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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