基于丝素/MXene复合纳米纤维柔性薄膜的制备及其导电性能

摘要/Abstract

摘要： 为获得具有良好导电性和响应时间的柔性传感器，以丝素蛋白(SF)作为基体，自制Ti3C2Tx MXene为功能材料，通过控制加入MXene的量，采用静电纺丝技术制备出不同配比的SF/MXene复合膜。采用扫描电子显微镜、傅里叶变换红外光谱、X射线衍射及2400源表对复合膜的微观形貌、分子结构、导电性能以及传感性能进行了表征。结果表明：当添加4%质量分数的MXene时，复合膜具有最好的传感性能(电导率为1.24 mS/m)和机械性能(断裂应力为2.1 MPa)；复合膜经过6000次弯曲循环后电阻仍可以保持初始的大小，具有良好的稳定性和耐久性；且该传感器具有较快的响应(72 ms)和恢复时间(64 ms)。实验结果证明，SF/MXene复合膜作为一种柔性传感器具有良好的应用前景。

关键词: 丝素蛋白, MXene, 复合膜, 静电纺丝, 柔性传感器

Abstract: Flexible sensors have the characteristics of well flexibility, ductility, lightness and portability, can be bent or even folded, can adapt to the measurement of physiological signals of complex surfaces, and have a broad market in medical care, motion monitoring, robot human-computer interface, etc. However, there are still many problems to be solved in the development of flexible sensors. During fabrication of high-performance sensors, complex and costly manufacturing processes are often involved, such as 3D electronic printing, metal plasma deposition, silicon based etching and other technologies. It is difficult to achieve large-scale, low-cost, high-performance flexible sensor preparation. Therefore, it is still an urgent problem to develop flexible stress sensors with light weight, high reliability, high sensitivity, fast response, low hysteresis and good biocompatibility to adapt to different applications. MXene, as a new two-dimensional nano material, has excellent conductivity, good mechanical properties and high specific surface area. At present, MXene materials are mostly used in energy storage, catalysis, electromagnetic materials and other fields, and there is less research work in the field of flexible sensors. Therefore, studying the application of new material MXene in the field of flexible sensors and exploring its sensing mechanism will not only help broaden the application scope of MXene material, but also further develop the application of wearable electronic devices.
In order to obtain a flexible strain sensor with a large strain sensing range and high sensitivity, SF with excellent mechanical properties and good biocompatibility is used as the matrix. MXene material is obtained by etching Ti3AlC2 with HF as the additive material. The nanofiber composite membrane with high porosity, large specific surface area and high permeability is obtained by electrospinning after blending SF and MXene, and its structure and properties are analyzed. It is found that the flexible sensor prepared by this method not only has good mechanical and physical properties such as light weight, high stability, and good durability, but also has good sensing properties such as high conductivity, high sensitivity, and fast response speed, which can maintain the initial resistance after 6000 bending cycles.
MXene shows great application prospects in the field of flexible sensors. As a thin, portable and highly sensitive flexible sensor, SF/MXene sensor is convenient for people to monitor health, sports and other information anytime and anywhere, which is conducive to timely discovery, prevention or rehabilitation of diseases, and has good application prospects in medical care, sports monitoring and other fields.

Key words: silk fibroin, MXene, composite membrane, electrospinning, flexible sensor

中图分类号:

TP212

王寅, 丁新波, 刘涛, 仇巧华, 王艳敏. 基于丝素/MXene复合纳米纤维柔性薄膜的制备及其导电性能[J]. 现代纺织技术, 2023, 31(4): 63-73.

WANG Yina, DING Xinboa, LIU Taoa, b, QIU Qiaohuaa, WANG Yanminga. Preparation and conductive properties of flexible sensors based on silk fibroin/MXene composite nanofiber membranes[J]. Advanced Textile Technology, 2023, 31(4): 63-73.

参考文献

[1] ZHENG S H, WANG H, DAS P, et al. Multitasking MXene inks enable high-performance printable microelectrochemical energy storage devices for all‐flexible self‐powered integrated systems[J]. Advanced Materials, 2021, 33(10): e2005449.
[2] SALAUDDIN M, RANA S M S, SHARIFUZZAMAN M, et al. A novel MXene/ecoflex nanocomposite‐coated fabric as a highly negative and stable friction layer for high‐output triboelectric nanogenerators[J]. Advanced Energy Materials, 2021, 11(1): 2002832.
[3] MI X N, LI H, TAN R, et al. The TDs/aptamer cTnI biosensors based on HCR and Au/Ti3C2-MXene amplification for screening serious patient in COVID-19 pandemic[J]. Biosensors and Bioelectronics, 2021, 192: 113482.
[4] JIA C J, ZHU Y S, SUN F X, et al. A flexible and stretchable self-powered nanogenerator in basketball passing technology monitoring[J]. Electronics, 2021, 10(21): 2584.
[5] MAURYA D, KHALEGHIAN S, SRIRAMDAS R, et al. 3D printed graphene-based self-powered strain sensors for smart tires in autonomous vehicles[J]. Nature Communications, 2020, 11: 5392.
[6] LI Y, TIAN X, GAO S P, et al. Reversible crumpling of 2D titanium carbide (MXene) nanocoatings for stretchable electromagnetic shielding and wearable wireless communication[J]. Advanced Functional Materials, 2020, 30(5): 1907451.
[7] LIU Z K, ZHU T X, WANG J R, et al. Functionalized fiber-based strain sensors: Pathway to next-generation wearable electronics[J]. Nano-Micro Letters, 2022, 14(1): 61.
[8] LI C, CONG S, TIAN Z N, et al. Flexible perovskite solar cell-driven photo-rechargeable lithium-ion capacitor for self-powered wearable strain sensors[J]. Nano Energy, 2019, 60: 247-256.
[9] QIU A D, LI P L, YANG Z K, et al. A path beyond metal and silicon: Polymer/nanomaterial composites for stretchable strain sensors[J]. Advanced Functional Materials, 2019, 29(17): 1806306.
[10] LIU Y Q, HE K, CHEN G, et al. Nature-inspired structural materials for flexible electronic devices[J]. Chemical Reviews, 2017, 117(20): 12893-12941.
[11] ZHOU Z H, PANATDASIRISUK W, MATHIS T S, et al. Layer-by-layer assembly of MXene and carbon nanotubes on electrospun polymer films for flexible energy storage[J]. Nanoscale, 2018, 10(13): 6005-6013.
[12] JIA Z X, LI Z J, MA S F, et al. Constructing conductive titanium carbide nanosheet (MXene) network on polyurethane/polyacrylonitrile fibre framework for flexible strain sensor[J]. Journal of Colloid and Interface Science, 2021, 584: 1-10.
[13] LEVITT A S, ALHABEB M, HATTER C B, et al. Electrospun MXene/carbon nanofibers as supercapacitor electrodes[J]. Journal of Materials Chemistry A, 2019, 7(1): 269-277.
[14] GUO Y, ZHANG D Y, YANG Y, et al. MXene-encapsulated hollow Fe3O4 nanochains embedded in N-doped carbon nanofibers with dual electronic pathways as flexible anodes for high-performance Li-ion batteries[J]. Nanoscale, 2021, 13(8): 4624-4633.
[15] ZHANG X, ZHANG Z H, ZHOU Z. MXene-based materials for electrochemical energy storage[J]. Journal of Energy Chemistry, 2018, 27(1): 73-85.
[16] ZHU X Y, LIN L, WU R M, et al. Portable wireless intelligent sensing of ultra-trace phytoregulator α-naphthalene acetic acid using self-assembled phosphorene/Ti3C2-MXene nanohybrid with high ambient stability on laser induced porous graphene as nanozyme flexible electrode[J]. Biosensors and Bioelectronics, 2021, 179: 113062.
[17] SHAHZAD F, ALHABEB M, HATTER C B, et al. Electromagnetic interference shielding with 2D transition metal carbides (MXenes)[J]. Science, 2016, 353(6304): 1137-1140.
[18] CHERTOPALOV S, MOCHALIN V N. Environment-sensitive photoresponse of spontaneously partially oxidized Ti3C2 MXene thin films[J]. ACS Nano, 2018, 12(6): 6109-6116.
[19] LI N, JIANG Y, ZHOU C H, et al. High-performance humidity sensor based on urchin-like composite of Ti3C2 MXene-derived TiO2 nanowires[J]. ACS Applied Materials & Interfaces, 2019, 11(41): 38116-38125.
[20] CHIA H L, MAYORGA-MARTINEZ C C, ANTONATOS N, et al. MXene titanium carbide-based biosensor: strong dependence of exfoliation method on performance[J]. Analytical Chemistry, 2020, 92(3): 2452-2459.
[21] JIAN M Q, XIA K L, WANG Q, et al. Flexible and highly sensitive pressure sensors based on bionic hierarchical structures[J]. Advanced Functional Materials, 2017, 27(9): 1606066.
[22] SANG Z, KE K, MANAS‐ZLOCZOWER I. Design strategy for porous composites aimed at pressure sensor application[J]. Small, 2019, 15(45): e1903487.
[23] YANG K, YIN F X, XIA D, et al. A highly flexible and multifunctional strain sensor based on a network-structured MXene/polyurethane mat with ultra-high sensitivity and a broad sensing range[J]. Nanoscale, 2019, 11(20): 9949-9957.
[24] 唐培朵, 戴俊, 韦凌志, 等. 丝素蛋白纳米纤维静电纺制备的研究[J]. 生物化工, 2018, 4(4): 118-120, 128.
TANG Peiduo, DAI Jun, WEI Lingzhi, et al. Research progress of the electrospinning preparation of silk fibroin nanofibers[J]. Biological Chemical Engineering, 2018, 2018, 4(4): 118-120, 128.
[25] ZHANG H R, ZHAO J T, XING T L, et al. Fabrication of silk fibroin/graphene film with high electrical conductivity and humidity sensitivity[J]. Polymers, 2019, 11(11): 1774.
[26] 严国荣, 廖喜林, 刘让同, 等. 静电纺丝纳米纤维的应用研究进展[J]. 上海纺织科技, 2018, 46(5): 1-6.
YAN Guorong, LIAO Xilin, LIU Rangtong, et al. Advances in application of electorstatic spinning nanofibers[J]. Shanghai Textile Science, 2018, 46(5): 1-6.
[27] 袁文凤, 王军凯, 夏启勋, 等. Ti3C2 MXene柔性应力/应变传感器的制备及应用研究进展[J]. 硅酸盐学报, 2022, 50(5): 1447-1454.
YUAN Wenfeng, WANG Junkai, XIA Qixun, et al. Research progress on preparation and application of flexible stress/strain sensors based on two-dimensional Ti3C2 MXene[J]. Journal of the Chinese Ceramic Society, 2022, 50(5): 1447-1454.
[28] SHARMA S, CHHETRY A, KO S, et al. Highly sensitive and stable pressure sensor based on polymer-mxene composite nanofiber mat for wearable health monitoring[C]//33rd International Conference on Micro Electro Mechanical Systems (MEMS). Vancouver, BC, Canada. IEEE, 2020: 810-813.
[29] 王子婧. MXene的表面改性及气体传感特性研究[D]. 西安: 陕西科技大学, 2021.
WANG Zijing. Study on Surface Modification and Gas Sensing Characteristics of MXene[D]. Xi’an: Shanxi University of Science and Technology, 2021.
[30] LIANG X Y, REN X F, YANG Q Y, et al. A two-dimensional MXene-supported metal-organic framework for highly selective ambient electrocatalytic nitrogen reduction[J]. Nanoscale, 2021, 13(5): 2843-2848.
[31] NAGUIB M, KURTOGLU M, PRESSER V, et al. Two‐dimensional nanocrystals produced by exfoliation of Ti3AlC2[J]. Advanced Materials, 2011, 23(37): 4248-4253.
[32] 周晓伟. Ti3C2Tx的制备表征及其SERS应用研究[D]. 天津: 天津大学, 2018.
ZHOU Xiaowei. The Synthesis, Characterization of Ti3C2Tx and Applying on Sers Study[D]. Tianjin: Tianjin University, 2018.
[33] XUE Q, ZHANG H J, ZHU M S, et al. Photoluminescent Ti3C2 MXene quantum dots for multicolor cellular imaging[J]. Advanced Materials, 2017, 29(15): 1604847.
[34] LUO J M, TAO X Y, ZHANG J, et al. Sn4+ ion decorated highly conductive Ti3C2 MXene: promising lithium-ion anodes with enhanced volumetric capacity and cyclic performance[J]. ACS Nano, 2016, 10(2): 2491-2499.
[35] 田申. 二维Ti3C2Tx材料的制备、改性及其对TPU松弛行为的影响研究[D]. 淮南: 安徽理工大学, 2021.
TIAN Shen. Study on the Preparation and Modification of 2D Ti3C2Tx Material and Its Effect on TPU Relaxation Behavior[D]. Huai’nan: Anhui University of Science and Technology, 2021.
[36] 时志强, 吕国霞. 二维层状材料Ti3C2Tx的制备及其电化学储钠性能[J]. 天津工业大学学报, 2018, 37(6): 48-54.
SHI Zhiqiang, LÜ Guoxia. Preparation and performance of electrochemical sodium storage of two-dimension Ti3C2Tx material[J]. Journal of Tianjin Polytechnic University, 2018, 37(6): 48-54.
[37] RIAZI H, NEMANI S K, GRADY M C, et al. Ti3C2 MXene-polymer nanocomposites and their applications[J]. Journal of Materials Chemistry A, 2021, 9(13): 8051-8098.
[38] 李萌. Ti3C2Tx修饰的纸基/织物基电化学汗液传感器[D]. 上海: 东华大学, 2021.
LI Meng. Ti3C2Tx Modified Paper/Fabric Based Electrochemical Sweat Sensors[D]. Shanghai: Donghua University, 2021.
[39] 汪小亮, 冯雪为, 潘志娟. 双喷静电纺聚酰胺6/聚酰胺66纳米蛛网纤维膜的制备及其空气过滤性能[J]. 纺织学报, 2015, 36(11): 6-11, 19.
WANG Xiaoliang, FENG Xuewei PAN Zhijuan. Preparation of PA6/PA66 nano-net membranes by double-needle electrospinning and its air filtration properties[J]. Journal of Textile Research, 2015, 36(11): 6-11, 19.
[40] LI Y, ZHU J D, CHENG H, et al. Developments of advanced electrospinning techniques: A critical review[J]. Advanced Materials Technologies, 2021, 6(11): 2100410.
[41] 熊艳娜. 高强度丝素蛋白膜的制备[D]. 青岛: 青岛科技大学, 2016.
XIONG Yanna. The Preparetion of High-strength Silk Fibroin Film[D]. Qingdao: Qingdao University of Science and Technology, 2016.
[42] 梁晴晴. 光照对丝素蛋白溶解及成膜性能的探究[D]. 青岛: 青岛科技大学, 2018.
LIANG Qingqing. Light Irradiation on the Dissolution of Silk Fibroin and Its Film Formation Prorerties[D]. Qingdao: Qingdao University of Science and Technology, 2018
[43] 蒋幸子. 丝素蛋白基复合水凝胶的制备及其药物释放研究[D]. 合肥: 安徽大学, 2021.
JIANG Xinzi. Preparation of Silk Fibroin Based Composite Hydrogels and Its Drug Release Behaviors[D]. Hefei: Anhui University, 2021.