基于Ti3C2Tx材料在钠离子电池中的应用进展

doi:10.11868/j.issn.1001-4381.2022.000094

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摘要

MXene由于具有独特的层状结构、高电子导电性和丰富的表面化学特性，在储能、电磁干扰屏蔽、催化、医药等方面有广泛的应用前景。Ti₃C₂T_x作为最早发现的MXene材料，其固有的金属导电特征、宽层间距和丰富的表面官能团，引起了钠离子电池领域研究人员的关注。本文综述了近年来Ti₃C₂T_x基材料在钠离子电池中的研究进展。首先从Ti₃C₂T_x材料的制备展开，概述多层和少层两类Ti₃C₂T_x材料的结构与电化学特性。随后结合研究的应用趋势，总结两类Ti₃C₂T_x材料的层间距改性、掺杂改性、形貌调控等手段对其储钠行为的影响。同时也分析了两类Ti₃C₂T_x基复合材料应用于钠离子电池负极的结构设计思路，指出合理的结构设计对电池性能至关重要。最后对Ti₃C₂T_x基复合材料在钠离子电池领域中面临的问题和挑战提出了一些建议。

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	曾敏
	陈淋
	李星
	王明珊

关键词 ：二维材料, MXene, Ti₃C₂T_x, 钠离子电池, 复合材料

Abstract：

MXene has a wide application prospect in energy storage, electromagnetic interference shielding, catalysis, medicine and other fields due to its unique layered structure, high electronic conductivity and rich surface chemical properties.Ti₃C₂T_x, as the earliest discovered MXene material, has the possibility to achieve both high energy density and power density in the field of sodium ion batteries because of its inherent metal conductive characteristics, wide layer spacing and abundant surface functional groups, which is attracted by many researchers. Based on this, the research progress of Ti₃C₂T_x based materials in sodium ion batteries in recent years was reviewed in this paper. Firstly, the structure and electrochemical properties of Ti₃C₂T_x materials with multi-layer and few-layer were summarized by introducing the preparation of Ti₃C₂T_x. Then, combined with the application trend of the study, the influences of layer spacing modification, doping modification and morphology regulation on the sodium storage behavior of the two kinds of Ti₃C₂T_x materials were summarized. The structural design ideas of the two kinds of Ti₃C₂T_x based composites applied to the anode of the sodium ion battery were also analyzed. It was pointed out that the reasonable structural design is vital to the battery performance. Finally, some suggestions for the problems and challenges faced by Ti₃C₂T_x based composites in the field of sodium ion batteries were given.

Key words： two-dimensional material MXene Ti₃C₂T_x sodium-ion battery composites

收稿日期: 2022-02-14 出版日期: 2023-02-20

中图分类号:

TQ152

基金资助:国家自然科学基金面上基金项目(52072322);四川省科技厅重点研发计划项目(2022YFG0294);四川省成都市国际科技合作项目(2019-GH02-00052-HZ)

通讯作者: 王明珊 E-mail: ustbwangmingshan@163.com

作者简介: 王明珊(1986—)，女，副教授，博士，研究方向为电化学储能材料开发及应用，联系地址：四川省成都市新都区新都大道8号西南石油大学(610500)，E-mail：ustbwangmingshan@163.com

引用本文:

曾敏, 陈淋, 李星, 王明珊. 基于Ti₃C₂T_x材料在钠离子电池中的应用进展[J]. 材料工程, 2023, 51(2): 1-14.
Min ZENG, Lin CHEN, Xing LI, Mingshan WANG. Progress in application of Ti₃C₂T_x materials in sodium-ion batteries. Journal of Materials Engineering, 2023, 51(2): 1-14.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2022.000094 或 http://jme.biam.ac.cn/CN/Y2023/V51/I2/1

Fig.1 Ti₃C₂T_x的结构与制备
(a)MAX相和MXene的结构^[7]；(b)从MAX相到少层MXene纳米片制备流程示意图^[19]；(c)Ti₃AlC₂(Ⅰ)、氢氟酸刻蚀手风琴状多层Ti₃C₂T_x(Ⅱ)、DMSO插层多层Ti₃C₂T_x(Ⅲ)与剥离后的Ti₃C₂T_x (Ⅳ)的XRD谱图^[20]；(d)氢氟酸刻蚀法所得的手风琴状多层Ti₃C₂T_x SEM图^[21]；(e)氟化锂/盐酸刻蚀法所得的块状多层Ti₃C₂T_x的SEM图^[21]；(f)单层与双层Ti₃C₂T_x的TEM图^[22]

Fig.2 Ti₃C₂T_x基钠离子电池负极材料的设计策略

Fig.3 多层Ti₃C₂T_x的改性
(a)碱金属离子柱撑Ti₃C₂制备工艺示意谱图^[31]；(b)碱金属离子柱撑Ti₃C₂的XRD谱图^[31]；(c)S原子共价柱撑Ti₃C₂的XRD图^[32]

Fig.4 硫族化合物/多层Ti₃C₂T_x复合材料的性能
(a)MoS₂/Ti₃C₂T_x复合材料制备示意图^[40]；(b)MoS₂/Ti₃C₂T_x复合材料的SEM图^[40]；(c)SnSe₂/Ti₃C₂T_x复合材料的制备示意图^[43]；(d)SnSe₂/Ti₃C₂T_x复合材料的循环性能^[43]

Fig.5 碳/少层Ti₃C₂T_x复合材料
(a)rGO/Ti₃C₂T_x异质结构自支撑薄膜制备示意图^[50]；(b)HC-MX自支撑电极的制备示意图^[51]；(c)rGO/Ti₃C₂T_x异质结构的TEM图^[50]；(d)MXene@NCRib复合材料的SEM图^[52]

Fig.6 金属硫族化合物/Ti₃C₂T_x复合材料的性能
(a)(CoSNP@NHC)@MXene复合材料的TEM图^[65]；(b)(CoSNP@NHC)@MXene复合材料的循环性能^[65]；(c)Sb₂S₃/Ti₃C₂T_x复合自支撑薄膜电极制备示意图^[66]；(d)Sb₂S₃/Ti₃C₂T_x复合自支撑薄膜的循环性能^[66]；(e)MX-H-MoS₂@NC复合自支撑电极截面SEM图^[67]；(f)MX-H-MoS₂@NC复合自支撑电极的循环性能^[67]

Composite	Sample	Electrolyte	Voltage window/V	Electrochemical performance	Reference
Carbon based composite	Ti₃C₂T_x/CNT-SA	1 mol·L^-1 NaClO₄ in EC/PC with 5%(mass fraction, the same below)FEC	0.01-3	0.1 A·g^-1, 175 mAh·g^-1 after 100 cycles	[70]
	Freestanding-rGO/TiC	1 mol·L^-1 NaClO₄ in EC/DEC	0.01-3	1 A·g^-1, 110 mAh·g^-1 after 2000 cycles	[71]
	MXene/rGO heterostructured films	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-3	0.5 A·g^-1, 220 mAh·g^-1 after 100 cycles	[50]
	HC-MX-2∶1 film	1 mol·L^-1 NaClO₄ in EC/DEC	0.01-3	0.2 A·g^-1, 273.2 mAh·g^-1 after 1500 cycles	[51]
	MXene@NCRib	1 mol·L^-1 NaClO₄ in EC/DMC	0.01-3	1 A·g^-1, 210.2 mAh·g^-1 after 1000 cycles	[52]
Alloy based composite	TNDs/P	1 mol·L^-1 NaClO₄ in EC/DEC with 10%FEC	0.01-2	0.1 A·g^-1, 400 mAh·g^-1 after 150 cycles	[54]
	BP/Ti₃C₂ composite	1 mol·L^-1 NaClO₄ in EC/PC	0.01-3	0.1 A·g^-1, 121 mAh·g^-1 after 100 cycles	[55]
	Phosphorene/MXene	1 mol·L^-1 NaClO₄ in EC/PC	0.01-3	1 A·g^-1, 298 mAh·g^-1 after 1000 cycles	[56]
	PDDA-BP/Ti₃C₂	1 mol·L^-1 NaClO₄ in EC/DMC/EMC with 5%FEC	0.01-3	1 A·g^-1, 658 mAh·g^-1 after 2000 cycles	[57]
	Sb/p-Ti₃C₂T_x	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-2.5	0.2 A·g^-1, 216.8 mAh·g^-1 after 300 cycles	[58]
	Bi/MXene	1 mol·L^-1 NaClO₄ in PC with 5%FEC	0.01-1.5	5 A·g^-1, 301 mAh·g^-1 after 2500 cycles	[59]
Metal oxide based composite	Sb₂O₃/MXene	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-2.5	0.5 A·g^-1, 395 mAh·g^-1 after 100 cycles	[60]
	TiO₂@Ti₃C₂T_x	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-3	0.96 A·g^-1, 116 mAh·g^-1 after 5000 cycles	[61]
	VO₂/MX	1 mol·L^-1 NaClO₄ in EC/DEC with 5%FEC	0.01-3	0.1 A·g^-1, 281 mAh·g^-1 after 200 cycles	[62]
Metal sulfide based composite	SnS₂ QDs/Ti₃C₂ composite	1 mol·L^-1 NaClO₄ in EC/DMC/EMC	0.01-3	0.1 A·g^-1, 345.3 mAh·g^-1 after 600 cycles	[72]
	Ni₃S₂/d-Ti₃C₂	1 mol·L^-1 NaClO₄ in EC/DMC with 5%FEC	0.01-3	1 A·g^-1, 193.8 mAh·g^-1 after 800 cycles	[73]
	f-Ti₃C₂/CoS₂@NPC hybrids	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-3	2 A·g^-1, 200.6 mAh·g^-1 after 1500 cycles	[64]
	SnS/Ti₃C₂T_x-O	1 mol·L^-1 NaClO₄ in EC/DMC with 5%FEC	0.01-3	0.1 A·g^-1, 565 mAh·g^-1 after 70 cycles	[74]
	Bi₂S₃/MXene composite	1 mol·L^-1 NaSO₃CF₃ in DGM	0.5-2.8	0.5 A·g^-1, 155 mAh·g^-1 after 250 cycles	[75]
	CoS/MXene	1 mol·L^-1 NaSO₃CF₃ in DGM	0.4-2.9	2 A·g^-1, 265 mAh·g^-1 after 1700 cycles	[76]
	(CoS NP@NHC)@ MXene	1 mol·L^-1 NaClO₄ in EC/DMC with 5%FEC	0.01-3	2 A·g^-1, 420 mAh·g^-1 after 600 cycles	[65]
	Co-NiS/MXene composite	1 mol·L^-1 NaClO₄ in EC/DMC/EMC with 5%FEC	0.01-3	0.1 A·g^-1, 409 mAh·g^-1 after 100 cycles	[77]
	Sb₂S₃/Ti₃C₂T_x	1 mol·L^-1 NaClO₄ in PC with 5%FEC	0.01-1.5	1 A·g^-1, 464 mAh·g^-1 after 500 cycles	[66]
	L-Sb₂S₃/Ti₃C₂ composite	1 mol·L^-1 NaClO₄ in EC/DEC with 5%FEC	0.01-3	0.1 A·g^-1, 455.5 mAh·g^-1 after 100 cycles	[78]
	MSe-MXene-CNRib	1 mol·L^-1 NaClO₄ in EC/DMC	0.01-3	1 A·g^-1, 480.7 mAh·g^-1 after 1000 cycles	[68]
	Fe_x-1Se_x/MXene/ FCR	1 mol·L^-1 NaClO₄ in EC/DMC	0.01-3	10 A·g^-1, 348.1 mAh·g^-1 after 2000 cycles	[79]
	MX/SnS₂	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-2.5	0.1 A·g^-1, 322 mAh·g^-1 after 200 cycles	[69]
	MoSe₂/MXene	1 mol·L^-1 NaClO₄ in EC/PC with 5%FEC	0.01-3	2 A·g^-1, 384 mAh·g^-1 after 400 cycles	[80]
	Co_xFe_1-xS₂@ S-Ti₃C₂	1 mol·L^-1 NaSO₃CF₃ in DGM	0.5-3	5 A·g^-1, 399 mAh·g^-1 after 600 cycles	[81]
	MX-H-MoS₂@NC	1 mol·L^-1 NaPF₆ in DOL/DGM	0.01-3	5 A·g^-1, 198.3 mAh·g^-1 after 2000 cycles	[67]
	NiSe₂@C@MXene composites	1 mol·L^-1 NaClO₄ in EC/DEC with 5%FEC	0.01-3	2 A·g^-1, 327 mAh·g^-1 after 4000 cycles	[82]

Table 1 少层Ti₃C₂T_x基复合材料的钠离子储存性能

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