Sb<sub>2</sub>S<sub>3</sub>基负极材料的制备及储能性能研究进展

姚洪志; 李瑞; 连恺; 纪向飞; 赵团

doi:10.13801/j.cnki.fhclxb.20220106.001

Sb₂S₃基负极材料的制备及储能性能研究进展

doi: 10.13801/j.cnki.fhclxb.20220106.001

陕西应用物理化学研究所　应用物理化学国家重点实验室，西安 710061

详细信息

通讯作者:
姚洪志，博士，高级工程师，研究方向为电磁兼容、新型复合材料　E-mail: yhz305@163.com

中图分类号: TB331
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出版历程
- 收稿日期: 2021-11-04
- 修回日期: 2021-12-13
- 录用日期: 2021-12-23
- 网络出版日期: 2022-01-06
- 刊出日期: 2022-06-01

Research progress on preparation and energy storage properties of Sb₂S₃-based anode materials

Science and Technology on Applied Physical Chemistry Laboratory, Shaanxi Applied Physics-Chemistry Research Institute, Xi′an 710061, China

摘要

摘要: 由于在低电位范围内的合金化/脱合金化反应机制，硫化锑(Sb₂S₃)材料的理论放电比容量高达946 mA·h·g⁻¹，是一种有发展前景的锂/钠/钾离子电池负极材料。然而，在电化学反应过程中Sb₂S₃材料的聚集性和较差的导电性限制了离子/电子转移，导致了较差的电化学性能，严重阻碍了其实际应用。有必要对Sb₂S₃基负极材料的结构设计和储锂/钠/钾机制及近几年来的一些重要工作进行总结。本文综述了近年来Sb₂S₃基化合物材料的研究进展，主要包括合理的结构设计和/或与碳基材料结合等策略及所涉及的电化学反应机制，并提出了进一步改善Sb₂S₃化合物负极材料的展望。
- Sb₂S₃基负极材料 /
- 电化学性能 /
- 锂离子电池(LIBs) /
- 钠离子电池(SIBs) /
- 钾离子电池(PIBs)
Abstract: Due to the alloying/dealloying reaction mechanism in the low potential range, the theoretical discharge specific capacity of antimony sulfide (Sb₂S₃) material is as high as 946 mA·h·g⁻¹, which is a promising anode mater-ial for lithium/sodium/potassium ion batteries. However, the aggregation and poor conductivity of Sb₂S₃ materials limit ion/electron transfer, resulting in poor electrochemical performance and severely hindering its practical application. It is necessary to summarize the structural design and lithium/sodium/potassium storage mechanism of Sb₂S₃-based anode materials and some important work in recent years. This article reviews the research progress of Sb₂S₃ based compound materials in recent years, mainly including reasonable structure design and/or combining with carbon-based materials and the electrochemical reaction mechanism involved, and puts forward the prospect of further improving Sb₂S₃ compound anode materials.
- Sb₂S₃-based anode materials /
- electrochemical property /
- lithium ion batteries (LIBs) /
- sodium ion batteries (SIBs) /
- potassium ion batteries (PIBs)

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图 1 锂离子电池(LIBs)中Sb₂S₃-150电极在0.1 mV·s⁻¹扫描速率时前三个循环的CV曲线^[13]

Figure 1. CV curves of Sb₂S₃-150 electrode for the first three cycles at a scan rate of 0.1 mV·s⁻¹ in lithium ion batteries (LIBs)^[13]

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图 2 Sb₂S₃/碳-硅氧化物(Sb₂S₃/CS)复合材料的制备流程图^[32]

Figure 2. Schematic diagram of the preparation of Sb₂S₃/carbon-silicon oxide ( Sb₂S₃/CS) composite^[32]

DMF—Dimethyl formamide; TEOS—Tetraethyl orthosilicate; PVP—Polyvinyl pyrrolidone

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图 3 (a) 自支撑多孔Sb₂S₃/TiO₂/C纳米纤维在LIBs中2000 mA·g⁻¹下的循环性能；(b) 自支撑多孔Sb₂S₃/TiO₂/C-LiFePO₄全电池的循环性能图(插图：可点亮16个LED的全电池的数字照片)^[33]

Figure 3. (a) Cycle performance of free-standing porous Sb₂S₃/TiO₂/C nanofibers at 2000 mA·g⁻¹ in LIBs; (b) Cycle performance of free-standing porous Sb₂S₃/TiO₂/C-LiFePO₄ full-cell (Inset: Digital photograph of a full cell that lights 16 LEDs)^[33]

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图 4 (a) MoS₂-Sb@Sb₂S₃@C样品的制备示意图；(b) LIBs中MoS₂-Sb@Sb₂S₃@C电极的倍率性能图；(c) 在电流密度为1 A·g⁻¹时，LIBs中MoS₂-Sb@Sb₂S₃@C电极的长期循环性能图^[40]

Figure 4. (a) Schematic illustration of the preparation of MoS₂-Sb@Sb₂S₃@C sample; (b) Rate performance of the MoS₂-Sb@Sb₂S₃@C electrode in LIBs; (c) Long-term cycling performance of the MoS₂-Sb@Sb₂S₃@C electrode at a current density of 1 A·g⁻¹ in LIBs^[40]

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图 5 钠离子电池(SIBs)中Sb₂S₃电极在0.05 mV·s⁻¹扫描速率时前五个循环的CV曲线^[41]

Figure 5. CV curves of Sb₂S₃ electrode for the first five cycles at a scan rate of 0.05 mV·s⁻¹ in sodium ion batteries (SIBs)^[41]

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图 6 (a) Sb₂S₃@FeS₂/N掺杂的石墨烯(SFS/C)复合材料制备工艺示意图；(b) 在5 A·g⁻¹高倍率下，SFS/C复合材料在SIBs中的循环性能^[54]

Figure 6. (a) Schematic illustration for the fabrication process of Sb₂S₃@FeS₂/N doped graphene (SFS/C) composite; (b) Cycle performance at high rate of 5 A·g⁻¹ for SFS/C composite in SIBs^[54]

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图 7 (a) Sb₂S₃-Bi₂S₃@C@还原氧化石墨烯(rGO)微棒形成示意图；(b) SIBs中Sb₂S₃-Bi₂S₃@rGO电极在8 A·g⁻¹条件下的长期循环稳定性^[58]

Figure 7. (a) Schematic illustration of the formation of the Sb₂S₃-Bi₂S₃@C@reduced graphene oxide (rGO) microrods; (b) Long-term cycling stability of Sb₂S₃-Bi₂S₃@rGO electrode at 8 A·g⁻¹ in SIBs^[58]

PDA—Polydopamine; GO—Graphene oxide

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图 8 (a) Sb₂S₃@Ti₃C₂T_x合成工艺示意图；(b) 在SIBs中Sb₂S₃@Ti₃C₂T_x电极在100 mA·g⁻¹电流密度下的循环性能^[63]

Figure 8. (a) Schematic illustration of the synthetic process for Sb₂S₃@Ti₃C₂T_x; (b) Cyclic performances of Sb₂S₃@Ti₃C₂T_x electrode at a current density of 100 mA·g⁻¹ in SIBs^[63]

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图 9 (a) PIBs中电极在0.1 mV·s⁻¹扫描速率时前五个循环的CV曲线；(b) PIBs中Ti₃C₂-Sb₂S₃电极在100 mA·g⁻¹时的长循环性能^[64]

Figure 9. (a) CV curves of Ti₃C₂-Sb₂S₃ electrode for the first five cycles at a scan rate of 0.1 mV·s⁻¹ in PIBs;(b) Long cycling capability of Ti₃C₂-Sb₂S₃ at 100 mA·g⁻¹ in PIBs^[64]

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表 1 最近报道的Sb₂S₃基材料作为LIBs负极材料的合成方法和电化学性能

Table 1. Synthetic method and electrochemical property of Sb₂S₃-based electrodes used as anode for LIBs from recent reported

Sample	Synthesis method	Voltage range/V	Current density/(A·g⁻¹)	Cycle number	Final capacity/ (mA·h·g⁻¹)
Sb₂S₃^[23]	Two-step oxidation-sulfuration route	0.01-3.0	0.1	100	548
Sb₂S₃^[13]	Hydrothermal method	0.01-2.0	1	100	469
Sb₂S₃nanosheet^[26]	Exfoliation assisted by Li intercalation	0.01-3.0	0.2	200	800
Sb₂S₃@CNT^[27]	Vapor transport deposition system	0.01-3.0	0.47	160	845
Sb₂S₃-C^[28]	Plasma assisted milling	0.01-3.0	1	500	496.1
Sb₂S₃@EG′-S^[10]	Sulfur-mediated route	0.01-3.0	5	100	548
S-rGO/Sb₂S₃^[29]	In-situ sulfuration process	0.01-3.0	0.5	800	451
Sb₂S₃/CS^[32]	Electrospinning coupled with hydrothermal	0.01-2.0	0.2	200	566
Sb₂S₃/TiO₂/C^[33]	Electrospinning coupled with hydrothermal	0.01-2.5	2	800	454.1
NSSCs^[38]	Electrospinning technology	0.01-3.0	1	1000	490.3
CPC/Sb₂S₃^[39]	Hydrothermal method	0.01-3.0	0.1	200	1100
MoS₂-Sb@Sb₂S₃@C^[40]	Semi-sacrificial template and thermal carbonization	0.01-3.0	1	100	760
Notes: CNT—Carbon nanotube; NSSCs—N doped Sb₂S₃-carbon fiber; CPC—Carbon derived from coconut pulp.

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表 2 最近报道的Sb₂S₃基材料作为SIBs负极材料的合成方法和电化学性能

Table 2. Synthetic methods and electrochemical properties of Sb₂S₃-based electrodes used as anode for SIBs from recent reported

Sample	Synthesis method	Voltage range/V	Current density/(A·g⁻¹)	Cycle number	Final capacity/ (mA·h·g⁻¹)
Sb₂S₃nanosheeets^[26]	Exfoliation assisted by Li intercalation	0.01-3.0	0.2	200	500
More shells Sb₂S₃^[46]	Template method	0.01-2.0	1	50	>500
rGO/Sb₂S₃^[47]	Hydrothermal and solvothermal method	0.01-2.0	0.1	60	652
Sb₂S₃/CNT^[48]	Self-assembly method	0.01-1.5	0.1	50	704
Sb₂S₃@PPy^[49]	Hydrothermal method	0.01-3.0	0.5	150	632
Sb₂S₃@YP^[50]	Vaporization-condensation method	0.01-3.0	1.162	1000	476.5
Sb₂S₃@N-C^[53]	Coating method and heat treatment	0.01-3.0	1	1000	625
Sb₂S₃/SnO₂^[57]	Hydrothermal-solution method	0.01-2.0	0.05	100	582.9
SFS/C^[54]	Solvothermal method	0.1-3.0	5	1000	534.8
Sb₂S₃-Bi₂S₃@C@rGO^[58]	Cation exchange treatment	0.01-3.0	8	1100	460.5
Sb₂S₃after precycling Li^[60]	—	0.001-2.5	0.1	200	195
a-Sb₂S₃@CuSbS₂^[61]	Closed-space sublimation method	0.01-2.5	0.05	50	506.7
Sb-CNTs^[62]	Electrochemical approach	0.01-2.0	1	100	425
Sb₂S₃@Ti₃C₂T_x^[63]	Wet-chemistry synthesis method	0.01-3.0	0.1	100	215
Notes: PPy—polypyrrole; YP—YP80F carbon.

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表 3 最近报道的Sb₂S₃基材料作为钾离子电池(PIBs)负极材料的合成方法和电化学性能

Table 3. Synthetic methods and electrochemical properties of Sb₂S₃-based electrodes used as anode for potasssium ion batteries (PIBs) from recent reported

Sample	Synthesis method	Voltage range/V	Current density/(A·g⁻¹)	Cycle number	Final capacity/ (mA·h·g⁻¹)
Sb₂S₃/CNT^[48]	Self-assembly method	0.01-2.5	0.5	50	212.4
Sb₂S₃@PPy^[49]	Hydrothermal reaction	0.01-3.0	0.1 1	18 50	487 157
Sb₂S₃-Bi₂S₃@C@rGO^[58]	Cation exchange treatment	0.01-3.0	0.2	80	294.6
Sb₂S₃-SNG^[66]	Hydrothermal reaction	0.01-3.0	0.05	100	480
Ti₃C₂-Sb₂S₃^[64]	Solvothermal and calcination method	0.01-2.0	0.1	500	286
Sb₂S₃-C@Nb₂O₅-C NFs^[72]	Electrospinning technology	0.01-3.0	0.1 2	100 2200	347.5 96.1
Notes: SNG—S, N-codoped graphene framework; CNFs—Carbon nanofibers.

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参考文献(75)

[1]	XIE D H, ZHANG M, WU Y, et al. A flexible dual-ion battery based on sodium-ion quasi-solid-state electrolyte with long cycling life[J]. Advanced Functional Materials,2020,30(5):1906770. doi: 10.1002/adfm.201906770
[2]	WU J X, LIU J P, CUI J, et al. Dual-phase MoS₂ as a high-performance sodium-ion battery anode[J]. Journal of Mater-ials Chemistry A,2020,8(4):2114-2122. doi: 10.1039/C9TA11913B
[3]	LIANG S Z, CHENG Y J, ZHU J, et al. A chronicle review of nonsilicon (Sn, Sb, Ge)-based Lithium/Sodium-ion battery alloying anodes[J]. Small Methods,2020,4(8):2000218. doi: 10.1002/smtd.202000218
[4]	LIU Z M, WANG J, LU B A. Plum pudding model inspired KVPO₄F@3DC as high-voltage and hyperstable cathode for potassium ion batteries[J]. Science Bulletin,2020,65(15):1242-1251. doi: 10.1016/j.scib.2020.04.010
[5]	ZHANG Q, WANG Z J, ZHANG S L, et al. Cathode materials for potassium-ion batteries: Current status and perspective[J]. Electrochemical Energy Reviews,2018,1(4):625-658. doi: 10.1007/s41918-018-0023-y
[6]	YANG C, XIN S, MAI L Q, et al. Materials design for high-safety sodium-ion battery[J]. Advanced Energy Materials,2021,11(2):2000974. doi: 10.1002/aenm.202000974
[7]	SARKAR A, MANOHAR C, MITRA S. A simple approach to minimize the first cycle irreversible loss of sodium titanate anode towards the development of sodium-ion battery[J]. Nano Energy,2020,70:104520. doi: 10.1016/j.nanoen.2020.104520
[8]	MANTHIRAM A. A reflection on lithium-ion battery cathode chemistry[J]. Nature Communications,2020,11(1):1-9. doi: 10.1038/s41467-019-13993-7
[9]	ZHANG W L, MING J, ZHAO W L, et al. Graphitic nanocarbon with engineered defects for high-performance potassium-ion battery anodes[J]. Advanced Functional Materials,2019,29(35):1903641. doi: 10.1002/adfm.201903641
[10]	WANG S, CHENG Y, XUE H, et al. Multifunctional sulfur-mediated strategy enabling fast-charging Sb₂S₃ micro-package anode for lithium-ion storage[J]. Journal of Materials Chemistry A,2021,9(12):7838-7847. doi: 10.1039/D0TA11954G
[11]	ZHAI H L, JIANG H F, QIAN Y, et al. Sb₂S₃ nanocrystals embedded in multichannel N-doped carbon nanofiber for ultralong cycle life sodium-ion batteries[J]. Materials Chemistry and Physics,2020,240:122139. doi: 10.1016/j.matchemphys.2019.122139
[12]	ZAKAZNOVA-HERZOG V P, HARMER S L, NESBITT H W, et al. High resolution XPS study of the large-band-gap semiconductor stibnite (Sb₂S₃): Structural contributions and surface reconstruction[J]. Surface Science,2006,600(2):348-356. doi: 10.1016/j.susc.2005.10.034
[13]	XIE J J, LIU L, XIA J, et al. Template-free synthesis of Sb₂S₃ hollow microspheres as anode materials for lithium-ion and sodium-ion batteries[J]. Nano-Micro Letters,2018,10(1):12. doi: 10.1007/s40820-017-0165-1
[14]	ZHOU X Z, BAI L H, YAN J, et al. Solvothermal synthesis of Sb₂S₃/C composite nanorods with excellent Li-storage performance[J]. Electrochimica Acta,2013,108:17-21. doi: 10.1016/j.electacta.2013.06.049
[15]	DONG Y C, YANG S L, ZHANG Z Y, et al. Enhanced electrochemical performance of lithium ion batteries using Sb₂S₃ nanorods wrapped in graphene nanosheets as anode materials[J]. Nanoscale,2018,10(7):3159-3165. doi: 10.1039/C7NR09441H
[16]	PAN J, WANG N N, ZHOU Y L, et al. Simple synthesis of a porous Sb/Sb₂O₃ nanocomposite for a high-capacity anode material in Na-ion batteries[J]. Nano Research,2017,10(5):1794-1803. doi: 10.1007/s12274-017-1501-y
[17]	WANG S, YUAN S, YIN Y B, et al. Green and facile fabrication of MWNTs@Sb₂S₃@PPy coaxial nanocables for high-performance Na-ion batteries[J]. Particle & Particle Systems Characterization,2016,33(8):493-499.
[18]	李志华, 凌云, 姜文娟, 等. Sb₂S₃纳米棒的制备及其性能研究[J]. 化工新型材料, 2009, 37(5):57-60. doi: 10.3969/j.issn.1006-3536.2009.05.021 LI Z H, LING Y, JIANG W J, et al. Preparation and properties of Sb₂S₃ nanorods[J]. New Chemical Materials,2009,37(5):57-60(in Chinese). doi: 10.3969/j.issn.1006-3536.2009.05.021
[19]	JARAMILLO-QUINTERO O, BENITEZ-CRUZ M, GARCIA-OCAMPO J, et al. Enhanced performance of S-doped Sb/Sb₂O₃/CNT/GNR nanocomposite as anode material in lithium-ion batteries[J]. Journal of Alloys and Compounds,2019,807:151647. doi: 10.1016/j.jallcom.2019.151647
[20]	YIN W H, CHAI W W, WANG K, et al. Facile synthesis of Sb nanoparticles anchored on reduced graphene oxides as excellent anode materials for lithium-ion batteries[J]. Journal of Alloys and Compounds,2019,797:1249-1257. doi: 10.1016/j.jallcom.2019.04.329
[21]	DENG M X, LI S J, HONG W W, et al. Octahedral Sb₂O₃ as high-performance anode for lithium and sodium storage[J]. Materials Chemistry and Physics,2019,223:46-52. doi: 10.1016/j.matchemphys.2018.10.043
[22]	LAKSHMI K, DEIVANAYAGAM R, SHAIJUMON M. Carbon nanotube ‘wired’octahedral Sb₂O₃/graphene aerogel as efficient anode material for sodium and lithium ion batteries[J]. Journal of Alloys and Compounds,2021,857:158267. doi: 10.1016/j.jallcom.2020.158267
[23]	YI Z, HAN Q G, CHENG Y, et al. Facile synthesis of symmetric bundle-like Sb₂S₃ micron-structures and their application in lithium-ion battery anodes[J]. Chemical Communications,2016,52(49):7691. doi: 10.1039/C6CC03176E
[24]	WANG Q H, ZHU L X, SUN L Q, et al. Facile synthesis of hierarchical porous ZnCo₂O₄ microspheres for high-performance supercapacitors[J]. Journal of Materials Chemistry A,2014,3(3):982-985.
[25]	SHEN L F, YU L, YU X Y, et al. Self-templated formation of uniform NiCo₂O₄ hollow spheres with complex interior structures for lithium-ion batteries and supercapacitors[J]. Angewandte Chemie International Edition,2015,54(6):1868-1872. doi: 10.1002/anie.201409776
[26]	YAO S S, CUI J, DENG Y, et al. Ultrathin Sb₂S₃ nanosheet anodes for exceptional pseudocapacitive contribution to multi-battery charge storage[J]. Energy Storage Materials,2019,20:36-45. doi: 10.1016/j.ensm.2018.11.005
[27]	WANG Q, DU Y Y, LAI Y Q, et al. Three-dimensional antimony sulfide anode with carbon nanotube interphase modified for lithium-ion batteries[J]. International Jour-nal of Minerals, Metallurgy and Materials,2021,28(10):1629-1635. doi: 10.1007/s12613-021-2249-7
[28]	LIU Y X, LU Z, CUI J, et al. Plasma milling modified Sb₂S₃-graphite nanocomposite as a highly reversible alloying-conversion anode material for lithium storage[J]. Electrochimica Acta,2019,310:26-37. doi: 10.1016/j.electacta.2019.04.104
[29]	ZHOU X Z, ZHANG Z F, YAN P F, et al. Sulfur-doped reduced graphene oxide/Sb₂S₃ composite for superior lithium and sodium storage[J]. Materials Chemistry and Physics,2020,244:122661. doi: 10.1016/j.matchemphys.2020.122661
[30]	JING X A, LI L, SJ A, et al. Free-standing SnS/C nanofiber anodes for ultralong cycle-life lithium-ion batteries and sodium-ion batteries[J]. Energy Storage Materials,2019,17:1-11. doi: 10.1016/j.ensm.2018.08.005
[31]	XIA J, JIANG K Z, XIE J J, et al. Tin disulfide embedded in N-, S-doped carbon nanofibers as anode material for sodium-ion batteries[J]. Chemical Engineering Journal,2019,359:1244-1251. doi: 10.1016/j.cej.2018.11.053
[32]	XIE J J, XIA J, YUAN Y T, et al. Sb₂S₃ embedded in carbon-silicon oxide nanofibers as high-performance anode materials for lithium-ion and sodium-ion batteries[J]. Journal of Power Sources,2019,435:226762. doi: 10.1016/j.jpowsour.2019.226762
[33]	XIA J, ZHANG X, YANG Y G, et al. Electrospinning fabrication of flexible, foldable, and twistable Sb₂S₃/TiO₂/C nano-fiber anode for lithium ion batteries[J]. Chemical Engineering Journal,2021,413:127400. doi: 10.1016/j.cej.2020.127400
[34]	YUAN Y, CHEN Z W, YU H X, et al. Heteroatom-doped carbon-based materials for lithium and sodium ion batteries[J]. Energy Storage Materials, 2020, 32: 65-90.
[35]	SAROJA A P V K, GARAPATI M S, SHYIAMALADEVI R, et al. Facile synthesis of heteroatom doped and undoped graphene quantum dots as active materials for reversible lithium and sodium ions storage[J]. Applied Surface Science,2020,504:144430. doi: 10.1016/j.apsusc.2019.144430
[36]	XIA J, YUAN Y T, YAN H X, et al. Electrospun SnSe/C nano-fibers as binder-free anode for lithium-ion and sodium-ion batteries[J]. Journal of Power Sources,2020,449:227559. doi: 10.1016/j.jpowsour.2019.227559
[37]	LIU J D, LIANG J J, WANG C Y, et al. Electrospun CoSe@N-doped carbon nanofibers with highly capacitive Li storage[J]. Journal of Energy Chemistry,2019,33:160-166. doi: 10.1016/j.jechem.2018.09.006
[38]	YIN H, HUI K S, ZHAO X, et al. Eco-friendly synthesis of self-supported N-doped Sb₂S₃-carbon fibers with high atom utilization and zero discharge for commercial full lithium-ion batteries[J]. ACS Applied Energy Materials,2020,3(7):6897-6906. doi: 10.1021/acsaem.0c00984
[39]	MULLAIVANANATHAN V, KALAISELVI N. Sb₂S₃ added bio-carbon: Demonstration of potential anode in lithium and sodium-ion batteries[J]. Carbon,2019,144:772-780. doi: 10.1016/j.carbon.2019.01.001
[40]	LI C R, SONG H, MAO C M, et al. A novel MoS₂ nanosheets-decorated Sb@Sb₂S₃@C tubular composites as anode material for high performance lithium ion battery[J]. Journal of Alloys and Compounds,2019,786:169-176. doi: 10.1016/j.jallcom.2019.01.315
[41]	PAN J, ZUO Z L, DEENG J Q, et al. Sb₂S₃ single crystal nanowires with comparable electrochemical properties as an anode for sodium ion batteries[J]. Surfaces and Interfaces,2018,10:170-175. doi: 10.1016/j.surfin.2017.10.010
[42]	DONG S H, LI C X, GE X L, et al. ZnS-Sb₂S₃@C core-double shell polyhedron structure derived from metal-organic framework as anodes for high performance sodium ion batteries[J]. ACS Nano,2017,11(6):6474-6482. doi: 10.1021/acsnano.7b03321
[43]	YAN C S, CHEN G, CHEN D H, et al. Double surfactant-directed controllable synthesis of Sb₂S₃ crystals with comparable electrochemical performances[J]. CrystEngComm,2014,16(33):7753-7760. doi: 10.1039/C4CE00871E
[44]	XIONG X H, WANG G H, LIN Y W, et al. Enhancing sodium ion battery performance by strongly binding nanostructured Sb₂S₃ on sulfur-doped graphene sheets[J]. ACS Nano,2016,10(12):10953-10959. doi: 10.1021/acsnano.6b05653
[45]	LUO W, GAUMET J J, MAI L Q. Antimony-based intermetallic compounds for lithium-ion and sodium-ion batteries: Synthesis, construction and application[J]. Rare Metals,2017,36(5):321-338. doi: 10.1007/s12598-017-0899-4
[46]	XIE F X, ZHANG L, GU Q F, et al. Multi-shell hollow structured Sb₂S₃ for sodium-ion batteries with enhanced energy density[J]. Nano Energy,2019,60:591-599. doi: 10.1016/j.nanoen.2019.04.008
[47]	WEN S Y, ZHAO J C, ZHAO Y, et al. Reduced graphene oxide (RGO) decorated Sb₂S₃ nanorods as anode material for sodium-ion batteries[J]. Chemical Physics Letters,2019,716:171-176. doi: 10.1016/j.cplett.2018.12.031
[48]	LI M, HUANG F B, PAN J, et al. Amorphous Sb₂S₃ nanospheres in-situ grown on carbon nanotubes: Anodes for NIBs and KIBs[J]. Nanomaterials,2019,9(9):1323. doi: 10.3390/nano9091323
[49]	SHI Y, LI F, ZHANG Y, et al. Sb₂S₃@PPy coaxial nanorods: A versatile and robust host material for reversible storage of alkali metal ions[J]. Nanomaterials,2019,9(4):560. doi: 10.3390/nano9040560
[50]	CHANG G L, YIN X P, SHI S S, et al. Sb₂S₃@YP nanostructured anode material synthesized by a novel vaporization-condensation method for long cycle-life sodium-ion battery[J]. Journal of the Electrochemical Society,2020,167(14):140531. doi: 10.1149/1945-7111/abc658
[51]	WANG Z Y, DONG K Z, WANG D, et al. Monodisperse multicore-shell SnSb@SnO_x/SbO_x@C nanoparticles space-confined in 3D porous carbon networks as high-performance anode for Li-ion and Na-ion batteries[J]. Chemical Engineering Journal,2019,371:356-365. doi: 10.1016/j.cej.2019.04.045
[52]	ZHAN W W, ZHU M, LAN J L, et al. 1D Sb₂S₃@ nitrogen-doped carbon coaxial nanotubes uniformly encapsulated within 3D porous graphene aerogel for fast and stable sodium storage[J]. Chemical Engineering Journal,2021,408:128007. doi: 10.1016/j.cej.2020.128007
[53]	DONG Y C, HU M J, ZHANG Z Y, et al. Nitrogen-doped carbon-encapsulated antimony sulfide nanowires enable high rate capability and cyclic stability for sodium-ion batteries[J]. ACS Applied Nano Materials,2019,2(3):1457-1465. doi: 10.1021/acsanm.8b02335
[54]	CAO L, GAO X W, ZHANG B, et al. Bimetallic sulfide Sb₂S₃@FeS₂ hollow nanorods as high-performance anode materials for sodium-ion batteries[J]. ACS Nano,2020,14(3):3610-3620. doi: 10.1021/acsnano.0c00020
[55]	YANG C H, LIANG X H, OU X, et al. Heterostructured nanocube-shaped binary sulfide (SnCo)S₂ interlaced with S-doped graphene as a high-performance anode for advanced Na⁺ batteries[J]. Advanced Functional Materials,2019,29(9):1807971. doi: 10.1002/adfm.201807971
[56]	ZHANG Z D, ZHAO J C, XU M L, et al. Facile synthesis of Sb₂S₃/MoS₂ heterostructure as anode material for sodium-ion batteries[J]. Nanotechnology,2018,29(33):335401. doi: 10.1088/1361-6528/aac645
[57]	CHANG G L, YIN X P, SHI S S, et al. Sb₂S₃@SnO₂ hetero-nanocomposite as high-performance anode material for sodium-ion battery[J]. International Journal of Green Energy,2020,17(15):1044-1050. doi: 10.1080/15435075.2020.1821692
[58]	LI K, LIU X F, QIN Y C, et al. Sb₂S₃-Bi₂S₃ microrods with the combined action of carbon encapsulation and rGO confinement for improving high cycle stability in sodium/potassium storage[J]. Chemical Engineering Journal,2021,414:128787. doi: 10.1016/j.cej.2021.128787
[59]	WANG S J, XIONG P, GUO X, et al. A stable conversion and alloying anode for potassium-ion batteries: A combined strategy of encapsulation and confinement[J]. Advanced Functional Materials,2020,30(27):2001588. doi: 10.1002/adfm.202001588
[60]	FU L, SHANG C Q, LI G C, et al. Lithium pre-cycling induced fast kinetics of commercial Sb₂S₃ anode for advanced sodium storage[J]. Energy & Environmental Materials,2019,2(3):209-215.
[61]	ZHOU J, DOU Q R, ZHANG L J, et al. A novel and fast method to prepare a Cu-supported α-Sb₂S₃@CuSbS₂ binder-free electrode for sodium-ion batteries[J]. Rsc Advances,2020,10(49):29567-29574. doi: 10.1039/D0RA05623E
[62]	LI X Y, QU J K, HU Z J, et al. Electrochemically converting Sb₂S₃/CNTs to Sb/CNTs composite anodes for sodium-ion batteries[J]. International Journal of Hydrogen Energy,2021,46(33):17071-17083. doi: 10.1016/j.ijhydene.2021.02.157
[63]	REN M X, CAO D, JIANG W, et al. Hierarchical composite of Sb₂S₃ decorated on highly crumpled Ti₃C₂T_x nanosheets for enhanced sodium storage properties[J]. Electrochimica Acta,2021,373:137835. doi: 10.1016/j.electacta.2021.137835
[64]	WANG T H, SHEN D Y, LIU H, et al. A Sb₂S₃ nanoflower/MXene composite as an anode for potassium-ion batteries[J]. ACS Applied Materials & Interfaces,2020,12(52):57907-57915.
[65]	LIU Y J, TAI Z X, ZHANG J, et al. Boosting potassium-ion batteries by few-layered composite anodes prepared via solution-triggered one-step shear exfoliation[J]. Nature Communications,2018,9(1):1-10. doi: 10.1038/s41467-017-02088-w
[66]	LU Y Y, CHEN J. Robust self-supported anode by integrating Sb₂S₃ nanoparticles with S, N-codoped graphene to enhance K-storage performance[J]. Science China Chemistry,2017,60(12):1533-1539. doi: 10.1007/s11426-017-9166-0
[67]	ZHANG W C, LIU Y J, GUO Z P. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering[J]. Science Advances,2019,5(5):eaav7412. doi: 10.1126/sciadv.aav7412
[68]	LI P, ZHENG X B, YU H X, et al. Electrochemical potassium/lithium-ion intercalation into TiSe₂: Kinetics and mechanism[J]. Energy Storage Materials,2019,16:512-518. doi: 10.1016/j.ensm.2018.09.014
[69]	DU C F, DINH K N, LIANG Q H, et al. Self-assemble and in situ formation of Ni_1−xFe_xPS₃ nanomosaic-decorated MXene hybrids for overall water splitting[J]. Advanced Energy Materials,2018,8(26):1801127. doi: 10.1002/aenm.201801127
[70]	ER D Q, LI J W, NAGUIB M, et al. Ti₃C₂ MXene as a high capacity electrode material for metal (Li, Na, K, Ca) ion batteries[J]. Acs Applied Materials & Interfaces,2014,6(14):11173-11179.
[71]	FAN L, MA R F, ZHANG Q F, et al. Graphite anode for a potassium-ion battery with unprecedented performance[J]. Angewandte Chemie International Edition,2019,58(31):10500-10505. doi: 10.1002/anie.201904258
[72]	LIU H Q, HE Y N, CAO K Z, et al. Stimulating the reversibility of Sb₂S₃ anode for high-performance potassium-ion batteries[J]. Small,2021,17(10):2008133. doi: 10.1002/smll.202008133
[73]	SHE L N, LI Q, ZHANG F, et al. Sulfur doping induced anionic oxidation of niobium-pentoxide-based anode for ultralong-life and high energy-density Na-ion capacitors[J]. Journal of Power Sources,2020,451:227744. doi: 10.1016/j.jpowsour.2020.227744
[74]	LIU Z C, DONG W J, WANG J B, et al. Orthorhombic Nb₂O_5-x for durable high-rate anode of Li-ion batteries[J]. Iscience,2020,23(1):100767. doi: 10.1016/j.isci.2019.100767
[75]	DENG Q L, CHEN F, LIU S, et al. Advantageous functional integration of adsorption-intercalation-conversion hybrid mechanisms in 3D flexible Nb₂O₅@hard carbon@MoS₂@soft carbon fiber paper anodes for ultrafast and super-stable sodium storage[J]. Advanced Functional Materials,2020,30(10):1908665. doi: 10.1002/adfm.201908665