Mohamad Alief Ramdhan - Tugas 2 Jurnal Review
Mohamad Alief Ramdhan - Tugas 2 Jurnal Review
Mohamad Alief Ramdhan - Tugas 2 Jurnal Review
PII: S2405-8297(20)30403-7
DOI: https://doi.org/10.1016/j.ensm.2020.10.026
Reference: ENSM 1392
Please cite this article as: Qitao Shi , Junhua Zhou , Sami Ullah , Xiaoqin Yang , Klaudia Tokarska ,
Barbara Trzebicka , Huy Quang Ta , Mark H. Rümmeli , A Review of Recent Developments
in Si/C Composite Materials for Li-ion Batteries, Energy Storage Materials (2020), doi:
https://doi.org/10.1016/j.ensm.2020.10.026
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Qitao Shia, Junhua Zhoua, Sami Ullaha, Xiaoqin Yanga,b, Klaudia Tokarskac, Barbara
Trzebickac, Huy Quang Tad, Mark H. Rümmelia,c,d,e*
a
Soochow Institute for Energy and Materials Innovation, College of Energy,Key Laboratory of
Advanced Carbon Materials and Wearable Energy Technologies of Jiangsu Province,
Soochow University, Suzhou 215006, China
b
School of Energy and Power Engineering, Xi’an Jiaotong University, No. 28, Xianning West
Road, Xi’an, Shanxi 710049, China
c
Centre of Polymer and Carbon Materials, Polish Academy of Sciences,M.
Curie-Sklodowskiej 34, Zabrze 41-819, Poland
d
Institute for Complex Materials, IFW Dresden, 20 Helmholtz Strasse, Dresden 01069,
Germany
e
Department of Chemistry, VŠB-Technical University of Ostrava, Czech Republic
*Corresponding author.
Qitao Shi received his bachelor of science degree from the Department of physics and
doctoral researcher at the Soochow Institute for Energy and Materials Innovations (SIEMIS)
and the College of Energy at Soochow University China in Prof. Mark H. Rümmeli‘s group.
His current research focuses on solving the pulverization issues of Si particles as anode
professor. He is also director of the characterization center at the College of Energy and
SIEMES. Moreover, he is a full professor of the Polish Academy of Sciences (CMPW PAN)
in Zabrze and has full habilitation rights. He obtained his Ph.D. from London Metropolitan
University and then worked as a postdoc at the German Aerospace Center. His research
Abstract: Rechargeable lithium batteries play an increasingly significant role in our daily
lives. Hence, the development of high capacity secondary lithium batteries has become a
research hotspot. In the past decade, silicon has been extensively studied as anode material for
Li-ion batteries because of its extremely high specific capacity. However, the dramatic
volume change and troublesome SEI (solid electrolyte interface) issues during lithiation and
carbon materials have been widely utilized in composites with Si materials due to their
composite materials facilitate the design of novel Si/C composites. Different forms of carbon
2
can improve the electrochemical performance of silicon materials in different ways.
Advanced characterisation techniques further verify and explain the contribution of carbon
materials to the performance improvement of Si. Si/C composite materials are anticipated to
be the anode material for the next generation of commercial lithium batteries.
1. Introduction
The advent of portable electronic products and alternative fuel vehicles has led to an increased
demand for advanced lithium (Li)-ion batteries. High performance Li-ion batteries provide
electric endurance support in electronic products [1, 2], wherein battery performance is
primarily affected by the battery‘s anode materials. Graphite is a popular low-cost commercial
anode material with high conductivity and stable reversibility. However, the material‘s
Electrochemical alloys of Li metal with other compounds (e.g. Si, Sn, P, and Sb) can be used
as alternatives. Si-based anode materials are a popular candidate for next generation Li-ion
batteries due to an extremely high specific capacity of over 10 times that of commercial
graphite.[3, 4] However, Si-based anodes exhibit large volume changes and form an unstable
solid electrolyte interface (SEI) during electrochemical processes (Figures. 1(a-c)) [5].
Recently, composites of carbon and Si (Si/C) based on various carbon materials and structural
designs have been developed to overcome these issues concerning volume expansion and
continuous SEI formation (Figures. 1(d-f)) [6-8]. Carbon coating and controlled porosity have
been found to prevent the pulverization of Si particles [6]. Carbon coating can also ensure the
stability of the solid electrolyte interphase, thus preventing the consumption of the inner Si by
the continuously formed SEI [7]. Careful design of Si/C material structures can ensure strong
bonding between the electrode materials and current collector [8]. Overall, the improved
performance of Si-based anode materials has been attributed to unique structural designs and
the excellent properties of the carbon materials. Several literature reviews have explored the
3
development of Si/C composite anode materials for Li-ion batteries from different
perspectives. For instance, Dou et al. [9] assessed Si/C composite materials with different
dimensions in great detail, Zhang et al. [10] introduced nanostructured Si/C materials and
related electrolytes and binders, and Shen et al. [11] summarized the progress in Si/C
introducing various Si/C composite anode materials and their preparation methods along with
advanced characterization techniques has not yet been published. This review focuses on the
use and preparation of carbon materials to enhance the performance of Si materials, giving a
(CNTs), two-dimensional (2D) graphene (G) sheets and transition metal carbides and
performance of Si/C composites is further verified and explained using several advanced
carbon black in this category. In addition, research on Si/carbon black composites is rarely
Different Si materials have been designed and synthesized for Li-ion batteries using various
chemical vapor deposition (CVD) [14], Si-nanoparticle synthesis by the reverse micelles
method [15], and Si-film deposition using a radiofrequency/direct current (RF/DC) magnetron
and has been described in several review articles [20, 21]. Thus, the synthesis of Si materials
4
is not discussed in this review. Instead, novel preparation methods of various carbon materials
Carbon materials are typically prepared utilizing six methods: electrospinning, Hummer‘s
carbonization. The CVD method is generally used to coat graphitic carbon on solid Si
materials, and it can be used to synthesize carbon nanotubes. Thermal treatment is mainly
used to produce amorphous carbon coatings and to convert graphene oxide (GO) coatings
2.1.1. Electrospinning
melt is sprayed in a strong electric field. The electric field changes the shape of the droplet at
the needle point from spherical to conical, where a fibrous filament extends from the tip of the
cone. These polymer filaments have nanoscale diameters and are thus classified as 1D
shown in Figure. 2 [22]. The carbon precursor to produce CNFs requires a careful selection,
as it determines the carbon structure formed upon carbonization. This CNF structure formed
at high temperature can significantly affect the composite material‘s electrical, chemical, and
mechanical properties.
5
Hummer‘s method is an effective method for production of graphene sheets and was first
proposed in 1958 by William S. Hummer. JR [23]. Numerous studies have since contributed
to the optimization of this method to produce graphene [24, 25]. Graphene oxide is produced,
and further processing under high temperature is required to produce 2D graphene sheets for
the fabrication of a Si/G composite. Some studies have synthesized graphene directly after the
formation of graphene oxide [26, 27], but most studies have mixed the graphene oxide with Si
particles to strengthen the bond between the two components before further processing. This
mixing has been found to lead to the formation of Si/G composite materials displaying
and platinum wire as the working and counter electrodes, respectively [33]. After exfoliation,
the product is collected by vacuum filtration, washed with deionized water to remove any
remaining residues and sonicated for further removal of non-exfoliated graphite aggregates.
The product is centrifuged to form dispersed graphene sheets. This approach avoids the
over Hummer‘s method. As graphene oxide is not generated, the product is easily converted
to graphene sheets, and a regular commercial microwave within seconds can provide the
energy for graphene transformation under inert gas protection. Further, electrochemical
exfoliation is relatively simple and is performed rapidly under mild conditions. Lastly, while
graphene produced by Hummer‘s method typically exhibits high sheet resistance due to flake
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damage caused by the oxidation and exfoliation processes [32]. these effects can be avoided
CVD has gained popularity in the growth of graphene materials for use in electronic and
optoelectronic devices, chemical sensors, nanocomposites, and energy storage [34]. CVD
breaks down gaseous reactants carried into a tube furnace to produce atomic species, which
are subsequently deposited onto a substrate surface. The CVD process is depicted in Figure. 3.
CVD is mainly used to produce graphitic carbon-coated Si and carbon nanotubes, which are
classified as 1D carbon and can be further composited with Si materials. Further, CVD can
deposit Si onto a substrate using SiH4 or SiHCl3. CVD is a relatively convenient and easily
controlled synthesis method because it involves mostly mechanized operation that requires
Most carbon deposition precursors are organic compounds, namely poly(methyl methacrylate)
(PMMA) [35], propylene [36], acetylene [37, 38], methane [39], ethanol [39] and toluene [40].
However, a novel approach has been proposed in which an inorganic CO2 precursor (solid,
liquid, or gaseous) was used for carbon deposition [41, 42]. Under high temperatures, solid
carbon precursors decompose into atomic species, liquid precursors are typically transferred
into the tube using an inert gas, and gaseous precursors are fed directly into the tube furnace.
Regardless of precursor state, the deposition process is the same, and either amorphous carbon
the CVD method, but can be performed using the same equipment. Organic carbon precursors
7
are converted to inorganic carbon during thermal treatment by removal of the hydrogen and
oxygen components under high temperature. The process is performed in an inert gas to
prevent the formation of undesirable carbon compounds, while a high temperature is applied
to provide the energy required to remove hydrogen and oxygen from the carbon source. The
organic carbon precursor or organic carbon coated material is placed within a tubular furnace
in advance to ensure that the entire process proceeds without contamination by foreign carbon
sources, as the carbon source can have significant effects on the product. Thermal treatment is
A liquid carbon source may also be used in thermal treatment, including sucrose [43],
resorcinol-formaldehyde resin [44, 45], polydopamine [46, 47], sodium dodecyl benzene
sulfonate [48], and styrene [49]. Further, solid carbon sources can be dissolved in an
appropriate solvent to serve as a liquid carbon precursor. Si materials must be coated in the
same solvent before transfer to the furnace tube. Thermal treatment converts the organic
Hydrothermal reaction processing is a general term for chemical reactions conducted in water,
1100 ℃ and pressures of up to 1 GPa owing to its reliable sealing system and explosion-proof
design. A typical hydrothermal approach was used by Jeong et al [50]. Si was ultra-sonicated
in distilled water with sucrose, oxalic acid, cetyltrimethylammonium bromide, and polyvinyl
pyrrolidone, transferred to a Teflon-lined stainless steel autoclave, and held at 200 °C for 10 h.
The solution was cooled, filtered, washed with distilled water, and carbonized under argon
particles in the void space within the carbon skeleton. Moreover, the carbon skeletons
Carbon nanotubes (CNTs) and CNFs are 1D carbon materials that can be used to form
Si/carbon nanotube and nanofiber composite materials. CNTs are widely used in photonics,
materials show great promise for use in Li-ion batteries due to several advantages, including
high electrical conductivity and impressive mechanical and thermal stabilities [51]. These
processing.
Wang et al. reported, for the first time, the synthesis of heterostructures comprising vertical
produced using a simple two-step liquid injection CVD process (Figure. 4(a)) [52]. The space
between the multiwall CNTs facilitated homogenous deposition of the Si nanoparticles on the
CNT surfaces, and this prevention of Si nanoparticle agglomeration alleviated the strain
caused by the volume change of Si. Further, the hybrid Si/CNT nanostructure provided rapid
electron and ion transportation. The hybrid anode exhibited a high reversible capacity of
~2000 mAh/g and high Columbic efficiency over the first 25 discharge/charge cycles (Figure.
4(b)). Thereafter, the cycling tests revealed a rapid loss in performance due to fragmentation
of the attached Si particles, weakening of the Si-CNTs interface, and continuous SEI growth.
Thus, this hybrid structure prevented the agglomeration of Si particles and supported electron
and ion transportation but did not solve the pulverization and SEI issues. These issues remain
before compositing with CNTs. Su et al. designed 3D porous anode materials comprising Si
and SiO2 decorated in-situ with CNTs (Figure. 5(a)) [53]. SiO2 was heated with Mg to convert
SiO2 to Si clusters, leaving behind a small amount of SiO2. Fe was deposited on the surface of
the product (so called pSS particles) and served as a catalyst. Subsequently, the pSS powder
was loaded into a tube furnace under Ar/H2 atmosphere carrying toluene at 750 ℃. The
toluene interacted with the surface of the Fe particles and led to the in situ growth of CNTs.
This carbon source was in turn deposited on the surface of the Si particles. The pSS/CNT
composite anode performed better than a regular pSS anode (Figure. 5(b)). Electrochemical
impedance spectroscopy (EIS) indicated that the carbon layer and interconnected CNTs
contributed to the overall improvement in the conductivity of the pSS-based material (Figure.
5(c)). The pSS/CNT composite exhibited more stable long-term cycling performance than the
Si/CNT composite [52] due to the additional carbon coating on the Si particles. This carbon
coating acted as an electrolyte blocking layer and prevented continuous SEI formation, thus
facilitating high Coulombic efficiency [54]. Further, the layer alleviated the strain caused by
the volume change, which prevented the typical rapid cracking and pulverization of Si
particles. Yi et al. proposed a similar method for growing CNTs on porous Si [55], where Si
micro- and nanospheres were cross-linked by highly elastic carbon nanotubes. While CNTs
are often directly composited with Si materials, they can also be used as a soft membrane
shield for traditional polymer separators [56], thus providing additional space to buffer the
Recently, Zhang et al. designed a robust hierarchical 3D Si/CNT composite with a void and
carbon shell as Li-ion battery anodes [57]. CNTs and commercial Si nanoparticles were
well by the CNTs. The extra carbon shell outside the Si/CNT composite particle effectively
prevented the electrolyte from contacting the Si nanoparticles and provided channels for
10
rapidly passing Li ions. In addition, the void inside the carbon shell adequately
accommodated the Si volume increase during the lithiation process to avoid damage. The 3D
1000 cycles at the rate of C/5, which was attributed to its special structure.
To take advantage of the inner space of the CNTs, Cui et al. used anodic aluminium oxide
(AAO) as a template to grow CNT arrays (AAO/CNTs) using a CVD method [58]. In
addition, they used liquid paraffin as an inexpensive carbon resource. Si nanoparticles were
then injected into the CNT arrays by the pressure difference, with the as-grown AAO/CNT
membrane serving as a barrier layer to separate the device into two parts, thus isolating the
silicon suspension from the air. Next, another carbon layer was deposited to completely wrap
the Si nanoparticles. Finally, a CNTs–Si–CNTs sandwich structure was obtained after etching
away the AAO template, and the resulting composite anode manifested a high specific
capacity of 1050 mAh/g after 500 cycles owing to its structural stability and the excellent
CNFs were first prepared by Thomas Edison in 1879, where cotton and bamboo were
carbonized. The technique has been further developed and applied in both fundamental
scientific research and practical settings [59, 60]. The structure of a CNF is dependent on the
morphology of its precursor and the processing conditions. CNFs generally exhibit high
thermal and chemical stabilities, good thermal and electrical conductivities, and excellent
stress resistance, thereby leading to broad application prospects in composite materials, Li-ion
battery anode materials, nanoelectronic devices, and hydrogen storage materials. CNFs may
be synthesized using CVD [61], electrospinning, or solid-phase synthesis [62], where the vast
majority of CNFs used for Si/C composite anode materials are synthesized by electrospinning.
Xu et al. reported 3D Si/C fibre paper electrodes for Li-ion batteries fabricated using a
nanofiber paper (Figure. 6(a)), which was carbonized to form carbon-coated Si clusters
between CNFs. The use of PAN as a carbon precursor led to a superior CNF structure [59].
The Si/C fibre paper acted as a free-standing electrode with superior electrochemical
performance and was a viable alternative current collector to replace Cu metal, offering light
weight, excellent electric conductivity, and good mechanical properties [64]. The cycling
performance of the Si/C fibre papers with various Si mass loadings were evaluated (Figure.
6(d)). The electrode exhibited stable cycling behaviour and high Coulombic efficiency, even
at the highest mass loading of 1.7 mg/cm2, thereby demonstrating the robustness of the 3D
Si/C paper architecture. An impressive capacity was achieved under different discharge and
charge rates, even at a high current density of 8 A/g (Figure. 6(b)). The electrochemistry was
evaluated on the basis of cyclic voltammetry (CV) curves (Figure. 6(c)) and was found to be
consistent with that reported previously [65]. A similar free-standing electrode composed of
reported by Chen et al [66]. In this study, Si nanoparticles were directed inside the CNFs, and
While CNFs can act as a tight net to hold and electrically connect Si particles, there are many
other ways to composite Si materials with CNFs. These approaches include Si nanoparticles
anchored onto CNFs [67, 68], branched CNFs on Si nanowires [69], branched CNFs on Si
particles [70], and Si core-carbon shell fibres [71]. Scalable production of Si core-carbon shell
nanoparticles mixed with PMMA were injected into the core channel of the dual nozzle, while
PAN dissolved in DMF was injected into the shell channel of the nozzle. Electrospinning and
carbonization were conducted to form the SiNPs@C core−shell 1D fibres (Figure. 7(a)).
SiNPs@C exhibited excellent cycling performance, where only 1% of the initial capacity was
12
lost after 300 cycles at a high current density of 3 C (2.75 A/g) (Figure. 7(b)). Further, the
Coulombic efficiency was often greater than 100%, indicating that a stable SEI was formed
on the SiNPs@C surface. The abnormally high efficiency was linked to continuous changes
in the arrangement of Si nanoparticles during cycling, which caused a fluctuation in the ionic
and electric conductivities. Therefore, some residual Li stored in previous cycles can be
extracted additionally. The EIS measurements further confirmed the presence of a stable SEI
(Figure. 7(c)). Testing under different current densities revealed that the composite anode
exhibited stable capacity, even at 12 C (11 A/g) (Figure. 7(d)). The remarkable performance
of the material was attributed to the excellent mechanical and electrochemical properties of
Kong‘s group designed necklace-like Si@CNFs as robust anode materials by using SiO2
nanospheres as the Si source for electrospinning [72]. The SiO2 nanospheres were synthesized
necklace-like Si@CNFs. During this process, SiO2 nanospheres were reduced to smaller Si
nanoparticles, and the polymer wrapping the original SiO2 nanospheres became a CNF shell
encapsulating the Si nanoparticles. The diversity of carbon and silicon sources makes
Most reports on Si/1D carbon composite materials involved the exposure of Si particles, with
and without a thin carbon layer coating, to the electrolyte [52, 67, 69, 74-77]. Consequently,
these electrodes suffer from varying degrees of capacity fading due to continuous SEI
formation, where the Si content of the composite material is consumed. Thus, an appropriate
carbon coating on the surface of Si particles is required to protect the material from the
material [78]. Graphene exhibits excellent electrical, mechanical, and thermal properties due
to its unique single atom thickness [79]. Graphene is widely used for energy storage,
and Li-S batteries [80]. The use of chemically doped graphene has attracted much research
interest, where a band gap is created by doping with elements such as boron and nitrogen to
produce more useful properties [81]. Consequently, doped graphene has been incorporated in
Graphene sheets in Si/2D graphene composite materials for Li-ion batteries are primarily
modification of Hummer‘s method was proposed by Xin for production of a unique Si/G
[28]. Graphene oxide sheets were formed, and a modified sol-gel method was used to produce
SiO2@GO with tetraethyl orthosilicate (TEOS) as the SiO2 precursor. SiO2@GO was treated
with a magnesium thermal reduction method to convert the graphene oxide sheets to graphene
(G) sheets, thus forming the unique Si@G (Si/G) nanocomposite. To ensure a tight Si@G
composite structure, the graphene oxide solution was mixed, stirred, ultrasonicated, spray
dried, and annealed to form the 3D porous graphene coated Si@G (Figure. 8(a)). The Si/G
was much higher than that in the case of the Si@G nanosheets (Figure. 8(b)). This superior
Additionally, the Si/G nanocomposite exhibited increasing capacity in the initial 15 cycles
phenomenon [64]. This was also confirmed by the CV measurements (Figure. 8(c)). The
Nyquist plots (Figure. 8(d)) illustrated that the charge transfer resistance of the Si/G
nanocomposite was much smaller than that in the Si@G nanosheets, which was attributed to
14
the 3D architecture and additional graphene. The Si particles in the simpler Si@G nanosheets
were exposed to the electrolyte, and the Si particles and graphene sheets were not strongly
bound, leading to the loss of Si particles. These issues led to rapid capacity fading, but were
resolved by the 3D architecture and extra graphene sheets in the Si/G nanocomposite.
The relatively simple Hummer‘s method can be creatively adapted to design uniquely
graphene was designed by Sun et al [29]. Graphene oxide was synthesized by oxidizing
The dried graphene oxide and Si nanoparticles were scaled, uniformly dispersed in deionized
water, and vacuum filtered. This filtering–transferring process was repeated several times to
prepare a multi-layered Si–GO structure. The composite was immersed in HBr and held at
120 ℃ for 2 h to reduce the graphene oxide and obtain the Si–re-G alternating strata
(Figure. 9(a)). The Si–re-G composite was cut into individual electrodes using a razorblade.
The CV curves of the composite (Figure. 9(b)) were in good agreement with those of
previously reported Si–C composites [82]. Excellent capacity retention of about 1500 mAh/g
was observed after 100 cycles (Figure. 9(c)), with no obvious capacity decline. This
remarkable performance was further demonstrated under testing at different current densities
(Figure. 9(d)). The performance of the Si–re-G alternating strata composite was far superior to
exhibit a continuous capacity decay [83, 84]. The alternating strata structure facilitated
electron movement between the Si particles and served as a flexible cushion to alleviate the
strain caused by volume change. Moreover, the strata structure maintained the integrity of the
recent work [85], wherein graphite microsheets acted as mats to sandwich Si nanoparticles.
15
In Si/G composites produced from graphene synthesized by Hummer‘s method, graphene
production is one of the simplest production steps. Further processing of graphene oxide and
Si particles to form a functional Si/G composite material is often more complex. To ensure
secure attachment between the Si particles and reduced graphene oxide, Si particles are often
functionalized before mixing with the graphene oxide, typically through organic
functionalization of the non-oxidized Si surfaces [86]. Si particles can be mixed with various
organic compounds, such as PDDA [82, 87], PVP [88], APTMS [89], and APS [90].
Graphene oxide typically contains hydroxyl (-OH) and carboxyl (-COOH) groups, and the
organic species on the surface of functionalized Si particles bind to the -OH and -COOH
groups by chemical bonding. Functionalized Si particles and reduced graphene oxide have
been found to form a strong bond to prevent the loss of Si particles, which improves the
vaporized by spray drying or freeze drying [91-94], while graphene oxide is often reduced to
graphene by thermal reduction. Microwave irradiation can also be used for graphene oxide
The two applications based on Hummer‘s method that have been presented utilized
free-standing electrodes, where the composites were used directly as an anode material in
Li-ion batteries without a current collector. This ability was attributed to the tight bonding
achieved between the graphene oxide and Si particles, as well as the tough structure of the
reduced graphene oxide and good overall structural design of the composite. Si/G composite
materials have been reported in which Si particles were deposited onto graphene sheets and
bonded by covalent immobilization [33, 95]. However, the electrode comprising Si deposited
onto graphene sheets did not perform as well as the other free-standing electrodes. The raw
structure has a higher exposure of the Si particles to the electrolyte, which led to capacity
fading. Although 2D graphene provides a better overall electrode conductivity and better
distribution of the Si particles, protecting the Si particles from being consumed by the
16
electrolyte and preventing Si vacancies in the graphene sheets remains a challenge. Thus,
control over the weight ratio of Si to graphene, selection of an appropriately sized Si particle,
In contrast with the 2D graphene listed above, Lin et al. grew graphene nanowalls (GNWs) on
system [96]. Then, the Si material was deposited onto the as-grown GNWs to synthesize a
GNWs@Si composite. The tube furnace, GNWs, and GNWs@Si are shown schematically in
Figure. 10(a–c). The Raman spectra (Figure. 10(d)) indicated that the GNWs exhibited a
relatively low degree of graphitization and possessed abundant intergranular defects, which
could introduce a large number of charge carriers into the conductive network formed by the
2D GNWs. Owing to its stable structure, flexibility, and excellent conductivity without
additives or other complex fabrication processes, the GNWs@Si composite anode featured a
In addition to graphene, MXenes are another popular 2D carbon material [97] that consist of
transition metal carbides, nitrides, or carbonitrides with a thickness of several atomic layers.
MXenes are produced by the selective etching of the A element from MAX phases, which are
metallically conductive, layered solids connected by strong metallic, ionic, and covalent
bonds, such as Ti2AlC, Ti3AlC2, and Ta4AlC3. These new 2D materials were named MXenes
to emphasize the loss of the A element from the MAX parent phase and to highlight their 2D
nature, which is similar to graphene. Their 2D morphologies, combined with their metallic
batteries, MXenes can be used as current collectors [98], multifunctional binders [99, 100],
free-standing agents [101, 102] , and simple composite materials [103, 104].
[103], layered Ti3C2Tx MXenes were formed by etching away Al layers from the Ti3AlC2
MAX phases using hydrofluoric acid (HF). TEOS was used as the silicon source to deposit
17
SiO2 on MXene, followed by magnesiothermic reduction. After pyrolyzing the PMMA
MXene/Si@SiOx@C was obtained. Figure. 11(a) depicts a schematic diagram of the synthesis
(HRTEM) to verify the structure (Figure. 11(b-g)). Figure. 11(h) shows that
MXene/Si@SiOx@C exhibited stable and high cycling performance, which varied with the
different amounts of silicon. When the composite contained 72.8 wt% silicon, the
delivered a stable capacity of 1547 mAh/g after 200 cycles. This anode also exhibited a high
rate capability, as shown in Figure. 11(i). Its extraordinary performance was attributed to the
favourable electronic conductivity, rapid Li ion mobility, flexible layer spacing, and rich
Because MXene has excellent properties similar to those of graphene, it would be worth
composites could be used to design and synthesize related Si/MXene composite materials.
current-collector-free, and binder-free anodes, and the results well met the expectations.
However, as MXene is generally synthesized by top-down methods, MXene has not yet been
The main types of 3D carbon materials are graphene and amorphous carbon-coated Si
particles, porous carbon, and graphite. However, Si particles wrapped in graphene sheets are
Si/C composite with a core-shell (yolk-shell) structure is obtained. This carbon shell can
18
effectively prevent the degradation of the Si core by the electrolyte. Furthermore, this
yolk-shell structure reserves space to allow for Si volume expansion, thus ensuring that the Si
A typical Si core-graphene shell structure was developed by Shi et al. by direct vertical
graphene (vG) growth on commercial SiO microparticles (d-SiO@vG) using CVD with
methane as the carbon source [39]. During graphene synthesis, the SiO microparticles were
amorphous SiO2 surface layer was formed during the initial heating of the reaction, thus
providing numerous catalytic nucleation sites for the synthesis of graphene. This layer also
prevented the formation of SiC. The unique vertical graphene coating led to a significant
improvement in electrical conductivity of the SiO on the single-particle level and electrode
level (Figure. 12(a)). Further, the structure provided transport channels for lithium ions. In
addition, the structure of the vertical graphene encapsulated SiO particles was maintained
after repeated lithiation and delithiation (Figure. 12(b)). The cathodic scan exhibited a peak at
0.65 V in the first cycle, which subsequently disappeared in the following cycles. This
observation was attributed to the irreversible formation of a stable SEI layer (Figure. 12(c)).
The stability of this SEI film was confirmed by the Nyquist plot based on EIS (Figure. 12(d)).
At a high areal mass loading of 1.5 mg/cm2, the d-SiO@vG electrode exhibited high specific
capacity with minimal fading over 100 cycles (Figure. 12(e)). Moreover, the d-SiO@vG
electrode exhibited superior capacity (~450 mAh/g) when compared to that of commercial
graphite at a high current density of 1600 mA/g (Figure. 12(f)). The stable rate performance
of the electrode further demonstrated the great advantages of vertically grown graphene.
A granadilla-like Si/C composite was proposed by Zhang et al., where clusters of yolk-shell
units were synthesized by a combination of a modified templating method and CVD [37].
Each yolk-shell unit comprised a Si particle and carbon shell separated by a void space. The
CaCO3@Si composite was placed into a tube furnace for CVD treatment with an acetylene
carbon source. The sacrificial CaCO3 layer disappeared to produce a Si core-carbon shell
cluster with interconnected void spaces. Typically, an SiO2 sacrificial layer is initially
produced by the hydrolysis of tetraethyl orthosilicate (TEOS) [44, 46] to form the void space.
However, SiO2 is expensive, complex to work with, and not environmentally friendly, while
the use of CaCO3 is less expensive, simpler, and less toxic. The granadilla-like Si composite
framework, carbon deposition, and removal of the carbonate templates using HCl (Figure.
13(a)). EIS plots of the granadilla-like Si composites with different Si contents were evaluated
(Figure. 13(b)). The 30@Si-granadilla composite had a high carbon content and exhibited the
lowest resistance to Li-ion transfer and highest conductivity. However, the high carbon
content led to a lower overall specific capacity of the electrode (Figure. 13(c)). The
50@Si-granadilla composite exhibited the highest cycling capacity, which was attributed to
its high Si content and optimal structure. All the granadilla-like Si composite samples
exhibited good cycling stability over 200 cycles, which was linked to a good rate performance
(Figure. 13(d)). The unique structure of the composite allowed for Si volume expansion and
avoided the loss of Si particles from the current collector after cracking. Further, the Si core
did not form a thick SEI. The well-connected carbon network maintained good electrode
The novelty of some Si/3D carbon composites lies in the unique structure of the Si or carbon
components. Another granadilla-like porous Si/C structure proposed by Guan [105] was
synthesized by mixing SiO2 coated Si (SiO2/Si) with PVP to form a homogeneous suspension.
granadilla-like porous Si/C composite. The porous structure of the Si microparticles can be
achieved with an appropriate precursor, such as SiO2 [106], zeolite SSZ-13 [107], or Mg2Si
20
[108]. Carbon coating is typically conducted to further enhance the electrical properties of the
In addition to carbon surface coatings, porous carbon could provide fast electron and ion
transport channels along with abundant void spaces. Generally, porous carbon frameworks are
derived from various organic carbon materials, such as pitch filtration and decomposition
[109], calcination of a mixture of glucose and calcium carbonate [110], gelation of multiple
organic species [111], and the etching and calcination of natural rape pollen [112].
carbon nanoshell was proposed by Li‘s group [113], and their preparation method is shown in
Figure. 14(a). Poly(styrene-co-vinylbenzyl chloride) (PSV), Si powder, and oleic acid were
mixed to form Si-embedded porous microsphere via emulsification. The porous microspheres
adding an extra carbon source and controlling the pH to complete the carbon encapsulation,
the as-formed product was carbonized to obtain the final carbon-encapsulated porous Si/C
microsphere. Figure. 14(b) shows the morphology of the porous microspheres before
implantation with Si, exhibiting abundant micropores. Figure. 14(c–d) illustrates the
microspheres implanted with micron-sized Si powder with increasing content. They explored
carbon-encapsulated porous Si/C microsphere anode far outperformed the bare Si anode, as
shown in Figure. 14(e-f). The superior retention of n-Si compared with that of u-Si should
correlate with the smaller volume variation of the smaller n-Si. In addition, the extra carbon
coating on the Si/C microsphere further maintained the integrity of the electrode. Owing to
exhibited a high initial capacity of 3320 mAh/g and a good retention of 90% after 100 cycles.
In summary, porous carbon materials provide high electron and ion conductivity and void
21
space, all of which are vital to improving Si anodes, and the extra carbon coating on Si
Compared with the above 3D carbon materials, Si/graphite composites are more attractive
because they have been commercialized. Future applications of graphite anodes are limited by
their low specific capacity, and the severe volume change and SEI issues associated with Si
anodes also hinder their commercialization. Thus, the Si/graphite composite has been deemed
to be the most appropriate approach for realizing a high energy density in current commercial
Si/graphite composite anodes for next-generation LIB, in addition to solving the problems
associated with Si anode, other aspects to consider are ensuring tight contact between the
silicon and graphite and finding the best weight ratio of silicon and graphite. Very recently,
Cho et al. comprehensively reviewed the research progress in integrated graphite and silicon
anodes and reviewed their prospects for their commercialization in high-energy Li-ion
batteries [114]. Therefore, we will not further review Si/graphite composites herein.
Compared to the common conductive agent carbon black, whose contact with Si is
point-to-point, 1D, 2D and 3D carbon materials possess better electrical conductivity over
electrical contact with Si materials because of increased contact sites. 1D carbon materials can
form conductive networks that improve electron and Li-ion transport pathways. Some 1D
carbon materials release stress caused by volume change and decrease weak electrical contact
electron conductivity and higher thermal and mechanical stability than other carbon materials.
stability, and in some specially designed electrodes, graphene sheets can work as the current
collector. This facilitates more active material within the limited cell space. Compared to 1D
carbon materials, 2D graphene sheets provide more contact sites because of extremely high
specific surface. Although the contact between Si materials and 1D/2D carbon materials is
22
relatively intimate, poor structural design of Si/1D carbon or Si/2D carbon composites
continues to allow exposure of Si particles to electrolyte. The resulting Si particle loss and
continuous SEI formation consumes the outer layer of Si particles and leads to capacity fading.
3D graphene and carbon-coated on Si surface are designed to protect Si particles from wetting
by electrolyte. During electrochemical processes, electrolyte forms a stable SEI film with the
graphene/carbon shell alleviates the volume expansion of Si so that Si particles will not be
pulverized. The unique yolk-shell structure of Si/3D graphene/carbon composites could even
reserve proper space for Si particle expansion and contraction instead of departure from the
coating is quite effective in protecting Si anodes and achieving high battery performance.
different Si/C composites anodes, we tabulated the capacities of the various Si/C composite
anodes mentioned above, along with their structures and synthetic methods, in Table 1.
materials in LIBs.
Initial Mass
Cycling Stability
Anodes Capacity Initial CE Loading Structure Synthetic Method Ref.
mAh/g
mAh/g mg/cm2
Si/CNFs ~1400 87.5% ~1250 after 100 0.6 core−shell fibers electrospinning [71]
23
cycles at 0.24 A/g
Stöber method,
reduction
Kovtyukhova‘s
1500 after 100 alternating
Si/graphene over 5000 47% 2.7 method, filtering– [29]
cycles at 1.35 Ag stratum
transferring
GNWs@Si
1116 after 200
Si/graphene 3798 48.3% — nanowall PECVD [96]
cycles
network
ball milling, HF
1547 after 200
Si/Mxene ~1800 — ~1 layer-by-layer etching, Stöber [103]
cycles at 0.84 A/g
method
emulsification,
thermal treatment
reflux technique,
~500 after 50 Si coated
catalytic
Si/graphite 525 93.8% cycles at 1.75 — edge-activated [115]
hydrogenation,
mA/cm graphite
CVD
high-energy
method
and performance of a material are highly dependent on its microstructure. Long-term cycling
performance, rate performance, cyclic voltammetry measurements, and EIS are common
macroscopic performance tests used in the study of Li-ion batteries. These parameters provide
sample preparation and transportation technique used for electron microscopy, which can be
used to directly observe liquid, semi-liquid, and electron-beam-sensitive samples. Huang et al.
visualized the structure and chemistry of the SEI on silicon anodes using atomic-resolution
carbonate) electrolyte, the lithiated Si (Li15Si4) was interfaced with a bilayer SEI, consisting
of an inner amorphous LixSiOy layer from the lithiation of the SiOx and an outer layer
consisting of amorphous LEDC (Li ethylene dicarbonate) and crystalline Li2O arising from
the decomposition of EC. Upon delithiation, Li2O first reacted with Si to form LixSiOy, which
could be further delithiated, and organic carbonates such as LEDC were oxidized. In addition
to observing the SEI, cryo-EM can also be used to investigate other sensitive materials such
as lithium dendrites [118]. Thus, cryo-EM can be expected to promote the understanding of
electrochemical processes.
25
However, ex-situ characterization does not provide insight into the electrochemical process.
Owing to the widespread use, convenience, and ease of use of ex-situ characterization
techniques, these are not detailed in this review. Recent advances in in-situ characterization
have allowed for the real-time observation of structural changes and compound evolution
TEM provides atomic-level resolution and has become increasingly popular in material
characterization. In-situ TEM has made great advances, thereby facilitating the real-time
observation of a wide variety of details during the electrochemical process. This is a distinct
A SiC-free graphene-coated Si composite material was designed by Son et al., and the
lithiation and volume expansion of the graphene-coated Si particles was monitored in real
time using in-situ TEM analysis (Figure. 15(a)) [119]. The schematic of the in situ TEM
device is shown in Figure. 15(b). The graphene-coated Si particles were placed onto a
gold-fixed electrode and lithiated using an electrode with a Li/LiO2 tip, which caused the
particles to swell. The particles fully encapsulated by graphene with no obvious defects (red
and orange circles in Figure. 15(a)) exhibited a diameter increase of ~30%. Particles with a
defective graphene coating exhibited pulverization of the inner Si particle and rupture through
the defect (green and blue circles in Figure. 15(a)). The interlayer distance of graphene layers
increased by the end of lithiation due to Li-ion intercalation [120]. Liu et al. also applied
in-situ TEM to study the structural change of pomegranate-inspired yolk-shell clusters of Si/C
composite [44]. The in-situ TEM data shows that initial well-defined void spaces and chosen
nanoparticles can ensure Si particles expand inside the carbon shell with little change to both
size of ~150 nm neither cracked nor fractured after the first lithiation process, while larger
particles exhibited surface cracking and particle fracture [121]. This novel finding provided
important insight for the selection of Si nanoparticles in the design of Si/C composite anode
materials.
In-situ XRD measurements rely on the design of the in-situ cell, as a poorly designed cell can
give rise to signal artefacts that interfere with the signals of interest. Several different types of
in-situ cells have been reported for in-situ XRD, such as modified coin cells and modified
X-ray characterization is shown in Figure. 16(a). Further, cells used for synchrotron-based
in-situ XRD should be designed as simple as possible to allow easy assembly and disassembly
in the synchrotron facility [122]. One should also be able to incorporate the cell into the
beamline setup and accommodate the X-ray optics. The cell should be highly reproducible
and the cell components and materials must be carefully selected and constructed to avoid
interference from inactive cell components. In addition to external noise, beam damage
should also be considered. Intermittent probing of the sample can reduce the total amount of
X-ray radiation during acquisition. While performing this technique can be complex, in-situ
XRD is a powerful tool to study crystal, structural, and phase transformations within electrode
Synchrotron-based in-situ XRD was used by Yang to study the structural changes in
Synchrotron-based X-ray sources provide higher intensities and greater photon energies,
which facilitate higher penetration power and better signal-to-noise ratios for favourable
in-situ capabilities [124]. However, battery materials are easily damaged by the high-energy
27
beam and analysis should be conducted with care [122]. The in-situ XRD patterns of a
peak broadening and intensity reduction of the (111), (220), and (311) reflexes (Figure. 16(b))
[123]. This indicated that the lithium intercalation of the Si powder involved the conversion of
the Si crystals to either the amorphous state or Li–Si alloy nanocrystals. Moreover, the
changes in graphite‘s (002) reflection indicated that lithium first intercalated into graphite,
and then into Si. In-situ XRD characterization of a bare Si electrode for comparison revealed
that the Li–Si alloy formed in the carbon-coated composite was distributed more uniformly
with a lower concentration of lithium. This led to higher utilization of the active Si materials
Raman spectroscopy is based on the Raman scattering effect discovered by Indian scientist
C.V. Raman. The scattering spectra are measured at frequencies differing from the incident
light to study molecular vibration and rotation, thus characterizing molecular structure.
Inelastic scattering caused by the interaction of molecular vibrations, optical phonons in solids,
and laser excitation is referred to as Raman scattering. Many structural, mechanical, and
chemical changes within electrodes during electrochemical cycling can be studied by in-situ
Raman spectroscopy [125, 126]. Raman spectroscopy does not require long-range structural
ordering, and amorphous compounds or electrode materials with poor crystallinity can be
Raman spectra provided direct evidence of Si particle lithiation during the first discharge,
where the Si signal completely disappeared as the voltage dropped below 0.1 V as Li 3.5Si was
formed [128]. The gradual loss of Raman Signal intensity below 0.4 V was attributed to
28
multiple factors, including the skin depth effect and initial insertion of lithium on the Si
surface. The inset in Figure 10c shows the Raman spectra of the Si/C composite during the
first charge cycle, where peaks attributed to crystalline structures related to the formation of
Li–Si alloy phase were not observed. These observations revealed that the electrode
comprised mixed phases (amorphous Si and Li–Si alloy) after the first cycle.
Atomic force microscopy (AFM) uses a microcantilever to observe and magnify the force
between the tip probe on the cantilever and the atoms of the sample to achieve atomic-scale
resolution. Owing to the special working principle, AFM can observe both conductor and
Recently, the development of in situ AFM has promoted studies of Si-based materials,
especially the analysis of volume evolution. Breitung et al [129]. applied in situ AFM to study
both the macroscopic (volume change) and microscopic (cracks and pinholes) mechanical
degradation that occurs in individual Si particles (Figure. 18(a)). AFM revealed that during
the first lithiation cycle, significant structural changes caused capacity loss (Figure. 18(b));
later, the capacity did not further fade, and coulombic efficiency was well retained, which
accords with the observation that nanoparticles can withstand stress induced cracking (Figure.
18(c)). Additionally, in-situ AFM was applied to analyse both lateral and vertical expansion of
Si [130], detect the thin SEI film during electrochemical cycling [131], and investigate
Nuclear magnetic resonance (NMR) is a physical process in which a nucleus with non-zero
magnetic field populates a low-energy spin state of the atomic nucleus; when a second
29
magnetic field is applied, nuclei in a low-energy spin state absorbed energy and are converted
to a high-energy spin state. Net energy absorption is called resonance. Nuclear resonance is
frequency vs. Energy absorbed. Schematics of the a typical electrochemical cell and the set-up
for the in situ NMR measurements is shown in Figure. 19 [133]. In Si-based anode materials,
amorphous phase transitions. Ogata et al. utilized in situ 7Li NMR spectroscopy to investigate
the second and subsequent lithiation behaviors of amorphous Si in SiNWs [134]. The
electrochemical and NMR sprectra of the process revealed the over-lithiation of c-Li3.75Si that
occurs below 50 mV and the formation of small clusters within the Li3.75Si phase on charge
which was only formed during the second electrochemical cycle. The defects formed within
this phase can act as nuclei for the growth of larger Si clusters, which can then grow and form
crystalline Si.
Besides the mentioned in-situ characterization techniques, in situ X-ray and neutron
radiography was combined to detect the Li–Si distribution and the alloying-induced volume
changes. It was visualized that many Si particles did not undergo lithiation during the initial
lithiation inside Si-based LIBs [135]. In-situ neutron reflectometry was also used to evaluate
SEI formed on silicon electrodes, indicating that the contracted by up to 22% during lithiation
further understand the chemical composition of the SEI on silicon electrodes, it was
spectroscopy with an adjustable penetration depth [137]. This investigation revealed that
effects of the SEI on the capacity degradation include both chemical degradation (i.e. a
chemical reaction between electrolyte and electrode surface) during initial cycling and
chemical-mechanical degradation (i.e. from the repeated SEI formation and particle fracture)
30
after prolonged cycling. Meanwhile, to apply in-situ XPS to observe the lithiation and
delithiation reactions of Si anode, Endo et al. deposited a Si film on a solid electrolyte, which
could compensate for the shortcomings of XPS [138]. The observed phase transformations
were consistent with those in previous reports [139, 140]. In summary, the various in-situ
characterization techniques are powerful tools for studying the structural and chemical
properties of Si/C composite materials when applied to batteries or other fields. The
of a material‘s properties and its chemical and structural changes can guide the practical
A wide range of strategies can be applied to synthesize Si/C composite materials. CVD and
electrospinning methods are typically used to produce 1D carbon nanofiber and carbon
graphite, and CVD or thermal treatment are used to coat 3D carbon on the surface of Si.
Neither Si nor carbon electrodes alone meet the requirements of next generation commercial
batteries, but the Si content can be optimized to enhance the overall capacity of most Si/C
composite electrode materials, while carbon content stabilizes the performance of Si. These
properties can be combined to produce efficient commercial battery materials with stable and
high-performance capabilities.
processing, thus providing more insight than ex-situ characterization. However, in-situ
31
characterization is associated with higher costs than ex-situ characterization techniques.
Moreover, there is an increased risk of equipment and sample damage during operation.
Many types of carbon precursors can be used to produce Si/C composite materials. Some of
these chemicals are harmful to the environment and human body, including methane and
toluene. Thus, the use of a non-toxic carbon source is encouraged. The quality of the
synthesized carbon material is largely dependent on the carbon source, and is thus another
important consideration. Among the wide variety of carbon sources for carbon material
synthesis, non-toxic, low-cost, and high quality carbon precursors must be further developed.
Contact between the Si particles and carbon materials should be optimized as the capacity of
the Si/C composite electrode is mainly attributed to its Si component. Stronger physical
The formation of void spaces, namely, pores in the electrode and voids within the structure, is
unavoidable in these electrode materials. The controlled design of void spaces can provide
room to accommodate the stress attributed to Si volume expansion and shrinkage. Thus, the
loss of electrode materials from the electrode is minimized. Furthermore, proper void space
ensures optimal contribution of active materials and, in turn, stable high performance. SEI can
accumulate inside pores upon cycling if the pore size is too large, subsequently inhibiting
ionic percolation. Thus, the pore size and number should be carefully controlled.
The total volume capacity of a Si/C electrode may be improved by increasing the Si/C weight
ratio, but one must ensure that other changes do not affect the Si performance. The
performance of the electrode must be maximized and stabilized for commercial application,
and the Si/C ratio should be optimized based on different carbon materials and structure
designs.
32
Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.
☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:
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Figure 1. (a-c) Fundamental problems associated with Si-based anodes in Li-ion batteries.
Reproduced with permission [5]. Copyright 2017, Wiley-VCH. (d) Hierarchical core-shell
Copyright 2016, Elsevier. (e) Carbon coating to ensure the stability of SEI layers. Reproduced
with permission [7]. Copyright 2016, Elsevier. (f) Concrete-like structural design to enhance
the strength of the electrode. Reproduced with permission [8]. Copyright 2015, Elsevier.
45
Figure 2. Scheme of fundamental setup for electrospinning. Reproduced with permission [22].
Copyright 2012, Wiley-VCH.
46
Figure 4. (a) Schematic of Si/CNT hybrid nanostructure fabrication. (b) Cycling capacity and
Coulombic efficiency curves of a coin cell over 25 cycles. Reproduced with permission [52].
Figure 5. (a) Schematic of pSS/CNTs synthesis. (b) Cycling performance of the pSS/CNT
anode. (c) EIS measurements of the pSS/CNT anode. Reproduced with permission [53].
47
Figure 6. (a) Schematic of the synthesis and architecture of a flexible 3D Si/C fibre paper
electrode before and after carbonization. (b) Rate capability of the flexible 3D Si/C fibre
paper electrode. (c) Cyclic voltammograms of the flexible 3D Si/C fibre paper electrode in the
1st, 2nd, and 5th cycles. (d) Cycling stability and Coulombic efficiency of flexible 3D Si/C
fibre paper electrodes with different overall loading masses. Reproduced with permission [63].
48
Figure 7. (a) Electrospinning with a dual nozzle and subsequent carbonization. (b) Cycling
performance of SiNPs@C at 3 C rate. (c) EIS measurements of SiNPs@C at the 25th, 50th,
100th, 200th, and 300th cycles. (d) Rate capability test of SiNPs@C. Reproduced with
49
Figure 8. (a) Preparation and microstructural characteristics of the Si/G nanocomposite. (b)
Capacity of the Si/G nanocomposite and Si@G nanosheets cycled at 100 mA/g. (c) Cyclic
voltammograms of the Si/G nanocomposite from the first to the sixth cycle. (d) Nyquist plots
of the Si/G nanocomposite and Si@G nanosheets, where solid circles represent results after
the first cycles and the hollow circles represent results after rate performance. Reproduced
50
Figure 9. (a) Schematic of a proposed composite comprising alternating strata of Si
nanoparticles and graphene (Si–re-G). (b) Cyclic voltammograms of the first three cycles of
the alternating strata Si–re-G composite. (c) Capacity–cycle profile of the alternating strata
Si–re-G composite anode with nine layers. (d) Specific capacity of five-layered (S1) and
nine-layered (S2) alternating strata Si–re-G composite anodes between 1.2 and 0.01 V at
current densities. Reproduced with permission [29]. Copyright 2013, The Royal Society of
Chemistry.
51
Figure 10. Schematics of (a) the RF plasma-enhanced horizontal tube furnace deposition
system, (b) GNWs prepared on the Ni foam, and (c) GNWs@Si composite prepared on the Ni
foam. (d) Raman spectrum of GNWs synthesized on the Ni foam, (e) cycling performance of
LIBs based on GNWs, pure silicon, and the GNWs@Si composite. Reproduced with
52
Figure 11. (a) Schematic of the preparation procedure for MXene/Si@SiOx@C nanohybrids.
SEM images of (b) MXene, (c) MXene/Si, and (d)MXene/Si@SiOx@C. (e) TEM and (f, g)
53
Figure 12. (a) Schematic of SiO microparticles encapsulated with vertical graphene. (b)
Stable electrical connection between SiO particles by interconnection of the vertical graphene
2nd, and 5th cycles. (d) Nyquist plots of d-SiO@vG electrodes before and after cycling. (e)
Specific capacity and cycling efficiency of d-SiO and d-SiO@vG electrodes at a current
density of 320 mA/g. (f) Rate performance of the d-SiO@vG electrode, where 1 C =1600
mA/g. Reproduced with permission [39]. Copyright 2017, American Chemical Society.
54
Figure 13. (a) Schematic of the granadilla-like Si composite design. (b) Electrochemical
(c) Cycling properties and (d) rate performance of the 30@Si-granadilla, 40@Si-granadilla,
Wiley-VCH.
microsphere. SEM images of porous microspheres implanted with various u-Si contents of (b)
0 wt%, (c)25 wt%, (d) 50 wt%. Stability of capacities obtained during the charge process at a
constant current of 420 mA/g and the corresponding CE for (a) @u-Si and u-Si cells and (b)
@n-Si and n-Si cells. Reproduced with permission [113]. Copyright 2020, Elsevier.
55
Figure 15. (a) Gr–Si NPs attached to the surface of an Au wire and a Li/LiO2 electrode before
and after lithiation. Reproduced with permission [119]. Copyright 2015, Springer Nature. (b)
Figure 16. (a) In situ/operando electrochemical coin cell designs for synchrotron-based X-ray
characterization. Reproduced with permission [122]. Copyright 2018, Springer Nature. (b)
In-situ XRD patterns of a graphite-mixed carbon-coated Si electrode during the first discharge.
56
Figure 17. In-situ micro-Raman signal of Si as a function of the first discharge and charge
(inset) voltages, where the solid blue lines are the fit to the experimental spectra. Reproduced
Figure 18. (a) Schematic showing the setup used for in situ and operando AFM of nano-Si
electrodes containing polymer binder and carbon black additive. Upon lithiation (charging),
the Si particles expand in volume and probably fracture to some extent. In addition, SEI
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formation on the free electrode surface occurs. (b) SEM-like images of a nano-Si electrode at
different potentials. The dashed circle indicates a surface region with significant structural
changes during the first lithiation cycle. (c) AFM height images of a nano-Si electrode
obtained in situ a) before cycling and in (b, first cycle; d, 2nd cycle) a ―fully‖ lithiated and (c,
first cycle) delithiated state. Each image shows the same area of the top surface. Reproduced
Figure 19. Schematics of the electrochemical cell and the set-up for the in situ 7Li NMR
Society.
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