MXene纤维的制备、性能及应用研究进展

梁程; 程群峰

doi:10.13801/j.cnki.fhclxb.20220725.003

MXene纤维的制备、性能及应用研究进展

doi: 10.13801/j.cnki.fhclxb.20220725.003

梁程,
程群峰^,

北京航空航天大学　化学学院，北京 100191

基金项目: 国家重点研发计划(2021 YFA0715700)；国家杰出青年科学基金(52125302)；国家自然科学基金(22075009；51961130388；21875010；51522301；21273017；51103004)；牛顿高级学者基金(NAF\R1\191235)；北京市自然科学基金(JQ19006)；111引智计划(B14009)

详细信息

通讯作者:
程群峰，博士，教授，博士生导师，研究方向为仿生功能纳米复合材料　E-mail: cheng@buaa.edu.cn

中图分类号: TB34
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出版历程
- 收稿日期: 2022-05-26
- 录用日期: 2022-07-08
- 网络出版日期: 2022-07-26
- 刊出日期: 2022-08-22

Progress in preparation, properties and applications of MXene fiber

LIANG Cheng,
CHENG Qunfeng^,

School of Chemistry, Beihang University, Beijing 100191, China

Funds: National Key Research and Development Program of China (2021 YFA0715700), the National Science Fund for Distinguished Young Scholars (52125302), National Natural Science Foundation of China (22075009, 51961130388, 21875010, 51522301, 21273017, 51103004), Newton Advanced Fellowship (NAF\R1\191235), Beijing Natural Science Foundation (JQ19006), and 111 Project (B14009)

摘要

摘要: 二维过渡金属碳/氮化物(MXenes)是一种新颖的二维纳米材料，具有优异的电学、力学性能及丰富的表面官能团，在功能材料领域受到了广泛关注，常被作为基元材料构筑宏观复合材料，其中MXene纤维有望成为继石墨烯纤维后另一种结构-功能一体化纤维材料，在多功能织物、传感、能源、电磁屏蔽等领域显示出巨大的应用前景。但目前MXene复合纤维的力学和电学性能与MXene纳米材料本征性能差距较大，主要原因是组装MXene纳米片过程中产生的褶皱、无序结构、界面作用力弱等问题，往往导致MXene纤维内部的孔隙、缺陷存在及纤维外形不规则等。针对MXene纤维研究过程中存在的问题及未来研究方向，本文做了详细综述，首先介绍MXene纤维的制备方法，然后详细阐述MXene复合纤维的力学和电学性能，并讨论提升其性能的策略。同时通过一些实例，综述了MXene复合纤维的应用。最后总结了MXene纤维存在的关键科学问题和挑战，并对MXene纤维的未来发展和前景进行了展望及对未来MXene纤维的研究和应用提供一些帮助。
- MXene纤维 /
- 构筑 /
- 力学性能 /
- 电导率 /
- 应用
Abstract: 2D transition metal carbides and nitrides (MXenes) are a novel two-dimensional nanomaterial, which attracted extensive attention in the field of functional materials due to outstanding electrical, mechanical properties and abundant surface terminations. Therefore, it often has been used as building block for constructing macroscopic composites, such as MXene fibers, which are expected to be another structure-function integrated fiber after graphene fiber, and have widespread applications prospect in numerous fields, including smart textiles, sensing, energy, electromagnetic shielding, etc. However, the mechanical and electrical properties of MXene composite fibers are far lower than the intrinsic properties of MXene flakes. The main problems are that the existence of defects and voids in the MXene fiber caused by the wrinkling, disorder and weak interface interactions of MXene flakes during assembly, as well as the irregular shape of the fibers. In view of the existing problems as well as the future development direction, this review first introduces the fabrication approaches of MXene fiber. Then, we statement the mechanical and electrical properties of MXene composite fibers in detail, and discuss the strategies for improving the mechanical and electrical properties. Meanwhile, we outline the applications of MXene composite fibers by some instances. Finally, the existing scientific problems and challenges of MXene fiber are summarized, and the upcoming trends in MXene fiber are prospected, and some helpful viewpoint is provided for the research and application of MXene fiber in the future.
- MXene fiber /
- fabrication /
- mechanical properties /
- electrical conductivity /
- application

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图 1 二维过渡金属碳/氮化物(MXenes)复合纤维的制备研究进展

Figure 1. Research progress in preparation of 2D transition metal carbides and nitrides (MXenes) composite fiber

CNT—Carbon nanotube; CNC—Cellulose nanocrystal; GO—Graphene oxide; TOCNFs—2,2,6,6-tetramethylpiperidine-1-oxylradical-mediated oxidized cellulose nanofibril

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图 2 MXene复合纤维的制备策略：(a) 涂覆法^[26]；(b) 湿法纺丝^[30]；(c) Biscrolling法^[24]；(d) 静电纺丝法^[37]

Figure 2. Preparation strategy of MXene composite fiber: (a) Coating^[26]; (b) Wet spinning^[30]; (c) Biscrolling^[24]; (d) Electrospinning^[37]

L-Ti₃C₂—Large size Ti₃C₂; S-Ti₃C₂—Small size Ti₃C₂; LC—Liquid crystal

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图 3 MXene纤维的力学性能与增强策略：(a) 高浓度MXene液晶油墨的光学图像^[30]；不同拉伸比制备的MXene纤维的密实度、孔隙率 (b) 和拉伸强度-应变曲线 (c) (MF-1、MF-2和MF-3分别指在拉伸比为1、2、3下制备的MXene纤维)^[32]； (d) 具有芯壳结构的MXene@GO纤维的截面SEM图像^[28]；(e) 带正电的质子和带负电的纳米片之间静电相互作用的示意图^[41]；(f) 纤维素纱线和MXene包覆的纤维素纱线的拉伸强度-应变曲线^[26]

Figure 3. Mechanical properties and strengthening strategy of MXene fibers: (a) Optical image of the concentrated MXene liquid crystal inks^[30]; Density, porosity (b) and tensile strength-strain curves (c) of MXene fibers for each draw ratio (MXene fibers obtained through draw ratios of 1, 2 and 3 were denoted as MF-1, MF-2 and MF-3, respectively)^[32]; (d) Cross-sectional SEM image of the MXene@GO fiber with core-shell structure^[28]; (e) Schematic illustration of the electrostatic interactions between the positive protons and the negatively charged nanosheets^[41]; (f) Tensile strength-strain curves of cellulose yarns and MXene-coated cellulose yarns^[26]

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图 4 MXene复合纤维的电导率与提升策略：(a) 高度取向的带状MXene纤维截面SEM图像^[31]；(b) MF-3纤维的截面SEM图像；(c) 不同拉伸比的MXene纤维的电导率^[32]；(d) MXene/PEDOT:PSS纤维的界面结构示意图^[40]；(e) 用不同浓度和尺寸的MXene分散液制备的MXene/尼龙纱线的电导率^[37]；(f) 不同MXene含量的MXene/CNC纤维的电导率^[33]

Figure 4. Electrical conductivity and improving strategy of MXene composite fiber: (a) Cross-sectional SEM image of MXene fiber with flat orientation^[31]; (b) Cross-sectional SEM image of MF-3 fiber; (c) Electrical conductivity of MXene fibers for each draw ratio^[32]; (d) Schematic diagram of interfacial cross-linking structure of MXene/PEDOT:PSS fiber^[40]; (e) Electrical conductivity of MXene/nylon yarns produced by different MXene concentrations and flake sizes^[37]; (f) Electrical conductivity of MXene/CNC fibers with different MXene contents^[33]

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图 5 MXene复合纤维用于多功能织物和传感器：((a)~(c)) MXene包覆的纤维素纱线用于多功能织物：(a) 多功能织物概念图；(b) 针织压力传感器实物图和传感性能；(c) 针织压力传感器在14.1%应变下的相对电容变化的循环稳定性^[26]；((d)~(f)) Kevlar/MXene纤维用于智能感知口罩和手套：(d) 智能感知口罩实物图；(e) 智能感知口罩在定时呼吸时的电阻-时间曲线；(f) 智能感知手套在不同速度靠近和远离热水的电阻-时间曲线^[52]；((g)~(i)) MXene/rGO纤维用于气体传感器：(g) 实验服上的气体传感器实物图；(h) 基于MXene薄膜、rGO纤维和MXene/rGO纤维的传感器的电阻响应对比；(i) MXene/rGO纤维传感器在不同NH₃浓度下的动态电阻响应^[53]

Figure 5. MXene composite fibers for multifunctional fabrics and sensors: ((a)-(c)) MXene-coated cellulose yarns for multifunctional fabrics: (a) Concept illustration of multifunctional fabrics; (b) Digital photo and sensing performance of the knitted pressure sensor; (c) Cyclic stability of relative capacitance change of knitted pressure sensors at 14.1% strain^[26]; ((d)-(f)) Kevlar/MXene fiber for smart sensory mask and glove: (d) Photograph of smart sensory mask; (e) Resistance-time curve of smart sensory mask during breathing regularly; (f) Resistance-time curve of smart sensory glove when approaching and removing hot water at different speeds^[52]; ((g)-(i)) MXene/rGO fiber for gas sensor: (g) Photograph of gas sensor on the lab coat; (h) Comparison of resistance responses of sensor based on MXene film, rGO fiber and MXene/rGO fiber; (i) Dynamic resistance response of MXene/rGO fiber sensor at different NH₃ concentrations^[53]

C—Capacitance; C₀—Initial capacitance; R—Resistance; R₀—Initial resistance; d—Distance; RT—Room temperature

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图 6 MXene复合纤维用于能量储存与转化：(a) 测量MXene纤维电容性能的三电极装置示意图^[31]；(b) 三种MXene纤维在不同扫描速率下的体积电容对比^[31]；(c) MXene/CNT纱线作为储能纺织给手表和计时器供电^[24]；(d) 基于MXene/CNT纱线的超级电容器的电容循环稳定性^[24]；(e) 基于Au纳米颗粒(AuCNS)包覆的MXene/CNT/聚氨酯(PU)(MCP)复合纤维(AuCNS@MCP)纤维的摩擦纳米发电机用于收集水能的机制图^[60]；(f) 摩擦纳米发电机在不同水流速率下的输出电流^[60]

Figure 6. MXene composite fibers for energy storage and transformation: (a) Schematic of the three-electrode setup for measuring the capacitive performance of MXene fiber^[31]; (b) Volumetric capacitance comparison of three MXene fibers at different scan rates^[31]; (c) MXene/CNT yarn as energy storage textile to power watch and timer^[24]; (d) Capacitance retention of the supercapacitors based on MXene/CNT yarn^[24]; (e) Schematic illustration of the mechanism of the triboelectric nanogenerators based on Au nanoparticles (AuCNS) coated MXene/CNT/polyurethane(PU) (MCP) composite fibers (AuCNS@MCP) fiber for collecting water energy^[60]; (f) Output current of the triboelectric nanogenerators under different water flow rates^[60]

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图 7 MXene复合纤维用于电磁干扰(EMI)屏蔽、导线及无线通信：(a) 在可穿戴EMI屏蔽和电热综合应用的概念图^[50]；不同层数下再生纤维素(RC)@GO/MXene织物的EMI屏蔽效率 (b) 和EMI屏蔽机制对比 (c)^[50]；(d) MXene纤维用作耳机电线^[30]；(e) MXene@藻朊酸盐(A)纤维弹簧的制备机制图^[61]；(f) MXene@A弹簧天线在收缩和松弛状态下的回波损耗频率分布图^[61]

Figure 7. MXene composite fibers for electromagnetic interference (EMI) shielding, wire and wireless communications: (a) Concept illustration of integrated applications in wearable EMI shielding and electro-thermal^[50]; EMI shielding efficiencies of regenerated cellulose (RC)@GO/MXene textiles under different thickness (b) and comparison of the EMI shielding mechanisms (c)^[50]; (d) MXene fiber for earphone wire^[30]; (e) Schematic illustration of MXene@alginate (A) springs^[61]; (f) Return loss-frequency profiles of the antenna with MXene@A springs under contraction state and relaxation state^[61]

SE_Total—Total EMI; SE_A—EMI absorption; SE_R—EMI reflection

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表 1 MXene纤维的制备方法和性能

Table 1. Summary of the preparation methods and properties of MXene fiber

Composition	Preparation method	MXene content/wt%	Tensile strength/MPa	Failure strain/%	Young’s modulus/GPa	Toughness/ MJ·m⁻³	Conductivity/ S· cm⁻¹	Years	Ref.
MXene fiber	Wet spinning	100	40.5	1.7	—	~0.34	7750	2020	[29]
MXene fiber	Wet spinning	100	63.9	0.22	29.6	0.09	7713	2020	[30]
MXene fiber	Wet spinning	100	118	1.85	—	~1.09	7200	2021	[31]
MXene fiber	Wet spinning	100	343.68	0.28	121.97	~0.48	12503.78	2021	[32]
MXene/rGO fiber	Wet spinning	88	116.1	1.3	13.3	0.94	72.3	2017	[23]
MXene/rGO fiber	Wet spinning	90	12.9	3.4	1.2	~0.22	290	2017	[22]
MXene/CNT fiber	Biscrolling	90	38.4	4.7	—	~0.90	2.7	2018	[25]
MXene/CNT yarn	Biscrolling	97.5	26.6	15.1	0.09	~2.01	26	2018	[24]
MXene/TOCNFs fiber	3D printing	50	75.6	3.75	4.7	~1.42	2.11	2019	[27]
MXene/PEDOT: PSS fiber	Wet spinning	70	58.1	1.1	7.5	~0.32	1489.8	2019	[40]
MXene-coated cotton yarn	Coating	78	468.4	~0.1	5.0	~0.23	198.5	2019	[26]
MXene@GO fiber	Coaxial wet spinning	50	290	1.5	30	~2.18	24	2020	[28]
Tungstate/MXene fiber	Wet spinning	10	220	3.9	—	~4.29	—	2020	[41]
MXene/nylon nanoyarn	Electrospinning	90	29	1.85	3.94	~0.27	1195	2020	[37]
MXene@ANF fiber	Coaxial wet spinning	—	130	10.8	0.033	~7.02	25.15	2021	[49]
MXene/ANF fiber	Wet spinning	—	104	7.9	—	~4.11	1025	2021	[42]
MXene/CNC fiber	Wet spinning	75	62	0.9	1.17	0.37	2978	2022	[33]
GO/MXene@RC fiber	Coaxial wet spinning	70	92.2	4	9.0	~3.0	167.5	2022	[50]
ANF@MXene	Coaxial wet spinning	—	502.9	13.1	—	48.1	3000	2022	[51]
Notes: rGO—Reduced graphene oxide; PEDOT: PSS—Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonic acid); ANF—Aramid nanofiber; RC—Regenerated cellulose.

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