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化学进展 2020, Vol. 32 Issue (10): 1592-1607 DOI: 10.7536/PC200322 前一篇   后一篇

• 综述 •

柔性导电高分子复合材料在应变传感器中的应用*

潘朝莹1, 马建中1,**(), 张文博2,**(), 卫林峰3   

  1. 1.陕西科技大学轻工科学与工程学院 国家轻工化学实验工程示范中心 西安 710021
    2.陕西科技大学 陕西省轻化工助剂化学与技术协同创新中心 化学与化工学院 西安 710021
    3.陕西科技大学 材料科学与工程学院 西安 710021
  • 收稿日期:2020-03-24 修回日期:2020-05-10 出版日期:2020-10-24 发布日期:2020-09-02
  • 通讯作者: 马建中, 张文博
  • 基金资助:
    国家自然科学基金项目(21908141); 国家自然科学基金项目(52073164); 陕西省重点研发计划资助(2019GY-171)
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Flexible Conductive Polymer Composites in Strain Sensors*

Zhaoying Pan1, Jianzhong Ma1,**(), Wenbo Zhang2,**(), Linfeng Wei3   

  1. 1. National Demonstration Center for Experimental Light Chemistry Engineering Education, College of Bioresources Chemical and Materials Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China
    2. College of Chemistry and Chemical Engineering, Shaanxi Collaborative Innovation Center of Industrial Auxiliary Chemistry and Technology, Shaanxi University of Science & Technology, Xi’an 710021, China
    3. School of Materials Science Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China
  • Received:2020-03-24 Revised:2020-05-10 Online:2020-10-24 Published:2020-09-02
  • Contact: Jianzhong Ma, Wenbo Zhang
  • About author:
    **e-mail:(Jianzhong Ma)
    (Wenbo Zhang)
  • Supported by:
    National Natural Science Foundation of China(21908141); National Natural Science Foundation of China(52073164); Key Research and Development Program of Shaanxi Province(2019GY-171)

柔性和可穿戴传感器最近十几年来的发展,使得它们在个性化医疗、人机交互和智能机器人等方面拥有良好的应用前景。由导电材料和弹性聚合物组成的柔性导电高分子复合材料具有高的可拉伸性、良好的柔韧性、优异的耐久性等优点,可用来制备传感范围宽、灵敏度高的柔性应变传感器。本文综述了基于柔性导电高分子复合材料的可拉伸应变传感器的分类(填充型、三明治型、吸附型应变传感器)和传感机理(隧穿效应,分离机制,裂纹扩展),并详细介绍了传感器所用复合材料的结构设计,包括内部结构(双逾渗网络、隔离、多孔、“砖混”结构)、表面结构(微裂纹、褶皱结构)和宏观结构(纤维状、网状、薄膜结构)。内部结构设计可降低材料的逾渗阈值,表面结构设计可提高传感器性能,每个宏观结构都有自己的特点。最后对应变传感器的材料选择、制备工艺、结构设计、附加性能、集成技术和应用方向等方面进行了展望。

关键词： 柔性, 导电高分子, 复合材料, 应变, 传感器

The development of flexible and wearable sensors in the past decade has made them have good application prospects in personalized medicine, human-computer interaction and intelligent robots. Flexible conductive polymer composite materials composed of conductive materials and elastic polymers, which have high stretchability, excellent flexibility, durability and other characteristics, can be used to prepare flexible sensors with wide sensing range and high sensitivity. This article reviews the composite types (filled type strain sensors, sandwich type strain sensors, adsorption type strain sensors) and sensing mechanisms (tunneling effect, disconnection mechanism, crack propagation) of stretchable strain sensors based on flexible conductive polymer composite materials. The structure design of the composite materials used for the sensor is introduced in detail, including the internal structure (double percolation structure, segregation structure, porous structure, and “brick-and-mortar” structure), surface structure (wrinkles structure and microcrack structure) and macro structure (fiber structure, net structure, film structure). The internal structure design can reduce the materials’ percolation threshold, the surface structure design can improve the sensor performance, and each macro structure has its own characteristics. Finally, the developments of the sensors in material selection, preparation technology, structure design, compound mode, additional performance and application direction are prospected.

Contents

1 Introduction

2 Types of strain sensors based on flexible conductive polymer composites

2.1 Filled-type strain sensors

2.2 Sandwich-type strain sensors

2.3 Adsorption-type strain sensors

3 Internal structures of flexible conductive polymer composites for strain sensors

3.1 Double percolation structure

3.2 Segregation structure

3.3 Porous structure

3.4 “Brick-and-mortar” structure

4 Surface structures of flexible conductive polymer composites for strain sensors

4.1 Wrinkles structure

4.2 Microcrack structure

5 Macro structures of flexible conductive polymer composites for strain sensors

5.1 Fiber structure

5.2 Net structure

5.3 Film structure

6 Sensing mechanisms of strain sensors based on flexible conductive polymer composites

6.1 Tunneling effect

6.2 Disconnection mechanism

6.3 Crack propagation

7 Conclusion and outlook

Key words: flexible, conductive polymer, composites, strain, sensor
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图1 填充型应变传感器的制备过程示意图[34]
Fig.1 Schematic diagram of the filled type strain sensor fabrication process[34]. Copyright 2018, American Chemical Society
图2 三明治型BGB应变传感器的制备工艺图[45]
Fig.2 Fabrication process of sandwich type BGB strain sensor[45]. Copyright 2020, American Chemical Society
图3 基于rGOPEB的吸附型应变传感器制作过程示意图[51]
Fig.3 Fabrication process of adsorption type strain sensor based on rGOPEB[51]. Copyright 2019, John Wiley and Sons Ltd
图4 SBR/NR-GE双逾渗网络结构的(a、b)TEM图像(区域A为SBR相,区域B为含f-GE的NR相)及(c)结构示意图[53]
Fig.4 TEM images (a and b) and structure diagram (c) of SBR/NR-GE double percolation network. Region A corresponds to the SBR phase and region B represents the NR phase containing f-GE[53]. Copyright 2016, Royal Society of Chemistry
图5 PDMS/MWCNTs复合材料隔离结构示意图及SEM图像[57]
Fig.5 Structure diagram and SEM image of segregation structure of PDMS/MWCNTs composite material[57]. Copyright 2017, Royal Society of Chemistry
图6 GPN-PDMS复合材料的多孔结构示意图(a)及SEM图像(b、c)[72]
Fig.6 Structure diagram (a) and SEM images (b,c) of porous structure of GPN-PDMS composite materials[72]. Copyright 2016, American Chemical Society
图7 Ti3C2Tx-AgNW-PDA/Ni2+复合薄膜“砖混”结构示意图(a)和SEM图像(b)[76]
Fig.7 Schematic illustration (a) and SEM image (b) of the Ti3C2Tx-AgNW-PDA/Ni2+ nanocomposite film based on the “brick-and-mortar” architecture[76]. Copyright 2018, American Chemical Society
表1 不同复合材料的内部结构及其优缺点
Table 1 The internal structure of different composites and their advantages and disadvantages
Internal structure Advantage Disadvantage ref
Double percolation structure Low percolation threshold Conditions are difficult to control 53
Segregation structure Lower percolation threshold High technical requirements 58
Porous structure High sensitivity The preparation process is complex 50
“Brick-and-mortar” structure Good mechanical properties High percolation threshold 76
表2 不同复合材料的表面结构及其优缺点
Table 2 The surface structure of different composites and their advantages and disadvantages
Surface structure Advantage Disadvantage ref
Wrinkles structure High stretchability Low sensitivity 85
Microcrack structure High sensitivity Worse stability 92
图8 (a)PEA基底上沉积rGO的褶皱结构的SEM图像和示意图;(b)HWETC在不同应变下的褶皱结构变化[85]
Fig.8 (a) SEM images and illustrations of typical hierarchical wrinkles in the rGO layer deposited on the released PEA substrate; (b) Wrinkles structure changes under different strain of HWETC and SEM images are shown of short- and long-period wrinkles under the different HWETC strains[85]. Copyright 2016, Wiley-Blackwell
图9 CCTSS的裂纹结构示意图及SEM图像[92]
Fig.9 Crack structure diagram and SEM image of CCTSS[92]. Copyright 2019, American Chemical Society
表3 不同复合材料的宏观结构及其优缺点
Table 3 The macro structure of different composites and their advantages and disadvantages
Macro structure Advantage Disadvantage ref
Fiber structure Various preparation methods Bad stability 96
Net structure Good breathability Bad stability 101
Film structure Various structural design Bad breathability 104
图10 同轴纤维的光学照片(a、b)和SEM图像(c、d)及其在手指弯曲监测中的响应(e)[96]
Fig.10 Optical photos (a, b) and SEM images (c, d) of coaxial fiber and response (e) of sensor in monitoring finger bending[96]. Copyright 2018, American Chemical Society
图11 MXene/PU复合纤维的单股(a)和四股(b)的针织物网络结构示意图;(c)用四股MXene/PU复合纤维编织的肘套在伸直、弯曲时的照片及肘部套筒的应变传感响应曲线[101]
Fig.11 Single jersey textiles knitted by using (a) single- and (b) four-ply yarn of MXene/PU composite fiber and their schematic illustrations. (c) Photos of Elbow sleeve knitted by using four-ply yarn of MXene/PU composite fiber as-knitted on an elbow at straight and bent conditions and its strain sensing response curve[101]. Copyright 2020, Wiley-VCH Verlag
图12 (a)薄膜应变传感器的光学照片;(b)睡眠呼吸暂停测试[104]
Fig.12 (a) Optical photo of thin film strain sensor; (d) Obstructive sleep apnea test by the human subject[104]. Copyright 2019, American Chemical Society
图13 包含隧穿效应的CNT导电网络示意图[109]
Fig.13 Schematic view of CNT conductive network including tunneling effect[109]. Copyright 2014, American Institute of Physics
图14 石墨/丝纤维传感器分离机制示意图及等效电路图[112]
Fig.14 Schematic diagram of separation mechanism of graphite/silk fiber sensor and the equivalent electrical diagram[112]. Copyright 2016, American Chemical Society
图15 CNTs薄膜/ PDMS应变传感器的裂纹扩展机理(a)将CNTs/ PDMS复合材料从0%拉伸到60%的光学图像;(b)模拟了裂纹形态从非应变状态到应变状态的变化;(c)平均间隙宽度与应变加载之间关系;(d)传感单元的电阻模型[113]
Fig.15 Crack propagation mechanism of CNTs films/PDMS strain sensors. (a) Series of optical images of the CNTs films/PDMS composite being stretched from 0% to 60%; (b) Chinese paper cuttings simulating the change of crack morphology from unstrained to strained states; (c) Average gap width versus strain loading; (d) The resistance model of a sensing unit[113]. Copyright 2018, Royal Society of Chemistry
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