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High-Performance Porous Silicon/Nanosilver Anodes from Industrial

Low-Grade Silicon for Lithium-Ion Batteries
Fengshuo Xi, Zhao Zhang, Xiaohan Wan, Shaoyuan Li,* Wenhui Ma,* Xiuhua Chen, Ran Chen,
Bin Luo,* and Lianzhou Wang
Cite This: https://dx.doi.org/10.1021/acsami.0c14157 Read Online

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ABSTRACT: Silicon (Si) has been considered as one of the most

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promising candidates for the next-generation lithium-ion battery

(LIB) anode materials owing to its huge theoretical specific
capacity of 4200 mA h g−1. However, the practical application of Si
anodes in commercial LIBs is facing challenges because of the lack
of scalable and cost-effective methods to prepare Si-based anode
materials with proper microstructure and competitive electro-
chemical performances. Herein, we report a facile and scalable
method to produce multidimensional porous silicon embedded
with a nanosilver particle (pSi/Ag) composite from commercially
available low-cost metallurgical-grade silicon (MG-Si) powder.
The unique hybrid structure contributes to fast electronic transport
and relieves volume change of silicon during the charge−discharge process. The pSi/Ag composite exhibits a large initial discharge
capacity (3095 mA h g−1 at a high current of 1 A g−1), an excellent cycling performance (1930 mA h g−1 at 1 A g−1 after 50 cycles),
and outstanding rate capacities (up to 1778 mA h g−1 at a higher current of 2 A g−1). After the samples are modified by reduced
graphene oxide, the capacities of the pSi/Ag@RGO composite electrode can still be maintained over 1000 mA h g−1 after 200 cycles.
This study provides a simple and effective strategy for production of high-performance anode materials.
KEYWORDS: lithium-ion battery, silicon anode, nanosilver particles, porous silicon, metallurgical-grade silicon

■ INTRODUCTION
With the rapid development of renewable energy technologies
to meet the increasing needs, developing high-energy-density
rechargeable lithium-ion batteries (LIBs) has attracted much
attention.1,2 Utilizing the large theoretical capacity electrode
materials is the most effective way to satisfy the escalating
requirement of the high energy density of next-generation
LIBs. Among all kinds of anode candidate materials, silicon
(Si) material is considered as the most promising one for
replacing the traditional graphite anodes because of its huge
theoretical capacity (4200 mA h g−1), which is 10 times higher
than that of commercial graphite (370 mA h g−1).3,4
Unfortunately, the application of Si-based anodes for LIBs is
still limited. The biggest challenges of Si anodes are their
unavoidable severe volume change (>300%) and poor
electrical conductivity during the lithiation−delithiation
process.5,6 Because of the large volume expansion, the cracking
and pulverization of Si occur and then lead to electrical loose
contact between the current collectors and active materials.7
Moreover, volume expansion of Si further results in an
inhomogeneous solid electrolyte interphase film on the Si
surface, which will continuously consume the electrolyte.8
Consequently, those factors always result in quick capacity fade
and poor electrochemical performance during the electro-
chemical cycle process.9,10
Recently, a lot of works have been done to overcome the
above-mentioned problems of Si anodes. In order to effectively
relieve the internal strain and the large expansion/contraction
problems, different Si-based structures are designed, including
thin films,11,12 nanotubes,13 nanowires,14 nanosheets,15 hollow
nanospheres,16 porous structures,17,18 and so forth. On the
other hand, the combination of Si and conductive materials
(such as metal nanoparticles,19 carbonaceous matrixes,16,20
polymers,21 MXene,22 and so forth) has been demonstrated to
improve the conductivity of silicon electrode and further buffer
silicon volume change during the cycles, leading to a
significantly enhanced electrochemical performance. Although
significant progress in improving Si anode electrochemical
properties has already been achieved by all kinds of Si-based
structures and hybrids, the preparation of these Si-based
Received: August 6, 2020
Accepted: October 6, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsami.0c14157

A ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
Figure 1. Illustration of preparing Si nanoparticles and the pSi/Ag composite.
material usually involved high-cost raw materials, harsh
reaction conditions, and cost-complicated processes.23,24
Seeking simple and cost-effective synthesis methods of high-
performance Si-based anode materials is becoming more
anticipated and pressing.
Thus, in order to simultaneously enhance the electro-
chemical performance and reduce the cost of Si anodes, more
efforts should focus on the cost-effective silicon source
selection, proper Si-based structure construction, and feasible
preparation method.25,26 It is well-known that metallurgical-
grade silicon (MG-Si) is a low-grade silicon source with the
characterization of large production and a cheaper price, which
is widely used as a raw material to produce solar-grade silicon
in the industry.27 On the other hand, the metal-assisted
chemical etching (MACE) method has been widely studied to
prepare porous silicon structures or silicon nanowires for
texturing silicon wafer surfaces because of its advantages of
convenience, low cost, and microstructure controllability.28−30
In order to obtain high-quality porous structures, the MACE
process usually needs to be carried out with an acid wash step
to clean the deposited metallic nanoparticles in pore
channels.31−33 If the MACE process were controlled by the
appropriate metallic nucleation and contain them in pore
channels, it can be predicted that the electrical conductivity of
the Si-based composites would be greatly improved.
Herein, we report a multidimensional porous silicon
embedded with a nanosilver particle (pSi/Ag) composite
from a commercially available low-cost MG-Si source and used
for enhancing the LIB Si anode’s electrochemical performance.
The porous structure and nanosilver particle composite have
been synchronously achieved by the improved MACE
approaches, which could provide reserved spaces to release
the volume changes of Si. Meanwhile, the hybrid nanosilver
particles in the pores further make the Si anodes more
conductive. As a consequence, the pSi/Ag composite anodes
exhibit improved cyclic stability and outstanding rate perform-
ance. The cyclic performance of pSi/Ag can be further
improved by coupling with reduced graphene oxide (RGO).
This study not only shows a simple way to enhance the
electrochemical properties of Si-based anodes but also is
expected to provide a feasible pathway for the scalable
production of high-performance anode materials in the future.
■ MATERIALS AND METHODS
Materials. The MG-Si drunks (∼0.8 $/kg) with a purity of ∼99%
(the main impurities are indicated in Table S1) were used in this
research, which were ground into finer powders by ball milling. The
other reagents including copper nitrate (Cu(NO3)2·3H2O), hydro-
fluoric acid (HF), nitric acid (HNO3), hydrogen peroxide (H2O2),
silver nitrate (AgNO3), sodium alginate, conductive carbon Super P,
and ethyl alcohol were all of analytical-grade purity.
Fabrication of Si Nanoparticles and the pSi/Ag Composite.
All the MG-Si powders were commercially available and directly used
without further purification and the whole experimental process was
carried out at room temperature. The MG-Si powders were first
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treated by the one-step copper-assisted chemical etching process
(CuACE-I) to refine Si particles with dipping 3 g of MG-Si powders
into 100 mL of mixed aqueous solution (containing 3.45 M HF, 40
mM Cu(NO3)2, 0.15 M H3PO3, and 15% ethanol) and stirring for 2 h
using a self-assembly experimental equipment. After the CuACE-I
procedure, the deposits of Cu nanoparticles in the Si nanoparticles
were removed by 20% dilute aqueous nitric acid and then washed
with deionized water. After that, the Si nanoparticles were treated via
the AgACE-I process to prepare the pSi/Ag composite. Different from
the CuACE-I process, the AgACE-I procedure needs to be carried out
in a dark room. The 100 mL mixed aqueous solution contained 10
mM AgNO3, 4.6 M HF, and 15% ethanol and the stirring time was 2
h. In order to obtain the pSi/Ag composite, the obtained samples
were not treated with the acid wash step but only using deionized
water to wipe off the extra acid liquor and impurity ions. Afterward,
the final composite was obtained after being dried at 80 °C for 10 h.
For the RGO coating process, the MG-Si and pSi/Ag composites
were dispersed in the graphene oxide solution and stirred for 2 h,
respectively, and then the filter residues were annealed in the vacuum
conditions at 700 °C.
Characterization. The interior structure of the morphologies was
measured and elemental analysis was performed by a transmission
electron microscope (Tecnai G2 TF30 S-Twin, FEI) equipped with
an energy-dispersive X-ray spectrometer (Bruker Quantax) and
scanning transmission electron microscopy (STEM). The surface
morphologies and microstructures were characterized by a field
emission scanning electron microscope (QUANTA 200, FEI). An
electron probe microanalyzer (JXA8230, JEOL) was used to detect
the morphology and microstructure of impurity precipitates in MG-Si.
The crystalline structure of materials was detected by X-ray diffraction
(XRD) measurements (X′pert 3, PANalytical). Information of pSi/Ag
composite surface states was determined by X-ray photoelectron
spectroscopy (XPS, K-Alpha+). Pore size distribution and specific
surface area of the samples were determined with the Brunauer−
Emmett−Teller method (NOVA2200e, Quantachrome). Functional
groups of the samples were characterized by Fourier transform
infrared (FTIR, Nicolet iS10, Thermo Fisher Scientific). Concen-
trations of impurities in Si were tested by inductively coupled plasma
(ICP) atomic emission spectrometer (OPTIMA 8000, PerkinElmer)
Electrochemical Measurements. Active materials (60 wt %),
sodium alginate binder (20 wt %), and carbon black (20 wt %) were
mixed in deionized water to form a homogeneous slurry, which was
uniformly cast on Cu foil as working electrodes. The whole electrodes
were first dried in a vacuum oven at 80 °C for 4 h and then were cut
into a disc with a diameter of ∼14 mm (mass of active substance is
approximately 1 mg). Afterward, the obtained electrodes were further
dried in the above vacuum oven condition for 2 h. After that, CR2032
coin-type half-cells with lithium metal foil as the counter electrode
were prepared in an argon-filled glovebox. A polyethylene membrane
as the separator and 1 M LiPF6 in ethylene and diethyl (ethylene:
diethyl = 1:1) were utilized as the electrolyte. The obtained cells were
tested within the voltage range of 2.0−0.01 V using an electro-
chemical test system (XWJ Neware Tech. Co., BTS3000, China). An
electrochemical workstation (Ametek, PMC-1000dc, America) was
applied to measure the cyclic voltammetry (CV) curve and
electrochemical impedance spectroscopy (EIS). The CV curve was
tested in the potential of 2.0−0.01 V at 0.2 mV s−1 scan rate, and the
EIS was tested in the frequency range of 0.1−100 kHz.
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Figure 2. FESEM images of (a) MG-Si powder, (b) Si nanoparticles, (c) pSi/Ag composite, and (d) TEM and (e) HRTEM images of the pSi/Ag
composite. (f) STEM image of the pSi/Ag composite. (g−i) STEM mapping images of the pSi/Ag composite.

Figure 3. (a) N2 adsorption−desorption isotherms and (b) pore size distribution of MG-Si and Si nanoparticles.

■ RESULTS AND DISCUSSION

The fabrication of Si nanoparticles and the pSi/Ag composite
by the improved MACE process is schematically illustrated in
Figure 1. Commercial low-cost MG-Si (∼0.8 $/kg) derived
from cheap silica ores was used as the raw material, where its
purity is approximately 99% (as in Table S1). The MG-Si bulks
were first crushed into fine powders by ball milling before
being refined into Si nanoparticles by the CuACE-I process.
Subsequently, the Si nanoparticles were further treated by the
AgACE-I process to prepare porous silicon, during which
nanosilver particles were retained in the pores, leading to the
pSi/Ag composite.
The morphology and microstructure of the as-obtained
products were characterized by field-emission scanning
emission microscopy (FESEM) and TEM. It is shown in
Figure 2a that many small and white spots spread on a typical
MG-Si powder surface, which are the impurities exposed from
the crystal boundaries and dislocations during the grinding
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process.32,34 In the macroscopic view, some large microscale
silicon particles also can be found (Figure S1a), indicating that
it is difficult to obtain uniform and nanoscale silicon powders
from the ball milling process. After the CuACE-I treatment, Si
nanoparticles with a size of ∼50−300 nm are obtained, which
are shown in Figure 2b. Compared with MG-Si raw material,
the size of Si particles are effectively reduced (Figure S1b)
because of the “chemical cracking effect” on MG-Si powders by
CuACE-I. Moreover, the Si nanoparticles present a clean and
rough surface (Figure 2b) as well as much improved purity in
comparison to MG-Si (99.97%, Table S1). It can be seen from
Figure 3a that the N2 adsorption−desorption curve of Si
nanoparticles are turning from style II to style IV, illustrating
that the Si nanoparticles were effectively modified and some
mesopores, macropores, or slit-pores exist on the Si surface.
The Barrett−Joyner−Halenda pore size distributions of Si
nanoparticles further showed a narrow pore size distribution
with an evident peak that corresponds to pores with a diameter
of 3−10 nm (Figure 3b), verifying the existence of these
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ACS Applied Materials & Interfaces
Figure 4. (a) XRD pattern of MG-Si, Si nanoparticles, and pSi/Ag; (b) FTIR spectra of MG-Si and pSi/Ag; (c) pSi/Ag composite XPS spectra of
Si 2p and (d) Ag 3d.
porous structures. The texture properties’ comparison between
MG-Si powders and Si nanoparticles in Table S2 can also
explain the significant surface modification of Si nanoparticles.
After treating with AgACE-I, the multidimensional structure of
porous Si was obtained, and the purity of MG-Si can be further
improved to 99.99% (Table S1). Then, the retained nanosilver
particles in the pores further result in the pSi/Ag composite,
which can be recognized in Figure 2c. The types of pores on
the surface of silicon particles mainly are macropores and
nanopores, which could work as adequate self-buffer spaces to
relieve silicon volume change and provide sufficient channels
for ion transportation during the electrochemical cycles.35,36 It
can also be found that the nanosilver particles are embedded
into the pores successfully, which would provide electron
pathways from the current collector to the whole surface of
Si.37 According to the testing results of ICP, the amount of Ag
accounts for 2.68 wt % of the pSi/Ag composite (Table S1)
further verified the good crystalline nanosilver particles. In
such a case, the electrical conductivity of the pSi/Ag composite
is significantly enhanced, resulting in a high level of
accessibility and diffusivity of Li+ ions in Si anodes. The pSi/
Ag composite is further investigated by TEM, and more details
about the structure of pSi/Ag composite are provided in Figure
2d,e. The nano-silver particles have a small size of around 5−
10 nm and are well inserted into the Si substrate. The high-
resolution TEM (HRTEM) image in Figure 2e illustrates that
the formed nanosilver particles are of good crystallinity with a
lattice spacing of 2 Å, corresponding to the (200) planes of
crystalline Ag. Besides, it was also found that a thin amorphous
SiO2 of around 5 nm formed on the Ag/Si composite surface,
which would suppress the volume expansion and enhance
electrochemical performances of Si anodes.38 Furthermore,
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STEM and their corresponding elemental mapping were
carried out to further confirm the elemental distribution of
Si, Ag, and O in the pSi/Ag composite (as shown in Figure 2f
to 2i). It is clearly observed from the images that the nanosilver
particles are uniformly distributed along with the silicon matrix
and the element O also has a uniform distribution on the pSi/
Ag composite surface, which are consistent with the TEM
imaging results.
To further study the crystalline structure information and
surface properties of the pSi/Ag composite, the XRD patterns,
FTIR, and XPS spectra were collected, as shown in Figure 4.
For the MG-Si powders and Si nanoparticles, only six distinct
diffraction peaks of (111), (220), (311), (400), (331), and
(422) were found, which are the characteristic peaks of
crystalline silicon. It is clearly shown in Figure 4a that the peak
width of Si nanoparticles widens significantly when compared
with MG-Si powders, indicating that the silicon grain was
effectively fined after the CuACE-I process. For the pSi/Ag
composite, several other new diffraction peaks of (111), (200),
(220), (311), and (222) can be detected by XRD, attributed to
the well crystalline silver. The XRD did not detect the silicon
oxide in the pSi/Ag composite, indicating that the SiO2 mainly
exists as an amorphous structure and the small amount is not
enough to be detected by the XRD. Nevertheless, a special
stretching vibration Si−O−Si bond of the characteristic peak at
1051.31 cm−1 is detected in the pSi/Ag composite by FTIR
spectra, which verified the existence of SiO2 (Figure 4b). In
comparison with MG-Si, the other newly formed peak located
at 878.94 cm−1 is also detected by FTIR spectra in the pSi/Ag
composite, attributed to Si−OH asymmetric stretching and
bending vibration. The form of the Si−OH bond will have a
good combination of sodium alginate binder, which can to
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ACS Applied Materials & Interfaces
Figure 5. Schematic of the mechanism proposed for the formation of the pSi/Ag composite (a) and volume change comparison with pristine Si (b)
during the lithiation−delithiation process.
some extent release the volume expansion of Si anodes during
the lithiation−delithiation process.39,40 Chemical bonding
states of the pSi/Ag composite were further studied by XPS
spectra. The typical XPS survey spectra in Figure 4c,d confirm
the presence of Si and Ag in the pSi/Ag composite. As shown
in Figure 4c, three peaks could be derived from the high-
resolution XPS spectrum of Si 2p. The sharp peaks at 99.91
and 99.29 eV were related to the Si 2p1/2 and Si 2p3/2,
indicating the presence of crystalline silicon. The characteristic
peak at 103.48 eV refers to the Si−O−Si bond, proving that
some SiO2 layers were formed. The Ag 3d spectrum (Figure
4d) shows two types of peaks, and those at 367.8 and 373.8 eV
with the slitting of the 3d doublet of ∼6.0 eV, indicating the
formation of Ag(0).41
In order to gain a better understanding of the pSi/Ag
composite fabrication, the chemical reactions and mechanism
of forming the pSi/Ag composite during the improved MACE
processes are proposed. As shown in Figure 5a, the Cu0
nanoparticles (Cu NPs) will first form and deposit on the Si
surface by the reduction of Cu2+ ions as Cu has a positive
electronegativity than Si during the CuACE-I process, which
leads to the formation of holes (h+)42 (reaction 1). Besides, the
addition of reductant H3PO3 provides a strong reducing
environment, which could accelerate Cu0 formation and
increase Cu NP size to deposit on the Si surface43 (reaction
2). Then, holes (h+) produced by reactions 1 and 2 will be
injected into the Si valance band, which lead to HF etching of
Si that is connected to Cu0. However, because of the low
oxidation capability of Cu2+, the pores formed by CuACE-I on
the Si are shallow. Nevertheless, the CuACE-I treatment would
have a different “chemical cracking effect” on MG-Si compared
to bare Si.44 As mentioned above, the MG-Si used in the
experiment has a low purity of ∼99% and contains some
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impurities (Table S1). The impurities in the MG-Si are easy to
gather together to form impurity precipitates owing to their
various liquidus temperatures during the melting process,
which mainly present as island phases or strip phases in the
MG-Si.45 Figure S2 shows typical precipitated impurities in the
MG-Si, mainly consisting of Si−Fe, Si−Fe−Al, Si−Fe−Al−Ca,
Si−Fe−Ti, Si−Ti−V, and Si−Ti−Ni phases. The impurity
phases being much more active than the Si substrate will lead
to preferential absorption and nucleation of Cu2+ on impurity
phases over bare Si. On the other hand, the reductant H3PO3
provides a strong reducing etching environment, which
enhances the dissolution of impurity phases and the
surrounding Si substrate. Therefore, the impurity phases
were removed and special corrosive pits or pores would be
created by CuACE-I. For these reasons, the etching speed of
special corrosive pits and pores are much faster than bare Si,
leading to the MG-Si powders being broken into finer
nanoparticles, as shown in Figure 5a.
Cu cathode side
2Cu 2 + → Cu 0 + 2h+ (1)
Cu 2 + + H3PO3 + H 2O → Cu 0 + H3PO4 + 2H+ (2)
Anode side
Si + 6HF + 4h+ → H 2SiF6 + 4H+ (3)
The AgACE-I process was performed on the Si nano-
particles, which was obtained by the above CuACE-I process
(Figure 5a). Similar to the CuACE-I process, Ag also has a
more positive electronegativity than Si, Ag nucleation will
happen, and it will be deposited on the Si surface with the
reduction of Ag+ ions46 (reaction 4). Moreover, the Ag+ has a
stronger oxidation capability than Cu2+, which will lead to
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Figure 6. (a) EIS results of Si nanoparticles and the pSi/Ag composite electrodes; discharge−charge potential profiles of (b) Si nanoparticles and
the (c) pSi/Ag composite at 1A g−1; (d) rate capability of the pSi/Ag composite and Si nanoparticle electrodes; (e) cycling performance of MG-Si,
Si nanoparticles, and the pSi/Ag composite electrodes at 1A g−1; (f) long-term cycling performance of pSi/Ag@RGO anodes at 0.5 A g−1.

more abundant holes (h+) in the former. The details of the
AgACE-I etching process is shown in Figure 5a, in which it can
be observed that most holes are injected into the Si surface that
contacts with nanosilver particles, causing oxidation of
silicon31,47 (reaction 5). After that, the silicon oxide between
the Si substrate and nanosilver particles will be dissolved by
HF48 (reaction 6). Therefore, the Si that has contact with
nanosilver particles can be etched rather faster by HF than bare
Si and result in the porous structures. Although most holes are
concentrated at the Si/Ag interface, some will also diffuse to
the sidewalls of the pores. Therefore, the off-Ag areas or
sidewalls of pores will also be etched, which form the shallow
nanopores or a rough surface (Figure 5a). After the AgACE-I
treatment, the Si with porous structures will provide more
sufficient spaces than pristine Si (Figure 5b) to accommodate
volume change during the lithiation process. Moreover, as
shown in Figure 5a, the nanosilver particles in the pores can
further play a significant role in improving the electrical
conductivity of Si anodes, which improved the accessibility and
diffusivity of Li+ ions.
Ag cathode side
2Ag + → Ag 0 + 2h+
Anode side
Si + 2H 2O + 4h+ → SiO2 + 4H+ (5)
SiO2 + 6HF → H 2SiF6 + 2H 2O (6)
The electrochemical performance was measured in half-cells.
As shown in Figure 6a, the EIS results of Si nanoparticles and
the pSi/Ag composite electrodes are obtained. Compared with
the Si nanoparticle electrode, the plot of the pSi/Ag composite
electrode has a smaller semicircle, indicating that the pSi/Ag
composite holds a smaller charge-transfer resistance, revealing
the enhanced reaction kinetics of the pSi/Ag composite
electrode.49 The remarkable improvement of electrochemical
properties for pSi/Ag can be ascribed to nanosilver particles
that are effectively inserted into Si nanoparticles, which
improved the conductivity of the pSi/Ag composite electrode.
The first five cyclic voltammograms of the pSi/Ag composite
electrode in the potential of 0.01 and 2.0 V at 0.2 mV s−1 scan
rate are presented in Figure S3. Although Ag can alloy with
lithium,50 the reactions between Ag and lithium are not
detected, which can be ascribed to the low content nanosilver
particles in the composite. The result also proved that the
small amount of nanosilver particles in the pSi/Ag composite
will not consume Li+ ions or affect the Si anode capacity.
(4) The discharge and charge potential profiles of Si nano-
particles and the pSi/Ag composite electrodes were measured
at a galvanostatic current density of 1 A g−1. As shown in
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Figure 6b,c, the Si nanoparticle electrode has an initial Table 1. Comparison of Electrochemical Performance of the
reversible discharge and charge capacity of 2803 and 2424 pSi/Ag Composite in This Work with Previous Reports on
mA h g−1, whereas the initial discharge and charge capacity of MG-Si-Derived Anode Materials
the pSi/Ag composite anodes can reach 3095 and 2757 mA h
g−1, respectively. Furthermore, the pSi/Ag composite anodes special
1st
cycle
also exhibit a high Coulombic efficiency (CE) of 89.09%. capacity cycle current CE
Although the small amounts of nanosilver particles have active materials (mA h g−1) number density (%) refs
reduced the effective content of silicon in the pSi/Ag pSi/Ag composite 1930 50 1000 89.09 this
mA g−1 work
composite anodes, the initial discharge and charge capacities
silicon/carbon 849 50 50 mA g−1 52
are still higher than those of Si nanoparticle anodes, which can nano-branches
be ascribed to the activation and conductivity enhancement of nanometer-sized ∼1920 140 1/6 C 53
the pSi/Ag composite. After 10 cycles, the discharge and silicon
charge capacity of the pSi/Ag anodes are 2364 and 2307 mA h porous silicon/C ∼778 200 500 54
g−1; however, the Si nanoparticle anodes are only 1252 and composites μA cm−2
1187 mA h g−1, indicating that the pSi/Ag anodes have higher nano M-Si 1354 50 400 mA/g 79 55
reversibility than Si nanoparticles. Rate performance is another MG-SiNW 2111 50 0.2 C 56
important standard for the practical application of anode porous silicon/C 1240 50 50 mA/g 57
composites
materials.51 It can be seen from Figure 6d that the discharge
capacity of the pSi/Ag composite anodes gradually decreases
from 3677 to 1778 mA h g−1 with the current densities
increasing from 0.1 to 2 A g−1. Remarkably, the reversible
capacity raises to 2660 mA h g−1 quickly after the initial
current density was abruptly switched to 0.1 A g−1. In sharp
contrast, the pSi/Ag composite anodes maintain higher
discharge capacity than Si nanoparticles anodes at each current
density, demonstrating that pSi/Ag composites are favorable to
improve the rate performance. Figure 6e shows the cycling
performance of the MG-Si, Si nanoparticles, and pSi/Ag
electrodes under a current density of 1 A g−1. After 50 cycles,
the discharge capacity of MG-Si anodes quickly decreased from
2948 to 172.9 mA h g−1, which only have a low capacity
retention of 5.86%. It was found that the cycling performance
of the Si nanoparticle electrode is improved, which remained at
589.2 mA h g−1 at 1 A g−1 after 50 cycles. This can be ascribed
to the small size of Si nanoparticles, which allowed some
expansion of the silicon during the charge−discharge process.
Nevertheless, Figure 6e also shows that the improvement of
the Si nanoparticles anode was not enough, and its capacity
fading degree can be as high as 78.98%. After the Si
nanoparticles were made into the porous Si/Ag composite,
the pSi/Ag anodes exhibited excellent electrochemical
performance that was much better than the MG-Si anodes or
Si nanoparticle anodes, which still remain at 1930 mA h g−1
even at the high current of 1 A g−1 after 50 cycles. In addition, Figure 7. SEM images of the (a,c) MG-Si and (b,d) pSi/Ag electrode
as shown in Table 1, the pSi/Ag composite in this work before and after 100 cycles at 1 A g−1.
presents its advantages over other MG-Si-derived Si anodes in
LIBs reported in the literatures in terms of cyclic stability and
specific capacity at high currents. Furthermore, the porous Si/
Ag composite is further modified by RGO, which is shown in the MG-Si electrode, Figure 7b, which lead to the
Figure S4. Although some aggregations of Ag nanoparticles are disconnection of the current collector and active material.
found in the pSi/Ag@RGO composite, the capacities of the Nevertheless, compared to the MG-Si electrode, the surface of
pSi/Ag@RGO composite can still be maintained over 1000 the pSi/Ag composite electrode before cycling is quite
mA h g−1 after 200 cycles at a constant of 0.5 A g−1 (as shown homogeneous, as shown in Figure 7c. This result further
in Figure 6f). These further confirmed the excellent perform- proved the efficient chemical cracking effect of the CuACE-I
ance of the pSi/Ag composite and can be expected as an pretreatment process. Figure 7d shows the structure of the
effective technology for preparing LIB anodes. pSi/Ag electrode after cycling, in which it is difficult to see any
The structural evolution and cyclic stability of the electrodes fragmentation or cracks. Furthermore, some voids are also
were further studied by morphological imaging. As shown in found on the electrode, indicating that the pSi/Ag electrode
Figure 7, the structure changes of the MG-Si and pSi/Ag structure contains the porous structure, which could buffer the
composite electrodes before and after cycling are tested. It can huge volume expansion of silicon during the charge−discharge
be seen from Figure 7a that micrometer-sized aggregates and process. These observations further demonstrate the excellent
large Si particles filled the MG-Si electrode surface. After 100 structure integrity of the pSi/Ag electrode during the charge−
cycling, serious fragmentation and large cracks are formed in discharge process.
G https://dx.doi.org/10.1021/acsami.0c14157
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces
■
CONCLUSIONS
In this study, a simple and scalable method was developed to
obtain multidimensional pSi/Ag for high-performance LIBs
anodes by using commercially available low-grade MG-Si raw
material. The pSi/Ag composite exhibited a large initial
discharge capacity (3095 mA h g−1 at a high current of 1 A
g−1), an excellent cyclic performance (1930 mA h g−1 at 1 A
g−1 after 50 cycles), and outstanding rate capacities (up to
1778 mA h g−1 at a high current of 2 A g−1). The good
electrochemical properties can be attributed to the Si
nanoparticles obtained by the CuACE-I treatment, which
could release a certain amount of stress generated by volume
expansion of the silicon during cycling. At the same time, the
porous structures and nanosilver particles in the pSi/Ag
composite further have a synergistic effect on accommodating
silicon large volume change and shortening the Li+ ion
diffusion pathway during the lithiation−delithiation process.
Moreover, the electrochemical performance of the pSi/Ag
composite can be further improved by integrating with RGO.
The discharge capacity of the pSi/Ag@RGO composite can be
maintained over 1000 mA h g−1 after 200 cycles. The present
study may provide a new effective and promising way for the
development of next-generation Si-based anode materials with
high performance.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.0c14157.
Additional SEM images, electron-probe microanalysis
maps, CV curves, impurity contents in silicon, and
structural properties of MG-Si powders and Si nano-
particles (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Shaoyuan Li − State Key Laboratory of Complex Nonferrous
Metal Resources Clean Utilization and Faculty of Metallurgical
and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China; School of Photovoltaic
and Renewable Energy Engineering and Australian Centre for
Advanced Photovoltaics, University of New South Wales, Sydney
2052, Australia; orcid.org/0000-0002-8124-8408;
Email: lsy415808550@163.com
Wenhui Ma − State Key Laboratory of Complex Nonferrous
Metal Resources Clean Utilization and Faculty of Metallurgical
and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China; Email: mwhsilicon@
126.com
Bin Luo − Nanomaterials Centre, Australian Institute for
Bioengineering and Nanotechnology and School of Chemical
Engineering, The University of Queensland, St. Lucia,
Queensland 4072, Australia; orcid.org/0000-0003-2088-
6403; Email: b.luo1@uq.edu.au
Authors
Fengshuo Xi − State Key Laboratory of Complex Nonferrous
Metal Resources Clean Utilization and Faculty of Metallurgical
and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China; Nanomaterials Centre,
Australian Institute for Bioengineering and Nanotechnology and
H https://dx.doi.org/10.1021/acsami.0c14157
www.acsami.org Research Article
School of Chemical Engineering, The University of Queensland,
St. Lucia, Queensland 4072, Australia
Zhao Zhang − State Key Laboratory of Complex Nonferrous
Metal Resources Clean Utilization and Faculty of Metallurgical
and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China
Xiaohan Wan − State Key Laboratory of Complex Nonferrous
Metal Resources Clean Utilization and Faculty of Metallurgical
and Energy Engineering, Kunming University of Science and
Technology, Kunming 650093, China
Xiuhua Chen − Institution of Materials Science and Engineering,
Yunnan University, Kunming 650091, China
Ran Chen − School of Photovoltaic and Renewable Energy
Engineering and Australian Centre for Advanced Photovoltaics,
University of New South Wales, Sydney 2052, Australia
Lianzhou Wang − Nanomaterials Centre, Australian Institute
for Bioengineering and Nanotechnology and School of Chemical
Engineering, The University of Queensland, St. Lucia,
Queensland 4072, Australia; orcid.org/0000-0002-5947-
306X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.0c14157
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors acknowledge financial support from the National
Key R&D Program of China (grant nos. 2018YFC1901805
and 2018YFC1901801), the National Natural Science
Foundation of China (grant nos. 51762043, 51904134,
51974143, 61764009), the Program for Innovative Research
Team in University of Ministry of Education of China (grant
no. IRT_17R48), the Major Science and Technology Projects
in Yunnan Province (grant no. 2019ZE007), and the Key
Project of Yunnan Province Natural Science Fund (grant no.
2018FA027). S.L. acknowledges the support by Yunnan Ten
Thousand Talents Plan Young & Elite Talents Project. F.X.
acknowledges the support from the Chinese Scholarship
Council. The authors also thank the support from the
Australian Research Council through its Linkage Project and
Discovery Projects.
■
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