Energy Storage Materials 39 (2021) 21-44 - Na Ion Battery

Energy Storage Materials 39 (2021) 21–44
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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm
Sn-based metal oxides and sulfides anode materials for Na ion battery
Gracita M. Tomboc a, Yunting Wang a,b, Heryn Wang c, Jinghong Li d,∗, Kwangyeol Lee a,∗
a
Department of Chemistry and Research Institute for Natural Sciences, Korea University, Seoul 02841, Republic of Korea
b
School of Chemical and Environmental Engineering, China University of Mining and Technology of Beijing, Beijing 100083, China
c
Department of Chemistry, University of Pennsylvania, Philadelphia, PA 19104-6323 USA
d
Department of Chemistry, Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Tsinghua University Beijing 100084, China
a r t i c l e i n f o a b s t r a c t
Keywords: The extensive search for high-capacity negative electrodes for sodium-ion batteries had led to the investigation
Na ion battery of various nanomaterials capable of storing sodium ions in their structures through the combined conversion and
Tin metal oxides alloying reactions. Among many nanomaterials, tin metal oxides and tin metal sulfides are considered highly
Tin metal sulfides
promising compounds due to their high theoretical capacities. However, there have been growing concerns re-
Sn-based anode
garding the inability of these materials to deliver substantial reversible capacities, which often leads to an in-
Solid-electrolyte interphase
complete conversion-alloying reaction. In this review, particular attention is paid to the recent advances in the
development of Sn-based anodes for SIBs to understand in detail the obstacles hindering the full utilization of
these materials. We first present a short overview of sodium storage mechanisms of Sn-based materials and the
synthetic strategies used to prepare various Sn-based nanostructures. We focus on the approaches to mitigate the
structural deformation of these materials. In addition, we highlight efforts devoted to understanding the formation
and evolution of solid-electrolyte interface during the continuous sodiation-desodiation process, which is signif-
icantly different from the phenomena in the lithium-ion batteries and thus requires different approaches. This
review further addresses the standing challenges in developing Sn-based materials and points to future research
directions in hope to usher the practical applications of the sodium-ion batteries.
1. Introduction Na ions are about 55% larger in radius than Li-ions (1.02 vs, 0.76 Å),
making it more difficult for them to be reversibly inserted into and ex-
The investigation for the electrochemical energy storage capacity of tracted from the host materials [16]. The sluggish kinetics of larger-sized
sodium-ion batteries (SIBs) began in the early 1980s, alongside lithium- Na ions results in low energy density and incompetent cycling stability,
ion batteries (LIBs) [1]. However, the relatively inferior energy density which greatly hinder the development of SIBs. Besides, the structural
of SIBs led the scientists to focus primarily on LIBs [2–8]. LIBs have collapse of Na material caused by physical changes during continuous
been extensively used as power sources for high technology devices like reaction poses significant challenges [17].
cellular phones, laptops, electric tools, automobile power sources, and Ever since the interest in SIBs has re-emerged, significant develop-
electric vehicles (EVs). The demand for these technologies, especially for ments for cathode compartments have been reported [18–23]. However,
EVs, which are the most sought-after alternative for petroleum fuel vehi- the anode side of this battery system still requires further investigation
cles, has exceedingly grown over the decades. However, the possibility and optimization to attain high energy density and excellent cycling
of lithium shortage and the huge economic and geopolitical issues of stability. Specifically, the development of appropriate anode materials
countries with most readily available lithium sources are dawning great with large reversible capacity within a wide voltage range, good rate
challenges on the future sustainability of LIBs. Due to the heightened performance, and low material cost is very urgent for commercializing
limitations of the lithium market, the scientific community’s interest in SIBs.
SIBs has re-emerged from the beginning of 2010 [9–12]. The negative electrodes of SIBs are categorized into three groups
Since Na minerals are cheaper, more abundant, and available world- based on the associated reaction mechanism: (1) insertion reaction-based
wide, SIBs serve as promising rechargeable batteries that are highly cost- anodes, including carbon materials (i.e., graphitic carbon, hard carbon,
effective [13–15]. More importantly, the physiochemical similarities be- reduced graphene oxide, heteroatom doped carbon) and titanium-based
tween sodium- and lithium-chemistry led the researchers to believe that materials (i.e., TiO2 , spinel lithium titanate (Li4 Ti5 O12 ), sodium-titanate
less technological efforts are needed to establish SIBs system. However, compounds (Na2 Ti3 O7 ), [24–26] (2) conversion reaction-based anodes in-
∗
Corresponding authors.
E-mail addresses: [email protected] (J. Li), [email protected] (K. Lee).
https://doi.org/10.1016/j.ensm.2021.04.009
Received 4 February 2021; Received in revised form 19 March 2021; Accepted 7 April 2021
Available online 11 April 2021
2405-8297/© 2021 Elsevier B.V. All rights reserved.
G.M. Tomboc, Y. Wang, H. Wang et al. Energy Storage Materials 39 (2021) 21–44
cluding transition metal oxides (TMOs) (i.e., Fe3 O4 , Fe2 O3 , Co3 O4 , SnO, SnO2 + 4Na+ + 4e− ↔ Sn + 2Na2 O (2)
SnO2 , CuO, MoO2 , NiO, Mn3 O4 ) and transition metal sulfides (TMSs)
(i.e., CoS, CoS2 , Mo2 S, MoS2 , FeS, FeS2 , SnS, SnS2 . CuS, MnS, NiS, TiS, Sn + xNa+ + xe− ↔ Nax Sn (0 < x < 4) (3)
WS2 , ZnS), [27–32] and (3) alloying reaction-based anodes including Na-
metals in group 14 or 15 of the periodic table (i.e., Sn, Bi, Si, Ge, As, Sb, Eqs. (1) and (2) represent the conversion reactions that take place in
and P). [21,33,34] potentials 3.0~0.8 V (region I) and 0.8~0.1 V (region II), respectively.
Among these many materials, Sn-based anode materials (Sn, SnOx , Region I corresponds to Na ion insertion into SnO2 nanocrystals, fol-
SnSx ) undergoing combined conversion-alloying reactions have shown lowed by the reduction of SnO2 (from NaSnO2 ) to metallic Sn via the
a great potential as competent and efficient negative electrodes for SIBs formation of Na2 O (region II) Eq. (3). describes the Na–Sn alloying re-
[35–41]. Tin metal oxides (SnOx ) and tin metal sulfides (SnSx ) are action that occurs in 0.1~0.01 V (region III), which is correlated to the
cheap, non-toxic, and easy to synthesize. Both compounds have been formation of amorphous Nax Sn nanoparticles dispersed in Na2 O matrix
considered as electrode materials for SIB because of their high total the- and the formation of SEI on the electrode’s surface. [56,57] With further
oretical sodium storage capacity. SnSx appeals to have better structural Na insertion, Nax Sn is crystallized into Na15 Sn4 (x = 3.75); upon ex-
stability compared to SnOx attributed to its inherent layered structure, traction of Na (desodiation), Nax Sn is transformed to Sn nanoparticles.
which can allow easier Na ion insertion and extraction. Unfortunately, [15,38] Notably, Sn nanoparticles tend to form hollow structures due
the potential of Sn-based anodes for SIBs has not yet been fully demon- to the severe volume expansion (~420%) associated with the continu-
strated due to their known limitations, including poor electrochemical ous sodiation-desodiation process [58]. On the other hand, the charge
reversibility at higher current rates associated with their low intrinsic curves of SnO2 nanocrystals present two well-defined slope regions:
electrical conductivity, low initial Coulombic efficiency, and inadequate from 0.01 V to 0.5 V and from 0.5 V to 1.3 V. The low-potential re-
cyclability. The greatest challenge of Sn-based anodes is the large vol- gion indicates the dealloying process of Nax Sn, while the high-potential
ume expansion (severe swelling and shrinking of the active material) region signals the regeneration of SnO2 through the reaction between
caused by the sodiation/desodiation process during continuous cycles, Sn and Na2 O.
which results in a severe capacity fading. [42,43] Besides, the formation
2.2. Sn-based metal sulfides
of the unstable solid-electrolyte interface (SEI) on the negative electrode
surface greatly holds back the development of efficient, long-lasting, and
Sn-based metal sulfides can exist in two stable forms, namely, SnS2
highly safe SIBs [44–46].
and SnS. The two forms of this material show different layered struc-
Although there are several reviews that provide comprehensive
tures: a CdI2 -type layered structure for SnS2 and a GeS-type layered
overviews of the progress of the development in SIBs, including the ad-
structure for SnS. [28,59] The layered structures of Sn-based metal sul-
vancements in the cathode and anode compartments of the battery, none
fides can provide reaction sites for charge storage, facilitate the elec-
focuses on the breakthroughs of Sn-based materials as negative elec-
tron/ion transport and electrolyte diffusion, and improve the insertion
trodes for sodium-ion battery system [47–53]. Because Sn-based ma-
of ions. Similar to Sn-bases metal oxides, SnSx anode materials can ac-
terials like SnO2 and SnSx possess physical, chemical, and electronic
commodate Na ions through a combined conversion and alloying mech-
properties that are highly desirable for SIBs, it is significant and nec-
anisms, allowing them to own high reversible theoretical capacities of
essary to expound on their up-to-date contributions and development.
1022 mAh g−1 (SnS) and 1136 mAh g−1 (SnS2 ). [36,60,61] The elec-
This review briefly describes the sodium storage mechanisms of SnO2
trochemical reaction mechanism between SnSx and Na+ is described as
and SnSx and explores the different synthetic methods typically used
following [62–66].
to prepare various Sn-based nanostructures. More importantly, we or-
ganized in articulate way the structural optimization strategies often SnS2 + 2Na+ + 2e− ↔ Sn + Na2 S2 (4)
employed to relieve the large volume expansion of Sn-based anode ma-
terials, which led to a prominent enhancement of the catalytic activity 4Sn + 15Na+ + 15e− ↔ Na15 Sn4 (Na3.75 Sn) (5)
and durability of SIBs. Also, the progress in forming stable and active
solid electrolyte interphase on the surface of a negative electrode, which During the discharging process, when the cell voltage is above 0.8
is a critical factor that drives the battery operation, is presented in this V (vs. Na/Na+ ), the main reaction that occurs between SnS2 and Na
review. We highlight the different approaches taken to control the for- ions is the conversion reaction, in which Sn nanoparticles and amor-
mation of SEI in Na ion cell, as well as the theoretical attempts made phous Na2 S2 are generated (Eq. 4). Before all SnS2 is consumed, Sn
to understand the evolution and the composition of this vital passiva- metal and Na ions begin to undergo alloying reaction to form the Na-Sn
tion layer. Finally, we provide perspectives on the future development alloy phases. This stage, in which the conversion and alloying reactions
of safe and high-performance sodium-ion batteries. co-occur, is defined as the ‘conversion+alloying’ region. With further
discharge, the alloying reaction dominates the process until the potential
reaches below 0.3 V, wherein Na2 S2 matrix and nanosized Na3.75 Sn are
2. Sn-based anodes for Na ion battery produced (Eq. 5) [64]. Upon charging, the reactions are reversed at their
entirety, resulting in the dealloying of Na3.75 Sn and the subsequent for-
2.1. Sn-based metal oxides mation of Sn metal. Then Sn metal further reacts with Na2 S2 to reform
the SnS2 phase. Between 1.0 to 1.5 V, the alloying and conversion reac-
Tin metal oxide (SnO2 ), an n-type semiconductor material with a tions happen simultaneously once again. As all the Na-Sn alloy phases
rutile structure (space group P42 /mnm), is a promising anode material are converted to Sn metal phases, the conversion reaction becomes the
for Na ion batteries due to its ability to store sodium ions in its struc- main reaction, similar to the reaction at the beginning of discharge. The
ture through the combined conversion and alloying reactions. The total difference is that the final SnS2 phase formed in the charging process is
theoretical sodium storage capacity of SnO2 is 1378 mAh g−1 , in which no longer crystalline but becomes amorphous (Fig. 1b).
711 mAh g−1 is obtained from a conversion reaction and 667 mAh g−1 The main difference in the electrochemical reaction mechanisms of
through an alloying reaction. [32,38] Based on the discharge and charge SnS2 and SnS with Na ions lies in the formation of Sn nanoparticles after
profiles of SnO2 nanocrystals during the first cycle (Fig. 1a), the sodium the conversion reaction. The 𝛽-Sn phase is formed after the conversion
storage mechanism of SnO2 was suggested to follow the reaction steps reaction between SnS2 and Na+ , while the 𝛼-Sn is the dominant phase
shown below: [54,55] for SnS. Because the total energy difference between 𝛼-Sn and Na3.75 Sn
(7.125 eV) is smaller than that of 𝛽-Sn and Na3.75 Sn (7.66 eV), the al-
SnO2 + Na+ + e− → NaSnO2 (1) loying reaction of Na with 𝛼-Sn to form Na3.75 Sn occurs more quickly
22
Fig. 1. Electrochemical reaction mechanism between Sn-based anode and Na+ ion based on (a) discharge and charge profiles of SnO2 nanocrystals during the 1st,
2nd, 5th, 10th, and 20th cycles. Reproduced with permission from ref. [54]. Copyright 2013 Owner Societies (b) Synchrotron X-ray diffraction results of SnS2 -rGO
electrodes at different discharge and charge states. Reproduced with permission from ref. [64]. Copyright 2015 American Chemical Society.
than that with 𝛽-Sn, resulting in higher intercalation capacity and better During the hydrothermal treatment, strongly coordinated Sn-thiourea
rate capability. [67,68] was subjected to decomposition to produce SnS QDs. Then, SnS QDS
were annealed at 500°C for 2 h under Ar atmosphere, in which PDA
3. Synthetic methods for the preparation of Sn-based anode nanospheres were converted into carbon nanospheres enriched with ni-
materials trogen, inducing the formation of SnS QDs@NC nanospheres.
Xu et al. designed a nitrogen and phosphorus co-doped porous car-
With the successful development of Sn-based anode materials in bon (NPC) as a scaffold material for SnS2 nanosheets with fully exposed
sodium-ion batteries, a series of reliable synthetic strategies have been (001) and (100) facets [73]. By exercising facile control over Sn precur-
explored to prepare the Sn-based anode materials. Here, we focus on the sors, solvents, and reaction temperature during the solvothermal treat-
hydro/solvothermal method, direct deposition method, electrochemical ment, the group obtained three kinds of SnS2 nanosheets with various
method, and thermal decomposition method. layered structures, namely, dozen- (D-SnS2 ), few- (F-SnS2 ), and small
few- (SF-SnS2 ) layered SnS2 (Fig. 2c). Specifically, the products pre-
pared in the ethanol/deionized water mixed solution and pure ethanol,
3.1. Hydro/Solvothermal method
respectively, exhibited more than 20 atoms layered nanosheets (D-
SnS2 @NPC) and around 10 atoms layered nanosheets (F-SnS2 @NPC),
The hydrothermal or solvothermal method has been recognized as
while the composite fabricated in a mixed solution of ethylene glycol
a crucial technique in synthesizing various Sn-based anode materials
and ethanol had thinner and smaller nanosheets (SF-SnS2 @NPC). Sim-
due to its low energy consumption, high yield, and facile control over
ilarly, Wang et al. presented a solvothermal approach followed by car-
the properties of the materials used (i.e., crystallinity, morphology, and
bonization to prepare hierarchical assemblies of thin SnS2 nanosheets
size). This method is typically followed by subsequent processes like
coated with carbon (Fig. 2d) [76]. Initially, L-cysteine and Sn precur-
carbonization, sulfurization, phosphorization, etc [69–76]. For exam-
sors were dissolved in N-methyl pyrrolidine (NMP). The homogeneous
ple, Zheng et al. fabricated SnS/SnO2 heterostructures by coupling the
solution was then transferred into a Teflon-lined steel autoclave and
hydrothermal reaction with the sulfidation process [69]. As shown in
heated at 180 °C for 6 h. Note that NMP is not conventionally used as
Fig. 2a, graphite oxide was first obtained through a modified Hum-
a solvent for solvothermal reaction due to its high boiling point and
mers’ method followed by two-steps hydrothermal treatment. During
low viscosity. Nonetheless, the group took advantage of the solvent in
the first treatment at 160°C for 10 h, the graphene surface was cov-
their product preparation. Also, NMP possesses suitable surface energy
ered with SnO2 nanoparticles to form SnO2 @graphene. An amorphous
for numerous 2D materials. Thus, it is presumed to stabilize the for-
carbon layer was then anchored to the pre-formed material upon sub-
mation of the nanosheets and prevent severe aggregation. The product
sequent treatment with glucose, forming the C@SnO2 @graphene com-
obtained from the solvothermal reaction was further coated with carbon
pound. The as-prepared material was further submitted to a sulfuriza-
layer via self-polymerization of dopamine hydrochloride in presence of
tion step with thiourea at 350°C for 6 h under argon condition to form
tris(hydroxymethyl) aminomethane, followed by the carbonization un-
C@SnS/SnO2 @graphene architecture. Notably, graphene nanosheets
der Ar. The final product displayed a hierarchical nanosheets architec-
fully supported both SnS and SnO2 nanoparticles, which are in tight con-
ture with the 2H-SnS2 crystal structure and surface carbon layer.
tact with each other, thereby creating heterojunctions in the interfacial
area. Veerasubramani et al. prepared ultrasmall SnS quantum dots (QDs)
anchored onto nitrogen-enriched carbon (SnS QDs@NC) nanospheres 3.2. Direct deposition
via hydrothermal method and subsequent carbonization using poly-
dopamine (PDA) as carbon and nitrogen sources (Fig. 2b) [70]. PDA con- The direct deposition technique aims to deposit a compound or sub-
tains abundant active surface functional groups such as -OH and -NH2 , stance directly on the substrate to obtain the target materials. Com-
conducive to anchoring Sn ions. SnCl2 and thiourea were mixed into mon representatives of this technique include chemical vapor deposition
PDA solution and heated at 160°C for 4 h in a Teflon-lined autoclave. (CVD), [77–79] electrostatic spray deposition (ESD), [80,81] oblique an-
23
Fig. 2. Schematic illustration of the formation procedures of: (a) C@SnS/SnO2 @Gr architectures via sequential Hummer’s method, hydrothermal treatment carbon
coating, and sulfidation. Reproduced with permission from ref. [69]. Copyright 2016 Wiley-VCH (b) Ultrasmall SnS quantum dots anchored onto N-enriched carbon
(SnS QDs@NC) nanospheres via stepwise hydrothermal and carbonization method. Reproduced with permission from ref. [70]. Copyright 2020 American Chemical
Society (c) SnS nanosheets loaded on nitrogen and phosphorus co-doped porous carbon with overlooking SEM images of D-SnS2 @NPC, F-SnS2 @NPC, and SF-
SnS2 @NPC. Reproduced with permission from ref. [73]. Copyright 2019 Wiley-VCH. (d) Hierarchical assemblies of thin SnS2 nanosheets in N-methyl-2-pyrrolidone
via combined solvothermal reaction and annealing process. Reproduced with permission from ref. [76]. Copyright 2017 The Royal Society of Chemistry.
gle deposition (OAD), [82] atomic layer deposition (ALD), [83] liquid ogy since the obtained morphologies within 260~300°C temperature
phase deposition (LPD), [84] and chemical bath deposition (CBD) [85]. range are similar.
CVD has been considered as one of the most efficient techniques for ESD is a unique process to engineer electrode materials with dense,
the direct fabrication of Sn-based metal, metal oxides, metal sulfides, fractal-like, sponge-like, and cross-linked porous structures that have
and composite films onto the surface of conductive collector without the been proven effective in synthesizing metal oxides (i.e., TiO2 , Fe2 O3 ,
aid of any binder or carbon black. Zhou et al. fabricated SnS2 nanowall CoO, SnO2 ) and metal sulfides (i.e., MoS2 , WS2 , and SnS2 ) anode mate-
arrays (SnS2 NWAs) on stainless steel via one-step pulsed spray evapo- rials. [80,81,86–88] Similar to CVD, this technique requires no poly-
ration chemical vapor deposition (PSE-CVD), as shown in Fig. 3a [78]. mer binder or additive to grow materials onto the surface of a cur-
The group varied the substrate temperature and the chamber pressure rent collector. A standard ESD setup only involves a nozzle connected
to investigate the growth mechanism of SnS2 NWAs on the stainless- to a syringe used to provide the precursor solution at a constant rate
steel substrate while forming SnS2 nanoparticles as a controlled exper- (precursor-providing system), a heated substrate, and a high DC volt-
iment. Notably, the chamber pressure greatly affected the nucleation age supply. For example, Zhu et al. prepared carbon-coated 3D porous
growth rate of the material. At lower chamber pressure (1000 Pa), the SnS/C nanocomposites via ESD technique (Fig. 3b) [81]. In this exper-
partial pressure of the reactants is particularly low. Thus, SnS2 crystal iment, the precursor solution was prepared by dissolving SnCl2 and L-
nuclei were formed only on the substrate’s defective sites, on which the cysteine in 1,2-propanediol. The prepared solution was transferred into
primary nanoparticles would continue to grow. Conversely, at higher a syringe connected to a metal nozzle (d = 1.6 mm), in which it was at-
chamber pressure (10000 Pa), a much faster nucleation rate was ob- omized into aerosol upon the application of 8 kV voltage. Subsequently,
served owing to the larger partial pressure of the reactants. Eventually, the charged droplets were attracted to and deposited on the heated ti-
the nucleation occurred over the entire surface of the substrate, followed tanium substrate (238°C). At a high temperature, the Sn2+ -L-cysteine
by the growth of the nanoparticle. The group further verified that the complex was decomposed to form SnS while the polyol oligomers de-
substrate temperature was not a key factor in controlling the morphol- rived from 1,2-propanediol evaporated, resulting in a large number of
24
Fig. 3. Schematic illustration of the formation procedures of: (a) SnS2 NWAs and SnS2 NPs on stainless steel via one-step pulsed-spray evaporation chemical vapor
deposition (PSE-CVD). Reproduced with permission from ref. [78]. Copyright 2017 American Chemical Society. (b) Carbon‐coated 3D porous interconnected SnS
using ESD technique. Reproduced with permission from ref. [81]. Copyright 2015 Wiley-VCH. (c) SnOx NHs fabricated directly on a Cu substrate via an oblique angle
deposition method with illustration of structural changes occurred after discharging and charging processes. Reproduced with permission from ref. [82]. Copyright
2019 American Chemical Society. (d) Hierarchical SnS/SnOx hollow nanospheres during the anodization treatment. Reproduced with permission from ref. [106].
Copyright 2019 Wiley-VCH.
voids in the charged droplets. The deposited SnS droplets were then sub- ture) and produce films with notable uniformity and consistency [92–
mitted to an annealing process under Ar, wherein highly crystalline 3D 95]. For instance, an ultrathin TiO2 (~2 nm) layer was successfully
porous interconnected SnS nanorods were formed. The excess L-cysteine deposited on the surface of SnS2 nanosheet arrays via facile ALD tech-
and remaining 1,2-propanediol were converted to amorphous carbon, nique [96]. SnS2 nanosheet arrays were uniformly coated on the surface
coating the fabricated material. of nanoporous N-doped carbon nanoplates by hydrothermal treatment.
OAD is a well-known method to fabricate nanostructured films with Using TiCl4 and H2 O vapor as Ti and O2 precursors, TiO2 film with con-
a vast range of morphologies, including inclined columnar, zigzag, he- trolled thickness of 2 nm was coated on the surface of SnS2 via ALD
lix, S-shaped, and C-shaped structures. [81,89–91] By simple manipu- technique. The morphology of SnS2 nanosheets remained intact after
lation of the degree of tilting and rotation of the substrate, this method the deposition step, proving the good shape controlling property of ALD
can create a nanoporous structure that is different from the traditional method. [83,97]
dense thin film. In OAD technique, the substrate is positioned at an off- LPD technique is a wet process employed to form a homogenous,
normal direction to obtain a larger deposition angle (oblique angle), thin metal oxide or hydroxide films on various substrates that are im-
which induces a “shadowing effect”. This phenomenon prevents the fu- mersed in the aqueous solution of reactants. [84,98] It is a simple and
sion of nanoparticles deposited on the surface, thus allowing the growth highly versatile soft chemical technique based on the slow hydrolysis
of individual and well-aligned nanowires. The substrate can be rotated of metal-fluoro complex species at a temperature below 60 °C. The hy-
in multiple ways, opening up the feasibility of creating complex three- drolysis occurs via an equilibrium reaction. Fluoride ions from the inner
dimensional nanostructures. The recent work of Choi et al. serves as a coordination sphere of the metal complex are slowly replaced by OH−
prime example of OAD [82]. The group fabricated an array of amor- ions and/or water molecules, thereby yielding mixtures of metal hy-
phous tin oxide (a-SnOx ) with nanohelixes (NHs) directly deposited on dro/oxyhydroxides. Likewise, CBD is a well-known wet technique for
Cu foil via OAD method (Fig. 3c). SnO2 precursor powder was used for the deposition of thin metal films on large surfaces at low processing
electron-beam deposition. The vapor flux of SnOx had an oblique in- temperature. Due to its simplicity, cost-effectiveness and economical
cident angle (𝜃) of 80 degrees with respect to the normal axis of the reproducibility, it is widely utilized to synthesize metal sulfide, metal
substrate. A cluster of nanoscale nuclei formed on the substrate during oxide, and multi-component composite [99]. In this process, a suitable
the initial stage of the deposition created a self-shadowed region that complexing agent is vital to release the metal ion (M2+ ) in an aqueous
inhibits further deposition of vapor flux on other areas, resulting in the bath where a conductive substrate is immersed. Xia et al. used a simple
formation of a porous film composed of slanted nanorods. The substrate chemical bath deposition approach to synthesize layered SnS nanosheets
was then rotated every 2 s at 1 rpm and stopped for 12 s, which led to for sodium-ion batteries at low temperatures [85]. The carbon fiber pa-
the formation of a porous film composed of a vertically aligned array per (CFP) was immersed into the homogeneous N2 -saturated ethanol
of 6-turn NHs. Impressively, individual NHs vertically aligned on the solution of SnCl2 ·2H2 O and thioacetamide. The metal sulfide was then
substrate were equally distanced from each other with empty spaces in deposited on CFP at 40°C for 2 h. As a result, the ultrathin 2D SnS
between. nanosheets with a thickness of ~10 layers were uniformly grown on
ALD method has great potential for wide application in the fields the CFP substrate.
of micro-nano electronics and nanomaterials relative to its capability to
control the deposition parameters (thickness, composition, and struc-
25
3.3. Electrochemical method in hydrogen/argon (5% H2 and 95% Ar) gas using thiourea as the sul-
fur source, resulting in the final 3D SnS/C product. The structure and
Electrodeposition is extensively adopted to uniformly grow metal electrochemical performance of the composites can be regulated by the
and metal oxides of various sizes and morphologies on a conductive amount of tin source and sulfidation temperature. On the other hand,
substrate. The electrodeposition process typically involves the appli- Zhang et al. reported a fixed bed assisted sulfurization method to pre-
cation of potential to the conductive substrate with respect to a ref- pare SnO2 /SnS2 /CNTs composites as SIBs anode [109]. A mixed sol-
erence electrode, wherein the metal salt is reduced to metallic state vent of alcohol and water (1:1, v/v) containing CNTs and SnCl4 ·5H2 O
and deposited on the substrate surface. Various electrochemical tech- was hydrothermally treated at 160°C for 16 h to synthesize SnO2 /CNTs
niques are used to execute electrodeposition, including cyclic voltam- composite. Then, the as-prepared SnO2 /CNTs composite was heated to
metry (CV), chronoamperometry (CA), chronopotentiometry (CP), and 400°C in N2 with a flow rate of 40 sccm in a fixed-bed reactor. Subse-
chronocoulometry [100–102]. The composition and structure of the quently, SnO2 /SnS2 /CNTs composites were synthesized at 400°C for 4
electrode material synthesized by this method can be easily adjusted h under a standard gas mixture consisting of H2 S and N2 (1:199, v/v)
by varying the deposition parameters and the electrolyte composition. with the same flow rate.
Also, electrodeposition is a low-cost, solution-based technique that is Tao et al. have synthesized few-layer SnS2 nanosheets with a
feasible under ambient conditions, thus possessing great potential for nitrogen-doped graphene sheet composite (SnS2 /NGS) by a facile ther-
industrial expansion. Dirican et al. reported the synthesis of carbon con- mal decomposition method [110]. SnCl4 ·5H2 O and thiourea (CH4 N2 S)
fined SnO2 /porous carbon nanofiber (PCNF@SnO2 @C) composites via were dissolved in deionized water-dispersed graphene oxide and were
electrodeposition and chemical vapor deposition [103]. To prepare a freeze-dried for 24 h. The as-formed Sn4+ –CH4 N2 S composites uni-
working electrode, the electrospun PCNFs were first oxidized through formly distributed on the GO layer, were subsequently transformed into
cyclic voltammetry in an acidic solution. After oxidation, SnO2 nanopar- SnS2 /NGS hybrid composite via calcination under Ar at 400°C for 2
ticles were deposited on the surfaces of PCNFs at an applied potential of h. Niu et al. prepared amorphous SnO2 subnanoclusters attached to N,
-0.2 V (vs. Ag/AgCl/4.0 M KCl) for 20 h. The composite was annealed in O-doped porous carbon nanosheets (A-SnO2 @PCNS) by heat-treatment
Ar at 700°C and further coated with amorphous carbon layers via CVD [111]. With cattle bone powder as precursors, hierarchically porous car-
method to form PCNF@SnO2 @C composite. bon nanosheet (HPCNS) with abundant N and O heteroatoms was syn-
The fabrication of SnOx nanostructures on tin metal via anodization thesized by pyrolysis to be used as the carbon support. The HPCNS was
technique was recently realized when oxalate solution was incorporated then mixed with SnCl2 ·2H2 O in an organic solvent (isopropanol/acetic
in the electrolyte, in which the small surface areas of the anodic tin acid solution) and heat-dried at 400°C for 1 h under Ar atmosphere to
oxide nanostructures inhibit the catalytic performance [104–107]. Li form A-SnO2 @PCNS. Similarly, Yang et al. synthesized SnS2 /C com-
et al. have previously reported the synthesis of C-coated porous SnOx posites via confined annealing of SnO2 /C particles with sulfur powder
nanosheets on the copper foil via a modified anodization method cou- [112]. Sealed in an evacuated reactor with sulfur powder, SnO2 /C pow-
pled with carbonization process [107]. Sn/Cu bilayer films with a thick- der was annealed at 400°C for 4 h in a muffle furnace to form SnS2 /C
ness of ~10 μm (4μm Sn sublayer) prepared by cold-rolling were an- composites. The solid-gas reaction, in which sulfur vapor was diffused
odized and heated to 300°C for 2 h in Ar atmosphere to fabricate porous into SnO2 /C particles, ensured the complete transformation of oxide into
SnOx nanosheet arrays on the Cu substrate (SnOx /Cu). The anodization sulfide.
process was carried out in a glycerol/H2 O (85/15, v/v) solution with
0.2 M ammonium fluoride and 0.1 M oxalate acid at potential of 5 V 3.5. Other methods
for 3600 s, using a home-made two-electrode cell composed of rolled
Cu/Sn bilayer and Pt coil as anode and cathode, respectively. The fabri- Besides the methods presented above, various other techniques are
cated SnOx /Cu was immersed in glucose solution at 60°C overnight and available for the preparation of Sn-based anode materials. Here, we pro-
carbonized at 400°C in Ar for 2 h to obtain C-coated SnOx nanosheets vide a brief overview of electrospinning, microwave-assisted syntheses,
directly assembled on Cu foil. The group also applied the anodization polyol process, and plasma treatment.
technique for the first time to construct SnS/SnOx hollow nanostruc- Electrospinning process fabricates nanofibers on the substrate us-
tures, as illustrated in Fig. 3d [106]. The anodization process was con- ing a high voltage and a fluid flow jet. To date, a variety of Sn-based
ducted again in a glycerol-based electrolyte with 0.05 M Na2 S, 0.1 M materials such as SnO2-x /C nanofibers, [113] SnO2 /NiO@C hetero-
NH4 F, and 3 vol% H2 O. Upon the application of a positive potential to junction hollow nanotubes, [114] SnS2 /C nanofibers, [115] and SnS/C
the anode, a barrier layer was instantly formed, which gradually covered nanofibers [116] have been successfully prepared via electrospinning.
the whole surface. Oxygen bubbles emerged on the surface of the barrier Yan et al. synthesized SnS/C nanofiber membrane (SnS/C NFM) by
layer, acting as a template for the deposition of tin oxides and tin sul- the combination of electrospinning, high-temperature carbonation, and
fides. The metals covered the entire bubble from the bottom up, forming low-temperature vulcanization (Fig. 4b) [116]. The precursor solution
hierarchical hollow nanospheres. The anodization parameters (anodiza- of ball-milled SnO2 nanoparticles, polyvinylpyrrolidone (PVP), poly-
tion voltage, fluoride ions concentration, and time) were adjusted to acrylonitrile (PAN), and N, N-Dimethylformamide (DMF) was electro-
control the self-assembly of the SnS/SnOx nanospherical particles onto spun into a nanofiber membrane at 18 kV. The collected precursor
the metal substrate. nanofibers membrane was stabilized in a tube furnace at 200°C for 3
h. Then, the stabilized membrane was carbonized at 700°C for 3 h in Ar
3.4. Thermal decomposition using PVP as the carbon source to form SnO2 /C nanofiber membrane
(SnO2 /C NFM). Furthermore, SnO2 /C NFM was sulfurized by decompos-
The thermal decomposition process is an efficient method for the ing thiourea at 250°C for 3 h in Ar to form SnS/C nanofiber membrane
direct synthesis of nanoparticles under dry conditions. Xue et al. syn- (SnS/C NFM).
thesized nanoconfined SnS in 3D interconnected macroporous carbon Microwave irradiation provides a fast and highly efficient means
(3D SnS/C) using silica opals as template by carbonization and sulfu- of synthesizing nanoparticles. Thangavel et al. proposed a one-pot mi-
ration route (Fig. 4a) [108]. Silica nanospheres were first mixed with crowave irradiation technique to synthesize nanostructured few-layered
SnCl2 ·2H2 O and polyvinylidene fluoride (PVDF), which were dissolved SnS2 /graphene (SnS2 /G) [117]. The graphene oxide suspension con-
in N-methyl pyrrolidone (NMP). After drying at 60°C for 12 h, the as- taining SnCl2 and thiourea (1:5.3 mol. ratio) was transferred into a
obtained sample was calcined at 500°C for 2 h in the N2 atmosphere, microwave oven and exposed to microwave irradiation (Daewoo, 700
followed by dispersion into NaOH solution to form 3D SnO2 /C com- W) for 20 min. During such process, the defect sites on the graphene
posite. The composite was then subject to sulfidation at 350°C for 12 h sheet provided nucleation sites for the formation of SnS crystals while
26
Fig. 4. Schematic illustration of the formation procedures of: (a) nanoconfined SnS in 3D interconnected microporous carbon via facile thermal decomposition.
Reproduced with permission from ref. [108]. Copyright 2018 Elsevier Ltd. (b) SnS/C nanofiber by electrospinning technique followed by two-steps thermal treatment:
carbonization and sulfidation. Reproduced with permission from ref. [116]. Copyright 2020 Elsevier B.V (c) Ternary tin selenium sulfide carbon-coated (SnSe0.5 S0.5 /C)
nanocomposites through polyol-method followed by hydrothermal treatment and sintering process. Reproduced with permission from ref. [129]. Copyright 2017
Elsevier Ltd. (d) SnO2 NWs via solvo-plasma assisted fabrication technique followed by the HCl based cleaning-etching process. Reproduced with permission from
ref. [131]. Copyright 2017 Elsevier B.V.
thiourea supplied sufficient sulfur atoms for sulfidation. Other exam- for 1~2 min to obtain SnO2 NWs. Finally, pure SnO2 NWs were obtained
ples of Sn-based materials prepared via microwave-assisted method via a cleaning process with HCl and calcination at 550°C for 12 h.
include SnO2 @graphene/N-doped carbons, SnO2 @graphene/N-doped
carbons, Co-SnO2 /carbon cluster, and SnO2 /graphene nanocomposites
[118–121]. 4. Strategies to relieve the stress from large volume expansion of
Polyol method is one of the most common and facile approaches Sn-based anode materials
for the preparation of nanostructured metal oxide (Vx Oy , TiO2 , PbO,
and SnO2 ) and sulfide (Cu2-x S, Sb2 S3 , SnS2 ), in which the shape and As aforementioned, Sn-based materials (i.e., Sn, SnO2 , and SnSx )
the size of the nanoparticles are effectively controlled by using high- have been considered as prominent anodes for SIBs owing to their high
boiling point glycerol or glycol as a stabilizing agent [122–129]. Tang theoretical capacities, low toxicity, and low cost. However, severe vol-
et al. synthesized SnSe0.5 S0.5 /C nanocomposites through facile polyol- ume expansion of these materials triggered by sodiation/desodiation
method and hydrothermal process [129]. The procedure for the prepara- during continuous cycles is causing rapid capacity fading due to the
tion of SnSe0.5 S0.5 /C nanocomposites is illustrated in Fig. 4c. Sulfur and serious particle pulverization. Nanosizing of Sn-based materials is one
selenium powders were first mixed by grinding them in an agate mor- of the first practical approaches proposed to suppress structural distor-
tar. The mixed powders were dissolved in diethylene glycol (DEG) in an tion. Nanosized Sn, SnOx , or SnSx provide numerous active sites and
N2 statured three-neck flask. Then, ethylenediamine (EN) was added to reduce Na+ ion diffusion pathway, ensuring full utilization of the ac-
the mixture, which was further refluxed at 140°C in an oil bath. After tive materials and superior rate capability. Notably, the degree of crys-
30 min, SnCl4 ·5H2 O was added and the resulting mixture refluxed once tallinity of Sn-based materials is an important factor for the develop-
again at 180~200°C for 2 h to obtain brown powders. Finally, the as- ment of optimization strategy. For example, Fan et al. reported that
synthesized brown powders were hydrothermally reacted with glucose amorphous SnO2 nanoparticles show better performances in overcom-
at 180°C for 3 h followed by calcination in the Ar atmosphere to obtain ing electrode degradation from extreme volume change in comparison
SnSe0.5 S0.5 /C nanocomposites. with crystalline SnOx . [132,133] The amorphous SnO2 retained a high
Plasma treatment, a fast and scalable method, has also been devel- specific capacity of 380.2 mAh g−1 even after 100 cycles at a current
oped by several groups to prepare Sn-based anode materials. Chao et density of 50 mA g−1 , which is almost three folds higher than that of
al. applied a facile and rapid C-plasma strategy to grow hierarchical crystalline SnO2 (138.6 mAh g−1 ). The advanced electrochemical per-
graphene bundles on the SnS networks uniformly [130]. Mukherjee et formance of these nanoparticles is attributed to the intrinsic isotropic
al. have fabricated SnO2 NWs using a novel solvo-plasma technique, as nature of amorphous SnO2 , the enhanced Na+ diffusion coefficient, and
shown in Fig. 4d [131]. SnO2 micro-particles and KOH pellets (1:1) were the strong interaction between the active nanomaterials and the con-
first thoroughly pulverized, then a small amount of water was added to ductive substrate. Importantly, a mainly amorphous phase of Sn-based
the mixture to form a thick paste. The as-synthesized SnO2 /KOH paste nanomaterials can possess a much-shortened solid-state diffusion chan-
was dried in air for 10~15 min and pasted onto a quartz slide, which nel for facile Na ion transport due to the enlarged lattice d-spacing aris-
was retained in the plasma arc of 1000~2000 W and 2.5 GHz frequency ing from the low crystallinity [134]. Such phenomenon is favorable to
the enhancement of the ion diffusion rates and the reduction of the
27
charge transfer resistances, which are directly associated with the rate with 81% capacity retention after 200 full sodiation/desodiation cycles;
capability. [135,136] in contrast, the reversible capacity of pure SnO2 rapidly declined from
Despite the discussed advantages, nanoscale active Sn-based materi- 147 to 49 mAh g−1 just after 50 cycles.
als are limited due to their low electronic conductivity, low volumetric Furthermore, Jiang et al. demonstrated that SnS2 nanocrystals (NCs)
capacity, and low stability. Several optimization strategies have been could be attached tightly to ethylenediamine functionalized-reduced
proposed to further modify the structural, compositional, and electronic graphene oxide (EDA-rGO) via interfacial chemical bonding to form a
properties of Sn-based materials to address stability and rate capability unique SnS2 /EDA-RGO hybrid architecture [144]. In brief, EDA-rGO ful-
issues. Herein, we highlight the progress in the development of strate- filled a dual role as an immediate electronic conductive channel and
gies optimizing Sn-based anodes and evaluate their influence on the en- as SnS2 nanocrystals holder. Theoretical calculations elaborated that
hancement of the electrochemical performances of Sn-based anodes. EDA is an ideal crosslinker while graphene nanosheets can provide high
surface area and remarkable flexibility. The strong chemical affinity
4.1. Hybridization with carbon materials of SnS2 to EDA-rGO restricted the random aggregation of the gener-
ated Sn nanoparticles (NPs) during sodium insertion and inhibited the
The distressing volume expansion of Sn-based anodes can be allevi- exfoliation of active SnS2 materials during repeated charge/discharge
ated by combining it with carbonaceous materials like carbon nanofiber cycles. The as-prepared SnS2 /EDA-RGO hybrid electrode maintained
(CNF), carbon nanotubes (CNT), graphene, glucose, and conductive high capacities of 680 mAh g−1 and 480 mAh g−1 after 100 and 1000
polymers. Such hybridization with carbon materials not only helps continuous cycles at high current densities of 200 mA g−1 and 1 A
buffer the volume expansion but also increases the contact area and g−1 , respectively. In order to reveal the critical mechanistic role of re-
electrical conductivity, which effectually improves the stability of the duced graphene oxide in SnS2 -rGO composite material, Ma et al. investi-
Sn-based anodes [137–140]. gated the relationship between Na insertion-extraction mechanisms and
Encapsulation of Sn-based nanoparticles within the carbon shell is the electrochemical performances of this anode material [64]. Fig. 5c
one of the earliest methods utilized to protect the structure of the ma- presents the schematic diagram of the proposed energy storage mecha-
terials against rapid deterioration. A solution-based carbon precursor nism of SnS2 -rGO composite. As shown in the diagram, the conversion
coating and following carbonization process results in the formation of reaction between SnS2 and Na ions occurred upon discharge, generating
a core-shell like Sn-derivatives/carbon composites. Xia et al. observed a Sn NPs and amorphous Na2 S2 . However, prior to the total consumption
thin protective carbon shell on the synthesized SnS/C hybrid electrode, of SnS2 , an alloy reaction between Sn NPs and Na ions commenced,
which played a critical role in enhancing the rate capability and cycling which led to the formation of Na-Sn alloy phase. Interestingly, aside
stability [85]. The as-prepared SnS nanosheets, uniformly encapsulated from being a suitable matrix to relieve the mechanical strain caused
by a carbon shell with ~4 to 6 nm thickness, delivered a reversible ca- by volume expansion during Na insertion-extraction, rGO reacted re-
pacity as high as 792 mAh g−1 after 100 cycles at a current density of versibly with Na ions in the first cycle, as revealed by Raman spectra.
100 mA g−1 . The hybridized electrode also showed remarkable rate ca- Although the amount of reversible capacity from rGO was not measured,
pability and remained stable during long-term cycling under high cur- the results serve as an inspiration to put more effort into realizing the
rent density (345 mAh g−1 after 500 cycles at 3 A g−1 ). In addition, roles of carbon materials in Sn-based composite anode for SIBs.
uniform carbon coating and nanostructure of the composite electrode
are imperative to the promotion of mechanical stability and structural 4.2. Heterostructure
robustness during sodiation/desodiation process [141].
Although various synthetic methods have been developed to prepare The poor intrinsic conductivity of both SnO2 and SnS2 causes serious
SnO2 /carbon composite, random agglomeration, and poor contact be- charge transfer resistance, leading to insufficient rate performance. It
tween the two materials have posed many challenges. Therefore, fur- was previously proposed that the construction of heterostructure might
ther modification schemes have been developed to resolve such prob- reduce the ion-diffusion resistance while accelerating the interfacial
lems. For example, Jahel et al. homogenously embedded SnO2 particles electron transport and improving the overall kinetics rates. [145,146]
into the micro/mesoporous carbon matrix (SnO2 @C-I) via liquid im- Theoretical calculations suggested that the combination of SnO2 and
pregnation of the carbon with diluted solution of a SnCl4 .5H2 O pre- SnS2 to form SnO2 @SnS2 heterostructure is highly desirable due to the
cursor in ethanol [142]. The group rationalized that the exceptional proper bandgap alignment between the two compounds. [69,147] In
rate capability and stability of SnO2 nanoparticles uniformly confined this hybrid structure, display in Fig. 6a, SnO2 is an n-type semiconduc-
in mesoporous carbon towards SIBs would not be feasible if the metal tor with a wide bandgap of 3.8 eV, while SnS serves as a narrow-bandgap
oxide particles were not confined and not well dispersed in the car- (1.3 eV) p-type semiconductor. Hence, SnS/SnO2 p-n heterojunction
bon pores, as evidenced by the poor results of SnO2 particles randomly is expected to induce a built-in electric field on the heterointerfaces,
dispersed along with the carbon matrix. The desirable pore size and which will greatly accelerate the charge-transfer kinetics and result in
pore connectivity of the carbon frame, along with the highly uniform high-rate capability [69]. The combination of SnO2 and SnS2 nanostruc-
confinement of SnO2 crystallites, efficiently accommodated the rapid tures to form a hybrid anode material is then suggested as a construc-
insertion-extraction of Na ions, which deterred the particle pulveriza- tive approach not only to assist Na+ ion and electron charge movement,
tion during volume expansion. The obtained SnO2 @C-I composite de- but also to alleviate internal stress and accommodate the large volume
livered exceptional catalytic activity as anode material for SIB in terms changes [106]. For example, Wang et al. anticipated that growing SnS2
of cyclability (more than 4000 cycles), with the Coulombic efficiency nanosheets on the surface of SnO2 hollow nanosphere would provide a
approaching as high as 99.5%. On the other hand, Ding et al. employed unique architecture with excellent structural stability and mechanical
a glucose-mediated hydrothermal self-assembly method to create SnO2 - integrity, which could deliver high sodiation capacity, better cycling
carbon (C-SnO2 ) nanocomposite with a large surface area (338 m2 g−1 ) stability, and superior rate performance [148]. As expected, SnO2 /SnS2
and Na-active carbon frame with internally embedded sub-5-nm SnO2 hybrid exhibited a high reversible sodium storage capacity at 300 mA
crystallites [143]. The group recognized a similar effect, in which the g−1 with a capacity retention of 78.7% after 100 cycles, which is much
superior cycling performance of C-SnO2 lies in its highly interconnected higher than 25.9% for bare SnO2 hollow nanospheres and 28.9% for
morphology with individual SnO2 nanocrystallites fully surrounded by bare SnS2 nanosheets. Such performance was correlated to the heteroin-
carbon material (Fig. 5a). The surrounding carbon served as a buffer to terface between the two nanostructures, which provided a continuous
minimize the macroscopic strain on the electrode and prevented rapid pathway for rapid Na+ ion transportation and electron charge transfer.
deterioration and agglomeration of the active SnO2 during cycling. As Similarly, the incorporation of secondary metal oxides (MO) or metal
shown in Fig. 5b, C-SnO2 electrode displayed an excellent cyclability sulfides (MS) to the structure of SnO2 /C or SnS2 /C to form heterostruc-
28
Fig. 5. (a) Bright field TEM micrograph of rutile SnO2 nanoparticles embedded in the carbon (C-SnO2 ) with corresponding indexed selected area diffraction pattern
as inset and (b) cycling performance of C-SnO2 and SnO2 at 0.5 A g−1 current density with corresponding coulombic efficiency. Reproduced with permission from ref.
[143]. Copyright 2015 The Royal Society of Chemistry. (c) Schematic diagram of the proposed energy storage mechanism of the SnS2 -rGO composite. Reproduced
with permission from ref. [64]. Copyright 2015 American Chemical Society.
Fig. 6. (a) Schematic illustration of SnS/SnO2 heterostructures showing the formed SnS/SnO2 p-n heterojunctions and the induced built-in electric field on the het-
erointerfaces. Reproduced with permission from ref. [69]. Copyright 2016 Wiley-VCH. (b) SEM, (c) TEM, (d,e) HRTEM images for the SnS2 /Mn2 SnS4 /carbon (SMS/C)
nanocomposite. (f) Schematic illustrating the highly reversible reactions in the SMS/C heterointerface. Reproduced with permission from ref. [152]. Copyright 2019
American Chemical Society.
29
ture SnO2 -MO/C or SnS2 -MS/C, respectively, is expected to improve the Another example of a 1D Sn-based anode is SnS2 embedded in nitro-
physicochemical and electrical properties of Sn-based materials. The gen and sulfur dual-doped carbon nanofibers (SnS2 /NSDC) [115]. Fab-
optimized combination of the components can induce synergistic ef- ricated via facile electrospinning technique, SnS2 /NSDC demonstrated
fects, provide richer redox chemistry, elevate electric conductivity, and the significance of 1D nanostructure in improving the electrochemi-
strengthen structural stability [149–151]. For example, Ou et al. ad- cal performances of SIBs. The morphology and the microstructure of
dressed the impending irreversible conversion reaction issue of SnS2 after-cycled composites were visualized in TEM and EDX elemental
anode by designing heterostructure SnS2 /Mn2 SnS4 /carbon nanoboxes mapping images (Fig. 7a-f), wherein no significant change in morphol-
(SMS/C NBs) via a facile wet-chemical method [152]. The heterojunc- ogy, size, and distribution was observed. Such observations further in-
tions formed between SnS2 and Mn2 SnS4 were confirmed through SEM, dicated that the carbon fibers provided robust mechanical properties
TEM, and HRTEM images (Fig. 6b-e), in which the grain boundaries be- to prevent the pulverization of active Sn nanoparticles. Also, the 1D
tween the two compounds were clearly observed. The surface chemical NSDC nanofibers effectively increased the electrical conductivity of the
state and the valence state of SMS/C NBs have shown significant changes composites and have accelerated the transfer of Na+ ions. As a result,
when compared to pristine SnS2 /C and MnS/C, which implied the en- SnS2 /NSDC nanofibers anode showed improved electrochemical perfor-
hanced interaction and strong coupling between SnS2 and Mn2 SnS4 . mance towards SIB application, including exceptional rate capability
Fig. 6f shows the intimate heterojunctions formed between SMS and C, (310.6 mAh g−1 at 4000 mA g−1 ) and long-term cycle stability (capac-
which played a vital role in providing high electronic conduction during ity retention of 380.1 mAh g−1 after 200 cycles at 500 mA g−1 ). Like-
the sodiation/desodiation process and strengthening the overall struc- wise, Yu et al. designed carbon-encapsulated 1D SnO2 /NiO heterojunc-
ture of the material to accommodate the volume expansion during cy- tion hollow nanotubes (SnO2 /NiO@C) through electrospinning method
cling. More importantly, the final structure of SMS/C NBs has effectively followed by polydopamine (PDA) chemical bath deposition and calci-
prevented the agglomeration and coarsening of Sn nanoparticles, which nation process under N2 gas, shown in Fig. 7g [114]. Fig. 7h-i display
was beneficial for improving the conversion-alloying reaction reversibil- the HRTEM images of SnO2 /NiO@C, in which the thickness of the car-
ity of SnS2 -based anode. The as-synthesized hybrid electrode achieved a bonized PDA layer is determined as ~5 nm. The 1D hollow structure has
first charge capacity of 841.2 mAh g−1 with a desirable initial Coulom- effectively lessened the degree of pulverization and aggregation of SnO2 -
bic efficiency of 90.8%, an excellent rate capability of 488.7 mAh g−1 at based anode during cycling, while the amorphous carbonized PDA layer
high current density of 10 A g−1 , and sustained 522.5 mAh g−1 capacity improved the structural stability and the electrical conductivity, enhanc-
even after 500 cycles at 5.0 A g−1 current rate. ing the battery performance. The SnO2 /NiO@C hollow nanotubes as an-
Furthermore, the uniform confinement of the discussed heterostruc- ode for SIB delivered a first high discharge capacity of 467.2 mAh g−1
ture compounds onto the surface of carbonaceous materials like N- and charge capacity of 322.2 mAh g−1 , yielding an initial Coulombic
doped graphene, polypyrrole (PPy)-derived N/S dual-doped carbon efficiency of 69.0% (Fig. 7j). Benefitted from the modified structural
shell, or S-doped graphene nanosheets can lead to enhanced diffusion features, the as-prepared electrode exhibited high reversible capacity of
kinetics and electrochemical performance towards SIBs. [147,150,151] 320 mA h g−1 after 200 cycles at 100 mA g−1 and maintained an ex-
These carbonaceous materials provide a more stable architecture for the cellent capacity of 160 mA h g−1 even after 1000 cycles at 800 mA g−1
heterostructure compound by inducing a stronger connection between (Fig. 7k).
metal oxides and metal sulfides. The robustness of the heterostructure
SnO2 -MO/C or SnS2 -MS/C increases the tolerance capacity for volume 4.3.2. 2D Sn-based anodes
changes upon cycling and moderates the stress-induced pulverization of Two-dimensional (2D) nanostructured anode materials have shown
electrode. good electrochemical performances owing to their large surface areas
that provide rich reactive sites for Na+ ions and great mechanical flex-
4.3. Morphology modification ibility that could buffer the volumetric changes during extensive cy-
cles. [21,35,59,65,144] It has been highlighted previously that ultra-
Although the performance of Sn-based anodes was substantially im- thin nanosheets can significantly accelerate the diffusion efficiency of
proved after the incorporation of carbonaceous materials (i.e., rGO, metal ions, consequently enhancing the electrochemical performance
CNF, CNT, conductive polymer) and/or secondary metal oxides and sul- in sodium storage. [111,156–158] For example, 2D SnS2 nanosheets
fides, such strategies alone would not suffice to meet the full require- with a thickness of 3~4 nm have shown exceptional enhancement in
ments of practical batteries. It has been noted by many that the careful sodium storage [159]. In a typical refluxing experiment, SnCl2 precur-
manipulation of the structure and the morphology of Sn-based compos- sor and 1,3,4-thiadiazole-2,5-dithiol were added into ethylene glycol
ites is beneficial to enhancing the sodium storage capability of the anode and 1-octadecene, then subjected to Ar gas for about 20 min under vig-
materials. orous stirring. The suspension was then heated to 140, 160, and 180
°C for 2 h, respectively, until brown precipitate was gradually obtained.
4.3.1. 1D Sn-based anodes The as-synthesized 2D nanomaterial was used as anode for SIB. It ob-
The development of one-dimensional (1D) Sn-based anode materi- tained an initial reversible specific capacity of 733 mAh g−1 at 0.1 A
als for SIBs has been considered as an effective approach to reduc- g−1 and retained 647 mAh g−1 after 50 cycles, obtaining 88.27% ca-
ing the diffusion length and relieving the mechanical stress during pacity retention. The ultrathin 2D nanosheet morphology promotes the
long-term charge-discharge cycles. [13,58,113–115,139,153–155] Car- electrochemical performance of the bare SnS2 by achieving fast Na dif-
bon nanotube (CNT) is a 1D-carbon material known to assist the volu- fusion kinetics and buffering the volume change [159]. Moreover, to
metric expansion of Sn-based anodes. The internal cavity, high conduc- further improve the electrochemical performance of SnO-based SIB an-
tivity, and superior flexibility of CNT have made it desirable to use SIBs odes, Zhang et al. manipulated the number of atomic layers stacked in
[153]. Targeting to achieve superior electrochemical performance, Cui 2D SnO nanosheets on carbon cloth by controlling the reaction time, pre-
et al. uniformly coated carbon nanotubes with amorphous SnO2 to fab- cursor concentration, solvents, reducing agents, and pH values [160].
ricate SnO2 /CNT composite electrode [134]. While the highly conduc- Fig. 8a-f show the TEM images of SnO nanosheets with varying atomic
tive CNTs successfully promoted the rapid transportation of electrons layers and thickness, denoted as SnO-2L, SnO-6L, and SnO-10L, which
and ions and accommodated the volume expansion, the layer of amor- bear 2-6, 6-10, and 10-20 SnO monolayers, respectively, and with 1-
phous SnO2 nanoparticles with enlarged d-spacing has accelerated the 3, 3-5, and 5-10 nm thickness, respectively (Fig. 8g). It can be observed
Na+ diffusion. A superior specific capacity of 630.4 mAh g−1 was de- that the size of SnO nanosheets increases as the number of atomic layers
livered at 100 mA g−1 , and a specific capacity of 223.2 mAh g−1 was increases. The SnO nanosheets with different number of atomic layers
maintained at a high rate of 1600 mA g−1 after 300 cycles. were used to investigate the effect of layered SnO towards SIBs. Among
30
Fig. 7. (a, b) TEM images of SnS2 /NSDC nanofibers electrode after cycling for 50 cycles at 50 mA g−1 in SIBs; (c-f) The EDX elemental mapping of the area, marked
by the red dotted rectangular in image (b) for C (c), N (d), S (e) and Sn (f). Reproduced with permission from ref. [115]. Copyright 2018 Elsevier B.V. (g) Schematic
illustration of the preparation process for SnO2 /NiO@C hollow nanotubes, (h) TEM and (i) HRTEM images of SnO2 /NiO@C hollow nanotubes. (j) CV curves of
the SnO2 /NiO@C hollow nanotubes in the initial three cycles at a scan rate of 0.1 mV s−1 and (k) long cycle stability of the SnO2 /NiO and SnO2 /NiO@C hollow
nanotubes at a current density of 800 mA g−1 . Reproduced with permission from ref. [114]. Copyright 2018 Elsevier B.V.
the sample materials, the thinnest SnO nanosheet anodes bearing two ample, Wang et al. fabricated SnS2 /rGO nanohybrid with a plate-on-
to six SnO monolayers (SnO-2L) have exhibited the best electrochemical sheet structure through a one-pot solvothermal method [161]. Fig. 8j-l
performance with high initial discharge and charge capacity of 1072 and shows the illustration and TEM images of the plate-on-sheet morphol-
848 mA h g−1 , respectively, display in Fig. 8h. The high surface area of ogy of SnS2 /rGO nanohybrid, in which the SnS2 nanoplates (~10 nm)
the material provides more active sites to enhance electrochemical per- are tightly confined by ultrathin (almost transparent-like) rGO sheets.
formance and gives more space to buffer the large volume change. The The available large space between the nanoplates is expected to buffer
excellent rate performance was evidenced by the reversible capacity of the mechanical strain, allow the electrolyte movement, and facilitate
665 mAh g−1 after 100 cycles at a current density of 0.1 A g−1 , and the rapid transfer of Na+ ions across the electrode/electrolyte interface.
452 mAh g−1 after 1000 cycles at a high current density of 1.0 A g−1 , Fig. 8m summarizes the first voltage profiles of SnS2 /rGO nanohybrid,
as shown in Fig. 8i. The results illustrate that manipulating the num- and bare SnS2 and rGO. It can be depicted that pure rGO and SnS2 de-
ber of atomic layers in 2D SnO nanostructures has significant influences livered lower charge capacity of only 71 and 178 mAh g−1 , respectively.
on the physical and electronic properties of the materials, which can In comparison, SnS2 /rGO nanohybrid delivered a much higher charge
control the volume changes during continuous battery operation. capacity of 649 mA h g−1 at 0.1 A g−1 , which is even higher than the
Likewise, nanocomposites composed of few-layer sulfide and car- theoretical capacity of bare SnS2 (549 mAh g−1 ). Such result imply the
bon materials such as graphene and reduced graphene oxide have gar- positive influence of the conducting and dispersing effects of rGO. The
nered a lot of attention as SIB anodes. [85,110,117,157,161] As an ex- SnS2 /rGO hybrid also maintained a charge capacity of 337 mAh g−1
31
Fig. 8. (a-f) TEM images of (a,b) SnO-2L, (c,d) SnO-6L, and (e,f) SnO-10L nanosheets, (g) schematic illustration of the SnO nanosheets with different number of
layers with the half-cell structure as inset, (h) Cycling performances of SnO-2L, SnO-6L, and SnO-10L nanosheet electrodes at 0.1 A g–1 for 100 cycles and (i) long-
term cycle stabilities of SnO-2L, SnO-6L, and SnO-10L electrodes at 1 A g–1 for 1000 cycles (0.1 A g–1 for the first 10 cycles and 1 A g–1 for the next 1000 cycles).
Reproduced with permission from ref. [160]. Copyright 2017 American Chemical Society. (j) Schematic diagram of few-layered SnS2 on ultrathin reduced graphene
oxide, (k) SEM and (l) TEM images of SnS2 /rGO; (m) first voltage profiles of SnS2 /rGO, SnS2 , and rGO. Reproduced with permission from ref. [161]. Copyright
2014 Wiley-VCH.
even at 12.8 A g−1 , and even retained a charge capacity close to 300 slow conversion and alloying reactions. As anode material for a hybrid
mAh g−1 after 1000 cycles at a high-rate of 800 mA g−1 . On a simi- capacitor, it exhibited a high reversible capacity of 535.5 mAh g−1 af-
lar note, Thangavel et al. prepared a few-layered and ultrathin 2D SnS2 ter 100 cycles at a current density of 0.2 A g−1 , a rate capability of
over few-layered graphene sheets as an anode for SIBs [117]. The well- 304.8 mAh g−1 even at an ultrahigh current density of 10 A g−1 and re-
dispersed and few-layered morphology of the hybrid provided a large markable capacity retention of ≈70% after 1000 cycles at 3 A g−1 . Sim-
number of reaction sites for sodium storage, leading to enhance capac- ilarly, Sang et al. constructed a 3D porous graphene nanosheet/SnS2
ity, rate capability, and stability. hybrid film (3D-GNS/SnS2 ) as a flexible anode for SIBs by a stepwise
assembling strategy [165]. Fig. 9f exhibits the schematic illustration of
4.3.3. 3D Sn-based anodes the fabrication process of the hybrid material, representative SEM im-
Designing three-dimensional (3D) structures for electrode materials ages of compact and porous 3D-GNS/SnS2 , and the proposed scheme
has always been a successful strategy to improve the performance cor- of ion/electron transport on the surface of the as-prepared nanostruc-
related to the ample inner space, fast ion and electron transportation, tures. Notably, the 3D interconnected porous framework owns a more
and high specific surface area. [81,106,108,162–169] [74,163,170] 3D distorted structure compare to the compacted film; thus, it has more ac-
nanostructure materials are usually fabricated by integrating lower- tive sites for Na storage and can facilitate faster electron/ion transport.
dimensional components. For example, Cui et al. reported the synthe- As an outcome, the flexible porous 3D-GNS/SnS2 film delivered a high
sis of transition metal dichalcogenide SnS2 /graphene-carbon nanotube reversible capacity of 385 mAh g−1 after 1000 cycles at 1.0 A g−1 .
aerogels (SnS2 /GCA) via the combination of hydrothermal, freeze- 3D hollow nanostructures have received great attention due to their
drying, and sulfidation methods (Fig. 9a) [170]. The hybrid is made remarkable properties, including a high specific surface area with in-
up of thin SnS2 nanoplatelets anchored on a 3D conductive graphene- terior voids, low density, excellent surface permeability, and shortened
carbon nanotube aerogels as the skeleton. SEM images show the hierar- transport lengths for both mass and charge movement [171–173]. Im-
chical porous structure of as-synthesized material (Fig. 9b-d), which is portantly, the hollow structure could provide enough void space to al-
expected to facilitate rapid electron/ion transport. The group suggested leviate the stress and accommodate the volume expansion/contraction
that the sodiation mechanism of SnS2 /GCA anode followed two steps to during the sodiation/desodiation process. Taking advantage of the 3D
overcome the kinetic barrier (Fig. 9e): ultrafast Na+ intercalation and hollow architecture, Bian et al. designed a hierarchical SnS/SnOx hol-
32
Fig. 9. (a) Schematic representation of fabrication of SnS2 /graphene-CNT aerogels (SnS2 /GCA) nanosheets, (b,c) low and high magnification SEM and (d) HRTEM
images of SnS2 /GCA,and (e) schematic illustration of proposed sodiation mechanisms of SnS2 /GCA. Reproduced with permission from ref. [170]. Copyright 2017
Wiley-VCH. (f) Schematic illustration of the fabrication of the porous 3D-GNS/SnS2 film and the comparative h-GNS/SnS2 films, the corresponding scanning electron
microscopy (SEM) images, and the scheme of ion/electron transport on them. Reproduced with permission from ref. [165]. Copyright 2020 Wiley-VCH. (g) SEM
and (h) TEM images of SnS/SnOx hollow nanospheres. (i) Cyclic performance of SnS/SnOx hollow nanospheres at 100 mA g−1 current density. Reproduced with
permission from ref. [106]. Copyright 2019 Wiley-VCH.
low nanosphere structure deposited on the Sn substrate via a convenient of 0.3 A g−1 have shown no drastic changes, indicating the stability of
one-step anodization method [106]. As illustrated by the SEM and TEM the hollow SnS/SnOx nanostructures for long-term cycling.
images in Fig. 9g-h, the obtained hollow nanospheres were composed of In addition, enclosing Sn-based materials into 3D carbon network
SnS inner shell covered by SnOx (x = 1, 2) nanoparticles which served nanostructure can further improve the electron and ion transfer kinet-
as an outer shell. The hollow nanostructure shortened the diffusion dis- ics of the overall electrode associated to the superior electrical conduc-
tance for sodium ion and accelerated the electron charge transfer, while tivity, large surface area, and continuous conductive network of car-
maintaining the morphology structure. As a result, this SnS/SnOx elec- bon. For example, Bai et al. synthesized nanoconfined SnS in 3D in-
trode showed a high capacity of 984 mA h g−1 at a current density of 100 terconnected macroporous carbon using silica opal as a template, fol-
mA g−1 and retained a capacity of over 550 mA h g−1 after 100 cycles lowing a carbonization and sulfuration process for sodium ion batter-
at 100 mA g−1 without using any carbonaceous substrate (Fig. 9i). The ies [108]. The uniform 3D porous carbon interconnected structure and
physical characterizations (SEM, XRD, TEM, XPS) of SnS/SnOx hollow nanoconfined SnS in carbon matrix not only improved the conductiv-
nanosphere electrode material after 600 cycles at a high current density ity, but also enhanced the cycling stability due to the enhanced struc-
33
Fig. 10. (a,b) X-ray diffraction (XRD) patterns of SnO2 and SnO2 @x/C electrodes. The lower three panels are the close-ups of the (110), (101), and (200) peaks. (c, d
XPS spectra of SnO2 and SnO2 @x/C electrodes: (b) Sn 3d, and (c) N 1s. Reproduced with permission from ref. [113]. Copyright 2018 Wiley-VCH. (e-g) TEM images
of hs-SnS2 ; (h) Comparison of STEM-EELS spectra recorded from two different positions, (i) Top view of optimized structures of the 3 × 3 SnS2 monolayer with S
vacancy (Sn9 S17 ) and without S vacancy (Sn9 S18 ), and (j,k) Band structures of the 3×3 SnS2 monolayer with and without S vacancy. Reproduced with permission
from ref. [181]. Copyright 2020 American Chemical Society.
tural integrity. Moreover, Zhao et al. presented a rational design for the intrinsic electronic conductivity. SnO2-x /C composite-based SIBs ex-
anchoring SnO2 nanosheets on a freestanding carbonized eggshell mem- hibited good electrochemical performance, including high reversible ca-
brane (CEM) to create high-performance anodes for SIBs [163]. The pacity, ultralong cyclability, and excellent rate capability. The initial
freestanding CEM consisting of massively interconnected carbon fiber discharge capacity was 1185 mAh g−1 , corresponding to the ICEs of
skeleton and interpenetrated pore network could provide a 3D, bicon- 55.2%. A reversible capacity of 565 mAh g−1 was maintained after 2000
tinuous electron and ion transport paths, which was conducive to the cycles at a high current density of 1000 mA g−1 . It is worth noting that
electrolyte access and diffusion and alleviated mechanical stress caused SnO2-x /C electrode also retained the reversible capacities of 602 mAh
by volume changes during sodiation/desodiation. With separate and in- g−1 at 0.2 Ag−1 and 447 mAh g−1 at 2 Ag−1 after 800 and 2500 cycles
terlaced SnO2 nanosheets anchored on the CEM substrate, the 3D net- with Coulombic efficiencies of 97.6% and 106%, respectively. Such no-
work anode showed superior electrochemical performance in SIBs in- table results were attributed to the synergy of the unique nanostructure
cluding a high reversible capacity of 656 mAh g−1 in the 5th cycle at and the gradual activation of active materials. However, it is important
0.1 A g−1 and maintained 420 mAh g−1 after 200 cycles at a higher to note that obtaining Coulombic efficiencies greater than 100% may
current density of 0.2 A g−1 . be correlated to multiple factors, including the varying amount of Na
ions during the charge-discharge process and side reactions occurring
4.4. Defect engineering between electrolytes and electrodes [113].
Sulfur vacancy also plays an important role in optimizing the elec-
Defects engineering on the electrode can provide more active sites trical conductivity of materials and increasing the energy storage loca-
and ion storage sites. It manipulates the insertion of metal ions in the tions for sodium-ion batteries [178–180]. Wang et al. reported a success-
structure, promoting a much more efficient charge transfer, which af- ful synthesis of hierarchical SnS2 microspheres with S vacancies via a
fects the capacity of electrode materials. Oxygen vacancy is the most one-step solvothermal method [181]. The TEM images (Fig. 10e-g) com-
commonly applied anion defect that is advantageous for its low forma- bined with electron energy-loss spectroscopy (EELS) analysis (Fig. 10h)
tion energy and easy formation. The introduction of oxygen vacancy indicated the existence of sulfur vacancies in the hierarchical SnS2 mi-
has been proved to effectively regulate the electronic structure and fa- crospheres. A 3 × 3 SnS2 monolayers with and without S vacancy illus-
cilitate the ion transfer, thereby improving the electrochemical perfor- tration was used in Na adsorption calculations: the calculation results
mance of the electrode material [174–177]. Accordingly, Zhang et al. showed that the introduction of S vacancies could narrow down the
prepared oxygen-vacancy-containing SnO2-x for Na ion battery using a bandgap between the top and bottom valence bans, which indicated the
sulfur-based template and electrospinning technique [113]. It is impor- possible enhancement of the electronic conductivity of SnS2 (Fig. 10i-k).
tant to note that the transformation of SnO2 to SnO2-x had introduced Consequently, the hierarchical SnS2 microspheres electrode has a supe-
multiple oxygen vacancies in the structure. As shown in XRD patterns rior sodium storage performance, in which a large capacity of 548 mAh
(Fig. 10a-b), the shift of the peak positions (110), (101), and (200) to g−1 can be achieved at 0.5 A g−1 after 100 cycles. A capacity of 486.2
lower angles reveals the formation of oxygen vacancies. XPS analysis mAh g−1 can also be maintained after 1000 cycles, which may be due
demonstrated a blue-shift of approximately 0.3 eV in SnO2-x /C elec- to the presence of S vacancies of hierarchical SnS2 microspheres.
trode compared to that of the above SnO2 , further substantiating the Heteroatom doping has been considered a capable technique for
presence of oxygen vacancies (Fig. 10c-d). The introduction of oxygen altering the electronic structure by creating more active sites and de-
vacancies is expected to reduce the reaction energy barrier and improve fects. [182,183] Wang et al. reported a 4% Co-doping strategy on SnS2
34
nanosheet (4Co-SnS2 ) using a facile hydrothermal method to enhance the fact that controlling the passivation layer is more difficult in Na
the electrochemical performance [184]. The characterization analysis cells than Li cells, since Na+ -based electrolyte solution is more sensi-
of 4Co-SnS2 showed abundant defects and discrete lattice fringes on tive to reductive decomposition. Such a phenomenon often leads to the
the nanosheets, which illustrated that the heteroatom Co doping could formation of numerous oxygen-enriched and insoluble products, includ-
enlarge the lattice spacing and generate lattice defects. The resulting ing sodium carbonate, alkyl carbonates, alkoxides, and -polycarbonates
vacancies and lattice defects were used as active sites to facilitate the [11]. Besides, the interaction between the electrolyte and the electrodes
intercalation of sodium ion and to enhance the electron/ionic conduc- during electrochemical processes not only affects the internal structure
tivity, thereby increasing the sodium storage capacity. Benefitting from of the active materials but also significantly influences the properties
Co-doping and 3D structure, 4Co-SnS2 /CC anode displayed an initial of SEI including stability, thickness, and ionic conductivity. Numerous
high discharge capacity of 2757.6 mAh g−1 with initial Coulombic ef- researchers have devoted intense efforts to fine-tune the formation of
ficiency of 57.4%. A superior discharge specific capacity of 1288 mAh SEI layer in SIBs and to understand its evolution.
g−1 was reached at 0.2 A g−1 after 100 cycles, and a reversible capacity The optimization of electrolyte composition such as solvents, elec-
of 800.4 mAh g−1 was maintained even at 2 A g−1 after 200 cycles. trolyte salts, additives, and binders has become an important task to
It is well known that low-cost carbon-based materials that exhibit enhance the rate capability and stability of anode materials for SIBs.
high stability and remarkable electronic conductivity are the most com- [45,202–207] As well-known, electrolyte is a vital component in the bat-
mon substrate materials for Na ion batteries. [147,185,186] For exam- tery system as it plays a key role in balancing and transferring charges
ple, Chen et al. prepared a sea-sponge structured C/SnS@C nanocom- in the form of ions between anode and cathode. The solvent in the elec-
posite via a hierarchical assembly process [187]. Raman results re- trolyte must contain polar groups to dissolve Na salts sufficiently. Sol-
vealed that the C/SnS@C contained more defects and vacancies than vents that are stable, cheap, and non-toxic are mostly preferred. Car-
carbon matrix, which could provide additional electrochemically active bonate ester polar solvents like ethylene carbonate (EC), propylene car-
sites and enhance the diffusion of sodium ions. Wang et al. synthesized bonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and
SnO2 /nitrogen-doped graphene (SnO2 /NG) nanohybrids for sodium-ion ethyl methyl carbonate (EMC) are widely used for practical LIBs due to
batteries via an in situ hydrothermal method [188]. Raman spectra of their wide potential window, high ionic conductivity, low toxicity, and
SnO2 /NG revealed an upshift of about 2 cm−1 for both D band and G controlled temperature [208–213]. Considering the similarities between
band with 1.33 intensity ratio (ID /IG ), correlated to the structural distor- LIBs and SIBs, it is rational to expect carbonate-ester-based solution con-
tion of graphene networks caused by the introduction of N heteroatoms. taining Na salts to serve as an appropriate electrolyte solvent for Na ion
A significant crumpling of NG layers was also observed attributed to battery as well. In line with this, Ponrouch et al. have put extensive
the generation of defective structures in the oxidation-reduction pro- efforts into searching for the most appropriate electrolyte formulation
cess. Nitrogen-doping of graphene networks increased the number of to stabilize the interface layer and enhance both the cell performances
electroactive sites in the SnO2 /NG structure and improved the electron and the safety of SIBs [209–213]. They reported that while the addi-
transfer between SnO2 and NG. Moreover, Zhou et al. designed and tion of EC to the pure PC electrolyte resulted in a significant increase in
prepared oriented SnS nanoflakes attached to S-doped-N-rich carbon the number of alkyl carbonates and polyethylene oxide, further incor-
nanosheets (SnS/CNS). [ 157 ] The introduction of N and S has induced poration of DMC co-solvent drastically reduced the electrolyte viscosity.
multiple defects in materials surface and enhance the conductivity of More importantly, the presence of the third electrolyte helped increase
carbon nanosheets, creating more active sites to strengthen Na+ adsorp- the ionic conductivity and control the final components of the SEI. On
tion and improving surface capacitive effects. This unique SnS/CNS an- the other hand, the usage of ether-based electrolytes is prohibited in
ode structure exhibited a high initial discharge capacity of 939 mAh LIBs due to the inferior property of passivation layer formed on both an-
g−1 , a large discharge capacity of 474 mAh g−1 at 1 A g−1 after 100 odes and cathodes, but they are gradually accepted as a new electrolyte
cycles with stable capacity retention (98%), as well as a superior rate option in SIBs owing to their ability to modify the anode solid elec-
capability of 250.7 mAh g−1 event at 20 A g−1 . trolyte interphases, reduce the solubility of intermediates, and decrease
the polarization. [214,215] Ether-based electrolytes have been widely
5. Formation of solid electrolyte interphase investigated for graphite, hard carbon, Bi-, and Sn-based electrodes due
to their generally enhanced compatibility with many anode materials.
Peled first introduced the concept of solid electrolyte interphase [152,216–225] For example, Song et al. constructed a high energy den-
[189]. He suggested that in a practical non-aqueous battery system, al- sity full SIB using micro-sized Sn anode and Na3 V2 (PO4 )3 /CNT com-
kali and alkaline earth metals are always covered by a surface layer with posite cathode in diethylene glycol dimethyl ether electrolyte [226].
a thickness of 15-25 Å. Upon the contact of metal to the solution, this The group observed the synergistic effect of Sn anode with ether-based
surface layer is instantly formed, in which some of the insoluble prod- electrolytes, which induced the formation of stable SEI during the initial
ucts adhere to its surface. SEI functions as an interphase between the cycles. In addition, the ether-based electrolyte promoted the formation
metal and the solution. It possesses the properties of a solid electrolyte, of a porous Na15 Sn4 intermediate, which assisted the high electron and
only allowing the ionic transport (i.e., Li+ and Na+ ) while hindering the Na+ -ion transport.
transport of both electrons and solvent molecules. Owing to these spe- Moreover, the solubility of Na-salt in the electrolyte is another pa-
cific terms, this surface layer is denoted as “solid electrolyte interphase”. rameter to consider as it can drastically alter the chemical and electro-
The surface passivation process for negative electrodes in LIBs and chemical stability, as well as the ionic conductivity of the SEI formed
SIBs has been extensively studied over the past decades, in which the during cell operation [227]. Passerini et al. carried out a detailed X-
construction of a stable and compact solid electrolyte interphase has ray photoelectron spectroscopy (XPS) investigation to study the ef-
been suggested as the most effective and feasible approach to enhance fect of various Na+ -ion conducting salts in the formation of passi-
the rate capacity and cycling performance of the anode materials [190– vation film on hard carbon (HC) electrode [207]. In this study, the
201]. Notably, a stable SEI must have the mechanical strength to sustain group employed sodium hexafluorophosphate (NaPF6 ), sodium perchlo-
the repeated swelling and contraction of the anode during continuous rate (NaClO4 ), sodium bis-(trifluoromethanesulfonyl) imide (NaTFSI),
cycles. Also, it must possess high Li+ or Na+ conductivity to assist the sodium bis (fluorosulfonyl)imide (NaFSI) and sodium fluorosulfonyl-
rapid ionic movement across the interface and must be stable toward (trifluoromethanesulfonyl)imide (NaFTFSI) as conducting salts: all dis-
operation conditions such as high electrochemical potentials. solved in the same solvent mixture (i.e., EC/DEC:1/1 by wt.). The anion
Thus far, many studies have been conducted concerning the nature of the electrolyte salt was found to govern the overall nature of SEI layer
of SEI layer in LIBs. However, much less is known about the forma- formed on HC, including the composition and the depth distribution of
tion of stable SEI in Na ions system. This is not surprising considering species within SEI. The group discovered that the organic content of SEI
35
Fig. 11. (a) Percentage of the different carbon species in the outermost SEI layer formed on HC electrodes sodiated in the above electrolyte formulations, (b-f) C1s
XPS spectra of HC electrodes sodiated in 1 M NaX salts dissolved in EC/DEC (1/1, wt.) electrolytes (b) NaPF6, (c) NaClO4 , (d) NaTFSI, (e) NaFTFSI, and (f) NaFSI.
Reproduced with permission from ref. [207]. Copyright 2018 Elsevier Ltd. (a) HAXPES curve fitted C 1 s spectra of Sn4 P3 electrodes cycled in 1 M NaFSI EC/DEC
(1:1) with 5vol% FEC with excitation energies of 2005 eV (left) and 6016 eV (right); (b) The relative amount of signal originating from the different peaks in the C
1 s spectra; and (c) O 1s and F 1s spectra of Sn4 P3 electrodes Reproduced with permission from ref. [196]. Copyright 2017 Elsevier Ltd.
decreases in the following order of conducting salts: NaPF6 > NaClO4 > Additives assist the transfer of the charges at the electrode-electrolyte
NaTFSI > NaFTFSI > NaFSI, as shown in Fig. 11a-f. In addition, NaClO4 - interfaces rather than in the bulk electrolyte [228–230]. Fluoroethylene
based electrolyte resulted in the thickest SEI layers, while those based carbonate (FEC) is found to play vital roles in controlling the SEI layer
on NaPF6 and NaTFSI resulted in thinner SEI layers. The variation of SEI on the surface of various anode materials for SIBs [231]. Ji et al. in-
properties was correlated to the rate of degradation of electrolyte sol- vestigated the effects of FEC additives to the formation of stable SEI
vents (EC and DEC) at higher potentials, which was hindered by NaFSI film onto a porous CNF-supported SnSb electrode [232]. The group ob-
and NaFTSI conducting salts. served that the presence of FEC not only helped reduce the decomposi-
Additives are also crucial components for the formation of stable SEI tion of electrolyte but also altered the structural and chemical compo-
layer because they can modify the composition of the interface layer, in- sition of the electrode surface passivation layer during cycling. Such
crease the wettability of the surface, and protect it against overcharging. event assisted the formation of a thin, highly stable, and robust SEI
36
film. The group also noted that FEC additive is specifically beneficial only on the surface of the Sn-based coating material showed significant
to porous CNF-SnSb electrode with carbonate-based electrolytes, which increase in ICE from 15.7% to 68.8% and delivered a reversible capac-
exhibit enhanced battery performance including the reversible capacity of 110 mAh g−1 at 5 A g−1 . On a similar note, Jin et al. proposed an
ity of 110 mAh g−1 at 20 C rate. Moreover, the selection of a suitable interfacial design principle to improve the rate capability and stability
binder is equally important to maximize the electrode performance in of a monolithic anode for SIBs [236]. The group investigated the role
SIBs. Poly(vinylidene fluoride) (PVDF) mixed with volatile organic sol- of chemical affinity of Na (sodiophilicity) in regulating the Na deposi-
vents such as N-methyl pyrrolidone (NMP) and water-soluble sodium tion interlayer, which greatly affects the cyclability of anode in SIBs.
carboxymethyl cellulose (CMC) have been widely used as binders to Specifically, SnO2 nanodots were sandwiched between rGO layers and
paste an electrode layer on the conductive substrate. [198,233] then pre-coated with NaF (NaF/SnO2 @rGO). The ultrafine SnO2 nan-
Mogensen et al. examined the thickness and composition of SEI layer odots were used a guiding agent to regulate the deposition of Na metal
formed on tin phosphide (Sn4 P3 ) anodes in Na half cells using an opti- while rGO layers and NaF serve as scaffold/matrix and artificial SEI film,
mized EC:DEC (1:1 vol ratio) electrolyte solution with 1 M NaFSI con- respectively. The resultant NaF/SnO2 @rGO electrode induced a prefer-
ducting salt and 5 vol% FEC additive [196]. They employed hard x- ential deposition of uniform interlayer Na plating between rGo layers,
ray photoelectron spectroscopy (HAXPES) using two excitation ener- which led to a stable SEI layer, as shown in Fig. 12c-d. The controlled
gies (2005 eV and 6015 eV) to completely view the depth of SEI layer growth of Na metal and stabilized SEI layer improved the cycling sta-
(Fig. 11g). A series of six cycled samples were measured at different bility of SnO2 /rGO anode with 99.87% CE after 3000 cycles.
states of sodiation and desodiation, namely, (1) upon contact to the
electrolyte (soaked), (2) full sodiation (before the first cycle), (3) 50% 6. Summary and Outlook
desodiation, (4) full desodiation, (5) 50% sodiation, and (6) full sodia-
tion (after 1st cycle) and were compared with the pristine sample. The Tin metal oxides and tin metal sulfides have received increasing at-
HAXPES measurements showed that the thickness of SEI layer on the tention as promising negative electrodes for Na ion batteries due to their
fully sodiated samples (No. 2 and 6) was between 15-30 nm, but it be- superior theoretical capacity, environmental benignity, low cost, and
came thinner than 15 nm on the 50% sodiated/desodiated and fully high electric conductivity. The total theoretical capacities of Sn-based
desodiated samples (No. 3, 4, 5). SEI layer formed during the sodiation anodes are 1378, 1136, and 1022 mAh g−1 for SnO2 , SnS2 , and SnS,
process was thick enough to cover both active and conductive materials respectively, thanks to their ability to undergo combined conversion-
of the anode; however, it reduced significantly upon desodiation. The alloying reaction mechanisms. Besides, these materials have become
large difference in SEI thickness between sodiated and desodiated sam- particularly popular for SIBs because of their easily controlled structure
ples reflects the variation of SEI composition during cycling, including and composition, making them very attractive over other anode materi-
organic and inorganic compounds such as oxygen species, carbonates, als. However, there have been many arguments regarding the inability
and fluorides as shown in Fig. 12h-i. However, the results from this of Sn-based anodes to fully reach their theoretical capacities because
study demonstrated that SEI formed on Sn4 P3 anode exposed in elec- of their incomplete conversion-alloying reactions. Such inefficiency is
trolyte with optimized composition is still not fully stable and likely mainly attributed to the rapid deterioration of the material due to se-
undergoes significant changes in thickness and composition, which can vere swelling and shrinking of the structure during cycling, which often
be connected to the state of sodiation and potential within the cell. leads to low capacity and poor capacity retention. Thus, to utilize the
In order to fully comprehend the composition and evolution of SEI full capacities of Sn-based materials, extensive efforts have been given
layer formed during the Na ion cell operation, Marquez et al. investi- to optimizing their physical, chemical, and electronic properties.
gated the surface of Na2 Ti3 O7 electrodes after electrochemical cycling In summary, we categorized the optimization strategies of Sn-based
using Auger parameter analysis for the first time to overcome the lim- materials into five methods: (1) nanosizing, (2) hybridization with car-
itations of XPS analysis [191]. The group confirmed that the SEI layer bon materials, (3) construction of heterostructure, (4) morphology mod-
formed upon discharge comprises chemisorbed oxygen, alkyl carbon- ification, and (5) defects engineering. Nanosizing of Sn-based materials
ates, and poly-ethylene oxide (PEO). These species have covered most of is one of the first practical approaches proposed to suppress structural
the solid layer of sodium carbonates, NaF, and NaCl. The group also ob- distortion. This method is easy to handle and effective in increasing the
served that SEI layer is partially dissolved upon every charging process, surface area, which is primarily needed to provide better accommoda-
a phenomenon correlated to the continuous degradation of the elec- tion for the stress associated with the repeated sodiation/desodiation
trolyte and binder. [208,232,234] Importantly, they realized that unlike process. We found that the degree of crystallinity of the nanomaterials
SEI formed in LIBs, SEI materialized in Na2 Ti3 O7 electrode is thinner affects the rate capability since it can influence the ion diffusion rate and
and contains more inorganic components than organic ones, with PEO the charge transfer resistance. The major drawbacks of the nanostruc-
and alkyl carbonates being partially soluble and initiating continuous tured materials include inferior electronic conductivity, low volumetric
reformation of SEI. The changes in the chemical, mechanical, electronic, capacity and inadequate stability. These limitations were addressed by
and ion transport properties of the SEI layer directly affect the battery combining SnO2 or SnSx nanostructures with carbonaceous materials
performance. Such observations are consistent with the previous reports to form hybrid or composite materials. The hybridization of Sn-based
regarding SEI formed on hard carbon anodes [208]. nanostructures and carbon has become the most common approach to
Aside from the electrolyte optimization discussed above, exploita- alleviating the large volume expansion and boosting up the electric
tion of ion-conducting hybrid coating and inert artificial layers are also conductivity, which commendably enhances the stability and the rate
considered to improve the properties of SEI layer formed on the surface capability of the electrode. Uniform encapsulation and distribution of
of negative electrode for SIBs. For example, Zhang et al. used SnS-SnS2 Sn-based nanostructures within the functionalized carbon shell or ma-
hybrid material to uniformly cover the surface of porous carbon elec- trix are often adopted for this strategy. Associated with the preparation
trode (AC@SnS-SnS2 ) to improve the initial Coulombic efficiency (ICE) of hybrid or composite nanomaterials, the formation of heterostructure
of SIBs (Fig. 12a) [235]. The group observed that the SEI layer was only is highly favorable to accelerating the overall charge-transfer kinetics,
formed on the SnS-SnS2 hybrid coating surface, which prevented the which can give higher rate capability. Aside from the combination of
direct contact of electrolyte to the inner pore surface of carbon and sup- single SnO2 or SnSx with carbon, the mixture of SnOx and SnSx , par-
pressed side reactions and maintained the electrochemically active sites ing of SnOx and metal oxides, and/or coupling of SnSx and metal sul-
of inner pores of carbon (Fig. 12b). In addition, the SnS-SnS2 hybrid fides, followed by the confinement within the carbon matrix have been
material not only contributed valuable capacitance (96 mAh g−1 ), but a trend for the formation of Sn-based heterostructures. Defect engineer-
also assisted the rapid desolvation and diffusion of Na+ -ions through the ing has also been acknowledged as a capable approach to provide more
coating layer. As a result, AC@SnS-SnS2 with a stable SEI layer formed active sites and ion storage sites to improve the insertion of Na ions.
37
Fig. 12. (a) Preparation of the ion-conducting SnS-SnS2 hybrid coating on the porous activated carbon (AC@SnS-SnS2 ) via facile oxidation of AC followed by
sulfidation. (b) Schematic illustration demonstrating how the ion-conducting SnS-SnS2 hybrid coating induced the formation of a stable SEI layer, which increased
the initial Coulombic efficiency of carbon-based anode. Reproduced with permission from ref. [235]. Copyright 2019 The Royal Society of Chemistry. Schematic
illustration of (c) formation of irregular growth of Na metal in between the rGO layers leading to broken SEI and (d) formation of stable SEI via the uniform Na
plating induced by NaF artificial SEI film. Reproduced with permission from ref. [236]. Copyright 2020 Elsevier B.V.
Heteroatom doping (N, P, S, B) into the carbon or metal lattice creates based material/carbon hybrid owning a yolk-shell nanostructure may
various lattice defects. Some of the most known defects are the oxygen consist of a hollow carbon shell and an inner Sn-based core/s. The
and sulfur vacancies, which regulate the electronic structure and the unique yolk-shell nanostructure is expected to improve the structural
reaction energy barrier of Sn-based nanostructure. stability and the rate capability of Sn-based anodes. The void space be-
The morphology manipulation method controls the specific surface tween the carbon shell and active Sn-based core allows minimal struc-
area and the porosity of Sn-based materials. Other than the standard tural damage and loss of active materials during the large volume expan-
1D, 2D, and 3D nanostructures, complex designs such as single or mul- sion associated with the sodiation/desodiation process. [74,237,238]
tiple yolk-shell nanostructures (rattle-like structures) are also possible More importantly, the protective carbon shells not only increase the
through careful morphology manipulation. In particular, a primary Sn- electric conductivity of the electrode but also serve as scaffold for SEI
38
Fig. 13. Summary of electrochemical performances of recent Sn-based anodes for SIBs according (a) type of electrode and (b) optimization strategies.
layer, thus isolating the core material from the electrolyte during cy- been considered as a crucial factor that controls the kinetics of the bat-
cling that helps reduce the detrimental electrolyte decomposition over tery systems and dictates the safety of the battery operation.
long cycles. To this point, the progress of SEI studies for Na ion batteries mainly
Fig. 13 displays the summary of the electrochemical performances include four major points: (1) identification of the interface compo-
of recent Sn-based anodes for SIBs. Based on the summary, we highlight nents, (2) evolution of SEI layer including thinness/thickness and sur-
the progress in the development of Sn-based anodes for SIBs and indi- face coverage, (3) optimization of the electrolyte composition, and (4)
cate the impact of the structural and composition optimization on bat- design guidelines for artificial SEI layer/film. The optimization of elec-
tery performance. We categorized Sn-based materials according to the trolyte composition evolved to the consideration of other types of elec-
type of electrode (Fig. 13a) and the optimization strategies (Fig. 13b). trolytes that can work for room-temperature SIBs. Ionic liquid-based
With respect to Coulombic efficiency, first charge capacity, and current electrolytes, aqueous liquid electrolytes coupled with abundant sodium
density, SnSx nanostructures hybridized with carbon materials and SnSx sources, solid electrolytes-like solid polymer and glass-ceramic elec-
composites consisting of Sn-based metal oxides and transition metal sul- trolytes, and gel-polymer electrolytes are the present selections for SIB
fides, respectively, have shown notable electrochemical performances. electrolytes. Moreover, the use of advanced nanoscale structural and
Although Sn-based metal oxides and metal sulfides can both accommo- chemical characterization tools such as cryogenic scanning transmis-
date Na ions through combined conversion and alloying reactions, it is sion electron microscopy (cryo-TEM), electron energy loss spectroscopy
important to note that Sn-based metal sulfides naturally own a flexible- (EELS) has become necessary, ion mass spectrometry (TOF-SIMS), and
layered nanostructure. This unique structure can provide multiple re- synchrotron radiation based on hard X-ray photoelectron spectroscopy
action sites for charge storage and facilitate the insertion-extraction of (HAXPES) and soft X-ray photoelectron spectroscopy (SOXPES) has be-
Na ions more efficiently. As a result, Sn-based metal sulfide anodes can come necessary [239]. These tools can identify the composition of SEI
consume a much higher theoretical capacity. Furthermore, assessing the and map the location and distribution of the interface components across
influence of the recent optimization strategies of Sn-based anodes to- the electrode surface. These advanced characterization techniques can
ward SIBs, the collective results show that the simultaneous efforts to provide new perspectives on the roles of SEI and its components.
modify the structure and composition of SnO2 or SnSx and their respec- In this review, we present the latest advances in this field, mainly
tive hybrid forms are more effective than their single counterparts. In focusing on the various strategies employed to manipulate the structure
particular, enhancing the structural stability and the rate capability of and composition of Sn-based anodes. The optimization strategies are
Sn-based materials by controlling the morphology and hybridizing with arranged articulately as an attempt to address the large volume expan-
carbon and/or other materials such as metal oxides or metal sulfides sion of Sn-based anodes and the formation of unstable SEI layer during
to form heterostructure, attain more remarkable results in terms of the long-term cycling process. Although the recent progress on Sn-based an-
number of cycles and the specific capacity. odes has demonstrated substantial improvement in their electrochemi-
However, based on the summary of electrochemical performances cal performance, there are still many tough challenges for future work.
with respect to the optimization strategies, it can be realized that al- Research on high-capacity Sn-based anodes for practical SIBs is still lim-
though there are noticeable improvements on the performances of modi- ited due to their sub-optimal physicochemical and electrical properties;
fied Sn-based anodes, much study needs to be conducted to unleash the hence, more efforts should be given on the development of Sn-based ma-
potential of these prominent materials fully. In line with this, efforts terials to maximize their distinct advantages. Material designs for practi-
to establish and understand the formation of stable and active solid- cal applications and reproducible-low-cost preparation methods are also
electrolyte interphase are highly necessary. As aforementioned, major- essential to realize the large-scale production of high-performance Sn-
ity of the recent studies on SIBs is merely focused on the investigation of based anodes. Finally, the assessment of suitability of Na ion batteries for
SEI on insertion-type anode material like hard carbon electrode. How- different high technology applications such as cellular phones, laptops,
ever, in the case of conversion-alloying materials like Sn-based anodes, electric vehicles, and other portable devices is stimulating and neces-
the accurate role/s of SEI is not yet fully understood. Because the re- sary, especially for the purpose of replacing LIBs in the future. We hope
peated formation of SEI can cover the entire electrode surface, it has that this review features the key turning points for the realization of the
practical applications of Na ion batteries using Sn-based anodes.
39
Declaration of Competing Interest [23] X. Meng, Atomic-scale surface modifications and novel electrode designs for high-
performance sodium-ion batteries via atomic layer deposition, J. Mater. Chem. A.
5 (2017) 10127–10149, doi:10.1039/c7ta02742g.
The authors declare that they have no known competing financial [24] H. Zhang, Y. Huang, H. Ming, G. Cao, W. Zhang, J. Ming, R. Chen, Recent advances
interests or personal relationships that could have appeared to influence in nanostructured carbon for sodium-ion batteries, J. Mater. Chem. A. 8 (2020)
the work reported in this paper. 1604–1630, doi:10.1039/c9ta09984k.
[25] W. Wang, W. Li, S. Wang, Z. Miao, H.K. Liu, S. Chou, Structural design of an-
ode materials for sodium-ion batteries, J. Mater. Chem. A. 6 (2018) 6183–6205,
Acknowledgements doi:10.1039/c7ta10823k.
[26] Y. Luo, Y. Tang, S. Zheng, Y. Yan, H. Xue, H. Pang, Dual anode materials
for lithium- and sodium-ion batteries, J. Mater. Chem. A. 6 (2018) 4236–4259,
This work was supported by National Research Foundation of Ko- doi:10.1039/c8ta00107c.
rea (NRF-2020R1A2B5B03002475 and NRF2019R1A6A1A11044070) [27] S. Fang, D. Bresser, S. Passerini, Transition metal oxide anodes for electrochemical
and the Hydrogen Energy Innovation Technology Development Pro- energy storage in lithium- and sodium-ion batteries, Adv. Energy Mater. 10 (2020),
doi:10.1002/aenm.201902485.
gram of the National Research Foundation of Korea funded by the [28] Z. Hu, Q. Liu, S.L. Chou, S.X. Dou, Advances and challenges in metal sul-
Korean government (Ministry of Science and ICT(MSIT)) (No. NRF- fides/selenides for next-generation rechargeable sodium-ion batteries, Adv. Mater.
2019M3E6A1064709). Y. Wang acknowledges the financial support 29 (2017) 1–24, doi:10.1002/adma.201700606.
[29] M.A. Kebede, Tin oxide-based anodes for both lithium-ion and
from the China Scholarship Council (CSC-201906430035). sodium-ion batteries, Curr. Opin. Electrochem. 21 (2020) 182–187,
doi:10.1016/j.coelec.2020.02.003.
References [30] Y. Mei, Y. Huang, X. Hu, Nanostructured Ti-based anode materials for Na-ion bat-
teries, J. Mater. Chem. A. 4 (2016) 12001–12013, doi:10.1039/c6ta04611h.
[1] C. Zhao, Y. Lu, Y. Li, L. Jiang, X. Rong, Y.-S. Hu, H. Li, L. Chen, Novel [31] T.H. Kim, J. Shin, K.S. Lee, E. Cho, Origin of the superior electrochemical per-
methods for sodium-ion battery materials, Small Methods 1 (2017) 1600063, formance of amorphous-phase conversion-reaction-based electrode materials for
doi:10.1002/smtd.201600063. Na-ion batteries: Formation of a bicontinuous metal network, ACS Appl. Mater.
[2] J. Wang, H. Tang, H. Wang, R. Yu, D. Wang, Multi-shelled hollow micro- Interfaces. 12 (2020) 22721–22729, doi:10.1021/acsami.9b22452.
/nanostructures: Promising platforms for lithium-ion batteries, Mater. Chem. Front. [32] D. Dixon, M. Ávila, H. Ehrenberg, A. Bhaskar, Difference in electrochemical mech-
1 (2017) 414–430, doi:10.1039/c6qm00273k. anism of SnO2 conversion in lithium-ion and sodium-ion batteries: Combined
[3] D. Aurbach, Y. Talyosef, B. Markovsky, E. Markevich, E. Zinigrad, L. Asraf, J.S. Gna- in operando and ex situ XAS investigations, ACS Omega 4 (2019) 9731–9738,
naraj, H.J. Kim, Design of electrolyte solutions for Li and Li-ion batteries: A review, doi:10.1021/acsomega.9b00563.
Electrochim. Acta. 50 (2004) 247–254, doi:10.1016/j.electacta.2004.01.090. [33] Y. Kim, K.H. Ha, S.M. Oh, K.T. Lee, High-capacity anode materials for sodium-ion
[4] D. Aurbach, Review of selected electrode-solution interactions which determine batteries, Chem. Eur. J. 20 (2014) 11980–11992, doi:10.1002/chem.201402511.
the performance of Li and Li ion batteries, J. Power Sources. 89 (2000) 206–218, [34] J. He, Y. Wei, T. Zhai, H. Li, Antimony-based materials as promising anodes for
doi:10.1016/S0378-7753(00)00431-6. rechargeable lithium-ion and sodium-ion batteries, Mater. Chem. Front. 2 (2018)
[5] M. Park, X. Zhang, M. Chung, G.B. Less, A.M. Sastry, A review of conduc- 437–455, doi:10.1039/c7qm00480j.
tion phenomena in Li-ion batteries, J. Power Sources. 195 (2010) 7904–7929, [35] H. Zhang, I. Hasa, S. Passerini, Beyond insertion for Na-ion batteries: Nanostruc-
doi:10.1016/j.jpowsour.2010.06.060. tured alloying and conversion anode materials, Adv. Energy Mater. 8 (2018),
[6] J. Zhang, J. Lee, A review on prognostics and health monitoring of Li-ion battery, doi:10.1002/aenm.201702582.
J. Power Sources. 196 (2011) 6007–6014, doi:10.1016/j.jpowsour.2011.03.101. [36] Z. Li, J. Ding, D. Mitlin, Tin and tin compounds for sodium ion battery anodes:
[7] S. Goriparti, E. Miele, F. De Angelis, E. Di Fabrizio, R. Proietti Zaccaria, C. Capiglia, Phase transformations and performance, Acc. Chem. Res. 48 (2015) 1657–1665,
Review on recent progress of nanostructured anode materials for Li-ion batteries, doi:10.1021/acs.accounts.5b00114.
J. Power Sources. 257 (2014) 421–443, doi:10.1016/j.jpowsour.2013.11.103. [37] H. Ying, W.Q. Han, Metallic Sn-based anode materials: Application in
[8] P.P.R.M.L. Harks, F.M. Mulder, P.H.L. Notten, In situ methods for Li-ion battery high-performance lithium-ion and sodium-ion batteries, Adv. Sci. 4 (2017),
research: A review of recent developments, J. Power Sources. 288 (2015) 92–105, doi:10.1002/advs.201700298.
doi:10.1016/j.jpowsour.2015.04.084. [38] D. Ma, Y. Li, P. Zhang, Z. Lin, Oxygen vacancy engineering in tin(IV) oxide based
[9] M.F. Oszajca, M.I. Bodnarchuk, M.V. Kovalenko, Precisely engineered colloidal anode materials toward advanced sodium-ion batteries, ChemSusChem 11 (2018)
nanoparticles and nanocrystals for Li-ion and Na-ion batteries: Model systems or 3693–3703, doi:10.1002/cssc.201801694.
practical solutions? Chem. Mater. 26 (2014) 5422–5432, doi:10.1021/cm5024508. [39] X. Huang, H. Wang, C. Niu, A.L. Rogach, SnO2 nanoarrays for energy storage and
[10] Y. Liu, X. Liu, T. Wang, L.Z. Fan, L. Jiao, Research and application progress on conversion, CrystEngComm 17 (2015) 5593–5604, doi:10.1039/c5ce00867k.
key materials for sodium-ion batteries, Sustain. Energy Fuels. 1 (2017) 986–1006, [40] D. Mohanta, M. Ahmaruzzaman, Tin oxide nanostructured materials: an overview
doi:10.1039/c7se00120g. of recent developments in synthesis, modifications and potential applications, RSC
[11] N. Yabuuchi, K. Kubota, M. Dahbi, S. Komaba, Research development on sodi- Adv 6 (2016) 110996–111015, doi:10.1039/C6RA21444D.
um-ion batteries, Chem. Rev. (2014). [41] M. Zhao, Q. Zhao, J. Qiu, H. Xue, H. Pang, Tin-based nanomaterials
[12] L. Chen, M. Fiore, J.E. Wang, R. Ruffo, D.K. Kim, G. Longoni, Readiness level of for electrochemical energy storage, RSC Adv 6 (2016) 95449–95468,
sodium-ion battery technology: A materials review, Adv. Sustain. Syst. 2 (2018) doi:10.1039/c6ra19877e.
1–37, doi:10.1002/adsu.201700153. [42] T. Li, U. Gulzar, X. Bai, M. Lenocini, M. Prato, K.E. Aifantis, C. Capiglia,
[13] H.G. Wang, S. Yuan, D.L. Ma, X.B. Zhang, J.M. Yan, Electrospun materi- R.Proietti Zaccaria, Insight on the failure mechanism of sn electrodes for sodium-
als for lithium and sodium rechargeable batteries: From structure evolution ion batteries: Evidence of pore formation during sodiation and crack formation
to electrochemical performance, Energy Environ. Sci. 8 (2015) 1660–1681, during desodiation, ACS Appl. Energy Mater. 2 (2019) 860–866, doi:10.1021/ac-
doi:10.1039/c4ee03912b. saem.8b01934.
[14] Y. Liu, Z. Sun, K. Tan, Di.K. Denis, J. Sun, L. Liang, L. Hou, C. Yuan, Recent progress [43] Y. Surace, F. Jeschull, T. Schott, S. Zürcher, M.E. Spahr, S. Trabesinger, Improving
in flexible non-lithium based rechargeable batteries, J. Mater. Chem. A. 7 (2019) the cycling stability of SnO2 -graphite electrodes, ACS Appl. Energy Mater. 2 (2019)
4353–4382, doi:10.1039/c8ta10258a. 7364–7374, doi:10.1021/acsaem.9b01344.
[15] J.Y. Hwang, S.T. Myung, Y.K. Sun, Sodium-ion batteries: Present and future, Chem. [44] M.Á. Muñoz-Márquez, D. Saurel, J.L. Gómez-Cámer, M. Casas-Cabanas, E. Castillo-
Soc. Rev. 46 (2017) 3529–3614, doi:10.1039/c6cs00776g. Martínez, T. Rojo, Na-ion batteries for large scale applications: A review on anode
[16] Z. Li, H. Zhao, Recent developments of phosphorus-based anodes for sodium ion materials and solid electrolyte interphase formation, Adv. Energy Mater. 7 (2017)
batteries, J. Mater. Chem. A. 6 (2018) 24013–24030, doi:10.1039/c8ta08774a. 1–31, doi:10.1002/aenm.201700463.
[17] Y. Zhao, L.P. Wang, M.T. Sougrati, Z. Feng, Y. Leconte, A. Fisher, M. Srinivasan, [45] H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X.Z. Liao, Z.F. Ma, Electrolyte design
Z. Xu, A review on design strategies for carbon based metal oxides and sulfides strategies and research progress for room-temperature sodium-ion batteries, Energy
nanocomposites for high performance Li and Na ion battery anodes, Adv. Energy Environ. Sci. 10 (2017) 1075–1101, doi:10.1039/c7ee00524e.
Mater. 7 (2017), doi:10.1002/aenm.201601424. [46] P. Verma, P. Maire, P. Novák, A review of the features and analyses of the solid
[18] L.P. Wang, L. Yu, M. Srinivasan, Z.J. Xu, X. Wang, Recent developments in elec- electrolyte interphase in Li-ion batteries, Electrochim. Acta. 55 (2010) 6332–6341,
trode materials for sodium-ion batteries, J. Mater. Chem. A. 3 (2015) 9353–9378, doi:10.1016/j.electacta.2010.05.072.
doi:10.1039/c4ta06467d. [47] W. Li, H. Wang, E. Matios, J. Luo, Combining theories and experiments to under-
[19] Y. Liang, W.H. Lai, Z. Miao, S.L. Chou, Nanocomposite materials for the sodium-ion stand the sodium nucleation behavior towards safe sodium metal batteries, Chem.
battery: A review, Small 14 (2018) 1–20, doi:10.1002/smll.201702514. Soc. Rev. 49 (2020) 3783–3805, doi:10.1039/d0cs00033g.
[20] F. Xie, L. Zhang, C. Ye, M. Jaroniec, S.Z. Qiao, The application of hollow structured [48] Q. Wang, C. Zhao, Y. Lu, Y. Li, Y. Zheng, Y. Qi, X. Rong, L. Jiang, X. Qi, Y. Shao,
anodes for sodium-ion batteries: From simple to complex systems, Adv. Mater. 31 D. Pan, B. Li, Y.S. Hu, L. Chen, Advanced nanostructured anode materials for
(2019) 1–8, doi:10.1002/adma.201800492. sodium-ion batteries, Small 13 (2017) 1–32, doi:10.1002/smll.201701835.
[21] J. Mao, T. Zhou, Y. Zheng, H. Gao, H.K. Liu, Z. Guo, Two-dimensional nanos- [49] G. Chang, Y. Zhao, L. Dong, D.P. Wilkinson, L. Zhang, Q. Shao, W. Yan,
tructures for sodium-ion battery anodes, J. Mater. Chem. A. 6 (2018) 3284–3303, X. Sun, J. Zhang, A review of phosphorus and phosphides as anode materi-
doi:10.1039/c7ta10500b. als for advanced sodium-ion batteries, J. Mater. Chem. A. 8 (2020) 4996–5048,
[22] N. Ortiz-Vitoriano, N.E. Drewett, E. Gonzalo, T. Rojo, High performance doi:10.1039/c9ta12169b.
manganese-based layered oxide cathodes: Overcoming the challenges of sodium ion [50] C. Zhu, P. Yang, D. Chao, W. Mai, H.J. Fan, Heterogeneous nanostructures for
batteries, Energy Environ. Sci. 10 (2017) 1051–1074, doi:10.1039/c7ee00566k.
40
sodium ion batteries and supercapacitors, ChemNanoMat 1 (2015) 458–476, F. Zhao, Y. Li, Engineering SnS2 nanosheet assemblies for enhanced electrochem-
doi:10.1002/cnma.201500091. ical lithium and sodium ion storage, J. Mater. Chem. A. 5 (2017) 25618–25624,
[51] H. Wang, A.L. Rogach, Hierarchical SnO2 nanostructures: Recent advances doi:10.1039/c7ta08056e.
in design, synthesis, and applications, Chem. Mater. 26 (2014) 123–133, [77] C. Gao, L. Li, A.R.O. Raji, A. Kovalchuk, Z. Peng, H. Fei, Y. He, N.D. Kim, Q. Zhong,
doi:10.1021/cm4018248. E. Xie, J.M. Tour, Tin disulfide nanoplates on graphene nanoribbons for full lithium
[52] Y.X. Wang, W.H. Lai, Y.X. Wang, S.L. Chou, X. Ai, H. Yang, Y. Cao, ion batteries, ACS Appl. Mater. Interfaces. 7 (2015) 26549–26556, doi:10.1021/ac-
Sulfur-based electrodes that function via multielectron reactions for room- sami.5b07768.
temperature sodium-ion storage, Angew. Chem. Int. Ed. 58 (2019) 18324–18337, [78] P. Zhou, X. Wang, W. Guan, D. Zhang, L. Fang, Y. Jiang, SnS2 nanowall arrays
doi:10.1002/anie.201902552. toward high-performance sodium storage, ACS Appl. Mater. Interfaces. 9 (2017)
[53] H. Kang, Y. Liu, K. Cao, Y. Zhao, L. Jiao, Y. Wang, H. Yuan, Update on an- 6979–6987, doi:10.1021/acsami.6b13613.
ode materials for Na-ion batteries, J. Mater. Chem. A. 3 (2015) 17899–17913, [79] G. Zhang, X. Xiao, B. Li, P. Gu, H. Xue, H. Pang, Transition metal oxides with
doi:10.1039/c5ta03181h. one-dimensional/one-dimensional-analogue nanostructures for advanced superca-
[54] D. Su, C. Wang, H. Ahn, G. Wang, Octahedral tin dioxide nanocrystals as high pacitors, J. Mater. Chem. A. 5 (2017) 8155–8186, doi:10.1039/c7ta02454a.
capacity anode materials for Na-ion batteries, Phys. Chem. Chem. Phys. 15 (2013) [80] X. Li, A. Dhanabalan, L. Gu, C. Wang, Three-dimensional porous core-shell
12543–12550, doi:10.1039/c3cp52037d. Sn@carbon composite anodes for high-performance lithium-ion battery applica-
[55] R.S. Kalubarme, J.Y. Lee, C.J. Park, Carbon encapsulated tin oxide nanocomposites: tions, Adv. Energy Mater. 2 (2012) 238–244, doi:10.1002/aenm.201100380.
An efficient anode for high performance sodium-ion batteries, ACS Appl. Mater. [81] C. Zhu, P. Kopold, W. Li, P.A. van Aken, J. Maier, Y. Yu, A general strategy to
Interfaces. 7 (2015) 17226–17237, doi:10.1021/acsami.5b04178. fabricate carbon-coated 3D porous interconnected metal sulfides: Case study of
[56] I.A. Courtney, J.R. Dahn, Electrochemical and in situ X-ray diffraction studies of SnS/C nanocomposite for high-performance lithium and sodium ion batteries, Adv.
the reaction of lithium with tin oxide composites, J. Electrochem. Soc. 144 (1997) Sci. 2 (2015) 1–8, doi:10.1002/advs.201500200.
2045–2052, doi:10.1149/1.1837740. [82] I.Y. Choi, C. Jo, W.G. Lim, J.C. Han, B.G. Chae, C.G. Park, J. Lee, J.K. Kim, Amor-
[57] R. Liu, N. Li, D. Li, G. Xia, Y. Zhu, S. Yu, C. Wang, Template-free synthesis of phous tin oxide nanohelix structure based electrode for highly reversible Na-ion
SnO2 hollow microspheres as anode material for lithium-ion battery, Mater. Lett. batteries, ACS Nano 13 (2019) 6513–6521, doi:10.1021/acsnano.8b09773.
73 (2012) 1–3, doi:10.1016/j.matlet.2011.12.035. [83] Y. Liu, X. Fang, M. Ge, J. Rong, C. Shen, A. Zhang, H.A. Enaya, C. Zhou, SnO2 coated
[58] M. Gu, A. Kushima, Y. Shao, J.G. Zhang, J. Liu, N.D. Browning, J. Li, C. Wang, carbon cloth with surface modification as Na-ion battery anode, Nano Energy 16
Probing the failure mechanism of SnO2 nanowires for sodium-ion batteries, Nano (2015) 399–407, doi:10.1016/j.nanoen.2015.07.010.
Lett 13 (2013) 5203–5211, doi:10.1021/nl402633n. [84] J. Yuan, Y. Hao, X. Zhang, X. Li, Sandwiched CNT@SnO2 @PPy nanocomposites
[59] Y. Shan, Y. Li, H. Pang, Applications of tin sulfide-based materials in lithium- enhancing sodium storage, Colloids Surfaces A Physicochem. Eng. Asp. 555 (2018)
ion batteries and sodium-ion batteries, Adv. Funct. Mater. 30 (2020) 1–31, 795–801, doi:10.1016/j.colsurfa.2018.07.023.
doi:10.1002/adfm.202001298. [85] C. Xia, F. Zhang, H. Liang, H.N. Alshareef, Layered SnS sodium ion battery
[60] Y. Han, G. Huang, S. Xu, Structural reorganization-based nanomaterials as anodes anodes synthesized near room temperature, Nano Res 10 (2017) 4368–4377,
for lithium-ion batteries: Design, preparation, and performance, Small 16 (2020) doi:10.1007/s12274-017-1722-0.
1–35, doi:10.1002/smll.201902841. [86] X. Li, C. Wang, Engineering nanostructured anodes via electrostatic spray depo-
[61] X. Xiong, C. Yang, G. Wang, Y. Lin, X. Ou, J.H. Wang, B. Zhao, M. Liu, Z. Lin, sition for high performance lithium ion battery application, J. Mater. Chem. A. 1
K. Huang, SnS nanoparticles electrostatically anchored on three-dimensional N- (2013) 165–182, doi:10.1039/c2ta00437b.
doped graphene as an active and durable anode for sodium-ion batteries, Energy [87] X.J. Zhu, Z.P. Guo, P. Zhang, G.D. Du, R. Zeng, Z.X. Chen, S. Li, H.K. Liu, Highly
Environ. Sci. 10 (2017) 1757–1763, doi:10.1039/c7ee01628j. porous reticular tin-cobalt oxide composite thin film anodes for lithium ion batter-
[62] M. Lao, Y. Zhang, W. Luo, Q. Yan, W. Sun, S.X. Dou, Alloy-based anode ma- ies, J. Mater. Chem. 19 (2009) 8360–8365, doi:10.1039/b913993a.
terials toward advanced sodium-ion batteries, Adv. Mater. 29 (2017) 1–23, [88] C. Zhu, X. Mu, P.A. Van Aken, J. Maier, Y. Yu, Fast Li storage in MoS2 -
doi:10.1002/adma.201700622. graphene-carbon nanotube nanocomposites: Advantageous functional integra-
[63] H. Tan, Y. Feng, X. Rui, Y. Yu, S. Huang, Metal chalcogenides: Paving the way for tion of 0D, 1D, and 2D nanostructures, Adv. Energy Mater. 5 (2015) 1–8,
high-performance sodium/potassium-ion batteries, Small Methods 4 (2020) 1–46, doi:10.1002/aenm.201401170.
doi:10.1002/smtd.201900563. [89] L. Chen, L. Andrea, Y.P. Timalsina, G.C. Wang, T.M. Lu, Engineering epitaxial-
[64] C. Ma, J. Xu, J. Alvarado, B. Qu, J. Somerville, J.Y. Lee, Y.S. Meng, Investigating the nanospiral metal films using dynamic oblique angle deposition, Cryst. Growth Des.
energy storage mechanism of SnS2 -rGO composite anode for advanced Na-ion bat- 13 (2013) 2075–2080, doi:10.1021/cg400142g.
teries, Chem. Mater. 27 (2015) 5633–5640, doi:10.1021/acs.chemmater.5b01984. [90] D. Ye, Partially ionized beam growth of tungsten oxide nanowires by
[65] Z. Wei, L. Wang, M. Zhuo, W. Ni, H. Wang, J. Ma, Layered tin sulfide and selenide oblique angle deposition, Cryst. Growth Des. 19 (2019) 2706–2711,
anode materials for Li- and Na-ion batteries, J. Mater. Chem. A. 6 (2018) 12185– doi:10.1021/acs.cgd.8b01827.
12214, doi:10.1039/c8ta02695e. [91] V. Kannan, A.I. Inamdar, S.M. Pawar, H.S. Kim, H.C. Park, H. Kim, H. Im, Y.S. Chae,
[66] T. Zhou, W.K. Pang, C. Zhang, J. Yang, Z. Chen, H.K. Liu, Z. Guo, En- Facile route to NiO nanostructured electrode grown by oblique angle deposition
hanced sodium-ion battery performance by structural phase transition from two- technique for supercapacitors, ACS Appl. Mater. Interfaces. 8 (2016) 17220–17225,
dimensional hexagonal-SnS2 to orthorhombic-SnS, ACS Nano 8 (2014) 8323–8333, doi:10.1021/acsami.6b03714.
doi:10.1021/nn503582c. [92] L. Zhang, J.H. Prosser, G. Feng, D. Lee, Mechanical properties of atomic layer
[67] Y.J. Cho, H.S. Im, H.S. Kim, Y. Myung, S.H. Back, Y.R. Lim, C.S. Jung, D.M. Jang, deposition-reinforced nanoparticle thin films, Nanoscale 4 (2012) 6543–6552,
J. Park, E.H. Cha, W. Il Cho, F. Shojaei, H.S. Kang, Tetragonal phase germa- doi:10.1039/c2nr32016a.
nium nanocrystals in lithium ion batteries, ACS Nano 7 (2013) 9075–9084, [93] X. Han, Y. Liu, Z. Jia, Y.C. Chen, J. Wan, N. Weadock, K.J. Gaskell, T. Li, L. Hu,
doi:10.1021/nn403674z. Atomic-layer-deposition oxide nanoglue for sodium ion batteries, Nano Lett 14
[68] H.S. Im, Y.J. Cho, Y.R. Lim, C.S. Jung, D.M. Jang, J. Park, F. Shojaei, H.S. Kang, (2014) 139–147, doi:10.1021/nl4035626.
Phase evolution of tin nanocrystals in lithium ion batteries, ACS Nano 7 (2013) [94] N. Yesibolati, M. Shahid, W. Chen, M.N. Hedhili, M.C. Reuter, F.M. Ross,
11103–11111, doi:10.1021/nn404837d. H.N. Alshareef, SnO2 anode surface passivation by atomic layer deposited
[69] Y. Zheng, T. Zhou, C. Zhang, J. Mao, H. Liu, Z. Guo, Boosted charge transfer in HfO2 improves li-ion battery performance, Small 10 (2014) 2849–2858,
SnS/SnO2 heterostructures: Toward high rate capability for sodium-ion batteries, doi:10.1002/smll.201303898.
Angew. Chem. Int. Ed. 128 (2016) 3469–3474, doi:10.1002/ange.201510978. [95] W. Ren, W. Zhou, H. Zhang, C. Cheng, ALD TiO2 -coated flower-like MoS2
[70] G.K. Veerasubramani, M.S. Park, J.Y. Choi, D.W. Kim, Ultrasmall SnS quantum nanosheets on carbon cloth as sodium ion battery anode with enhanced cycling
dots anchored onto nitrogen-enriched carbon nanospheres as an advanced anode stability and rate capability, ACS Appl. Mater. Interfaces. 9 (2017) 487–495,
material for sodium-ion batteries, ACS Appl. Mater. Interfaces. 12 (2020) 7114– doi:10.1021/acsami.6b13179.
7124, doi:10.1021/acsami.9b18997. [96] W. Ren, H. Zhang, C. Guan, C. Cheng, SnS2 nanosheets arrays sandwiched by N-
[71] Y. Yang, Z.Z. Pan, Y.Y. Wang, Y.C. Ma, C. Li, Y.J. Lu, X.L. Wu, Ionic-liquid- doped carbon and TiO2 for high-performance Na-ion storage, Green Energy Environ
bifunctional wrapping of ultrafine SnO2 nanocrystals into N-doped graphene net- 3 (2018) 42–49, doi:10.1016/j.gee.2017.09.005.
works: High pseudocapacitive sodium storage and high-performance sodium-ion [97] H. Zhang, W. Ren, C. Cheng, Three-dimensional SnO2 @TiO2 double-shell nan-
full cells, Nanoscale 11 (2019) 14616–14624, doi:10.1039/c9nr02542a. otubes on carbon cloth as a flexible anode for lithium-ion batteries, Nanotechnol-
[72] T.H.T. Luu, D.L. Duong, T.H. Lee, D.T. Pham, R. Sahoo, G. Han, Y.M. Kim, ogy 26 (2015) 274002, doi:10.1088/0957-4484/26/27/274002.
Y.H. Lee, Monodispersed SnS nanoparticles anchored on carbon nanotubes for [98] A. Yourdkhani, D. Caruntu, M. Vopson, G. Caruntu, 1D core-shell magnetoelectric
high-retention sodium-ion batteries, J. Mater. Chem. A. 8 (2020) 7861–7869, nanocomposites by template-assisted liquid phase deposition, CrystEngComm 19
doi:10.1039/c9ta13136a. (2017) 2079–2088, doi:10.1039/c7ce00101k.
[73] X. Xu, R. Zhao, B. Chen, L. Wu, C. Zou, W. Ai, H. Zhang, W. Huang, T. Yu, [99] P. Roy, J.R. Ota, S.K. Srivastava, Crystalline ZnS thin films by chemical bath de-
Progressively Exposing Active Facets of 2D Nanosheets toward enhanced pseu- position method and its characterization, Thin Solid Films 515 (2006) 1912–1917,
docapacitive response and high-rate sodium storage, Adv. Mater. 31 (2019) 1–8, doi:10.1016/j.tsf.2006.07.035.
doi:10.1002/adma.201900526. [100] B.J. Plowman, S.K. Bhargava, A.P. O’Mullane, Electrochemical fabrication of metal-
[74] Y. Wang, Y. Zhang, J. Shi, A. Pan, F. Jiang, S. Liang, G. Cao, S-doped porous carbon lic nanostructured electrodes for electroanalytical applications, Analyst 136 (2011)
confined SnS nanospheres with enhanced electrochemical performance for sodium- 5107–5119, doi:10.1039/c1an15657h.
ion batteries, J. Mater. Chem. A. 6 (2018) 18286–18292, doi:10.1039/c8ta06106h. [101] S.C.S. Lai, R.A. Lazenby, P.M. Kirkman, P.R. Unwin, Nucleation, aggregative
[75] L. Shi, D. Li, P. Yao, J. Yu, C. Li, B. Yang, C. Zhu, J. Xu, SnS2 nanosheets coating growth and detachment of metal nanoparticles during electrodeposition at elec-
on nanohollow cubic CoS2 /C for ultralong life and high rate capability half/full trode surfaces, Chem. Sci. 6 (2015) 1126–1138, doi:10.1039/c4sc02792b.
sodium-ion batteries, Small 14 (2018) 1–9, doi:10.1002/smll.201802716. [102] Z. Yan, H. Liu, Z. Hao, M. Yu, X. Chen, J. Chen, Electrodeposition of (hy-
[76] Y. Wang, J. Zhou, J. Wu, F. Chen, P. Li, N. Han, W. Huang, Y. Liu, H. Ye,
41
dro)oxides for an oxygen evolution electrode, Chem. Sci. 11 (2020) 10614–10625, kinetic properties for anodic use in next-generation sodium rechargeable batteries,
doi:10.1039/d0sc01532f. Small 12 (2016) 2510–2517, doi:10.1002/smll.201503168.
[103] M. Dirican, Y. Lu, Y. Ge, O. Yildiz, X. Zhang, Carbon-confined SnO2 - [127] Q. Peng, S. Zhang, H. Yang, B. Sheng, R. Xu, Q. Wang, Y. Yu, Boosting potassium
electrodeposited porous carbon nanofiber composite as high-capacity sodium-ion storage performance of the Cu2 S anode via morphology engineering and electrolyte
battery anode material, ACS Appl. Mater. Interfaces. 7 (2015) 18387–18396, chemistry, ACS Nano 14 (2020) 6024–6033, doi:10.1021/acsnano.0c01681.
doi:10.1021/acsami.5b04338. [128] S. Xiong, H.C. Zeng, Serial ionic exchange for the synthesis of multishelled
[104] A. Palacios-Padrós, M. Altomare, A. Tighineanu, R. Kirchgeorg, N.K. Shrestha, copper sulfide hollow spheres, Angew. Chem. Int. Ed. 51 (2012) 949–952,
I. Díez-Pérez, F. Caballero-Briones, F. Sanz, P. Schmuki, Growth of ordered an- doi:10.1002/anie.201106826.
odic SnO2 nanochannel layers and their use for H2 gas sensing, J. Mater. Chem. A. [129] Q. Tang, Y. Cui, J. Wu, D. Qu, A.P. Baker, Y. Ma, X. Song, Y. Liu, Nano Energy per-
2 (2014) 915–920, doi:10.1039/c3ta13704j. formance anode for lithium-ion and sodium-ion batteries, Nano Energy 41 (2017)
[105] A. Palacios-Padrós, M. Altomare, K. Lee, I. Díez-Pérez, F. Sanz, P. Schmuki, 377–386, doi:10.1016/j.nanoen.2017.09.052.
Controlled thermal annealing tunes the photoelectrochemical properties of [130] D. Chao, B. Ouyang, P. Liang, T.T.T. Huong, G. Jia, H. Huang, X. Xia,
nanochanneled tin-oxide structures, ChemElectroChem 1 (2014) 1133–1137, R.S. Rawat, H.J. Fan, C-plasma of hierarchical graphene survives SnS bundles
doi:10.1002/celc.201402002. for ultrastable and high volumetric Na-ion storage, Adv. Mater. 30 (2018) 1–6,
[106] H. Bian, Z. Li, X. Xiao, P. Schmuki, J. Lu, Y.Y. Li, Anodic synthesis of hierarchical doi:10.1002/adma.201804833.
SnS/SnOx hollow nanospheres and their application for high-performance Na-ion [131] S. Mukherjee, N. Schuppert, A. Bates, J. Jasinski, J.E. Hong, M.J. Choi,
batteries, Adv. Funct. Mater. 29 (2019) 1–9, doi:10.1002/adfm.201901000. S. Park, An electrochemical and structural study of highly uniform tin ox-
[107] H. Bian, X. Xiao, S. Zeng, M.F. Yuen, Z. Li, W. Kang, D.Y.W. Yu, Z. Xu, J. Lu, Y.Y. Li, ide nanowires fabricated by a novel, scalable solvoplasma technique as an-
Mesoporous C-coated SnOx nanosheets on copper foil as flexible and binder-free ode material for sodium ion batteries, J. Power Sources. 347 (2017) 201–209,
anodes for superior sodium-ion batteries, J. Mater. Chem. A. 5 (2017) 2243–2250, doi:10.1016/j.jpowsour.2017.02.060.
doi:10.1039/c6ta09720k. [132] L. Fan, X. Li, B. Yan, J. Feng, D. Xiong, D. Li, L. Gu, Y. Wen, S. Lawes, X. Sun,
[108] P. Xue, N. Wang, Y. Wang, Y. Zhang, Y. Liu, B. Tang, Z. Bai, S. Dou, Controlled SnO2 crystallinity effectively dominating sodium storage performance,
Nanoconfined SnS in 3D interconnected macroporous carbon as durable Adv. Energy Mater. 6 (2016) 1–13, doi:10.1002/aenm.201502057.
anodes for lithium/sodium ion batteries, Carbon 134 (2018) 222–231. [133] Y. Liu, Y. Yang, X. Wang, Y. Dong, Y. Tang, Z. Yu, Z. Zhao, J. Qiu, Flexible paper-
doi:10.1016/j.carbon.2018.04.003. like free-standing electrodes by anchoring ultrafine SnS2 nanocrystals on graphene
[109] S. Zhang, H. Zhao, L. Yue, Z. Wang, J. Mi, Fixed-bed assisted synthesis nanoribbons for high-performance sodium ion batteries, ACS Appl. Mater. Inter-
SnO2 /SnS2 /CNTs composite for enhanced sodium storage performance, J. Alloys faces. 9 (2017) 15484–15491, doi:10.1021/acsami.7b02394.
Compd. 717 (2017) 127–135, doi:10.1016/j.jallcom.2017.05.055. [134] J. Cui, Z.L. Xu, S. Yao, J. Huang, J.Q. Huang, S. Abouali, M.A. Garakani,
[110] S. Tao, D. Wu, S. Chen, B. Qian, W. Chu, L. Song, A versatile strategy for ultrathin X. Ning, J.K. Kim, Enhanced conversion reaction kinetics in low crystallinity
SnS2 nanosheets confined in a N-doped graphene sheet composite for high perfor- SnO2 /CNT anodes for Na-ion batteries, J. Mater. Chem. A. 4 (2016) 10964–10973,
mance lithium and sodium-ion batteries, Chem. Commun. 54 (2018) 8379–8382, doi:10.1039/c6ta03541h.
doi:10.1039/c8cc04255a. [135] Y.N. Sun, M. Goktas, L. Zhao, P. Adelhelm, B.H. Han, Ultrafine SnO2 nanopar-
[111] J. Niu, J. Liang, A. Gao, M. Dou, Z. Zhang, X. Lu, F. Wang, Micropore-confined ticles anchored on N, P-doped porous carbon as anodes for high performance
amorphous SnO2 subnanoclusters as robust anode materials for Na-ion capacitors, lithium-ion and sodium-ion batteries, J. Colloid Interface Sci. 572 (2020) 122–132,
J. Mater. Chem. A. 7 (2019) 21711–21721, doi:10.1039/c9ta06964j. doi:10.1016/j.jcis.2020.03.063.
[112] X. Yang, F. Xiao, S. Wang, J. Liu, M.K.H. Leung, D.Y.W. Yu, A.L. Rogach, Confined [136] Z. Zhao, H. Su, S. Li, C. Li, Z. Liu, D. Li, Ball-in-ball structured SnO2 @FeOOH@C
annealing-induced transformation of tin oxide into sulfide for sodium storage ap- nanospheres toward advanced anode material for sodium ion batteries, J. Alloys
plications, J. Mater. Chem. A. 7 (2019) 11877–11885, doi:10.1039/c9ta02660f. Compd. 838 (2020) 155394, doi:10.1016/j.jallcom.2020.155394.
[113] D. Ma, Y. Li, H. Mi, S. Luo, P. Zhang, Z. Lin, J. Li, H. Zhang, Robust SnO2-x [137] J. Yuan, Y. Hao, X. Zhang, X. Li, Sandwiched CNT@SnO2 @PPy nanocomposites
nanoparticle-impregnated carbon nanofibers with outstanding electrochemical per- enhancing sodium storage, Colloids Surfaces A Physicochem. Eng. Asp. 555 (2018)
formance for advanced sodium-ion batteries, Angew. Chem. Int. Ed. 57 (2018) 795–801, doi:10.1016/j.colsurfa.2018.07.023.
8901–8905, doi:10.1002/anie.201802672. [138] C. Ma, J. Jiang, Y. Han, X. Gong, Y. Yang, G. Yang, The composite of carbon nan-
[114] W. Zhang, P. Cao, L. Li, K. Yang, K. Wang, S. Liu, Z. Yu, Carbon-encapsulated otube connecting SnO2 /reduced graphene clusters as highly reversible anode mate-
1D SnO2 /NiO heterojunction hollow nanotubes as high-performance rial for lithium-/sodium-ion batteries and full cell, Compos. Part B Eng. 169 (2019)
anodes for sodium-ion batteries, Chem. Eng. J. 348 (2018) 599–607, 109–117, doi:10.1016/j.compositesb.2019.04.011.
doi:10.1016/j.cej.2018.05.024. [139] F.O. Agyemang, G.M. Tomboc, S. Kwofie, H. Kim, Electrospun carbon nanofiber-
[115] J. Xia, K. Jiang, J. Xie, S. Guo, L. Liu, Y. Zhang, S. Nie, Y. Yuan, H. Yan, carbon nanotubes coated polyaniline composites with improved electrochemi-
X. Wang, Tin disulfide embedded in N-, S-doped carbon nanofibers as an- cal properties for supercapacitors, Electrochim. Acta. 259 (2018) 1110–1119,
ode material for sodium-ion batteries, Chem. Eng. J. 359 (2019) 1244–1251, doi:10.1016/j.electacta.2017.12.079.
doi:10.1016/j.cej.2018.11.053. [140] G.M. Tomboc, B. Tesfaye Gadisa, M. Jun, N.K. Chaudhari, H. Kim, K. Lee, Carbon
[116] H. Yan, M. Yang, L. Liu, J. Xia, Y. Yuan, J. Liu, Y. Zhang, S. Nie, X. Wang, Syn- transition-metal oxide electrodes: Understanding the role of surface engineering for
thesis of SnS/C nanofibers membrane as self-standing anode for high-performance high energy density supercapacitors, Chem. - An Asian J. 15 (2020) 1628–1647,
sodium-ion batteries by a smart process, J. Alloys Compd. 843 (2020) 155899, doi:10.1002/asia.202000324.
doi:10.1016/j.jallcom.2020.155899. [141] S. Li, Z. Zhao, C. Li, Z. Liu, D. Li, SnS2 @C Hollow Nanospheres with Robust Struc-
[117] R. Thangavel, A. Samuthira Pandian, H.V. Ramasamy, Y.S. Lee, Rapidly Syn- tural Stability as High-Performance Anodes for Sodium Ion Batteries, Nano-Micro
thesized, Few-Layered Pseudocapacitive SnS2 Anode for High-Power Sodium Ion Lett. 11 (2019) 1–9, doi:10.1007/s40820-019-0243-7.
Batteries, ACS Appl. Mater. Interfaces 9 (2017) 40187–40196, doi:10.1021/ac- [142] A. Jahel, C.M. Ghimbeu, A. Darwiche, L. Vidal, S. Hajjar-Garreau, C. Vix-Guterl,
sami.7b11040. L. Monconduit, Exceptionally highly performing Na-ion battery anode using crys-
[118] B. Dursun, E. Topac, R. Alibeyli, A. Ata, O. Ozturk, R. Demir-Cakan, Fast talline SnO2 nanoparticles confined in mesoporous carbon, J. Mater. Chem. A. 3
microwave synthesis of SnO2 @graphene/N-doped carbons as anode mate- (2015) 11960–11969, doi:10.1039/c5ta01963j.
rials in sodium ion batteries, J. Alloys Compd. 728 (2017) 1305–1314, [143] J. Ding, Z. Li, H. Wang, K. Cui, A. Kohandehghan, X. Tan, D. Karpuzov,
doi:10.1016/j.jallcom.2017.09.081. D. Mitlin, Sodiation vs. lithiation phase transformations in a high rate-high sta-
[119] H. Lai, B. Feng, Y. Jiang, N. Shi, C. Liang, S. Chang, S. Guo, B. Cui, H. Cao, Fabrica- bility SnO2 in carbon nanocomposite, J. Mater. Chem. A. 3 (2015) 7101–7111,
tion of graphene supported SnO2 nanoparticles and their sodium storage properties, doi:10.1039/c5ta00399g.
Mater. Lett. 166 (2016) 292–295, doi:10.1016/j.matlet.2015.12.075. [144] Y. Jiang, M. Wei, J. Feng, Y. Ma, S. Xiong, Enhancing the cycling sta-
[120] V. Sridhar, H. Park, Hollow SnO2 @carbon core-shell spheres stabilized on re- bility of Na-ion batteries by bonding SnS2 ultrafine nanocrystals on amino-
duced graphene oxide for high-performance sodium-ion batteries, New J. Chem. functionalized graphene hybrid nanosheets, Energy Environ. Sci. 9 (2016) 1430–
41 (2017) 442–446, doi:10.1039/c6nj03212e. 1438, doi:10.1039/c5ee03262h.
[121] X. Lu, T. Yang, Q. Xiong, X. Hu, J. Guo, Z. Ji, Constructing hierarchi- [145] T. Kwon, M. Jun, J. Joo, K. Lee, Nanoscale hetero-interfaces between metals and
cal cobalt doped SnO2 /carbon cluster as high reversible and high capac- metal compounds for electrocatalytic applications, J. Mater. Chem. A. 7 (2019)
ity anodes for sodium storage, J. Electroanal. Chem. 848 (2019) 113327, 5090–5110, doi:10.1039/c8ta09494b.
doi:10.1016/j.jelechem.2019.113327. [146] J. Joo, T. Kim, J. Lee, S. Il Choi, K. Lee, Morphology-controlled metal sulfides
[122] P. Ragupathy, S. Shivakumara, H.N. Vasan, N. Munichandraiah, Preparation of and phosphides for electrochemical water splitting, Adv. Mater. 31 (2019) 1–23,
nanostrip V2 O5 by the polyol method and its electrochemical characterization as doi:10.1002/adma.201806682.
cathode material for rechargeable lithium batteries, J. Phys. Chem. C. 112 (2008) [147] S. Huang, M. Wang, P. Jia, B. Wang, J. Zhang, Y. Zhao, N-graphene
16700–16707, doi:10.1021/jp804182z. motivated SnO2 @SnS2 heterostructure quantum dots for high perfor-
[123] X. Jiang, T. Herricks, Y. Xia, Monodispersed spherical colloids of titania: Syn- mance lithium/sodium storage, Energy Storage Mater 20 (2019) 225–233,
thesis, characterization, and crystallization, Adv. Mater. 15 (2003) 1205–1209, doi:10.1016/j.ensm.2018.11.024.
doi:10.1002/adma.200305105. [148] K. Wang, Y. Huang, X. Qin, M. Wang, X. Sun, M. Yu, Synthesis of hollow SnO2/SnS2
[124] X. Jiang, Y. Wang, T. Herricks, Y. Xia, Ethylene glycol-mediated synthesis of metal hybrids and their application in sodium-ion batteries, ChemElectroChem. 4 (2017)
oxide nanowires, J. Mater. Chem. (2004) 695–703, doi:10.1039/b313938g. 2308–2313. https://doi.org/10.1002/celc.201700309.
[125] Y. Zhu, P. Nie, L. Shen, S. Dong, Q. Sheng, H. Li, H. Luo, X. Zhang, High rate [149] X. Wang, X. Li, Q. Li, H. Li, J. Xu, H. Wang, G. Zhao, L. Lu, X. Lin, H. Li,
capability and superior cycle stability of a flower-like Sb2 S3 anode for high-capacity S. Li, Improved electrochemical performance based on nanostructured SnS2 @CoS2 -
sodium ion batteries, Nanoscale 7 (2015) 3309–3315, doi:10.1039/c4nr05242k. rGO composite anode for sodium-ion batteries, Nano-Micro Lett 10 (2018) 1–12,
[126] E. Cho, K. Song, M.H. Park, K.W. Nam, Y.M. Kang, SnS 3D flowers with fuperb doi:10.1007/s40820-018-0200-x.
42
[150] Y.Q. Wu, H.X. Yang, Y. Yang, H. Pu, W.J. Meng, R.Z. Gao, D.L. Zhao, SnS2/Co3S4 nanoparticles as emerging electrocatalysts for renewable energy conversion reac-
hollow nanocubes anchored on S-doped graphene for ultrafast and stable Na-ion tions, Chem. Soc. Rev. 47 (2018) 8173–8202, doi:10.1039/c8cs00336j.
storage, Small. 15 (2019) 1–9. https://doi.org/10.1002/smll.201903873. [174] Y. Wang, X. Xiao, Q. Li, H. Pang, Synthesis and progress of new oxygen-vacant
[151] L. Cao, B. Zhang, X. Ou, C. Wang, C. Peng, J. Zhang, Synergistical coupling electrode materials for high-energy rechargeable battery applications, Small 14
interconnected ZnS/SnS2 nanoboxes with polypyrrole-derived N/S dual-doped (2018) 1–23, doi:10.1002/smll.201802193.
carbon for boosting high-performance sodium storage, Small 15 (2019) 1–11, [175] Y. Zhang, L. Tao, C. Xie, D. Wang, Y. Zou, R. Chen, Y. Wang, C. Jia, S. Wang,
doi:10.1002/smll.201804861. Defect engineering on electrode materials for rechargeable batteries, Adv. Mater.
[152] X. Ou, L. Cao, X. Liang, F. Zheng, H.S. Zheng, X. Yang, J.H. Wang, C. Yang, 32 (2020) 1–22, doi:10.1002/adma.201905923.
M. Liu, Fabrication of SnS2 /Mn2 SnS4 /carbon heterostructures for sodium-ion bat- [176] Y. Zhang, Z. Ding, C.W. Foster, C.E. Banks, X. Qiu, X. Ji, Oxygen vacancies evoked
teries with high initial coulombic efficiency and cycling stability, ACS Nano 13 blue TiO2 (B) nanobelts with efficiency enhancement in sodium storage behaviors,
(2019) 3666–3676, doi:10.1021/acsnano.9b00375. Adv. Funct. Mater. 27 (2017) 1–12, doi:10.1002/adfm.201700856.
[153] T.H.T. Luu, D.L. Duong, T.H. Lee, D.T. Pham, R. Sahoo, G. Han, Y.M. Kim, [177] S. Choi, Y. Park, H. Yang, H. Jin, G.M. Tomboc, K. Lee, Vacancy-
Y.H. Lee, Monodispersed SnS nanoparticles anchored on carbon nanotubes for engineered catalysts for water electrolysis, CrystEngComm 22 (2020) 1500–1513,
high-retention sodium-ion batteries, J. Mater. Chem. A. 8 (2020) 7861–7869, doi:10.1039/c9ce01883b.
doi:10.1039/c9ta13136a. [178] J. Liang, Z. Wei, C. Wang, J. Ma, Vacancy-induced sodium-ion storage in N-doped
[154] J. Patra, H.C. Chen, C.H. Yang, C. Te Hsieh, C.Y. Su, J.K. Chang, High dispersion carbon Nanofiber@MoS2 nanosheet arrays, Electrochim. Acta. 285 (2018) 301–
of 1-nm SnO2 particles between graphene nanosheets constructed using supercrit- 308, doi:10.1016/j.electacta.2018.07.230.
ical CO2 fluid for sodium-ion battery anodes, Nano Energy 28 (2016) 124–134, [179] Y. Zhu, G. Yu, Engineering surface vacancy to stabilize high-voltage battery cath-
doi:10.1016/j.nanoen.2016.08.044. odes, Chem 4 (2018) 1486–1487, doi:10.1016/j.chempr.2018.06.012.
[155] F. Li, G. Luo, W. Chen, Y. Chen, Y. Fang, M. Zheng, X. Yu, Rational design and con- [180] Y. Huang, Z. Wang, Y. Jiang, S. Li, Z. Li, H. Zhang, F. Wu, M. Xie, L. Li, R. Chen,
trollable synthesis of multishelled Fe2 O3 @SnO2 @C nanotubes as advanced anode Hierarchical porous Co0.85 Se@reduced graphene oxide ultrathin nanosheets with
material for lithium-/sodium-ion batteries, ACS Appl. Mater. Interfaces. 11 (2019) vacancy-enhanced kinetics as superior anodes for sodium-ion batteries, Nano En-
37295–37301, doi:10.1021/acsami.9b12012. ergy 53 (2018) 524–535, doi:10.1016/j.nanoen.2018.09.010.
[156] Y.X. Wang, Y.G. Lim, M.S. Park, S.L. Chou, J.H. Kim, H.K. Liu, S.X. Dou, Y.J. Kim, [181] J. Wang, J. Huang, S. Huang, H. Notohara, K. Urita, I. Moriguchi, M. Wei, Rational
Ultrafine SnO2 nanoparticle loading onto reduced graphene oxide as anodes for design of hierarchical SnS2 microspheres with S vacancy for enhanced sodium stor-
sodium-ion batteries with superior rate and cycling performances, J. Mater. Chem. age performance, ACS Sustain. Chem. Eng. 8 (2020) 9519–9525, doi:10.1021/ac-
A. 2 (2014) 529–534, doi:10.1039/c3ta13592f. ssuschemeng.0c02535.
[157] J. Sheng, L. Yang, Y.E. Zhu, F. Li, Y. Zhang, Z. Zhou, Oriented SnS nanoflakes bound [182] L. Fan, X. Li, X. Song, N. Hu, D. Xiong, A. Koo, X. Sun, Promising dual-
on S-doped N-rich carbon nanosheets with a rapid pseudocapacitive response as doped graphene aerogel/SnS2 nanocrystal building high performance sodium ion
high-rate anodes for sodium-ion batteries, J. Mater. Chem. A. 5 (2017) 19745– batteries, ACS Appl. Mater. Interfaces. 10 (2018) 2637–2648, doi:10.1021/ac-
19751, doi:10.1039/c7ta06577a. sami.7b18195.
[158] D. Chao, C. Zhu, P. Yang, X. Xia, J. Liu, J. Wang, X. Fan, S.V. Savilov, J. Lin, [183] T. Kwon, M. Jun, G.J. Bang, H. Yang, J. Joo, T. Kim, J. Kim, J.M. Kim, H. Baik,
H.J. Fan, Z.X. Shen, Array of nanosheets render ultrafast and high-capacity Y. Jung, J.Y. Kim, K. Lee, Dopant-assisted control of the crystallite domain size in
Na-ion storage by tunable pseudocapacitance, Nat. Commun. 7 (2016) 1–8, hollow ternary iridium alloy octahedral nanocages toward the oxygen evolution re-
doi:10.1038/ncomms12122. action, Cell Reports Phys. Sci. 1 (2020) 100260, doi:10.1016/j.xcrp.2020.100260.
[159] W. Sun, X. Rui, D. Yang, Z. Sun, B. Li, W. Zhang, Y. Zong, S. Madhavi, S. Dou, [184] L. Wang, Q. Zhao, Z. Wang, Y. Wu, X. Ma, Y. Zhu, C. Cao, Cobalt-doping SnS2
Q. Yan, Two-dimensional tin disulfide nanosheets for enhanced sodium storage, nanosheets towards high-performance anodes for sodium ion batteries, Nanoscale
ACS Nano 9 (2015) 11371–11381, doi:10.1021/acsnano.5b05229. 12 (2020) 248–255, doi:10.1039/c9nr07849e.
[160] F. Zhang, J. Zhu, D. Zhang, U. Schwingenschlögl, H.N. Alshareef, Two-dimensional [185] C. Cui, H. Wang, M. Wang, X. Ou, Z. Wei, J. Ma, Y. Tang, Hollow
SnO anodes with a tunable number of atomic layers for sodium ion batteries, Nano carbon nanobelts codoped with nitrogen and sulfur via a self-templated
Lett 17 (2017) 1302–1311, doi:10.1021/acs.nanolett.6b05280. method for a high-performance sodium-ion capacitor, Small 15 (2019) 1–7,
[161] Y. Zhang, P. Zhu, L. Huang, J. Xie, S. Zhang, G. Cao, X. Zhao, Few-layered SnS2 doi:10.1002/smll.201902659.
on few-layered reduced graphene oxide as Na-ion battery anode with ultralong [186] W. Yang, J. Zhou, S. Wang, W. Zhang, Z. Wang, F. Lv, K. Wang, Q. Sun, S. Guo,
cycle life and superior rate capability, Adv. Funct. Mater. 25 (2015) 481–489, Freestanding film made by necklace-like N-doped hollow carbon with hierarchical
doi:10.1002/adfm.201402833. pores for high-performance potassium-ion storage, Energy Environ. Sci. 12 (2019)
[162] P. Zhai, J. Qin, L. Guo, N. Zhao, C. Shi, E.Z. Liu, F. He, L. Ma, J. Li, C. He, Smart hy- 1605–1612, doi:10.1039/c9ee00536f.
bridization of Sn2 Nb2 O7 /SnO2 @3D carbon nanocomposites with enhanced sodium [187] S. Chen, K. Xing, J. Wen, M. Wen, Q. Wu, Y. Cui, Hierarchical assembly and superior
storage performance through self-buffering effects, J. Mater. Chem. A. 5 (2017) sodium storage properties of a sea-sponge structured C/SnS@C nanocomposite, J.
13052–13061, doi:10.1039/c7ta03021e. Mater. Chem. A. 6 (2018) 7631–7638, doi:10.1039/c8ta00833g.
[163] X. Zhao, M. Luo, W. Zhao, R. Xu, Y. Liu, H. Shen, SnO2 nanosheets anchored [188] X. Xie, D. Su, J. Zhang, S. Chen, A.K. Mondal, G. Wang, A comparative investigation
on a 3D, bicontinuous electron and ion transport carbon network for high- on the effects of nitrogen-doping into graphene on enhancing the electrochemical
performance sodium-ion batteries, ACS Appl. Mater. Interfaces. 10 (2018) 38006– performance of SnO2 /graphene for sodium-ion batteries, Nanoscale 7 (2015) 3164–
38014, doi:10.1021/acsami.8b11672. 3172, doi:10.1039/c4nr07054b.
[164] G.M. Tomboc, M.W. Abebe, A.F. Baye, H. Kim, Utilization of the superior properties [189] E. Buiel, J.R. Dahn, Li-insertion in hard carbon anode materials for Li-ion batteries,
of highly mesoporous PVP modified NiCo2 O4 with accessible 3D nanostructure and Electrochim. Acta. 45 (1999) 121–130, doi:10.1016/S0013-4686(99)00198-X.
flower-like morphology towards electrochemical methanol oxidation reaction, J. [190] H. Yildirim, A. Kinaci, M.K.Y. Chan, J.P. Greeley, First-principles analysis of defect
Energy Chem. 29 (2019) 136–146, doi:10.1016/j.jechem.2018.08.009. thermodynamics and ion transport in inorganic SEI compounds: LiF and NaF, ACS
[165] Z. Sang, X. Yan, D. Su, H. Ji, S. Wang, S.X. Dou, J. Liang, A flexible Appl. Mater. Interfaces. 7 (2015) 18985–18996, doi:10.1021/acsami.5b02904.
film with SnS2 nanoparticles chemically anchored on 3D-graphene framework [191] M.A. Muñoz-Márquez, M. Zarrabeitia, E. Castillo-Martínez, A. Eguía-Barrio,
for high areal density and high rate sodium storage, Small 16 (2020) 1–8, T. Rojo, M. Casas-Cabanas, Composition and evolution of the solid-electrolyte
doi:10.1002/smll.202001265. interphase in Na2 Ti3 O7 electrodes for Na-Ion batteries: XPS and auger parame-
[166] D. Zhou, X. Li, L.Z. Fan, Y. Deng, Three-dimensional porous graphene-encapsulated ter analysis, ACS Appl. Mater. Interfaces. 7 (2015) 7801–7808, doi:10.1021/ac-
CNT@SnO2 composite for high-performance lithium and sodium storage, Elec- sami.5b01375.
trochim. Acta. 230 (2017) 212–221, doi:10.1016/j.electacta.2017.02.016. [192] Y. Pan, Y. Zhang, B.S. Parimalam, C.C. Nguyen, G. Wang, B.L. Lucht, Investigation
[167] J. Cui, S. Yao, J.Q. Huang, L. Qin, W.G. Chong, Z. Sadighi, J. Huang, of the solid electrolyte interphase on hard carbon electrode for sodium ion batteries,
Z. Wang, J.K. Kim, Sb-doped SnO2 /graphene-CNT aerogels for high perfor- J. Electroanal. Chem. 799 (2017) 181–186, doi:10.1016/j.jelechem.2017.06.002.
mance Li-ion and Na-ion battery anodes, Energy Storage Mater 9 (2017) 85–95, [193] F.A. Soto, P. Yan, M.H. Engelhard, A. Marzouk, C. Wang, G. Xu, Z. Chen, K. Amine,
doi:10.1016/j.ensm.2017.06.006. J. Liu, V.L. Sprenkle, F. El-Mellouhi, P.B. Balbuena, X. Li, Tuning the solid elec-
[168] J. Zheng, X. Xiong, G. Wang, Z. Lin, X. Ou, C. Yang, M. Liu, SnS2 nanoparticles an- trolyte interphase for selective Li- and Na-ion storage in hard carbon, Adv. Mater.
chored on three-dimensional reduced graphene oxide as a durable anode for sodium 29 (2017), doi:10.1002/adma.201606860.
ion batteries, Chem. Eng. J. 339 (2018) 78–84, doi:10.1016/j.cej.2018.01.119. [194] V.A. Oltean, B. Philippe, S. Renault, R. Félix Duarte, H. Rensmo, D. Brandell, Inves-
[169] X. Xiong, C. Yang, G. Wang, Y. Lin, X. Ou, J.H. Wang, B. Zhao, M. Liu, Z. Lin, tigating the interfacial chemistry of organic electrodes in Li- and Na-ion batteries,
K. Huang, SnS nanoparticles electrostatically anchored on three-dimensional N- Chem. Mater. 28 (2016) 8742–8751, doi:10.1021/acs.chemmater.6b04086.
doped graphene as an active and durable anode for sodium-ion batteries, Energy [195] B.T. Young, D.R. Heskett, C.C. Nguyen, M. Nie, J.C. Woicik, B.L. Lucht, Hard X-ray
Environ. Sci. 10 (2017) 1757–1763, doi:10.1039/c7ee01628j. photoelectron spectroscopy (HAXPES) investigation of the silicon solid electrolyte
[170] J. Cui, S. Yao, Z. Lu, J.Q. Huang, W.G. Chong, F. Ciucci, J.K. Kim, Revealing interphase (SEI) in lithium-ion batteries, ACS Appl. Mater. Interfaces. 7 (2015)
pseudocapacitive mechanisms of metal dichalcogenide SnS2 /Graphene-CNT aero- 20004–20011, doi:10.1021/acsami.5b04845.
gels for high-energy Na hybrid capacitors, Adv. Energy Mater. 8 (2018) 1–12, [196] R. Mogensen, J. Maibach, W.R. Brant, D. Brandell, R. Younesi, Evolution of the solid
doi:10.1002/aenm.201702488. electrolyte interphase on tin phosphide anodes in sodium ion batteries probed by
[171] G.M. Tomboc, B.T. Gadisa, J. Joo, H. Kim, K. Lee, Hollow structured metal sul- hard x-ray photoelectron spectroscopy, Electrochim. Acta. 245 (2017) 696–704,
fides for photocatalytic hydrogen generation, ChemNanoMat 6 (2020) 850–869, doi:10.1016/j.electacta.2017.05.173.
doi:10.1002/cnma.202000125. [197] F.A. Soto, A. Marzouk, F. El-Mellouhi, P.B. Balbuena, Understanding ionic dif-
[172] T. Kwon, M. Jun, K. Lee, Catalytic nanoframes and beyond, Adv. Mater. 32 (2020) fusion through SEI components for lithium-ion and sodium-ion batteries: In-
1–30, doi:10.1002/adma.202001345. sights from first-principles calculations, Chem. Mater. 30 (2018) 3315–3322,
[173] J. Park, T. Kwon, J. Kim, H. Jin, H.Y. Kim, B. Kim, S.H. Joo, K. Lee, Hollow doi:10.1021/acs.chemmater.8b00635.
43
[198] L. Baggetto, P. Ganesh, R.P. Meisner, R.R. Unocic, J.C. Jumas, C.A. Bridges, [219] T. Palaniselvam, C. Mukundan, I. Hasa, A.L. Santhosha, M. Goktas, H. Moon,
G.M. Veith, Characterization of sodium ion electrochemical reaction with M. Ruttert, R. Schmuch, K. Pollok, F. Langenhorst, M. Winter, S. Passerini, P. Adel-
tin anodes: Experiment and theory, J. Power Sources. 234 (2013) 48–59, helm, Assessment on the use of high capacity “Sn4 P3 ”/NHC composite electrodes
doi:10.1016/j.jpowsour.2013.01.083. for sodium-ion batteries with ether and carbonate electrolytes, Adv. Funct. Mater.
[199] P. Bai, X. Han, Y. He, P. Xiong, Y. Zhao, J. Sun, Y. Xu, Solid electrolyte interphase 30 (2020) 1–12, doi:10.1002/adfm.202004798.
manipulation towards highly stable hard carbon anodes for sodium ion batteries, [220] H. Kim, S.W. Lee, K.Y. Lee, J.W. Park, H.S. Ryu, K.K. Cho, G.B. Cho, K.W. Kim,
Energy Storage Mater 25 (2020) 324–333, doi:10.1016/j.ensm.2019.10.006. J.H. Ahn, H.J. Ahn, Electrochemical properties of micron-sized SnO anode using a
[200] L.Y. Kuo, A. Moradabadi, H.F. Huang, B.J. Hwang, P. Kaghazchi, Struc- glyme-based electrolyte for sodium-ion battery, J. Nanosci. Nanotechnol. 18 (2018)
ture and ionic conductivity of the solid electrolyte interphase layer on 6422–6426, doi:10.1166/jnn.2018.15690.
tin anodes in Na-ion batteries, J. Power Sources. 341 (2017) 107–113, [221] H. Che, S. Chen, Y. Xie, H. Wang, K. Amine, X.Z. Liao, Z.F. Ma, Electrolyte design
doi:10.1016/j.jpowsour.2016.11.077. strategies and research progress for room-temperature sodium-ion batteries, Energy
[201] M. Zarrabeitia, F. Nobili, M.Á. Muñoz-Márquez, T. Rojo, M. Casas-Cabanas, Direct Environ. Sci. 10 (2017) 1075–1101, doi:10.1039/c7ee00524e.
observation of electronic conductivity transitions and solid electrolyte interphase [222] J. Feng, Z. Zhang, L. Li, J. Yang, S. Xiong, Y. Qian, Ether-based nonflammable
stability of Na2 Ti3 O7 electrodes for Na-ion batteries, J. Power Sources. 330 (2016) electrolyte for room temperature sodium battery, J. Power Sources. 284 (2015)
78–83, doi:10.1016/j.jpowsour.2016.08.112. 222–226, doi:10.1016/j.jpowsour.2015.03.038.
[202] C.Y. Li, J. Patra, C.H. Yang, C.M. Tseng, S.B. Majumder, Q.F. Dong, J.K. Chang, [223] P.M.L. Le, T.D. Vo, H. Pan, Y. Jin, Y. He, X. Cao, H.V. Nguyen, M.H. Engelhard,
Electrolyte optimization for enhancing electrochemical performance of antimony C. Wang, J. Xiao, J.G. Zhang, Excellent cycling stability of sodium anode enabled
sulfide/graphene anodes for sodium-ion batteries-carbonate-based and ionic liq- by a stable solid electrolyte interphase formed in ether-based electrolytes, Adv.
uid electrolytes, ACS Sustain. Chem. Eng. 5 (2017) 8269–8276, doi:10.1021/ac- Funct. Mater. 30 (2020) 1–11, doi:10.1002/adfm.202001151.
ssuschemeng.7b01939. [224] Q. Chen, B. Liu, L. Zhang, Q. Xie, Y. Zhang, J. Lin, B. Qu, L. Wang, B. Sa, D.L. Peng,
[203] L. Xia, L. Yu, D. Hu, G.Z. Chen, Electrolytes for electrochemical energy storage, Sodiophilic Zn/SnO2 porous scaffold to stabilize sodium deposition for sodium
Mater. Chem. Front. 1 (2017) 584–618, doi:10.1039/c6qm00169f. metal batteries, Chem. Eng. J. (2021) 404, doi:10.1016/j.cej.2020.126469.
[204] D.Y. Kim, O.L. Li, J. Kang, Maximizing the rate capability of carbon-based an- [225] H. Kim, J. Hong, Y.U. Park, J. Kim, I. Hwang, K. Kang, Sodium storage behavior
ode materials for sodium-ion batteries, J. Power Sources. 481 (2021) 228973, in natural graphite using ether-based electrolyte systems, Adv. Funct. Mater. 25
doi:10.1016/j.jpowsour.2020.228973. (2015) 534–541, doi:10.1002/adfm.201402984.
[205] K. Matsumoto, J. Hwang, S. Kaushik, C.Y. Chen, R. Hagiwara, Advances in sodium [226] M. Song, C. Wang, D. Du, F. Li, J. Chen, A high-energy-density sodium-
secondary batteries utilizing ionic liquid electrolytes, Energy Environ. Sci. 12 ion full battery based on tin anode, Sci. China Chem. 62 (2019) 616–621,
(2019) 3247–3287, doi:10.1039/c9ee02041a. doi:10.1007/s11426-018-9422-y.
[206] Q. Yang, Z. Zhang, X.G. Sun, Y.S. Hu, H. Xing, S. Dai, Ionic liquids and derived [227] Y. Li, B. Cheng, F. Jiao, K. Wu, The roles and working mechanism of salt-type ad-
materials for lithium and sodium batteries, Chem. Soc. Rev. 47 (2018) 2020–2064, ditives on the performance of high-voltage lithium-ion batteries, ACS Appl. Mater.
doi:10.1039/c7cs00464h. Interfaces. 12 (2020) 16298–16307, doi:10.1021/acsami.9b22360.
[207] G.G. Eshetu, T. Diemant, M. Hekmatfar, S. Grugeon, R.J. Behm, S. Laruelle, M. Ar- [228] J. Liu, Y. Wang, F. Liu, F. Cheng, J. Chen, Improving metallic lithium anode with
mand, S. Passerini, Impact of the electrolyte salt anion on the solid electrolyte NaPF6 additive in LiPF6 -carbonate electrolyte, J. Energy Chem. 42 (2020) 1–4,
interphase formation in sodium ion batteries, Nano Energy 55 (2019) 327–340, doi:10.1016/j.jechem.2019.05.017.
doi:10.1016/j.nanoen.2018.10.040. [229] T.R. Kartha, B.S. Mallik, Ionic conductance and viscous drag in water-in-salt elec-
[208] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki, T. Nakayama, A. Ogata, trolytes for lithium and sodium ion batteries and supercapacitors, Mater. Today
K. Gotoh, K. Fujiwara, Electrochemical Na insertion and solid electrolyte interphase Commun. 25 (2020) 101588, doi:10.1016/j.mtcomm.2020.101588.
for hard-carbon electrodes and application to Na-ion batteries, Adv. Funct. Mater. [230] C. Chen, M. Wu, J. Liu, Z. Xu, K. Zaghib, Y. Wang, Effects of ester-based electrolyte
21 (2011) 3859–3867, doi:10.1002/adfm.201100854. composition and salt concentration on the Na-storage stability of hard carbon an-
[209] A. Ponrouch, R. Dedryvère, D. Monti, A.E. Demet, J.M. Ateba Mba, L. Croguennec, odes, J. Power Sources. 471 (2020) 228455, doi:10.1016/j.jpowsour.2020.228455.
C. Masquelier, P. Johansson, M.R. Palacín, Towards high energy density sodium [231] S. Hong, M.H. Choo, Y.H. Kwon, J.Y. Kim, S.W. Song, Mechanisms for stable solid
ion batteries through electrolyte optimization, Energy Environ. Sci. 6 (2013) 2361– electrolyte interphase formation and improved cycling stability of tin-based battery
2369, doi:10.1039/c3ee41379a. anode in fluoroethylene carbonate-containing electrolyte, Adv. Mater. Interfaces.
[210] A. Ponrouch, D. Monti, A. Boschin, B. Steen, P. Johansson, M.R. Palacín, Non- 3 (2016), doi:10.1002/admi.201600172.
aqueous electrolytes for sodium-ion batteries, J. Mater. Chem. A. 3 (2015) 22–42, [232] L. Ji, M. Gu, Y. Shao, X. Li, M.H. Engelhard, B.W. Arey, W. Wang, Z. Nie,
doi:10.1039/c4ta04428b. J. Xiao, C. Wang, J.G. Zhang, J. Liu, Controlling SEI formation on SnSb-porous car-
[211] A. Ponrouch, E. Marchante, M. Courty, J.M. Tarascon, M.R. Palacín, In search of bon nanofibers for improved Na ion storage, Adv. Mater. 26 (2014) 2901–2908,
an optimized electrolyte for Na-ion batteries, Energy Environ. Sci. 5 (2012) 8572– doi:10.1002/adma.201304962.
8583, doi:10.1039/c2ee22258b. [233] L.O. Vogt, M. El Kazzi, E. Jämstorp Berg, S. Pérez Villar, P. Novák, C. Ville-
[212] A. Ponrouch, A.R. Goñi, M.R. Palacín, High capacity hard carbon anodes for sodium vieille, Understanding the interaction of the carbonates and binder in Na-ion bat-
ion batteries in additive free electrolyte, Electrochem. Commun. 27 (2013) 85–88, teries: A combined bulk and surface study, Chem. Mater. 27 (2015) 1210–1216,
doi:10.1016/j.elecom.2012.10.038. doi:10.1021/cm5039649.
[213] R. Dugas, A. Ponrouch, G. Gachot, R. David, M.R. Palacin, J.M. Tarascon, Na reac- [234] Y. Ding, X. Guo, Y. Qian, H. Gao, D.H. Weber, L. Zhang, J.B. Goodenough, G. Yu,
tivity toward carbonate-based electrolytes: The effect of FEC as additive, J. Elec- In situ formation of liquid metals via galvanic replacement reaction to build
trochem. Soc. 163 (2016) A2333–A2339, doi:10.1149/2.0981610jes. dendrite-free alkali-metal-ion batteries, Angew. Chemie. 132 (2020) 12268–12275,
[214] J. Zhang, D.W. Wang, W. Lv, L. Qin, S. Niu, S. Zhang, T. Cao, F. Kang, Q.H. Yang, doi:10.1002/ange.202005009.
Ethers illume sodium-based battery chemistry: Uniqueness, surprise, and chal- [235] S.W. Zhang, W. Lv, D. Qiu, T. Cao, J. Zhang, Q. Lin, X. Chen, Y.B. He, F. Kang,
lenges, Adv. Energy Mater. 8 (2018) 1–14, doi:10.1002/aenm.201801361. Q.H. Yang, An ion-conducting SnS-SnS2 hybrid coating for commercial activated
[215] K. Li, J. Zhang, D. Lin, D.W. Wang, B. Li, W. Lv, S. Sun, Y.B. He, F. Kang, carbons enabling their use as high performance anodes for sodium-ion batteries, J.
Q.H. Yang, L. Zhou, T.Y. Zhang, Evolution of the electrochemical interface in Mater. Chem. A. 7 (2019) 10761–10768, doi:10.1039/c9ta00599d.
sodium ion batteries with ether electrolytes, Nat. Commun. 10 (2019) 1–10, [236] X. Jin, Y. Zhao, Z. Shen, J. Pu, X. Xu, C. Zhong, S. Zhang, J. Li, H. Zhang,
doi:10.1038/s41467-019-08506-5. Interfacial design principle of sodiophilicity-regulated interlayer deposition in
a sandwiched sodium metal anode, Energy Storage Mater 31 (2020) 221–229,
[216] Z. Wang, K. Dong, D. Wang, S. Luo, Y. Liu, Q. Wang, Y. Zhang, A. Hao, C. Shi,
doi:10.1016/j.ensm.2020.06.040.
N. Zhao, A nanosized SnSb alloy confined in N-doped 3D porous carbon coupled
[237] N. Liu, H. Wu, M.T. McDowell, Y. Yao, C. Wang, Y. Cui, A yolk-shell design for
with ether-based electrolytes toward high-performance potassium-ion batteries, J.
stabilized and scalable Li-ion battery alloy anodes, Nano Lett 12 (2012) 3315–
Mater. Chem. A. 7 (2019) 14309–14318, doi:10.1039/c9ta03851e.
3321, doi:10.1021/nl3014814.
[217] J. Choi, N.R. Kim, K. Lim, K. Ku, H.J. Yoon, J.G. Kang, K. Kang, P.V. Braun, H.J. Jin, [238] Z.W. Seh, W. Li, J.J. Cha, G. Zheng, Y. Yang, M.T. McDowell, P.C. Hsu, Y. Cui,
Y.S. Yun, Tin sulfide-based nanohybrid for high-performance anode of sodium-ion Sulphur-TiO2 yolk-shell nanoarchitecture with internal void space for long-cycle
batteries, Small 13 (2017) 1–8, doi:10.1002/smll.201700767. lithium-sulphur batteries, Nat. Commun. 4 (2013), doi:10.1038/ncomms2327.
[218] J. Zhang, D.W. Wang, W. Lv, S. Zhang, Q. Liang, D. Zheng, F. Kang, Q.H. Yang, [239] W. Huang, H. Wang, D.T. Boyle, Y. Li, Y. Cui, Resolving nanoscopic and mesoscopic
Achieving superb sodium storage performance on carbon anodes through an ether- heterogeneity of fluorinated species in battery solid-electrolyte interphases by cryo-
derived solid electrolyte interphase, Energy Environ. Sci. 10 (2017) 370–376, genic electron microscopy, ACS Energy Lett 5 (2020) 1128–1135, doi:10.1021/ac-
doi:10.1039/c6ee03367a. senergylett.0c00194.
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