorder and the G band caused by
thesized from CO2 by magnesiothermic reduction, and the XRD carbon graphitization, respectively [46,47]. Furthermore, the re-
pattern of M-carbon is shown in Fig. 1(d). Apparently, the intensive sults of ID/IG (intensity ratios) are approximately 0.91, 0.88, 0.49 and
peak indicates that M-carbon has graphite-like domain with rela- 0.49 for M-carbon, NPSi@C-1, NPSi@C-2 and NPSi@C-3 samples,
tively good crystallinity, which is more suitable for electrode ma- respectively, suggesting that the excellent graphitization degree,
terial than amorphous carbon. Compared with the common which is consistent with the XRD results. It can also be seen that the
graphitization temperature of amorphous carbon (above 2000
C) graphitization degree of carbon obtained by the separate CO2
[40,41], the graphitized carbon is formed at a relatively low tem- reduction is lower than that of carbon obtained by the combined
perature (680
C), which is creative and energy-efficient. There CO2 and SiO2 co-reduction. The Brunauer-Emmett-Teller (BET)
have been many previous reports about the magnesiothermic measurement is carried out to characterize the porosity of the
reduction of SiO2/C mixtures, and many similar thorny problems materials. Fig. 2(b and c) displays the N2 adsorption/desorption
have always been encountered [42,43]. The generation of the SiC isotherm curves and Barret-Joyner-Halenda (BJH) pore size distri-
phase is a typical problem. Generally, the formation temperature of bution curves of RH-SiO2, RH-Si and NPSi@C composite materials.
SiC requires at least 1100
C [44]. However, due to the high heat Table 1 lists the data for surface analysis. It is found that all the
accumulation of magnesiothermic reduction, the instantaneous materials show type-IV curves with a H2 hysteresis, indicating the
actual temperature in the furnace is much higher than the reaction presence of typical mesoporous characteristics. Most of porous

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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 2. (a) Raman spectra of M-carbon and NPSi@C composite materials, (b) N2 adsorption/desorption isotherm curves and (c) BJH pore size distribution curves (the insert image is
the enlarged curves) of RH-SiO2, RH-Si and NPSi@C composite materials.

Table 1
Surface analysis data.

Samples BET Analysis BJH Analysis

1 1
2
Specific Surface Area (m g ) Pore Surface Area (m g 2
) Pore Volume (cm3 g1) Average Pore Diameter (nm)

RH-SiO2 231.3 168.5 0.267 3.81

RH-Si 221.6 202.2 0.728 6.09
NPSi@C-1 135.9 93.1 0.294 3.70
NPSi@C-2 270.5 188.1 0.37 3.69
NPSi@C-3 796.7 703.3 1.126 3.74

structures are inherited from rice husks. Compared with RH-SiO2, owing to the larger specific surface area than the other samples,
the specific surface area of RH-Si decreases and the pore size in- indicating the greater adsorbed volume during the N2 adsorption/
creases, indicating that the silicon nanoparticles have partially desorption process. Moreover, the BJH pore size distribution curve
melted [23,38]. The pore size distribution of NPSi@C composites is of NPSi@C-3 depicts an intensive peak around 3.70 nm, which
basically consistent with that of RH-SiO2. The porosity of the means more plentiful porous numbers and particular pore size
composites is also due to the removal of the MgO and SiO2 phase. distribution of the sample.
Meanwhile, the specific surface area of the composites increases Additionally, the thermal gravimetric (TG) analysis is conducted
significantly with the increase of carbon layer, indicating that car- to determine the proportion of carbon in the composites. Fig. 3(a)
bon is also porous and provides most of the specific surface area. displays the TG curves. The weight loss from 350 to 680
C is
Specifically, the N2 adsorption/desorption isotherm curve and BJH attributed to the combustion of carbon materials. It is found that
pore size distribution curve of NPSi@C-3 show a separate feature the weight loss ratios of NPSi@C-1, NPSi@C-2 and NPSi@C-3

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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 3. TG curves of NPSi@C composites (a); SEM images of RH-SiO2 (b), RH-Si (c), NPSi@C-1 (d), NPSi@C-2 (e) and NPSi@C-3 (f and g) samples; EDS mapping images of Si (h) and C
(i) elements in NPSi@C-3 sample.

samples are confirmed with 3.2%, 53.2% and 60.8%, respectively, in the particles of NPSi@C-1 sample. The appearance of NPSi@C-2
corresponding to the carbon contents of the composites. Therefore, sample is covered by some relatively compact carbon nano-
the carbon in NPSi@C-1 sample is not detected in the previous XRD particles (Fig. 3(e)). Comparatively, the carbon nanoparticles on the
results. The microstructure is observed via the SEM, and the SEM surface of NPSi@C-3 sample appear loose (Fig. 3(f and g)), which
images of RH-SiO2, RH-Si and NPSi@C composite materials are also explains that the specific surface area of NPSi@C-3 sample is as
displayed in Fig. 3(bef). It can be seen from Fig. 3(b) that RH-SiO2 high as 796.7 m2 g1. Fig. 3(h and i) shows the EDS mapping of Si
powders are essentially composed of many nanoparticles loosely and C elements in NPSi@C-3 sample, confirming a uniform distri-
connected to each other and retain the original shape of rice husk bution of Si and C elements. Notably, the EDS detection indicates
[48]. As shown in Fig. 3(c), the RH-Si nanoparticles are evenly that there is no Mg element in the sample.
dispersed and partially melted, which is consistent with the BET To further observe the micromorphology and structure of
result. Fig. 3(d) shows some SiC particles with smooth surface exist NPSi@C composites, the TEM and HRTEM techniques are
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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 4. TEM images of NPSi@C-1 (a), NPSi@C-2 (d) and NPSi@C-3 (g) samples; HRTEM images of NPSi@C-1 (b and c), NPSi@C-2 (e and f) and NPSi@C-3 (h and i) samples.

performed. As clearly demonstrated from TEM images in Fig. 4(a, further analyzed via the XPS technique. As presented in Fig. 5(a),
d and g), the black band-like graphitized carbon and light colored the full XPS spectra of the NPSi@C-2 sample demonstrates the co-
nanoporous silicon are uniformly dispersed in the NPSi@C pow- existence of Si, C, O and F elements on the surface. The F element
ders. Moreover, plenty of void spaces exist inside of the particles, originates from the process of HF solution etching. The corre-
which are generated from rice husks and the removal of MgO and sponding high-resolution XPS spectra of C 1s, O 1s and Si 2p are
SiO2 by acid etching. The corresponding HRTEM images (Fig. 4(b shown in Fig. 5(bed). It is found that the XPS spectra of C 1s are
and c)) of NPSi@C-1 sample show that SiCe2H and SiCe3C are fitted into three different binding energy peaks, which are attrib-
continuously distributed on the boundary. The corresponding uted to the CeC bonds derived from carbon in the composite, the
HRTEM images of NPSi@C-2 (Fig. 4(e and f)) and NPSi@C-3 (Fig. 4(h CeO bonds derived from the hydroxyl groups on the carbon surface
and i)) samples are similar. The graphitized carbon has excellent and the CeF bonds introduced by HF [8]. The XPS spectra of O 1s
crystal structure and distinct lattice stripes, with the crystal plane consist of OeSi, OeC and OeH bonds [50]. The XPS spectra of Si 2p
spacing of 0.34 nm, corresponding to the (002) crystal plane of further indicate SieO bonds come from the surface oxidation of Si,
graphite [49]. Obviously, as the amount of Mg powder increases, SieC bonds correspond to the presence of SiC phase and SieSi
the thickness of graphitized carbon layer increases. The interior is bonds belong to crystal silicon [43]. It can be inferred that the
composed of Si phase, and the crystal plane spacing of 0.31 nm is surface of Si particles in the composite occurs partial oxidation, and
consistent with the (111) crystal plane of silicon [29]. On the hydroxyl groups are introduced into the surface of carbon particles
boundary, SiCe2H phase is rarely and discontinuously distributed. after acid etching.
The chemical states of the surface elements of materials are Based on the systematic physical characterization including
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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 5. XPS survey spectra (a) and the high resolution XPS spectra (bed) of C 1s, O 1s and Si 2p of NPSi@C-2 sample.

morphology, structure and component of the NPSi@C composites, 2 Mg(l) þ CO2(g) / C(s) þ 2MgO(s) DH ¼ 827.89 kJ mol1, DG
the detailed schematic diagram and description of the preparation (680
C) ¼ 600.0 kJ mol1 (1)
process is demonstrated in Fig. 6. In order to construct NPSi@C
composites through inheriting the natural biomass structure from 2 Mg(g) þ SiO2(s) / Si(s) þ 2MgO(s) DH ¼ 595.05 kJ mol1, DG
rice husks and fabricating graphitized carbon at low temperature, (680
C) ¼ 336.5 kJ mol1 (2)
the experimental strategies and parameters are precisely consid-
ered and optimized. Firstly, rice husks are subjected to HCl solution By calculation, it is found that the free energy change for eqn (1)
reflux treatment to completely remove metal ions and related is lower than eqn (2), which suggests that the generation of carbon
impurities. This is necessary to prevent metal ions from catalyzing from CO2 reduction is thermodynamically preferred. Distinctly, due
the melting of RH-SiO2 during the calcination process [48]. Sub- to the high enthalpy change in magnesiothermic reduction reac-
sequently, the magnesiothermic reduction is carried out in a CO2 tion, the released powerful energy leads the carbon atoms to
atmosphere at 680
C, which is slightly higher than the melting rearrange and change their structure, resulting in the formation of
point of Mg (650
C). At this temperature, Mg powder is converted graphitized carbon and SiC impurities. The first deposition of some
into a vapor or liquid state, which facilitates magnesiothermic carbon materials hinders the reaction between Mg and SiO2,
reduction [29,51]. During the reaction process, Mg firstly forms resulting in the reduction of SiO2 conversion. Another consider-
Mg2Si and MgO with SiO2 through inward diffusion, then Mg2Si ation is that the open reactor can lead to the overflow of gaseous
continues to react with SiO2 to form Si [52]. Innovatively, the excess Mg, which is also an important factor in the incomplete reaction of
external Mg also interacts with CO2 used as a protective gas and the SiO2. Therefore, it is necessary to adjust the amount of Mg added to
carbon source to form the MgO/C mixture nanoparticles. The re- solve this problem.
action conditions such as the heating rate and CO2 flow rate have The lithium storage properties of the prepared materials are
been precisely controlled to promote the formation of graphitized evaluated in lithium half cells. Fig. 7(a and b) shows the initial three
carbon at low temperature and greatly reduce the production of CV curves of RH-Si and NPSi@C-2 composite electrodes between
SiC. Finally, NPSi@C composites are designed and self-assembled 0.005 and 3.0 V (vs. Liþ/Li) at a scan rate of 0.1 mV s1, which
after removing MgO and unreacted SiO2 by an acid etching pro- present a typical reaction mechanism of Si-based material. It is
cess. The magnesiothermic co-reduction process can be presented worth noting that there are two slightly broad peaks at around 0.83
by the following two chemical reaction equations: and 1.2 V in the first cathodic scanning of RH-Si electrodes and they

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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 6. Schematic diagram and description of the preparation process of NPSi@C composites.

disappear in the subsequent cycles, which is attribute to the gen- delithiated state after 100 cycles. The Nyquist plots and the fitted
eration of SEI film on the surface of electrode materials and the curves by the equivalent circuit model are depicted in Fig. 7(e). The
decomposition of electrolyte [33]. After the first cycle, two cathodic Nyquist plots of all electrodes consist of two successive proximate
peaks located at 0.01 V and 0.20 V and two anodic peaks centered at semicircles in the high-to-medium frequency region and an oblique
about 0.38 V and 0.53 V can be clearly observed, which are ascribed line in the low frequency region. Rs represents the solution resis-
to the alloying and de-alloying process of LixSi [32]. Specifically, the tance, which is generated by the migration of Liþ in the electrolyte.
CV curves of NPSi@C-2 composite electrode display two distinctly Rf stands for the film resistance, which is generated when Liþ enters
broad peaks at nearly 0.56 V and 1.64 V during the first cathodic the SEI layer. The charge-transfer resistance is denoted as Rct, which
scanning process and they disappear from the second cycle. comes from Liþ entering the surface of the active material. Zw
Moreover, the peak current intensity and integral area of NPSi@C-2 represents the Warburg impedance, which is formed by Liþ even-
are distinctly greater than that of RH-Si, indicating that the more tually diffusing into the void of the electrode material. Among
SEI formation and more electrolyte decomposition for NPSi@C-2 them, the Rct value can explain the conductivity of the active ma-
composite due to the larger specific surface area. The CV peak terial and the rapid Liþ diffusion kinetics [15,24]. After 100 cycles,
current intensities of the two samples increase after the first cycle, the Rct values of the electrodes of RH-Si, NPSi@C-1, NPSi@C-2 and
suggesting an activation process occurred. The corresponding NPSi@C-3 are estimated to be 68.6, 37.7, 19.9 and 38.6 U, respec-
charge/discharge profiles of RH-Si and NPSi@C-2 composite elec- tively. Obviously, the NPSi@C composite electrodes exhibit lower
trodes are presented in Fig. 7(c and d). It is found that both RH-Si charge transfer resistance than the RH-Si electrode, indicating that
and NPSi@C-2 samples display a long and flat plateau at about the introduction of graphitized carbon can significantly enhance
0.1 V in the initial discharging curve, corresponding to the alloying the electrical conductivity of the active materials.
process of Li and Si. Similarly, a platform is shown around 0.46 V in The rate capabilities of RH-Si and NPSi@C composite materials
the charging curve during the initial three turns, which is related to are displayed in Fig. 7(f). It is obvious that the NPSi@C composites
the de-alloying process of LixSi [19,37]. The initial discharge and show superior rate capabilities than RH-Si, which is ascribed to the
charge specific capacities of RH-Si are 1043.2 and 638.2 mA h g1, nanoporous structure and higher electrical conductivity of the
corresponding to 38.8% of the unrecoverable capacity loss, which is composites. Particularly, NPSi@C-2 delivers the average reversible
caused by the generation of SEI film and oxidation on the surface of capacities of 658.7, 697.7, 574.0, 434.1 and 294.2 mA h g1 at
Si particles. Whereas, NPSi@C-2 sample exhibits the initial different current densities of 0.1, 0.2, 0.5, 1.0 and 2.0 A g1,
discharge specific capacity of 1306.9 mA h g1 and the initial charge respectively. Due to the activation processes in the previous cycles,
specific capacity of 534.8 mA h g1, which is continuously activated the capacity at 0.1 A g1 is relatively low. Fig. 7(g) displays the
in the previous cycles and then stabilized. It may be due to the cycling performances at a current density of 0.2 A g1 and corre-
generation of some carbon with low graphitization degree in the sponding coulombic efficiency curves of RH-Si and NPSi@C com-
composite. The carbon remains some of lithium during delithiation posite materials. The cycling performance shows a gradual
process, resulting in a low initial capacity and irreversible capacity activation process in the previous cycles. Possessing a large specific
loss [49]. During the lithiation/delithiation process, due to the huge surface area results in a high irreversible capacity for the samples.
volume change, the silicon particles are severely smashed and lose After 100 cycles, the specific discharge capacities of RH-Si, NPSi@C-
electrical contact with the copper foil, leading to a rapid decrease of 1, NPSi@C-2 and NPSi@C-3 remained at 279.4, 563.5, 681.8 and
capacity [25]. 491.7 mA h g1, respectively. Obviously, the NPSi@C composites
The electrochemical behaviors of RH-Si and NPSi@C composite exhibit enhanced cycling performance. Whereas, the initial
electrodes are further investigated by EIS tests at the fully coulombic efficiencies of RH-Si, NPSi@C-1, NPSi@C-2 and NPSi@C-3

8
Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

Fig. 7. CV curves at 0.1 mV s1 (a and b) and Charge/discharge profiles (c and d) of RH-Si and NPSi@C-2 composite electrodes; Nyquist plots (inset showing the high-frequency
region and the equivalent circuit model for fitting the impedance spectra) after 100 cycles (e), Rate capabilities based on the discharge data (f), Cycling performances and cor-
responding coulombic efficiency curves (g) of RH-Si and NPSi@C composite electrodes.

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Z. Wang, B. Zheng, H. Liu et al. Journal of Alloys and Compounds xxx (xxxx) xxx

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Declaration of competing interest mechanism of the thermal effect on the porous silicon anode material prep-
aration via magnesiothermic reduction, J. Alloys Compd. 661 (2016) 27e37.
[24] J. Ge, Q. Tang, H. Shen, F. Zhou, H. Zhou, W. Yang, B. Xu, X. Cong, Low-tem-
The authors declare that they have no known competing perature fabrication of porous SiO with carbon shell for high-stability lithium
financial interests or personal relationships that could have ion battery, Ceram. Int. 46 (2020) 12507e12516.
appeared to influence the work reported in this paper. [25] K. Feng, M. Li, W. Liu, A.G. Kashkooli, X. Xiao, M. Cai, Z. Chen, Silicon-based
anodes for lithium-ion batteries: from fundamentals to practical applications,
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Acknowledgments [26] Z. Zhang, X. Han, L. Li, P. Su, W. Huang, J. Wang, J. Xu, C. Li, S. Chen, Y. Yang,
Tailoring the interfaces of silicon/carbon nanotube for high rate lithium-ion
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