REVIEW

[Link]

Challenges and Recent Progress on Silicon-Based Anode

Materials for Next-Generation Lithium-Ion Batteries
Chengzhi Zhang, Fei Wang, Jian Han, Shuo Bai, Jun Tan,* Jinshui Liu, and Feng Li*

LIBs cannot meet the ever-increasing

The electrode materials are the most critical content for lithium-ion batteries demands of long-range electric vehicles,
(LIBs) with high energy density for electric vehicles and portable electronics. portable electronic devices, and grid energy
Considering the high abundance, environmental friendliness, low cost, high storage, due to the limited theoretical
capacity of graphite (
372 mAh g1 for
capacity, and low operation potential of silicon-based anode, it has been
LiC6).[2] Output voltage and specific capac-
intensively studied as one of the most promising anode materials for high- ity mainly determined the energy density of
energy LIBs. However, the widespread application of silicon anode is impeded cell, the new-generation electrode materials
by the poor electrical conductivity, large volume variation, and unstable research must focus on higher capacities as
solid–electrolyte interfaces films. In the past decade, significant efforts have well as suitable working potentials.[3] As
shown in Figure 1a, alloy-type Si anode
been demonstrated to tackle these major challenges toward industrial appli-
has been intensively studied as one of
cations. Herein, the focus is on combining with advanced structure like the most promising anode materials for
nanostructure and composite with other materials, exploring various new high-energy LIBs because of its high capac-
polymer binders, improving electrolyte, different prelithiation strategies, and ity (
4200 mAh g1 for Li4.4Si, which is 10
Si/graphite design to meet commercialization requirements, particularly times higher than that of graphite) and
summarized the progress on areal capacity, initial Coulombic efficiency, and moderate electrochemical potential
(
0.4 V vs Liþ/Li) as well as it is the second
cost. Finally, the guidelines and trends for practical silicon electrodes are
most abundant element in the crust of
presented based on the recent reports. Earth and ecofriendly.[4]
Unfortunately, huge volume expansion
(
300%) of silicon is accompanied with
1. Introduction the lithiation and delithiation, which leads to series of conse-
quences (Figure 1b).[5] i) particle pulverization; ii) loss of electri-
The demand for lithium-ion batteries (LIBs) is not only high-level cal contact; and iii) unstable solid–electrolyte interface (SEI)
competence in long lifespan and environmental friendliness, but formation.[6] All these problems cause electrode collapse and
also in high energy/power density recently.[1] The graphite-based capacity fading. Furthermore, the poor intrinsic electron conduc-
tivity (Table 1) of Si also conduces to the sluggish electrochemical
kinetics.[4,7]
Dr. C. Zhang, J. Han, Prof. S. Bai, Prof. F. Li To tackle the aforementioned problems, tremendous efforts
Shenyang National Laboratory for Materials Science have been made to alleviate the volume expansion, improve
Institute of Metal Research electrode swelling, and build high elastic SEI film through
Chinese Academy of Sciences
the combination of advanced structures, binders, electrolytes,
Shenyang 110016, China
E-mail: fli@[Link] prelithiation, and Si/graphite design.[8] In this Review, we
Dr. C. Zhang, Prof. J. Tan summarize the recent progress on silicon-based anode materi-
Ji Hua Laboratory als about three aspects to achieve high-specific areal capacity.
Foshan, Guangdong 528000, China Meanwhile, more lithium consumed irreversibly during initial
E-mail: tanjun@[Link] cycle could cause the lack of lithium sources in electrolyte and
F. Wang, Prof. J. Liu cathode, which influenced the Coulombic efficient of battery
Hunan Province Key Laboratory for Advanced Carbon Materials and operation. The cheap cost of raw materials and fabrication
Applied Technology
College of Materials Science and Engineering processes is also non-negligible segment in commercial
Hunan University progress.[9] Therefore, areal capacity, initial Coulombic
Changsha 410082, China efficiency (ICE) and raw material cost are considerable factors
Prof. F. Li for practical application (Figure 2).[10] In view of the improve-
Shenyang Industrial Technology Research Institute of Energy Materials ment of these characteristics mentioned earlier, recent reports
and Devices have promoted the process of commercialization of Si anode
Shenyang 110016, China
materials, but the development of commercialization of Si
The ORCID identification number(s) for the author(s) of this article anode in LIBs is not enough. Herein, general perspectives
can be found under [Link] for guidelines and trends for next-generation Si composites
DOI: 10.1002/sstr.202100009 in LIBs anodes are outlined.

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2. Challenges of Si-Based Anodes

The electrochemical reaction between Si and Li gives rise to the
huge volume expansion.[11] A series of Si–Li phases (LiSi, Li12Si7,
Li13Si4, and Li22Si5) exists in the electrochemical process of Si
and Li. As shown in Figure 3a–c, the amorphous LixSi alloy shell
is developed during lithiation. The interface between amorphous
and crystalline is only
1 nm thickness. After the full lithiation,
the silicon nanowire obtained large expansion (
280%).[12] This
expansion could generate significant mechanical stress on the
surface of Si particles, leading to the swelling of electrode and
pulverization of Si particles.[2a,13] The electrode swelling could
cause the electrode materials to crack and peel off, which causes
the loss of electrical contact between Si particles as well as Si par-
ticles and current collector, resulting in formation of nonactive Si
Figure 1. Overview of Si-based anode for LIBs: a) merits and and low electrical conductivity. Figure 3d,e shows the typical deg-
b) fundamental challenges. radation and failure of silicon electrodes in LIBs.[14] Meanwhile,
it also squeezes the electrolyte into the pores of separator, which
Table 1. Electron conductivity of graphite and silicon.[106] blocks the diffusion of Li ion. Even worse, it causes swollen cells,
which raises safety issues.[7b,15] Another major challenge for the
Materials Electron conductivity [S cm1] practical application of Si anodes is stabilizing the SEI film with
Graphite
104 the electrolyte. The repetitive volume change exposes fresh sur-
Silicon
103
face of Si, which create the new SEI continuously. Finally, the
thicker SEI film cause the fatal problems, including
i) irreversible consumption of Li and excessive consumption
of Li ion in electrolytes; ii) poor electronic contact between Si
particles and conductive additive due to the electrically insulating
SEI film; iii) the increased lithium diffusion distance and elec-
trode impedance/polarization due to the passivation effects. In
addition, the intrinsic low electronic conductivity and Li-ion dif-
fusion of Si limit the development of full capacity and rate capa-
bility of Si anode.[1–4,7,11,13,15,16]

3. Efficient Strategies toward Si Anodes

In the past decade, tremendous efforts have been made to alle-
viate these issues of Si anode. To better adapt to commercial
needs, there are five main parts to optimize Si anode.
Concretely, structure, electrolytes, and Si/graphite designing
are the focused parts to relax the mechanical stress and strain
as well as to improve areal capacity of Si-based anodes. The pre-
lithiation is critical way to improve the ICE in addition to these
three parts, and new binders have been used to maintain the
integrity of electrode. In this section, structures, binders, electro-
lytes, prelithiation, and Si/graphite design are discussed.

3.1. Structure Design

Structure designing are the most specific and effective way to

accommodate volume variation of Si anode during discharg-
ing/charging process.[17] These structured designing included
the different nanostructured Si (nanoparticles,[9a,18] nano-
layers,[19] nanowires,[20] nanotubes[21]), morphological structures
of Si (core–shell,[22] yolk–shell,[23] porous[24]) and the atomic-scale
structures design of Si (doping,[25] lattice deformation,[26] heter-
Figure 2. Overview of Si-based anode for LIBs: a) structure, binder, elec- ostructure[27]). Importantly, the three structure design strategies
trolyte, Si/graphite design strategies and b) requirement toward practical both combined with various flexible and rigid materials, which
application. were clarified the promising methods for optimization of

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Figure 3. a) Pristine silicon nanowire with rough sidewalls due to faceting. b) Electron diffraction pattern from the pristine single-crystal silicon nanowire.
c) Partially lithiated silicon nanowire with LixSi layer surrounding the Si core and corresponding electron diffraction pattern indicating the amorphization
process. a-c) Reproduced with permission.[12] Copyright 2012, Springer Nature. Top-view scanning electron microscope images of electrode surface
morphology obtained after d) 3, e) 8, and f ) 50 cycles. Scale bar, 20 μm d–f ). d-f ) Reproduced with permission.[14] Copyright 2016, Springer Nature.

Si-based anode for LIBs.[28] The mechanical stress and strain in the relationship of remained pore size and lithiation extent.
such structures can be easily relaxed without fracture due to the The void of SMC1200 was almost covered after full lithiation with
available surrounding free space (Figure 4a). Therefore, there are no particle size change. In contrast, there was residual void in
main discussions about the design structures of Si with various SMC600 and obvious volume expansion (particles diameter
flexible and rigid materials. change from 2.08 to 2.60 μm) in SMC2000. The composites of
The flexible materials usually are carbon materials with doped voids and void-holes in the carbon framework (Si@V–V@C)
boron, nitrogen, which combine with Si-based materials via dop- with yolk–shell structure was synthesized via the polymerization-
ing and void.[29] Considering the cost of carbon materials in Si induced colloid aggregation method.[31] The volume change of Si
anodes, the pyrocarbon from pitch and polymers seems to be the anode could accommodate using well-developed elastic buffer
very good options and many works have been done.[30] These space of Si@V–V@C. This Si@V–V@C exhibits enhanced
designed materials could buffer silicon volume change, enhance cycling stability and excellent structural integrity. Otherwise,
electrical conductivity, and provide channels for ion transporta- the proper space design can effectively alleviate or avoid volume
tion. Individually, the nanocage-shaped silicon–carbon anode change of Si. The passivation layer of inorganic–organic hybrid
was prepared by spray drying, carbonization, and NaOH etching silicate, which is brought in porous Si material (Ni@N–G@Si)
processes,[19] and the coating thickness was controlled by chemi- by CVD, can prevent the direct contact of Si with electrolyte.[32]
cal vapor deposition (CVD) reaction time (three types of SMC The freestanding N–G@Si@hybrid silicate (N–G@Si@HSi)
series: SMC600, SMC1200, and SMC2000). Figure 4b shows film with porous structure is obtained after dissolving Ni

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Figure 4. a) Schematic illustration of thin Si film, yolk–shell, porous structures. b) Lithiation extent (%) versus remained pore size in silicon nanolayer–
carbon micrometer cage series graph. Reproduced with permission.[19] Copyright 2019, Wiley-VCH. c-i) Finite element simulations models of the silicon
porous nanosphere-coated Ti3C2Tx nanosheets (Si p-NS@TNSs) and the Si p-NS. c-ii, iii) Radial and hoop stress distributions of 30 sector area of the Si
p-NS@TNSs composite and the Si p-NS during lithiation process. Reproduced with permission.[33] Copyright 2020, American Chemical Society.

substrates by HCl. The designing of porous structure is effective Nano-/microporous silicon with boron doping and carbon nano-
way to reduce silicon volume change and provide channels for tube (CNT) wedging (B-Si/CNT) was synthesized by mechanical
ion transportation. Therefore, the N–G@Si@HSi anode shows milling.[24b] Obviously, there are abundant nano-/micropores in
high reversible capacities of 1286 mAh g1 after 1400 cycles at the porous silicon, and CNTs were firmly wedged inside the
0.5 C (1 C ¼ 4200 mA g1), the good stability is due to stable porous silicon via convolution and insertion, these could
Si/electrolyte interfaces and conductive N-doped graphene net- enhance conductivity of silicon. The B-Si/CNT can provide high
work. In addition, paired with LiFePO4 cathodes, more than reversible capacity of 1415 mAh g1 with 88.2% retention after
100 stable cycles can be readily realized in full batteries. 200 cycles at 2.0 A g1, which shows the excellent electron

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transport and great structural stability. Notably, the composite intensification on the surface layer, allowing nanospheres to
also exhibits impressive application in Li-ion full battery. It maintain their morphological integrity and promote the forma-
shows the excellent capacity retention of 82.5% even after 300 tion of stable SEI film during cycling. When tested under the
cycles and an outstanding energy density (8.0 mWh cm2) based industrial protocol, the full cell comprising nanosphere/graphite
on the large mass loading of the cathode (12.0 mg cm2). blended anode and lithium cobalt oxide cathode achieve average
The cathode is 2 mol% Al-doped full-concentration-gradient energy density of 2440.2 Wh L1 with capacity retention ratio of
Li[Ni0.76Co0.09Mn0.15]O2 (Al2-FCG76). 80% after 100 cycles. Various types of SiCx hollow structures with
Except for choosing the flexible materials with Si-based shells, tubes, and sheets can be synthesized by simply using dif-
anode, the designed structure of Si-based anodes also usually ferent morphologies of the carbon template. More importantly,
combine with MXene,[33,34] TiN,[35] metal oxide,[36] CuxSiy,[37] previous SiCx anodes were simply studied under half-cell config-
SiOx,[18b,22,28b,38] LixSi,[39] Ni–Sn,[40] Si3N4,[41] SiC,[42] uration exhibiting decorated superior cycling performance.
Li4Ti5O12,[43] ZnO,[44] zeolitic imidazolate frameworks,[45] liquid Therefore, there is strong motivation to develop feasible Si/
metal,[46] sulfur fusion yields quasimetallic,[47] etc. These rigid SiCx anode. SiCx hollow structures demonstrated high ICE of
materials could weaken the expansion of volume while electrode 89%, and higher capacity retention after cycles in the full-cell
reaction, improve the electrical conductivity and electrode stabil- configuration, because the majority failure mechanism of SiCx
ity of anodes. The tap density can be increased by fabricating sec- structures is not dominated by lithium consumption.[42]
ondary structures with inactive/active buffers through Among these SiCx hollow structures, the SiCx hollow sheet
nanocomposites. Recently, various Si-based architecture materi- has the thinnest SEI film on the surface. Consequently, different
als have been designed and applied in the construction of anodes. phases have various functions for Si-based anodes, but the
For instance, the core–shell structure of silicon porous important factors to be considered are the more simpler synthe-
nanosphere-coated Ti3C2Tx nanosheets (Si p-NS@TNSs) has sis process to obtain rational structure at low material cost for the
been prepared via the introduction of Ti3C2Tx nanosheets industrialization.
(TNSs) as robust tight and conductive were closely wrapped
on the surface of silicon porous nanospheres (Si p-NSs).[33]
The close wrapping of TNSs around Si p-NSs can protect the 3.2. New Binders
Si p-NSs from contacting with the electrolyte directly and the
strong Si-O-Ti interaction at the Si-Ti3C2Tx interface is beneficial Basically, the active material and conductive additive as well as
for reinforced interfacial electron transport and enhanced cycling current collector are glued by binders. Binder for the electrode is
stability. The origin of structural stability of the Si p-NS@TNSs commonly less than 10 wt%, but it plays a pivotal role in the
electrode during the lithiation process was simulated and shown whole battery, particularly in Si-based anodes.[7a,11d,50] There
in Figure 4c. The regions of the shell of the Si p-NS@TNSs are are several basic requirements for commercial binders,
red with high hoop stress. However, the stress at the interface i) affordable and ecofriendly, ii) wide electrochemical window,
between the Si p-NS and TNSs drops off sharply due to the con- iii) chemically and electrochemically stable. With the develop-
straint of the outer shell. More importantly, the Si p-NS@TNSs ment of high-performance LIBs, the role of binder gradually
electrode-based LIB full cell higher than that of the Si p-NSs full become main influence factor.[51] Up to now, apart from polyvi-
cell, which delivers a high energy uptake of 405 Wh kg1. The nylidene difluoride (PVdF) and carboxymethyl cellulose/styrene
intermediate single layer of interconnected Cu-silicide (CuxSiy) butadiene rubber (CMC/SBR), various new polymer binders
network, can facilitate high-density Si nanowire growth with have been reported, including binding actions of volume change
higher areal-loadings.[37] As a result, the anode exhibits stable alleviation,[52] dispersing function,[53] SEI contribution,[54,55] elec-
rate capability performance. It is evident that the anode upholds tronic conduction,[56] and ionic conduction.[11b,57]
the rate performance with only slight depletion at high current Particularly, the conductive binders can work as conductive
density, retaining reversible capacity greater than
750 mAh g1 additive to keep the contact among Si particle effective, but also
at 10 C, respectively. Using buffer materials to restrain the serve as binders, such as the derivative of polyacrylic acid,[50a]
volume effect is important for these alloy-mechanism materials. polyethylene glycol,[56a] polyvinylidene fluoride,[58] 1-pyrenemethyl
In addition, SiOx is the most used protective material to relieve methacrylate and polybutadiene,[59] sodium alginate,[53e] polyanili-
the volume change due to it can be generated as well as stable ne,[57a] carboxymethyl cellulose,[60] multiple-carboxyl polymer,[57b]
cycling performance and low volume expansion.[11e] and polyimide,[61] to increase the specific capacity of the anode,
Nevertheless, SiOx content above 3 wt% leads to elevate irrevers- promote the formation of SEI film, and enhance the long cycle
ible capacity losses, and the consequently low capacity retention stability of LIBs. The conductive polymer with both high specific
hinders the realization of high average energy density.[48] Herein, capacity and cycle stability for the Si anode was reported.[62] Up to
lamellar nanosphere structure comprising Si nanoparticles now, various types of conductive binders with different cross-
coated with SiOx/Si/SiOx/C layers was prepared by CVD in dif- linked structures have been reported.[56b,63]
ferent atmospheres, and utilized the finite element simulation Furthermore, multifunctional binder including volume
technique to show that the presence of stress management inter- change alleviation and SEI contribution can achieve the hard/soft
layer (SiOx) clamped between Si layers lowers stress. As a result, plastic/elastomer strategy to enhance the adhesion strength and
the aforementioned phenomenon allows one to preserve mor- ionic conductivity. For instance, N-P-LiPN binder (lithiated poly-
phological integrity and maintain thin and stable SEI film during acrylic acid (P-LiPAA) and Nafion (P-LiNF) via the hydrogen
cycling.[49] Specifically, SiOx is found to act as stress manage- bonding effect) have been prepared.[54] The hard polyacrylic acid
ment interlayer when it is located between Si and mitigates stress (PAA) and soft Nafion were chosen as precursors as they are rich

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in functional groups and can be partially lithiated.[64] The PAA mechanical strength and soft P-LiNF with excellent flexibility,
and Nafion were partially lithiated, named as P-LiPAA and which the P-LiPAA as the framework, holding the integrity of
P-LiNF. Finally, the electrode with Si@N-P-LiPN binder demon- electrode, the P-LiNF as the buffer, accommodating the huge vol-
strates stable performance for more than 100 cycles and ume change of Si. As a result, the N-P-LiPN binder has remark-
Coulombic efficiency in excess of 99%, which ascribes remark- able flexibility and strong mechanical strength simultaneously,
able mechanical properties, strong adhesion strength, and Liþ which can keep the integrity of electrode. In addition, the Li con-
transport facilitation of the N-P-LiPN, as shown in Figure 5a. tent of lithiated groups of N-P-LiPN binder is 5.67 wt%, which
To obtain the evidence visually that N-P-LiPN binder can accom- significantly enhances the ionic conductivity of the electrode
modate huge volume change, the scanning transmission electron with high ICE of 93.18% and stable cycling performance
microscopy (SEM) is used to observe the damage condition of for 500 cycles. Particularly, the ultrahigh areal capacity
electrode after cycling. Before cycling, the Si@N-P-LiNF, (49.59 mAh cm2) is also achieved.
Si@P-LiPAA, and Si@P-LiNF electrodes obtain smooth surface To the development of multifunctional binders, the electro-
morphology. After 50 cycles, both the Si@P-LiPAA and chemical performance mechanism and characterization meth-
Si@P-LiNF electrodes show many cracks, Si@N-P-LiPN ods of advanced binder are also important roles. The
electrode still retains crack free. This is mainly attributed to electrochemical performance is decided by these properties of
mutual complementation of hard P-LiPAA with strong adhesion force, peel stress, rheological behavior, mechanical
property, morphology evolution. The clear explanation for the
rational design of binders was reported. It was produced by inde-
pendently tailoring the degree of crosslinking density and the
grafting density of adhesion functionalities for Si-based electro-
des (Figure 5b).[65] The adhesion force between the Si and binder
has greatly impact on electrochemical performance, and evaluat-
ing the adhesion force is an important factor. The development
of advanced characterization methods is important to improve
the upgrade of high-performance binders. The polyimine binder
by molecular simulations and atomic force microscope test to
evaluate the adhesion force has reported.[66] The results show that
the N─H bonds are more stable than the aromatic C─H bonds,
but large number of C─H bonds possessing the physical adsorp-
tion with hydrogen bonds between the polyimine chains and the
surface of Si. The results indicate that compared with the interac-
tions between other binders (PAA, CMC, and PVdF) and Si, the
higher adhesion force exists between the polymeric materials and
surface of Si, which can accommodate the dramatic volume
changes during the repeated electrochemical process.

3.3. New Electrolyte and Additives

Electrolyte plays significant role in passivating the Si/electrolyte

during the initial lithiation process and transport ions to connect
the silicon-based anode with Li ion, isolate electrons and deter-
mine the electrochemical window.[13b,15b,67] Electrolyte compo-
nents of salts,[68] solvents,[9b,69] and additives[70] have profound
influence on the solvation structure, interfacial stability, elec-
trode dissolution, cost, safety, and overall electrochemical perfor-
mance. To passivate the interphase and decrease the continuous
side reactions between Si and the electrolyte during the repeated
lithiation and delithiation processes, cosolvents, and functional
additives, aimed at stabilizing the SEI film, have been widely
used in the electrolyte. Many electrolytes and additives were also
developed to further improve the Coulombic efficiency.[9b]
Carbonate electrolytes with fluoroethylene carbonate (FEC)
and/or vinylene carbonate as additives exhibit best cycle perfor-
Figure 5. a) Schematic illustration of the function mechanism of N-P-LiNP
binder in the Si electrode. Reproduced with permission.[54] Copyright
mance in Si-based anodes.[23a] Nevertheless, the thick and inho-
2020, Wiley-VCH. b) Illustration of the effect of grafting density of the mogeneous SEI on Si is still not robust enough to tolerate the
adhesion group and the degree of crosslinking density on backbone stiff- large volume change of microsized Si, which results in continu-
ness of the polymer binder. Reproduced with permission.[65] Copyright ous consumption of the Li and electrolyte, and loss of active Si.[71]
2019, American Chemical Society. Other functional additives including ethers,[72] silanes,[73]

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dimethylacrylamide,[70c] succinic anhydride,[74] citric acid,[75] lith- and elastic lithium fluoride (LiF)-based SEI with low adhesion
ium difluorooxalatoborate (LiFOB),[76] and lithium bis(oxalate) to lithiated alloy surfaces (Figure 6a). This enables the Si micro-
borate (LiBOB),[77] have been also investigated for Si-based particles to provide 2800 mAh g1 with 200 cycles, high ICE of
materials.[2a] >90% and Coulombic efficiency of >99.9% without pretreat-
Recently, universal electrolyte design principle for alloy ment. The safer concentrated LiFSI-based electrolyte consisted
anodes using microsized Si anodes has been reported.[9b] This of nonflammable mixture solvents of di-2, 2, 2-trifluoroethyl car-
work demonstrates that 2.0 M LiPF6 in 1:1 v/v mixture of tetra- bonate, and fluoroethylene carbonate. The electrolyte could
hydrofuran (THF) and 2-methyltetrahydrofuran (MTHF) enhance the cycling stability with high initial reversible capacity
(mixTHF) electrolyte promotes the formation of thin, uniform, of 2644 mAh g1 and low capacity fading rate toward the silicon

Figure 6. Effect of the SEI and electrolyte properties on the alloy anode particles. a,b) Schematic of the cycled alloy anode with organic, a) low Eint and
nonuniform Li alloy–SEI film, b) an inorganic, high Eint, and uniform Li alloy–SEI film. c) Electron localized function and Eint for the Li alloy–LiF interfaces.
d) Distribution of the Li ion solvates for the LiPF6 mix tetrahydrofuran (2.0 M) and LiPF6—ethylene carbonate—dimethyl carbonate (1.0 M) electrolytes
from molecular dynamics simulations. The PF6 and solvents with dLi–P < 4.4 or dLi–O < 2.8 Å, respectively, are included in the first Liþ solvation shell.
e) Reduction potentials of key electrolyte components with the first Liþ solvation shell indicated from quantum chemical calculations. G4MP2, solid
symbols; B3LYP/6-31þG(d,p) density functional theory (DFT), open symbols; salt reduction, red symbols; solvent reduction, blue symbols. Reproduced
with permission.[9b] Copyright 2020, Springer Nature. f ) Schematic illustration of the discharge process of Si anode in different electrolytes. Reproduced
with permission.[79] Copyright 2019, American Chemical Society.

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nanoparticle (SiNP) anode.[78] The performance enhancement open new possibilities for development of low cost, environmen-
mechanism is result from the robust SEI film which is formed tally benign, and high-capacity LIBs. Solution-based chemical
from fluorinated carbonates with high-concentrated salt. This prelithiation usually use reductive chemicals, and it promises
mechanism is the key factor for superior capacity retention. unparalleled reaction homogeneity and simplicity. However,
In addition, ionic liquids have drawn much interest because it the prelithiation of chemicals applied merely form SEI and can-
exhibit low vapor pressure, large electrochemical window, high not dope Li in Si-based anodes, leading to partially alleviate the
chemical/thermal stability, and nonflammability. However, few cycle irreversibility. Chemical prelithiation using Li-arene (i.e.,
studies have focused on the Si-based anodes chemistry in ionic aromatic hydrocarbon) complex with sufficiently low redox
liquids electrolytes. For example, fluorine-substituted ionic liq- potential drives active Li accommodation in Si-based anodes
uid by 0.1 M M(TFSI)x (M ¼ Al, Mg, Zn, and Ca) as second salt to enhance the electrochemical reversibility of SiOx/Si anodes.[9d]
into the electrolyte could stabilize the anode chemistry. The for- Stating time and temperature could achieve fine control over the
mation of Li–M–Si ternary phases during the charging process prelithiation degree and spatial uniformity of active Li through-
changes the Li–Si binary chemistry while minimally affecting sil- out the electrodes during immersion, promising both precision
icon electrochemical profiles and theoretical capacities and low cost of the process for large-scale production.
(Figure 6f ).[79] The result shows this mixed ionic liquid was bet- Electrochemical prelithiation stores lithium in advance to
ter than carbonate or F-free ionic liquid. This ionic liquid elec- form SEI film through electrochemical reactions. But most of
trolyte can form uniform SEI film and show improved cycle the electrochemical prelithiation reagents are highly reactive
stability. Otherwise, the organogel electrolyte not only acts as and sensitive to oxygen and moisture because of remaining Li
ion conductor, but also provides cohesion within the Si particles, trapping sites. Overlithiation reduces the Li-ion accommodation
maintaining electrode integrity, which suppresses the serious in the real first lithiation process, which difficult for practical
crack extension and thickness growth. As a result, compared with application. The developed prelithiation strategy using lithium
liquid electrolytes, the capacity retention of the Si anode upon naphthalenide to fully prelithiate sulfur-poly(acrylonitrile)
cycling in the cyanoresin organogel electrolyte was significantly (S-PAN) into Li2S-PAN cathode and to partially prelithiate nano-
improved.[69c] By focusing on the mechanisms of interfacial pro- silicon into LixSi anode created new Si-based LIBs linked with
cesses at the surface of amorphous silicon thin-film electrodes in sulfur.[83] The development of lithium naphthalenide
organic carbonate electrolytes, it unveil the origins of the inher- (Li-Naph) as prelithiation reagent was mainly based on its advan-
ent nonpassivating behavior of silicon anodes in LIBs. The chem- tages of easy synthesis, mild reactivity, and strong lithiation abil-
ical composition and thickness of the SEI film continuously ity. This LixSi||Li2S-PAN battery can demonstrate high specific
change during the charging/discharging cycles.[80] This SEI film energy of 710 Wh kg1, with high ICE of 93.5% and considerable
continuously change is directly related to the formation of lith- cyclability. The spontaneous-corrosion-driven-lithiation of lith-
ium ethylene dicarbonate (LiEDC) and LiPF6 decomposition ium metal on the anode surface of Si/FeSi2/graphite||
products during silicon lithiation, and the products subsequent LiNi0.6Mn0.2Co0.2O2 cells has been reported.[84] The additional
disappear upon delithiation. lithium is stored in the silicon, which acts as reservoir compen-
sating for lithium trapping. The silicon phase therefore plays an
essential role but without the detrimental effect of large volume
3.4. Prelithiation
variations. The spontaneous-corrosion-driven-lithiation leads to
more heterogeneous prelithiation compared with electrochemi-
Prelithiation is exciting strategy for next-generation high-capacity
cally driven-lithiation given that only the electrode area directly in
anodes with alternative lithium source for high ICE. Prelithiation
contact with the lithium metal is initially prelithiated. The
is a balance which degrades its available energy density and pre-
spontaneous-corrosion-driven-lithiation prelithiation method
vents the lithium in the electrode from being consumed during
could be implemented in industrial setup to produce high energy
side reactions of SEI formation in initial cycling.[2a,81] In practical
density and highly stable LIBs.
battery, the irreversible electrochemical reduction of electrolytes
Mechanical prelithiation is microscale-stabilized lithium
occurs during the forming of SEI on anodes in the initial cycle.
metal powder to use as lithium source. Mechanical prelithiation
This consumes the Li ion originally loaded in the cathode prior to
mechanically activate the stabilized lithium metal powder to fully
cycling and Coulombic efficiency (ideally 100%). The lower Li-
use lithium after depositing the stabilized lithium metal powder
ion concentration leads to decrease the fractional utilization of
onto the Si anode. By compressing the stabilized lithium metal
active materials that causes net capacity losses in the following
powder onto the surface of Si with mechanical process, the con-
cycles, significantly limiting the available energy density. There
tact area between the stabilized lithium metal powder and Si is
are three main ways (chemical prelithiation, electrochemical pre-
maximized. Proper lithium diffusion into the Si guaranteed this
lithiation, and mechanical prelithiation) to store lithium in ano-
step, which promotes stable SEI formation on the surface of Si
des (Figure 7). The chemical prelithiation is applying to LixSi
anode. The whole process is consistent with the present fabrica-
nanoparticles from chemically synthesis as potential prelithiation
tion of battery.
reagent,[82] electrochemical prelithiation is realized by lithium
foil with electrolyte-wetted anodes and mechanical prelithiation
directly using microscale stabilized lithium metal powder in Si 3.5. Coutilization of Si and Graphite
anodes through mechanical activation.[4a,81c]
The chemicals prelithiation approach is mild, efficient, and Although most of the well-designed Si-based anodes with
widely applicable to large range of Li-deficient electrodes, which advanced structure or new binders can achieve excellent

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Figure 7. Benefits of prelithiating high-capacity Si/SiOx anodes. a) Permanent loss of active Li during the initial electrochemical cycle of conventional LIB
containing anode with low ICE, resulting in net energy loss due to the underused cathode capacity. b) Maximized energy density of full-cell achieved with
prelithiated anode having extra Li to provide the ideal ICE. c) Lithiation/delithiation of pristine Si/SiOx during the initial electrochemical cycle in conven-
tional LIB accompanied with irreversible lithium trapping and SEI formation. d) Lithiation/delithiation of prelithiated Si/SiOx using Li-arene (e.g., 4, 4 0 -
dimethylbiphenyl) complex beforehand with volume expansion and active lithium loss prior to cell assembly. Reproduced with permission.[9d] Copyright
2020, Wiley-VCH.

electrochemical performance, the higher requirements about the solidification.[7b] The various synthetic methods influence the
volume expansion, electrode swelling and high-elastic SEI film distribution of Si in anode which determined to the electrode
restrict the commercial application seriously. It is necessary swelling. In the history of Si/graphite anode, the Si content
for the utilization of both graphite and Si, the commercial graph- was proved to have a remarkable effect on the cycling stability
ite endows relatively low capacity, volume change and good elec- and specific capacity. In addition, the link between the Si, carbon
trochemical behavior such as the formation of SEI as well as coating, graphite, also has significant effect on the electrochemi-
relatively high electrical conductivity.[15a,24b,48,85] The multiple cal performance.
advantages of graphite can help compensate for the weaknesses Herein, a series of Si/graphite materials with different Si sizes
of Si anode.[10c,86] In contrast, coutilization of Si and graphite also and distribution to verify the relationship between Si structures
can alleviate the electrode swelling, volume change, and perfect and electrode swelling/electrochemical performance has been
nearly the intact electrochemical performances at acceptable designed.[7b] Three types of typical Si/graphite anode were syn-
price (Figure 8).[87] The Si/graphite anode could be readily calen- thesized by liquid solidification (LSG), thermal CVD methods
dered due to the properties of graphite for high-volumetric (CSG), and spray drying (SSP/G). The SSP/G, LSG, and CSG
energy density.[85c,88] Up to now, top-performing electric vehicles obtained capacity retentions (50 cycles) of 90.8%, 94.2%, and
have used the Si/graphite anode (
10% Si) in 21 700 cell with 95.7% with ICE of 87.4%, 87.6%, and 92.6%, respectively.
specific energy of 269 Wh kg1. Therefore, the development of Furthermore, the structure changes before and after 50 cycles
Si/graphite anode is also one of the effective ways to realize com- in the electrodes were observed. The SSP/G electrode exhibits
mercial application of Si-based anode materials. However, the huge expansion from 47 to 106 μm and the structure of electrode
energy density is below expectations to develop more cost- became severely rugged. For the LSG electrode, it was swelled
effective Si/graphite anode. The preparation process of and even torn after cycling. In contrast, the CSG electrode, shows
Si/graphite anode greatly affects the properties, there are five slightly rough surface. The cross-sectional view by focus ion
main synthetic methods, including CVD,[89] ball milling,[85b] beam (FIB) of CSG electrode exhibits that the Si nanolayer exists
spray drying,[86b] thermochemical pyrolysis,[85a] and liquid both in the inner pores and on the surface of the graphite,

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Figure 8. Schematic illustration of Si/graphite anode.

indicating the uniform distribution of the Si in the electrode. The electrode swelling. Particularly, the photovoltaic silicon scrap
uniform distribution of Si in the anode results in low swelling. could be used as raw material, which meets the requirements
The cabbage-inspired graphite scaffold to accommodate the vol- of low cost and high output. For the preparation of Si/C materi-
ume expansion of silicon particles in interplanar spacing (Si@G/ als, oxidation and etching processes are key steps, which deter-
C) has been synthesized by multistep reaction, including sand mine the utilization of raw materials and void the distribution of
milling, spray drying, and CVD.[89] First, the micrometer-sized Si/C. The coating could use homogenous-doped carbon, which
silicon (D50
4–8 μm) was converted to nanoscale (
100 nm) guarantees an excellent stress relief in composites.
by the sand milling process (process I). After sand milling process,
the cross-linked poly (acrylamide-co-diallyldimethylammonium
chloride) PDDA was grafted on the surface of Si nanoparticles 4. Toward Practical Applications
(PDDA-Si) to prevent spontaneous agglomeration of Si nanopar-
ticles. To obtain better dispersion of PDDA-Si in graphite, the To meet the practical needs of small volume, high capacity, and
functional groups were grafted onto the surface graphite fast charging, the high areal capacity and rate capacity (energy
(O-CG) by acid oxidation (process II). After spray drying process density and power density) are basic requirement in limited
(process III), PDDA-Si nanoparticles and O-CG scaffold infiltrate space and demanding convenience of devices. The ICE is also
together via the electrostatic attraction. Finally, multilayer pro- non-negligible factor in commercial process for Si-based anodes
tected Si@G/C materials were fabricated via the CVD process due to the limited lithium sources in cathode and electrolyte,
(process IV). TEM image of the PDDA-Si exhibits the complete which could be consumed irreversibly during initial cycle.
polymeric layer coating on the surface of Si nanoparticles. SEM Meanwhile, the application can be hindered by high cost,
image of Si@G/C materials shows the homogeneous distribution
of Si particles on/in the expanded graphite without agglomeration.
The cross-sectional views of the Si@G/C electrode show the inti-
mate anchoring of the Si nanoparticles in between the expanded
graphite interlayer spacing. Finally, the Si@G/C anode delivers
area capacity of 4.4 mAh cm2 and mitigated volume change of
23%. Furthermore, the full-cell prototype exhibits a robust cyclabil-
ity with 88% capacity retention over 500 cycles and an energy den-
sity of 301.3 Wh kg1 at 0.5 C, which is produced by 10 kg of the
Si@G/C composite in the pilot line and pair this anode with a
LiNi0.8Co0.1Mn0.1O2 cathode in a 1 A h pouch-type cell.
More importantly, it was believed that the combination of
chemical method (oxidation and etching processes) and thermo-
chemical pyrolysis will likely become viable path to industrializa-
tion of Si-based anode in Figure 9, especially in high Si content
anodes because unique structure of Si/C could drastically reduce Figure 9. A viable path to industrialization.

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including the raw materials and fabrication processes. In this is an optional way to indirectly enhance the energy density of
section, areal capacity, ICE, and material cost are discussed. electrode in addition to the freestanding electrodes designs.
As shown in Figure 10b, 3D network binder with high strength
for high areal capacity Si anodes has been prepared.[53a] The
4.1. Areal Capacity and Rate Capacity
polymerization of furfuryl alcohol (PFA) resin was produced
For practical applications in limited space of cell, high areal by self-polymerization reaction of liquid FA monomer under
capacity is basic requirement to reduce the weight percentage the catalysis of oxalic acid, which shows stiff property compared
of inactive component, thereby achieve high energy densi- with elastic polyvinyl alcohol (PVA) hydrogel. The porous struc-
ty.[5b,90] As mentioned earlier, the huge volume variation, ture of Si anode is clearly observed in the SEM and transmission
the swelling of electrode and thick SEI film of Si makes it chal- electron microscope (TEM), which allows the infiltration of
lenging to acquire stable cycling at high areal mass loading. electrolyte and accommodate the volume expansion.[93] After
During lithiation/delithiation, Si particles severely expand/ the optimization of the proportion of PFA and PVA, such
contract, resulting in the electrode peeling off, especially in synthesized binder obtained stable cyclability under high areal
thick electrode. There are several strategies for cyclic stability capacity of >10 mAh cm2. When such Si anode was matched
under high areal mass loading, including free-standing elec- with the Li-rich manganese-based cathode, the pouch cell
trode design, utilization of polymer binders and porous mate- revealed high energy density with 300 Wh kg1. It is generally
rials with high tap density as well as fabrication of secondary recognized that nanostructure silicon materials endow low tap
microscale structure and microsized materials with inactive density, although it can solve silicon pulverization problem.
buffer.[91] In contrast, power density is also basic requirement Targeted structure design could accommodate high areal
for practical applications, especially in electric vehicle. Building mass loading to efficiently improve areal capacity. Generally,
high-rate capacity under high areal capacity condition can be nano/porous structure of Si-based anode materials is with
both exciting and challenging, which needs the electrode to low tap density, which is accompanied with large volume elec-
own enough ion/electron transfers channels, high electro- trode and low areal mass loading. The structure advance of
chemical reactivity, and stable structure under high mass load- microclusters structure Si-based anode is similar with nano
ing and high pressing density. or porous structure, and it exist high areal mass loading.
The freestanding structure design is the most effective Therefore, microclusters of kinked Si nanowires with high
method to increase the mass loading in electrode and the ratio tap density by recyclable iodide process have been synthe-
of Si. Meanwhile, it maximizes the utilization of active materials sized.[94] There are two merits in cyclic iodide process, includ-
in the finite space due to there is no metal foil current collectors. ing the synthesis of high-quality Si nanowires from low-grade
Freestanding electrode (Si@CNT/carbon microscroll, Si@CNT/ Si microparticles and reuse of iodine (I2). The cyclic iodide pro-
C-microscroll) with binder free, flexible, and 92% silicon content cess includes formation of SiI4 (Si(s) þ 2I2(g) ! SiI4(s)) and
designed by the self-rolling of cellulose nanosheets.[92] The SiNWs (SiI4(s) ! Si(s) þ 2I2(g)). Compared with common pre-
Si@CNT/C-microscrolls exhibits distinct morphology that is cursor (SiH4), SiI4 has simply preparation with nearly ideal
formed from ultralong fibers (>100 μm in length) with united micro/nanostructure process and high yield with 70%.
geometry and well-dispersed Si nanoparticles hang in bunched Microscale Si particles are composed of self-kinked Si nano-
CNTs. Abundant interior void space (meso/macroporous range wires clusters whose diameters of Si nanowires are less than
from 10 to 100 nm) exists in the synthesized Si@CNT/C- 20 nm. There are plenty void spaces between individual Si
microscrolls, which can accommodate the volume change of nanowires due to the self-kinked Si nanowires in the cluster,
Si nanoparticles during the cycling. The formation mechanism which can suppress huge volume variation as well as provide
of the well-designed Si@CNT/C-microscrolls, as shown in persistent pathway for Li ion and electron diffusion.[95] The
Figure 10a, involved ultrasonic treatment of cellulose nanosheets pyrolysis rate and morphologies of Si particles are determined
mixed solution, Si nanoparticles, and CNTs subsequent freeze by annealing temperature. Compared with other Si particles
drying and carbonization. The 2D laminate cellulose nanosheets synthesized at 800 and 1000–1100  C, which show flat cluster
can almost switch to the microscrolls after the freeze-drying pro- and coral-like surface morphology with large particle size,
cess. Consequently, the presence of Si nanoparticles causes respectively. Si particles produced at 900  C display ideal
uneven contraction stress of the cellulose nanosheets in micro-/nanostructure with spherical shape in microscale and
freeze-drying process, resulting to the cellulose nanosheets roll kinked Si nanowires, as shown in Figure 10c-i, ii. To further
up. Finally, the well-designed free-standing electrode ensures investigate the microstructure of Si nanowires clusters, TEM
excellent performance. The Si@CNT/C-microscrolls electrode image (Figure 10c-iii) of single Si particle shows transparency
obtained remarkable rate capability with reversible capacities due to the void spaces in the cluster. Finally, the Si nanowires
of 2710, 2320, 2085, 1611, and 1016 mA h g1 (tested at 0.2, clusters obtained excellent cyclability and high tap density
0.5, 1, 2, and 5 A g1, respectively) as well as high areal capacity (Figure 10c-iv). Apart from the Si nanowires, alloying Si with
with 5.58 mAh cm2 (2548 mA h g1, 2.19 mg cm2 at 0.2 A g1) other materials to form micrometer-sized particles is another
and great stability (>78% after 100 cycles). In contrast, the com- way to improve tap density. The procedures of pomegranate-
mercial graphite has achieved areal capacity of about like structure using industrially mature mechanical-based
3.3 mAh cm2. approach shown in Figure 10d-i, ii.[10a] As shown in
Inspired by the design concept of interweaving hard and soft Figure 10d-iii, high tap density of 0.91 g cm3 and high areal
polymer chains of binder,[54] the selection of rational binder also capacity of 3.5 mAh cm2 are achieved.

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Figure 10. a-i) Corresponding schematic illustration of the deformation process for Si@CNT/C-microscrolls. a-ii) SEM image of one microscroll.
a-iii) SEM images of Si@CNT/C-microscroll.[92] Copyright 2020, The Royal Society of Chemistry. b) Schematic illustration of the Si anode using the
hard and soft binder. Reproduced with permission.[53a] Copyright 2019, Wiley-VCH. c) Electron microscopy of silicon nanowire cluster (SiNC). SEM
image of c-i) SiNC particles and c-ii) single SiNC particle. c-iii) TEM image of single SiNC particle. The image of the same amount of the SiNC
and Si nanoparticle (SiNP, 100 nm). The tap densities of the SiNC and SiNP exhibit 0.509 and 0.127 g cm3, respectively. Reproduced with permission.[94]
Copyright 2020, Wiley-VCH. d) Mechanical fabrication of the nanostructured Si (nano-Si) secondary cluster. d-i, ii) Schematic illustration of the mechani-
cal-based nano-Si secondary clusters fabrication process. d-iii) Volume comparison on 0.4 g samples in 4 mL vials. From left to right, Si nanoparticle,
microemulsion produced cluster, and mechanically produced cluster, respectively.[10a] Copyright 2015, The Royal Society of Chemistry.

4.2. Initial Coulombic Efficiency microparticles and subsequent removal of the SiO2. The meso-
porous Si microparticle is coated by shell-like Si and encapsu-
The new issues such as poor ICE due to increased surface area lated with graphene cage (Figure 11a-i). Such design prevents
remain unsolved.[24c,34a,46,54,70b] The ICE of Si-based anode is in the electrolyte from diffusing into the interior and restricts
the range of 65–85%, much less than that of graphite anodes (90– SEI formation to the outer surface by coated Si, thus resulting
94%). Fortunately, there are the solutions, such as structural in improved ICE from 37.6% to 87.5% before and after Si coat-
design,[96] coating,[97] prelithiation,[9d] optimization of electroly- ing. Graphite-like-coated silicon (Si@G) material has been
tes,[9b] selection of binders containing Li,[54] and carbonization shown to be only partly useful in addressing the technological
of binder[51b] can effective improve the ICE of anodes. problems of high-capacity Si anodes. This is because of inevitable
Effective structure design can optimize the formation of SEI in and large internal stresses in Si@G structure induced by instan-
the initial lithiation reaction of Si-based anodes to improve the taneously explosive expansion of Si upon lithiation. The expan-
ICE. For instance, The surface-engineering strategy by deposit- sion destroys the graphitic matrix, leads to the uncontrolled
ing dense Si skin onto each mesoporous Si microparticle to sig- growth of SEI film, and severe capacity fading. Therefore, it is
nificantly improve both the ICE and Coulombic efficiency has vital to develop novel internal-stress-relief strategy for Si@G
been demonstrated.[97] Mesoporous Si microparticles are of the stable anodes. Herein, inspired by relief valve, designed
obtained by thermal disproportionation of low-cost SiO nitrogen-doped graphite-like layer coating on Si nanoparticles

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Figure 11. a-i) Design of Si coating on mesoporous Si microparticles. Without Si coating, electrolyte diffuses into the inner pores, resulting in excessive
SEI formation both inside and outside, and low ICE of 37.6%. After Si coating, electrolyte is prevented from diffusing into the interior space, restricting SEI
formation to the outer surface, and highly improved ICE of 87.5%. Reproduced with permission.[97] Copyright 2019, Elsevier. a-ii) Calculated surface area
in contact with electrolyte versus secondary particle diameter. Reproduced with permission.[9a] Copyright 2014, Springer Nature. b-i) Graphical illustration
of prelithiation process of c-SiOx electrode and b-ii) its scalable roll-to-roll process scheme. Reproduced with permission.[81c] Copyright 2016, Spriner
Nature. American Chemical Society. c-i) Schematic of the N-P-LiPN binder. Reproduced with permission.[54] Copyright 2020, Wiley-VCH. c-ii) Schematic
illustration of Si@GC anode. Reproduced with permission.[51b] Copyright 2019, Elsevier.

(Si@G–N) to effectively relief the volume expansion of Si Li-storage performance with the ICE to 84.5%. This is due to
spheres during lithiation.[98] Such homogenous N-doping in the reduction of onion-like carbon-coating, which reduces the
each graphitic layer generates uniformly distributed porous in defects and consumes less Li-ion in electrolyte to form SEI.
the G–N network and guarantees stress relief in the lithiated Pretreatment methods are efficient way to improve ICE of Si
Si@G–N to the maximum extent possible. Therefore, when anodes before cycling. The popular strategy is stores lithium to
tested as anode, Si@G–N shows high ICE of 90.3%, and it is form SEI film in advance through electrochemical reactions. In
confirmed that Si@G–N has thinner and more stable SEI film the store lithium process, Si anodes were in contact with a piece
than Si@G, which suggests that nitrogen doping of graphitic of Li metal foil in liquid environment of electrolyte through tem-
shell enable Si sphere superb ICE. In Figure 11a-ii, secondary porary cell under inert atmosphere (Figure 11b-i). Proper pre-
structures are formed with nanoscale blocking layers which treatment methods require delicate controlling. Insufficient
could adjust the electrode/electrolyte surface area. The designing lithiation cannot improve the ICE due to remaining Li trapping
microstructures with electrolyte blocking layers in the outer sur- sites, whereas overlithiation reduces Li-ion accommodation in
face can achieve higher ICE, which would decrease the side reac- the first lithiation process. Therefore, effective design pretreat-
tion between electrolyte and electrode.[99] Most preparation ment methods are crucial to improve ICE. In particular, the vari-
methods of disordered carbon coating to increase ICE are ous pretreatment methods are utilized to condition the porous
reported, but those ways are still complicated and difficult for Si-carbon anode and the initial voltage profiles for the porous
industrialized applications. An onion-like Si/C materials has Si-carbon cells.[81b] For the full-cell with contact pretreatment,
been designed through one-step injection pyrolysis using pyri- there is a significant change in slope from 100 to
dine as the carbon source.[96] This material exhibits great 300 mAh g1 in the first cycle.

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Rational binder selection is also an efficient way to improve 4.3. Materials Cost
ICE. Binders containing Li and carbonization of binder design
are two notable designs. As shown in Figure 11c-i, the Li of The cost of raw material is the basic guarantee of large-scale
lithiated groups of N-P-LiPN binder is 5.67 wt%, which signifi- commercial industrialization of nanostructured Si-based anode
cantly enhances the ICE (93.18%). As shown in Figure 11c-ii, materials.[10c,100] Si nanostructures are fabricated either from
the efficiency and versatile strategy for the synthesis of Si-based bottom-up (CVD) or top-down (chemical etching) method, which
anodes using low-cost biomass and commercially available Si typically involve either expensive high-purity Si sources or toxic
nanoparticles as precursors have been demonstrated via con- silane. Recently, various low-grade Si (untreated or initially
ventional slurry coating and low-temperature pyrolysis.[51b] treated raw material of Si) and natural sources can serve as
Due to the tailored and rational design, gelatin-derived carbon cost-effective sources to produce nanostructured Si.
with numerous heteroatoms not only acts as conductive matrix Si is the second most abundant element on Earth, widely dis-
to enhance the electron/ion transfer, but also simultaneously tributed in rocks, sands, and soils as various forms of Si dioxide
accommodate the Si expansion and immobilize the Si on the or silicates. Particularly, silica (SiO2)-enriched biomass materials
current collector via dual-interfacial bonding. Obviously, have attracted much attention as Si precursors because of their
without binder and conductive agents, the obtained Si-based high sustainability, abundance, and low cost. Many studies have
anode exhibits the ICE of 85.3%, likely due to low specific shown that Si materials with nanoscale, porous, and crystalline
surface area with conductive additive free and high conductiv- structure can be produced from these biomass resources, which
ity of electrode. exhibit much improved electrochemical performance in

Figure 12. Reduce raw materials cost ways: natural sources and low-grade Si. a-i) Schematic illustration of diatomite SiO2, diatomite-derived Si/SiO2, and
lithiated Si. (The green region represents SiO2 constituent). a-ii) SEM image of diatomite SiO2, diatomite-derived Si/SiO2 and lithiated Si/SiO2. a-iii)
Digital photographs of diatomite SiO2, diatomite-derived Si/SiO2, and lithiated Si/SiO2. Reproduced with permission.[104] Copyright 2020, Wiley-VCH. b-i)
Synthesis process of Corn-Si anode material. b-ii) Natural corn leaves. b-iii) SEM image of SiO2 precursor (inset: digital photograph). b-iv) SEM image of
SiO2 precursor. b-v) SEM image of the Corn-Si-1 sample. Reproduced with permission.[102] Copyright 2020, Wiley-VCH. c) Flow chart of the process for
producing Si/SiO2. Optical images of c-i) Si powder waste, c-ii) purified Si powder, c-iii) Si/SiO2 s, c-iv) quartz sand waste, and c-v) purified SiO2 powder.
c-vi) Schematic diagram illustrating the structure of Si/SiO2. Reproduced with permission.[105] Copyright 2019, Elsevier. d) Schematics of d-i) the multi-
wire slicing of SoG-Si ingots and d-ii) the typical diamond-wire saw. d-iii) Flow chart of the purification and surface modification processes of Si micro-
plates. Reproduced with permission.[103] Copyright 2015, The Royal Society of Chemistry.

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comparison with bulk Si powders. However, the nanovoids of microplates, the anchored alginate coating layer is formed on
these materials are not sufficient to accommodate the large vol- the Si surface based on the strong interactions between the oxi-
ume expansion of Si during long-term cycling. To overcome dized Si and alginate carboxylic groups, which helps to construct
these limitations, surface and interface engineering of nano-Si the robust conductive network around Si microplates and allows
have been proposed.[4b] Although the well-designed nano-Si the electrode architecture to be perfectly maintained even though
structures are beneficial to electrochemical performance, compli- the Si microplates are pulverized into nanoparticles. The recycled
cated structural design and secondary treatments are required, Si anode delivers high reversible capacity, superior rate capability
which inevitably increases preparation time and cost. and extraordinary cyclability. These new technologies not only
Hierarchically porous micrometer-sized Si particles is reported create a unique path toward sustainable and scalable production
from the low-cost diatomite (Figure 12a), which serves as both of high-performance micrometer-sized Si and low-cost Si source
the precursor and the template.[82] Through one-step magnesio- for LIBs, but also effectively resolve the waste disposal issue of
thermic reduction, the SiO2 constituent in diatomite is reduced the photovoltaic industry, which may therefore bring about enor-
to form Si/SiO2 network with 10–30 nm crystalline Si domains mous environmental and economic benefits.
embedded within amorphous SiO2 matrix. The optimal ratio of
the crystalline Si and amorphous SiO2 designed by the reduction
time, which shows the optional ratio structure with high capacity
5. Conclusion
and excellent cycling stability. The material maintains 90% capac- Si-based anode has been intensively studied as one of the most
ity after 500 cycles at 0.2 C without coating or prelithiation. promising anode materials for high-energy LIBs. The issues fac-
Otherwise, biomass materials are mentionable natural sources ing of this material include the poor electrical conductivity, large
for commercial Si-based anode materials, which including reed volume variation, and unstable SEI films. In this Review, the
leaf, rice husk, bamboo leaf, and sugarcane bagasse.[101] The con- focus is on combining with advanced structure, binders, electro-
version of corn leaves into Si anode materials is reported via a lyte systems, and prelithiation and Si/graphite design to meet
simple aluminothermic reduction reaction without other modi- commercialization requirements, including areal capacity, ICE,
fications (Figure 12b). The obtained Si material inherits the and cost.
structural characteristics of the natural corn leaf template deliv- Despite the great progresses, the Si-based anodes are still nec-
ers great rate capability of 1200 mA h g1 at 8 A g1.[102] essary to develop. There is a long way to go before large-scale
Moreover, low-grade Si, untreated or initially treated raw mate- industrial application. As discussed earlier, none of the strategies
rial, is an attractive choice because of its abundance and cheap can work out all the three problems simultaneously. As for the
price. In Figure 12c, it illustrates the detailed procedure for recy- future research on Si-based materials, which can provide high
cling industrial waste and preparation of Si/SiO2.[80] The Si/SiO2 ICE, high areal capacity, and low cost at the same time
are derived from Si loss slurry in solar industry and quartz sand (Figure 13). We believe that it should be devoted to the following
waste, and used for anodes. By inheriting the intrinsic advantage aspects: 1) Feasible, scalable, and controlled preparation methods
of Si and SiO2, the composites exhibit 992.8 mAh g1 after 400 of Si-based anode should be developed to relax the mechanical
cycles at 0.5 A g1 without capacity decay. When paired with stress and strain during cycling. It was believed that the combi-
LiCoO2, the superior electrochemical performance of prelithiated nation of chemical methods (oxidation and etching processes)
Si/SiO2 anode enables higher energy density (459.4 Wh kg1) of and thermochemical pyrolysis will likely become viable path to
the full cell. This process demonstrates that Si-based industrial industrialization of Si-based anodes. The photovoltaic Si scrap
waste can be cost-effective resources for high-performance ano- could be used as raw material, which meets the requirements
des through simple, scalable, and energy-efficient route. of low cost and high output; 2) Effective and controllable
Furthermore, highly scalable and low-cost route of recovering manufacturing technique of Si/graphite materials should be
high-purity Si microplates from photovoltaic industry waste developed to obtain low electrode swelling. Within 10% swelling
obtained during diamond-wire slicing of solar grade Si ingots is required in industrial application. However, Si/graphite exhib-
has been reported,[103] and have great potential to commercial ited electrode expansion of 20–100%. Meanwhile, achieving
anode materials as high-performance anode with ideal cost homogeneous distribution of the Si in the electrode is crucial
(Figure 12d). To accommodate the severe volume effect of Si challenges toward practical application of Si/graphite anodes.

Figure 13. Schematic showing the potential development for Si-based anode.

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Keywords
anodes, energy densities, lithium-ion batteries, nanostructures, silicon

Received: January 18, 2021

Revised: March 5, 2021
Published online:

[1] a) Y. Tang, Y. Zhang, W. Li, B. Ma, X. Chen, Chem. Soc. Rev. 2015, 44,
5926; b) F. Wu, G. Yushin, Energy Environ. Sci. 2017, 10, 435.
[2] a) F. Wu, J. Maier, Y. Yu, Chem. Soc. Rev. 2020, 49, 1569; b) Z. Lin,
T. Liu, X. Ai, C. Liang, Nat. Commun. 2018, 9, 5262.
[3] Z. P. Cano, D. Banham, S. Ye, A. Hintennach, J. Lu, M. Fowler,
Z. Chen, Nat. Energy 2018, 3, 279.
Figure 14. Comparison of the properties and performance of different [4] a) Y. Jin, B. Zhu, Z. Lu, N. Liu, J. Zhu, Adv. Energy Mater. 2017, 7,
strategies. 1700715; b) W. Luo, X. Chen, Y. Xia, M. Chen, L. Wang, Q. Wang,
W. Li, J. Yang, Adv. Energy Mater. 2017, 7, 1701083.
The short-term goal for the Si/graphite anode is to accomplish an [5] a) J. W. Choi, D. Aurbach, Nat. Rev. Mater. 2016, 1, 16013;
electrochemical performance with a specific capacity of b) M. N. Obrovac, V. L. Chevrier, Chem. Rev. 2014, 114, 11444.
550 mAh g1, a volumetric capacity (900 mAh cc1), a high [6] a) X. Su, Q. Wu, J. Li, X. Xiao, A. Lott, W. Lu, B. W. Sheldon, J. Wu, Adv.
ICE (>92 %), low electrode swelling, and cycle life (full-cell Energy Mater. 2014, 4, 1300882; b) X. Shen, Z. Tian, R. Fan, L. Shao,
capacity retention of 90% after 300 cycles); 3) For binder, poly- D. Zhang, G. Cao, L. Kou, Y. Bai, J. Energy Chem. 2018, 27, 1067.
meric binders with plentiful functional groups (e.g., ─OH, [7] a) Y. Shi, X. Zhou, G. Yu, Acc. Chem. Res. 2017, 50, 2642; b) S. Chae,
─COOH, ─NH2) boost chemical interactions (covalent bonds, S.-H. Choi, N. Kim, J. Sung, J. Cho, Angew. Chem., Int. Ed. 2020, 59,
hydrogen bonds etc.). Multifunctional binder including volume 110; c) J. Wu, Y. Cao, H. Zhao, J. Mao, Z. Guo, Carbon Energy 2019,
change alleviation and SEI contribution can achieve the hard/soft 1, 57.
[8] S. Chae, M. Ko, K. Kim, K. Ahn, J. Cho, Joule 2017, 1, 47.
plastic/elastomer strategy to enhance the adhesion strength and
[9] a) N. Liu, Z. Lu, J. Zhao, M. T. McDowell, H.-W. Lee, W. Zhao, Y. Cui,
ionic conductivity. Moreover, utilization of conductive binder
Nat. Nanotechnol. 2014, 9, 187; b) J. Chen, X. Fan, Q. Li, H. Yang,
could help to decrease the content of conductive agent, and
M. R. Khoshi, Y. Xu, S. Hwang, L. Chen, X. Ji, C. Yang, H. He,
increase the energy density of batteries. In contrast, polymeric C. Wang, E. Garfunkel, D. Su, O. Borodin, C. Wang, Nat. Energy
binder with self-healing ability to allow Si microparticle electro- 2020, 5, 386; c) T.-W. Kwon, Y. K. Jeong, E. Deniz,
des that are of long cycle; 4) Novel types of electrolyte and elec- S. Y. AlQaradawi, J. W. Choi, A. Coskun, ACS Nano 2015, 9,
trolyte additives suitable for high-capacity Si-based materials 11317; d) J. Jang, I. Kang, J. Choi, H. Jeong, K.-W. Yi, J. Hong,
should be researched. Electrolyte selection could be required M. Lee, Angew. Chem., Int. Ed. 2020, 59, 14473.
to produce SEI film with LiF-rich after cycling. The LiF ingredi- [10] a) D. Lin, Z. Lu, P.-C. Hsu, H. R. Lee, N. Liu, J. Zhao, H. Wang, C. Liu,
ent would enhance the plastic property of SEI film, resulting in Y. Cui, Energy Environ. Sci. 2015, 8, 2371; b) L. Zong, B. Zhu, Z. Lu,
excellent structure stability of Si particles, even Si microparticles. Y. Tan, Y. Jin, N. Liu, Y. Hu, S. Gu, J. Zhu, Y. Cui, Proc. Natl. Acad. Sci.
Compared with other strategies, the performance of LIBs by 2015, 112, 13473; c) M. Ko, S. Chae, J. Ma, N. Kim, H.-W. Lee, Y. Cui,
designing Si/graphite has its special advantages, such as high J. Cho, Nat. Energy 2016, 1, 16113.
ICE, low electrode swelling, and good stability (Figure 14). In [11] a) Y. Qi, G. Wang, S. Li, T. Liu, J. Qiu, H. Li, Chem. Eng. J. 2020, 397,
addition, by advanced structure design, more controllable 125380; b) Y. Yang, S. Wu, Y. Zhang, C. Liu, X. Wei, D. Luo, Z. Lin,
Chem. Eng. J. 2021, 406, 126807; c) B. Zhu, X. Wang, P. Yao, J. Li,
graphite-blended, molecular design, or hybrid binder material
J. Zhu, Chem. Sci. 2019, 10, 7132; d) T.-W. Kwon, J. W. Choi,
synthesis, reliable electrolyte design can be developed to achieve
A. Coskun, Chem. Soc. Rev. 2018, 47, 2145; e) Z. Liu, Q. Yu,
lower electrode swelling, higher areal capacity, and lower cost of Y. Zhao, R. He, M. Xu, S. Feng, S. Li, L. Zhou, L. Mai, Chem. Soc.
Si-based electrodes. It is expected that high energy density and Rev. 2019, 48, 285.
power density Si-based LIBs will undoubtedly be made soon. [12] X. H. Liu, J. W. Wang, S. Huang, F. Fan, X. Huang, Y. Liu, S. Krylyuk,
J. Yoo, S. A. Dayeh, A. V. Davydov, S. X. Mao, S. T. Picraux, S. Zhang,
J. Li, T. Zhu, J. Y. Huang, Nat. Nanotechnol. 2012, 7, 749.
Acknowledgements [13] a) F. Li, J. Xu, Z. Hou, M. Li, R. Yang, ChemNanoMat 2020, 6, 720;
C.Z. and F.W. contributed equally to this work. The authors acknowledge b) G. G. Eshetu, E. Figgemeier, ChemSusChem 2019, 12, 2515;
financial support from National Natural Science Foundation of China c) F. Dou, L. Shi, G. Chen, D. Zhang, Electrochem. Energy Rev.
(nos. 51525206 and 51902316), National Key R&D Program of 2019, 2, 149.
China (2016YFA0200102 and 2016YFB0100100), the Strategic [14] F. Shi, Z. Song, P. N. Ross, G. A. Somorjai, R. O. Ritchie,
Priority Research Program of the Chinese Academy of Sciences K. Komvopoulos, Nat. Commun. 2016, 7, 11886.
(XDA22010602), Liaoning Revitalization Talents Program (no. [15] a) P. Li, G. Zhao, X. Zheng, X. Xu, C. Yao, W. Sun, S. X. Dou, Energy
XLYC1908015). Key R&D Plan of Jihua Laboratory (no. X200191TL200). Storage Mater. 2018, 15, 422; b) Z. Xu, J. Yang, H. Li, Y. Nuli, J. Wang,
J. Mater. Chem. A 2019, 7, 9432; c) T. Chen, J. Wu, Q. Zhang,
X. Su, J. Power Sources 2017, 363, 126; d) X. Zuo, J. Zhu,
Conflict of Interest
P. Müller-Buschbaum, Y.-J. Cheng, Nano Energy 2017, 31,
The authors declare no conflict of interest. 113.

Small Struct. 2021, 2100009 2100009 (16 of 19) © 2021 Wiley-VCH GmbH
[Link] [Link]

[16] a) X. Chen, H. Li, Z. Yan, F. Cheng, J. Chen, Sci. China Mater. 2019, 62, [32] G. Huang, J. Han, Z. Lu, D. Wei, H. Kashani, K. Watanabe, M. Chen,
1515; b) K. Feng, M. Li, W. Liu, A. G. Kashkooli, X. Xiao, M. Cai, ACS Nano 2020, 14, 4374.
Z. Chen, Small 2018, 14, 1702737; c) L. C. Loaiza, L. Monconduit, [33] M. Xia, B. Chen, F. Gu, L. Zu, M. Xu, Y. Feng, Z. Wang, H. Zhang,
V. Seznec, Small 2020, 16, 1905260; d) J. Wu, F. Ma, X. Liu, C. Zhang, J. Yang, ACS Nano 2020, 14, 5111.
X. Fan, L. Shen, Z. Wu, X. Ding, X. Han, Y. Deng, W. Hu, [34] a) C. Zhang, S.-H. Park, A. Seral-Ascaso, S. Barwich, N. McEvoy,
C. Zhong, Small Methods 2019, 3, 1900158. C. S. Boland, J. N. Coleman, Y. Gogotsi, V. Nicolosi, Nat.
[17] a) S. Chiluwal, N. Sapkota, A. M. Rao, R. Podila, ACS Appl. Mater. Commun. 2019, 10, 849; b) H. Li, M. Lu, W. Han, H. Li, Y. Wu,
Interfaces 2020, 12, 34763; b) X. Han, Z. Zhang, H. Chen, W. Zhang, J. Wang, B. Zhang, J. Energy Chem. 2019, 38, 50.
Q. Zhang, S. Chen, Y. Yang, ACS Appl. Mater. Interfaces 2020, 12, [35] J. Tao, L. Lu, B. Wu, X. Fan, Y. Yang, J. Li, Y. Lin, Y. Y. Li, Z. Huang,
44840; c) X. Lin, A. Li, D. Li, H. Song, X. Chen, ACS Appl. Mater. J. Lu, Energy Storage Mater. 2020, 29, 367.
Interfaces 2020, 12, 15202. [36] a) Z. Wang, X. Zhang, X. Liu, Y. Wang, Y. Zhang, Y. Li, W. Zhao,
[18] a) L. Li, C. Fang, W. Wei, L. Zhang, Z. Ye, G. He, Y. Huang, Nano C. Qin, A. Mukanova, Z. Bakenov, J. Power Sources 2020, 449,
Energy 2020, 72, 104651; b) G. Zheng, Y. Xiang, L. Xu, H. Luo, 227550; b) Q. Chen, C. Zhang, L. Lin, Q. Xie, W. Xu, Y. Qiu,
B. Wang, Y. Liu, X. Han, W. Zhao, S. Chen, H. Chen, Q. Zhang, J. Lin, L. Wang, D.-L. Peng, J. Power Sources 2021, 481, 228833.
T. Zhu, Y. Yang, Adv. Energy Mater. 2018, 8, 1801718. [37] I. S. Aminu, H. Geaney, S. Imtiaz, T. E. Adegoke, N. Kapuria,
[19] Y. Son, J. Ma, N. Kim, T. Lee, Y. Lee, J. Sung, S.-H. Choi, G. Nam, G. A. Collins, K. M. Ryan, Adv. Fun. Mater. 2020, 30, 2003278.
H. Cho, Y. Yoo, J. Cho, Adv. Energy Mater. 2019, 9, 1803480. [38] a) X. Bai, Y. Yu, H. H. Kung, B. Wang, J. Jiang, J. Power Sources 2016,
[20] a) Z. Favors, H. H. Bay, Z. Mutlu, K. Ahmed, R. Ionescu, R. Ye, 306, 42; b) W.-F. Ren, J.-T. Li, S.-J. Zhang, A.-L. Lin, Y.-H. Chen,
M. Ozkan, C. S. Ozkan, Sci. Rep. 2015, 5, 8246; b) S. Cangaz, Z.-G. Gao, Y. Zhou, L. Deng, L. Huang, S.-G. Sun, J. Energy Chem.
F. Hippauf, F. S. Reuter, S. Doerfler, T. Abendroth, H. Althues, 2020, 48, 160; c) Q. Hua, D. Dai, C. Zhang, F. Han, T. Lv, X. Li,
S. Kaskel, Adv. Energy Mater. 2020, 10, 2001320; c) W. Kang, S. Wang, R. Zhu, H. Liao, S. Zhang, Nanoscale Res. Lett. 2018, 13, 134.
J.-C. Kim, D.-W. Kim, J. Power Sources 2020, 468, 228407; [39] H. Wang, X. Cao, H. Gu, Y. Liu, Y. Li, Z. Zhang, W. Huang, H. Wang,
d) Y. Wang, L. Ren, Y. Liu, X. Liu, K. Huang, X. Wei, J. Li, X. Qi, J. Wang, W. Xu, J.-G. Zhang, Y. Cui, ACS Nano 2020, 14, 4601.
J. Zhong, J. Energy Chem. 2014, 23, 105. [40] T. Azib, N. Bibent, M. Latroche, F. Fischer, J.-C. Jumas, J. Olivier-
[21] X.-Y. Zhang, W.-L. Song, Z. Liu, H.-S. Chen, T. Li, Y. Wei, D.-N. Fang, Fourcade, C. Jordy, P.-E. Lippens, F. Cuevas, J. Mater. Chem. A
J. Mater. Chem. A 2017, 5, 12793. 2020, 8, 18132.
[22] B. Jiang, S. Zeng, H. Wang, D. Liu, J. Qian, Y. Cao, H. Yang, X. Ai, ACS [41] Z. Xiao, C. Lei, C. Yu, X. Chen, Z. Zhu, H. Jiang, F. Wei, Energy Storage
Appl. Mater. Interfaces 2016, 8, 31611. Mater. 2020, 24, 565.
[23] a) Y. Li, K. Yan, H.-W. Lee, Z. Lu, N. Liu, Y. Cui, Nat. Energy 2016, 1, [42] S. Park, J. Sung, S. Chae, J. Hong, T. Lee, Y. Lee, H. Cha, S. Y. Kim,
15029; b) A. Baasner, S. Dörfler, M. Piwko, S. Desilani, J. Brückner, J. Cho, ACS Nano 2020, 14, 11548.
H. Althues, S. Kaskel, J. Mater. Chem. A 2018, 6, 14787; c) Y. Jin, S. Li, [43] M. Liu, H. Gao, G. Hu, K. Zhu, H. Huang, J. Energy Chem. 2020, 40,
A. Kushima, X. Zheng, Y. Sun, J. Xie, J. Sun, W. Xue, G. Zhou, J. Wu, 89.
F. Shi, R. Zhang, Z. Zhu, K. So, Y. Cui, J. Li, Energy Environ. Sci. 2017, [44] P. Wu, S. Chen, A. Liu, Nano Select 2020.
10, 580; d) J. Zhang, L. Zhang, P. Xue, L. Zhang, X. Zhang, [45] Y. Zeng, Y. Huang, N. Liu, X. Wang, Y. Zhang, Y. Guo, H.-H. Wu,
W. Hao, J. Tian, M. Shen, H. Zheng, J. Mater. Chem. A 2015, 3, H. Chen, X. Tang, Q. Zhang, J. Energy Chem. 2021, 54, 727.
7810. [46] B. Han, Y. Yang, X. Shi, G. Zhang, L. Gong, D. Xu, H. Zeng, C. Wang,
[24] a) W. An, B. Gao, S. Mei, B. Xiang, J. Fu, L. Wang, Q. Zhang, P. K. Chu, M. Gu, Y. Deng, Nano Energy 2018, 50, 359.
K. Huo, Nat. Commun. 2019, 10, 1447; b) P. Li, J.-Y. Hwang, Y.-K. Sun, [47] J. Ryu, J. H. Seo, G. Song, K. Choi, D. Hong, C. Wang, H. Lee,
ACS Nano 2019, 13, 2624; c) J. Ryu, D. Hong, M. Shin, S. Park, ACS J. H. Lee, S. Park, Nat. Commun. 2019, 10, 2351.
Nano 2016, 10, 10589; d) Y. Yu, L. Gu, C. Zhu, S. Tsukimoto, P. A. van [48] H. Uono, B.-C. Kim, T. Fuse, M. Ue, J.-I. Yamaki, J. Electrochem. Soc.
Aken, J. Maier, Adv. Mater. 2010, 22, 2247; e) X.-R. Wu, C.-H. Yu, 2006, 153, A1708.
C.-C. Li, Carbon 2020, 160, 255; f ) K. Zeng, T. Li, X. Qin, [49] J. Sung, J. Ma, S.-H. Choi, J. Hong, N. Kim, S. Chae, Y. Son, S. Y. Kim,
G. Liang, L. Zhang, Q. Liu, B. Li, F. Kang, Nano Res. 2020, 13, 2987. J. Cho, Adv. Mater. 2019, 31, 1900970.
[25] a) L. Zhang, C. Wang, Y. Dou, N. Cheng, D. Cui, Y. Du, P. Liu, M. Al- [50] a) S. Choi, T.-W. Kwon, A. Coskun, J. W. Choi, Science 2017, 357, 279;
Mamun, S. Zhang, H. Zhao, Angew. Chem., Int. Ed. 2019, 58, 8824; b) b) P. Parikh, M. Sina, A. Banerjee, X. Wang, M. S. D’Souza,
F. Xie, L. Zhang, C. Ye, M. Jaroniec, S.-Z. Qiao, Adv. Mater. 2019, 31, J.-M. Doux, E. A. Wu, O. Y. Trieu, Y. Gong, Q. Zhou, K. Snyder,
1800492. Y. S. Meng, Chem. Mater. 2019, 31, 2535; c) Y. K. Jeong,
[26] J. Im, E. K. Jang, S. Kim, S. Yoon, D.-H. Kim, K. Y. Cho, Chem. Eng. J. T.-W. Kwon, I. Lee, T.-S. Kim, A. Coskun, J. W. Choi, Energy
2020, 402, 126292. Environ. Sci. 2015, 8, 1224.
[27] S. Kilian, K. McCarthy, K. Stokes, T. E. Adegoke, M. Conroy, [51] a) Z. Xu, J. Yang, T. Zhang, Y. Nuli, J. Wang, S.-I. Hirano, Joule 2018, 2,
I. S. Amiinu, H. Geaney, T. Kennedy, K. M. Ryan, Small 2021, 950; b) R. Shao, J. Niu, F. Zhu, M. Dou, Z. Zhang, F. Wang, Nano
2005443. Energy 2019, 63, 103824.
[28] a) Y. Yan, Z. Xu, C. Liu, H. Dou, J. Wei, X. Zhao, J. Ma, Q. Dong, [52] a) Y. Pan, S. Ge, Z. Rashid, S. Gao, A. Erwin, V. Tsukruk,
H. Xu, Y.-S. He, Z.-F. Ma, X. Yang, ACS Appl. Mater. Interfaces K. D. Vogiatzis, A. P. Sokolov, H. Yang, P.-F. Cao, ACS Appl.
2019, 11, 17375; b) S. J. Lee, H. J. Kim, T. H. Hwang, S. Choi, Energy Mater. 2020, 3, 3387; b) K. T. Sarang, X. Li, A. Miranda,
S. H. Park, E. Deniz, D. S. Jung, J. W. Choi, Nano Lett. 2017, 17, 1870. T. Terlier, E.-S. Oh, R. Verduzco, J. L. Lutkenhaus, ACS Appl.
[29] J. Han, X. Tang, S. Ge, Y. Shi, C. Zhang, F. Li, S. Bai, J. Mater. Sci. Energy Mater. 2020, 3, 6985; c) S. Hu, Z. Cai, T. Huang,
Technol. 2021, 80, 259. H. Zhang, A. Yu, ACS Appl. Mater. Interfaces 2019, 11, 4311;
[30] a) Z. Luo, D. Fan, X. Liu, H. Mao, C. Yao, Z. Deng, J. Power Sources d) A. Miranda, X. Li, A. M. Haregewoin, K. Sarang, J. Lutkenhaus,
2009, 189, 16; b) F. Wang, Z. Hu, L. Mao, J. Mao, J. Power Sources R. Kostecki, R. Verduzco, ACS Appl. Mater. Interfaces 2019, 11,
2020, 450, 227692. 44090; e) X. Wang, S. Liu, Y. Zhang, H. Wang, A. A. Aboalhassan,
[31] C. Xie, Q. Xu, H. Maleki Kheimeh Sari, X. Li, Chem. Commun. 2020, G. Li, G. Xu, C. Xue, J. Yu, J. Yan, B. Ding, ACS Appl. Mater.
56, 6770. Interfaces 2020, 12, 38132; f ) D.-E. Yoon, C. Hwang, N.-R. Kang,

Small Struct. 2021, 2100009 2100009 (17 of 19) © 2021 Wiley-VCH GmbH
[Link] [Link]

U. Lee, D. Ahn, J.-Y. Kim, H.-K. Song, ACS Appl. Mater. Interfaces [70] a) J. Guo, A. Omar, A. Urbanski, S. Oswald, P. Uhlmann, L. Giebeler,
2016, 8, 4042. ACS Appl. Energy Mater. 2019, 2, 4411; b) C. Li, W. Zhu, B. Lao,
[53] a) T. Liu, Q. Chu, C. Yan, S. Zhang, Z. Lin, J. Lu, Adv. Energy Mater. X. Huang, H. Yin, Z. Yang, H. Wang, D. Chen, Y. Xu,
2019, 9, 1802645; b) Y. K. Jeong, J. W. Choi, ACS Nano 2019, 13, 8364; ChemElectroChem 2020, 7, 3743; c) G. Zhu, S. Yang, Y. Wang,
c) C. Luo, L. Du, W. Wu, H. Xu, G. Zhang, S. Li, C. Wang, Z. Lu, Q. Qu, H. Zheng, RSC Adv. 2019, 9, 435.
Y. Deng, ACS Sustainanle Chem. Eng. 2018, 6, 12621; d) Y. Cho, [71] A. L. Michan, G. Divitini, A. J. Pell, M. Leskes, C. Ducati, C. P. Grey,
J. Kim, A. Elabd, S. Choi, K. Park, T.-W. Kwon, J. Lee, K. Char, J. Am. Chem. Soc. 2016, 138, 7918.
A. Coskun, J. W. Choi, Adv. Mater. 2019, 31, 1905048; e) S. Kim, [72] T. Noguchi, T. Hasegawa, H. Yamauchi, I. Yamazaki, K. Utsugi, ECS
Y. K. Jeong, Y. Wang, H. Lee, J. W. Choi, Adv. Mater. 2018, 30, Trans. 2017, 80, 291.
1707594; f ) G. Zhang, Y. Yang, Y. Chen, J. Huang, T. Zhang, [73] S.-W. Song, S.-W. Baek, Electrochem. Solid-State Lett. 2009, 12, A23.
H. Zeng, C. Wang, G. Liu, Y. Deng, Small 2018, 14, 1801189. [74] G.-B. Han, M.-H. Ryou, K. Y. Cho, Y. M. Lee, J.-K. Park, J. Power
[54] Z. Li, Y. Zhang, T. Liu, X. Gao, S. Li, M. Ling, C. Liang, J. Zheng, Z. Lin, Sources 2010, 195, 3709.
Adv. Energy Mater. 2020, 10, 1903110. [75] C. C. Nguyen, D. M. Seo, K. W. D. K. Chandrasiri, B. L. Lucht,
[55] K. L. Browning, R. L. Sacci, M. Doucet, J. F. Browning, J. R. Kim, Langmuir 2017, 33, 9254.
G. M. Veith, ACS Appl. Mater. Interfaces 2020, 12, 10018. [76] S. Dalavi, P. Guduru, B. L. Lucht, J. Electrochem. Soc. 2012, 159, A642.
[56] a) T. Munaoka, X. Yan, J. Lopez, J. W. F. To, J. Park, J. B. H. Tok, Y. Cui, [77] N.-S. Choi, K. H. Yew, H. Kim, S.-S. Kim, W.-U. Choi, J. Power Sources
Z. Bao, Adv. Energy Mater. 2018, 8, 1703138; b) X. Liu, J. Zai, A. Iqbal, 2007, 172, 404.
M. Chen, N. Ali, R. Qi, X. Qian, J. Colloid Interf. Sci. 2020, 565, 270. [78] G. Zeng, Y. An, S. Xiong, J. Feng, ACS Appl. Mater. Interfaces 2019, 11,
[57] a) C. Zhang, Q. Chen, X. Ai, X. Li, Q. Xie, Y. Cheng, H. Kong, W. Xu, 23229.
L. Wang, M.-S. Wang, H. Yang, D.-L. Peng, J. Mater. Chem. A 2020, 8, [79] B. Han, C. Liao, F. Dogan, S. E. Trask, S. H. Lapidus, J. T. Vaughey,
16323; b) D. Liu, Y. Zhao, R. Tan, L.-L. Tian, Y. Liu, H. Chen, F. Pan, B. Key, ACS Appl. Mater. Interfaces 2019, 11, 29780.
Nano Energy 2017, 36, 206. [80] I. Hasa, A. M. Haregewoin, L. Zhang, W.-Y. Tsai, J. Guo, G. M. Veith,
[58] J.-I. Lee, H. Kang, K. H. Park, M. Shin, D. Hong, H. J. Cho, N.-R. Kang, P. N. Ross, R. Kostecki, ACS Appl. Mater. Interfaces 2020, 12, 40879.
J. Lee, S. M. Lee, J.-Y. Kim, C. K. Kim, H. Park, N.-S. Choi, S. Park, [81] a) C. Yao, X. Li, Y. Deng, Y. Li, P. Yang, S. Zhang, J. Yuan, R. Wang,
C. Yang, Small 2016, 12, 3119. Carbon 2020, 168, 392; b) B. F. Song, A. Dhanabalan, S. L. Biswal,
[59] Q. Ye, P. Zheng, X. Ao, D. Yao, Z. Lei, Y. Deng, C. Wang, Electrochim. J. Energy Storage 2020, 28, 101268; c) H. J. Kim, S. Choi, S. J. Lee,
Acta 2019, 315, 58. M. W. Seo, J. G. Lee, E. Deniz, Y. J. Lee, E. K. Kim, J. W. Choi,
[60] Y. Liu, Z. Tai, T. Zhou, V. Sencadas, J. Zhang, L. Zhang, Nano Lett. 2016, 16, 282; d) Y. Sun, H.-W. Lee, Z. W. Seh, N. Liu,
K. Konstantinov, Z. Guo, H. K. Liu, Adv. Mater. 2017, 29, 1703028. J. Sun, Y. Li, Y. Cui, Nat. Energy 2016, 1, 15008.
[61] D. Yao, Y. Yang, Y. Deng, C. Wang, J. Power Sources 2018, 379, 26. [82] J. Zhao, Z. Lu, N. Liu, H.-W. Lee, M. T. McDowell, Y. Cui, Nat.
[62] G. Liu, S. Xun, N. Vukmirovic, X. Song, P. Olalde-Velasco, H. Zheng, Commun. 2014, 5, 5088.
V. S. Battaglia, L. Wang, W. Yang, Adv. Mater. 2011, 23, 4679. [83] Y. Shen, J. Zhang, Y. Pu, H. Wang, B. Wang, J. Qian, Y. Cao, F. Zhong,
[63] R. Tang, L. Ma, Y. Zhang, X. Zheng, Y. Shi, X. Zeng, X. Wang, L. Wei, X. Ai, H. Yang, ACS Energy Lett. 2019, 4, 1717.
ChemElectroChem 2020, 7, 1992. [84] C. L. Berhaut, D. Z. Dominguez, D. Tomasi, C. Vincens, C. Haon,
[64] a) J. Xu, Q. Zhang, Y.-T. Cheng, J. Electrochem. Soc. 2015, 163, A401; Y. Reynier, W. Porcher, N. Boudet, N. Blanc, G. A. Chahine,
b) A. Magasinski, B. Zdyrko, I. Kovalenko, B. Hertzberg, R. Burtovyy, S. Tardif, S. Pouget, S. Lyonnard, Energy Storage Mater. 2020, 29, 190.
C. F. Huebner, T. F. Fuller, I. Luzinov, G. Yushin, ACS Appl. Mater. [85] a) C. Gan, C. Zhang, W. Wen, Y. Liu, J. Chen, Q. Xie, X. Luo, ACS Appl.
Interfaces 2010, 2, 3004. Mater. Interfaces 2019, 11, 35809; b) S. Huang, L.-Z. Cheong,
[65] P.-F. Cao, G. Yang, B. Li, Y. Zhang, S. Zhao, S. Zhang, A. Erwin, D. Wang, C. Shen, ACS Appl. Mater. Interfaces 2017, 9, 23672;
Z. Zhang, A. P. Sokolov, J. Nanda, T. Saito, ACS Energy Lett. 2019, c) S. Chae, N. Kim, J. Ma, J. Cho, M. Ko, Adv. Energy Mater. 2017,
4, 1171. 7, 1700071; d) S.-B. Son, L. Cao, T. Yoon, A. Cresce, S. E. Hafner,
[66] S. Gao, F. Sun, A. Brady, Y. Pan, A. Erwin, D. Yang, V. Tsukruk, J. Liu, M. Groner, K. Xu, C. Ban, Adv. Sci. 2019, 6, 1801007.
A. G. Stack, T. Saito, H. Yang, P.-F. Cao, Nano Energy 2020, 73, [86] a) H. Park, N. Yoon, D. Kang, C. Young, J. K. Lee, Electrochim. Acta
104804. 2020, 357, 136870; b) Z. Yan, J. Guo, Nano Energy 2019, 63, 103845;
[67] a) C. Stetson, Y. Yin, C.-S. Jiang, S. C. DeCaluwe, M. Al-Jassim, c) N. Kim, S. Chae, J. Ma, M. Ko, J. Cho, Nat. Commun. 2017, 8, 812;
N. R. Neale, C. Ban, A. Burrell, ACS Energy Lett. 2019, 4, 2770; d) R. Dash, S. Pannala, Sci. Rep. 2016, 6, 27449; e) S. Zhu, J. Zhou,
b) W. Ping, C. Yang, Y. Bao, C. Wang, H. Xie, E. Hitz, J. Cheng, Y. Guan, W. Cai, Y. Zhao, Y. Zhu, L. Zhu, Y. Zhu, Y. Qian, Small 2018,
T. Li, L. Hu, Energy Storage Mater. 2019, 21, 246. 14, 1802457.
[68] Y. Yin, E. Arca, L. Wang, G. Yang, M. Schnabel, L. Cao, C. Xiao, [87] R. Petibon, V. L. Chevrier, C. P. Aiken, D. S. Hall, S. R. Hyatt,
H. Zhou, P. Liu, J. Nanda, G. Teeter, B. Eichhorn, K. Xu, R. Shunmugasundaram, J. R. Dahn, J. Electrochem. Soc. 2016, 163,
A. Burrell, C. Ban, ACS Appl. Mater. Interfaces 2020, 12, 26593. A1146.
[69] a) N. Sanchez-Ramirez, B. D. Assresahegn, R. M. Torresi, [88] Z. Du, R. A. Dunlap, M. N. Obrovac, J. Electrochem. Soc. 2014, 161,
D. Bélanger, Energy Storage Mater. 2020, 25, 477; b) C. Cao, A1698.
I. I. Abate, E. Sivonxay, B. Shyam, C. Jia, B. Moritz, [89] M. Bai, L. Yang, Q. Jia, X. Tang, Y. Liu, H. Wang, M. Zhang, R. Guo,
T. P. Devereaux, K. A. Persson, H.-G. Steinrück, M. F. Toney, Joule Y. Ma, ACS Appl. Mater. Interfaces 2020, 12, 47490.
2019, 3, 762; c) Y.-G. Cho, H. Park, J.-I. Lee, C. Hwang, Y. Jeon, [90] Y. Gogotsi, P. Simon, Science 2011, 334, 917.
S. Park, H.-K. Song, J. Mater. Chem. A 2016, 4, 8005; d) F. Men, [91] H.-M. Cheng, F. Li, Science 2017, 356, 582.
Y. Yang, Y. Shang, H. Zhang, Z. Song, Y. Zhou, X. Zhou, [92] H. Wang, J. Fu, C. Wang, J. Wang, A. Yang, C. Li, Q. Sun, Y. Cui, H. Li,
H. Zhan, J. Power Sources 2018, 401, 354; e) W. Huang, J. Wang, Energy Environ. Sci. 2020, 13, 848.
M. R. Braun, Z. Zhang, Y. Li, D. T. Boyle, P. C. McIntyre, Y. Cui, [93] H. Wu, G. Yu, L. Pan, N. Liu, M. T. McDowell, Z. Bao, Y. Cui, Nat.
Matter 2019, 1, 1232; f ) Q. Huang, J. Song, Y. Gao, D. Wang, Commun. 2013, 4, 1943.
S. Liu, S. Peng, C. Usher, A. Goliaszewski, D. Wang, Nat. [94] Y. K. Jeong, W. Huang, R. A. Vilá, W. Huang, J. Wang, S. C. Kim,
Commun. 2019, 10, 5586; g) J. Wang, Y. Cui, Nat. Energy 2020, 5, 361. Y. S. Kim, J. Zhao, Y. Cui, Adv. Energy Mater. 2020, 10, 2002108.

Small Struct. 2021, 2100009 2100009 (18 of 19) © 2021 Wiley-VCH GmbH
[Link] [Link]

[95] a) I. Ryu, J. W. Choi, Y. Cui, W. D. Nix, J. Mech. Phys. Solids 2011, 59, b) L. Zong, Y. Jin, C. Liu, B. Zhu, X. Hu, Z. Lu, J. Zhu, Nano
1717; b) C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F. Zhang, Lett. 2016, 16, 7210.
R. A. Huggins, Y. Cui, Nat. Nanotechnol. 2008, 3, 31. [101] X. Luo, S. Chen, T. Hu, Y. Chen, F. Li, SusMat 2021.
[96] D. Wang, C. Zhou, B. Cao, Y. Xu, D. Zhang, A. Li, J. Zhou, Z. Ma, [102] A. Su, J. Li, J. Dong, D. Yang, G. Chen, Y. Wei, Small 2020, 16,
X. Chen, H. Song, Energy Storage Mater. 2020, 24, 312. 2001714.
[97] J. Wang, L. Liao, H. R. Lee, F. Shi, W. Huang, J. Zhao, A. Pei, J. Tang, [103] L. Zhang, L. Zhang, J. Zhang, W. Hao, H. Zheng, J. Mater. Chem. A
X. Zheng, W. Chen, Y. Cui, Nano Energy 2019, 61, 404. 2015, 3, 15432.
[98] Y. Zhou, Y. Yang, G. Hou, D. Yi, B. Zhou, S. Chen, T. D. Lam, [104] Y. Zhang, R. Zhang, S. Chen, H. Gao, M. Li, X. Song, H. L. Xin,
F. Yuan, D. Golberg, X. Wang, Nano Energy 2020, 70, Z. Chen, Adv. Fun. Mater. 2020, 30, 2005956.
104568. [105] H. Wu, L. Zheng, J. Zhan, N. Du, W. Liu, J. Ma, L. Su, L. Wang,
[99] a) Q. Xu, J.-Y. Li, Y.-X. Yin, Y.-M. Kong, Y.-G. Guo, L.-J. Wan, Chem. J. Power Sources 2020, 449, 227513.
Asian J. 2016, 11, 1205; b) S.-H. Park, D. Ahn, Y.-M. Choi, K. C. Roh, [106] a) C. Zhang, J. Ma, F. Han, H. Liu, F. Zhang, C. Fan, J. Liu, X. Li,
K.-B. Kim, J. Mater. Chem. A 2015, 3, 20935. J. Mater. Chem. A 2018, 6, 17982; b) T. L. Kulova, A. M. Skundin,
[100] a) L. Geng, D. Yang, S. Gao, Z. Zhang, F. Sun, Y. Pan, S. Li, X. Li, Y. V. Pleskov, E. I. Terukov, O. I. Kon’kov, J. Electroanal. Chem.
P.-F. Cao, H. Yang, Adv. Mater. Interfaces 2020, 7, 1901726; 2007, 600, 217.

Chengzhi Zhang received his B.S. and Ph.D. in carbon material from Hunan University, in 2015 and
2020, respectively. He is currently a postdoctoral research fellow in the Ji Hua Laboratory. Meanwhile, he
is currently a visiting scholar at Institute of Metal Research, Chinese Academy of Sciences. His current
research interests mainly focus on the synthesis and application of carbon-based composite materials for
electrochemical energy storage. He has published more than 16 papers in peer-reviewing journals
including Energy Storage Materials, Journal of Materials Chemistry A, etc. with 253 citations (H-index 7).

Fei Wang is currently a graduate student under the supervision of Prof. Jinshui Liu at Hunan University.
He received his B.S. in materials science and engineering from Hunan University, China, in 2019. His
research focuses on exploring designs and electrochemical mechanisms of carbon-modified metal
sulfides composite materials in alkali metal ions batteries. He has published more than five papers in
peer-reviewing journals including Advanced Functional Materials, etc.

Jun Tan is professor and director of Material Analysis and Testing Center of Advanced Manufacturing
Science and Technology GuangDong Laboratory (Ji Hua Laboratory). He was a professor in Institute of
Metal Research, Chinese Academy of Sciences (IMR, CAS). He received his Ph.D. in materials science at
IMR, CAS. His research activities focus on the techniques and principles of focused ion beam-scanning
electron microscope (FIB-SEM) and in situ transmission electron microscope (in situ TEM), supported
by CAS Key Technology Talent Program, in 2011.

Feng Li is a professor in Institute of Metal Research, Chinese Academy of Sciences (IMR, CAS). He
received his PhD in materials science at IMR, CAS. He mainly works on nanomaterials for energy
applications, such as for lithium-ion/lithium-sulfur batteries and electrochemical capacitors. He has
published more than 300 papers in peer-reviewed journals, such as Energy Environ. Sci., Adv. Mater.,
Nature Energy, etc. with more 45 000 citations and H-index about 90. He obtained the award of National
Science Fund for Distinguished Young Scholars by the National Foundation of Science, China and Highly
Cited Researcher by Clarivate Analytics.

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