聚氨酯-碳纳米管@碲化铋复合气凝胶的制备及传感性能

doi:10.15541/jim20250286

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 619-627.DOI: 10.15541/jim20250286 CSTR: 32189.14.jim20250286

聚氨酯-碳纳米管@碲化铋复合气凝胶的制备及传感性能

曹颖¹^,²(), 彭露¹, 夏双¹^,², 白菊¹, 张珽¹^,²(), 李铁¹^,²()

¹ 中国科学院苏州纳米技术与纳米仿生研究所, 苏州 215123
² 中国科学技术大学纳米科学技术学院, 苏州 215100

收稿日期:2025-07-08 修回日期:2025-10-21 出版日期:2026-05-20 网络出版日期:2025-11-11
通讯作者: 张珽, 研究员. E-mail: tzhang2009@sinano.ac.cn;
李铁, 研究员. E-mail: tli2014@sinano.ac.cn
作者简介:曹颖(2001-), 女, 硕士研究生. E-mail: cy13897985409@mail.ustc.edu.cn
基金资助:
江西省自然科学基金杰出青年基金(20224ACB212001);国家自然科学基金(62471466);国家自然科学基金(62125112);姑苏领军人才项目(ZXL2024378)

Polyurethane-carbon Nanotubes@Bismuth Telluride Hybrid Aerogel: Preparation and Sensing Properties

CAO Ying¹^,²(), PENG Lu¹, XIA Shuang¹^,², BAI Ju¹, ZHANG Ting¹^,²(), LI Tie¹^,²()

¹ Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, China
² School of Nano Science and Technology, University of Science and Technology of China, Suzhou 215100, China

Received:2025-07-08 Revised:2025-10-21 Published:2026-05-20 Online:2025-11-11
Contact: ZHANG Ting, professor. E-mail: tzhang2009@sinano.ac.cn;
LI Tie, professor. E-mail: tli2014@sinano.ac.cn
About author:CAO Ying (2001-), female, Master candidate. E-mail: cy13897985409@mail.ustc.edu.cn
Supported by:
Jiangxi Provincial Natural Science Foundation of Distinguished Young Scholars Fund Project(20224ACB212001);National Natural Science Foundation of China(62471466);National Natural Science Foundation of China(62125112);Gusu Leading Talent Program(ZXL2024378)

摘要/Abstract

摘要：

随着仿生人形机器人等智能装备的快速发展, 具有仿人手指触感功能的柔性触觉传感器技术受到广泛关注。然而, 现有多模态柔性触觉传感器所用敏感材料缺乏选择性响应能力, 导致其所输出信号易产生相互交叉干扰的现象, 难以满足系统轻量化、集成化的发展需求。基于此, 本研究设计并制备了一种新型聚氨酯-碳纳米管@碲化铋(WPU-CNT@Bi₂Te₃)复合气凝胶敏感材料, 通过组分比例优化, 其最大压缩应变可达60%、压缩强度为9.4 kPa。CNT的压阻效应可实现对机械压力刺激的响应, 而Bi₂Te₃的热电效应则能够快速响应外界温度的变化。基于这两种独立感知机制, 本研究构建的柔性触觉传感器实现了对压力与温度的高灵敏感知(压力灵敏度系数(GF)为-1.28 kPa^-1, 温度响应灵敏度为1.2 K^-1, 最小感知温差为0.4 K), 具有快速(压阻响应时间为0.14 s、恢复时间为0.18 s, 温度响应时间最快为0.28 s)、高稳定(1300次热循环输出值不衰减)且互不干扰的响应能力, 并赋予了所集成机械手对物体软硬及温度等性质的感知功能。

关键词: 气凝胶, 柔性传感器, 压阻效应, 热电效应

Abstract:

With the rapid development of intelligent equipment such as bionic humanoid robots, flexible tactile sensors have attracted increasing attention for their bionic haptic behaviors similar to human fingers. However, the existing sensing materials used for assembling multimodal flexible tactile sensors still lack the high-selective response capabilities, resulting in the cross-interference phenomenon of various output signals, which is difficult to meet the lightweight and integrated requirements of microsystems. In this study, a new-style polyurethane-carbon nanotubes@bismuth telluride (WPU-CNT@Bi₂Te₃) hybrid aerogel was designed and prepared, which exhibits a maximum compressive strain of 60% and a compressive strength of 9.4 kPa via the optimization of component ratios. Furthermore, according to the independent sensing principles of the piezoresistive effect of CNTs to mechanical pressure stimuli, and the thermoelectric effect of Bi₂Te₃ to changes in the external temperature, this hybrid aerogel derived flexible tactile sensor achieves high sensitivity (GF value of -1.28 kPa^-1, temperature response sensitivity of 1.2 K^-1, and minimum response temperature difference of 0.4 K) and rapid response behaviors (response and recovery times of 0.14 and 0.18 s for pressure, optimal response time of 0.28 s for temperature) to temperature and pressure, with high sensing stability (no degradation after 1300 thermal cycles) and non-mutual interference behaviors, endowing the equipped robotic hand with the perception capability to recognize both the hardness and temperature of various objects.

Key words: aerogel, flexible sensor, piezoresistive effect, thermoelectric effect

中图分类号:

TB332
O613

曹颖, 彭露, 夏双, 白菊, 张珽, 李铁. 聚氨酯-碳纳米管@碲化铋复合气凝胶的制备及传感性能[J]. 无机材料学报, 2026, 41(5): 619-627.

CAO Ying, PENG Lu, XIA Shuang, BAI Ju, ZHANG Ting, LI Tie. Polyurethane-carbon Nanotubes@Bismuth Telluride Hybrid Aerogel: Preparation and Sensing Properties[J]. Journal of Inorganic Materials, 2026, 41(5): 619-627.

图/表 12

图1 WPU、Bi2Te3、CNT@Bi2Te3及WPU-CNT@Bi2Te3的XRD图谱

Fig. 1 XRD patterns of WPU, Bi2Te3, CNT@Bi2Te3 and WPU-CNT@Bi2Te3

图2 WPU-CNT@Bi2Te3气凝胶的微观形貌结构及元素分布

Fig. 2 Microscopic morphology, structure and elemental distribution of the WPU-CNT@Bi2Te3 aerogel (a, b) SEM images of the microscopic porous morphology of the aerogel; (c) TEM images of the crystal structure of CNT@Bi2Te3 in the hybrid; (d) Elemental distribution mappings of C, O, Te and Bi in the aerogel

图3 基于WPU-CNT@Bi2Te3气凝胶的柔性触觉传感器的静态压力响应性能

Fig. 3 Static pressure response performance of the WPU-CNT@Bi2Te3 aerogel derived flexible tactile sensor (a) Resistance changing rates of the flexible tactile sensor under different pressures; (b) Corresponding response sensitivity of the flexible sensor; (c) I-V response curves of the flexible device under different pressures. Colorful figures are available on website

图4 基于WPU-CNT@Bi2Te3气凝胶的柔性触觉传感器的动态压力响应性能

Fig. 4 Dynamic pressure response performance of the WPU-CNT@Bi2Te3 aerogel derived flexible tactile sensor (a) Response and recovery time; (b) Relationship between strain and resistance changing rate; (c) Resistance changing rates under the stepwise compression-recovery gradient test; (d) Influence of compression rate on the resistance variation. Colorful figures are available on website

图5 基于WPU-CNT@Bi2Te3气凝胶的柔性触觉传感器的温度响应原理及基本性能

Fig. 5 Schematic diagram and basic response performance of the WPU-CNT@Bi2Te3 aerogel derived flexible tactile sensor for temperature variations (a) Schematic diagram of the temperature-response output; (b) Thermoelectric output voltages under different temperature differences; (c) Seebeck coefficient fitting result; (d) Thermoelectric output voltages during the dynamic process of continuous heating and cooling

图6 基于WPU-CNT@Bi2Te3气凝胶的柔性触觉传感器的温度动态区分性响应及稳定性能

Fig. 6 Dynamic temperature discriminatory response and stability of the WPU-CNT@Bi2Te3 aerogel derived flexible tactile sensor (a) Dynamic discriminatory response behavior and (b) response time to positive and negative temperature differences; (c) Response results to the tiny temperature difference between the sensor and the fingers; (d) Response stability of the sensor under 1300 thermal cycles. Colorful figures are available on website

图7 柔性触觉传感器的压力与温度响应互不干扰特性

Fig. 7 Non-interference characteristics of the flexible sensor regarding to the pressure and temperature response behaviors (a) Influence of compression deformation on the temperature response behavior; (b) I-V curves under the same pressure (3 N) with different temperature differences; (c) Influence of temperature difference on the pressure response behavior. Colorful figures are available on website

图8 集成柔性触觉传感器的机械手用于物体性质感知

Fig. 8 Practical performance of a robotic hand integrated with flexible sensor applied to recognize the properties of objects (a) Piezoresistive outputs for objects with different hardness and (b) corresponding linear relationship of hardnesses and outputs; (c) Thermoelectric voltages of water cups with different temperatures and (d) corresponding linear relationship of temperatures and outputs

图S1 WPU-CNT@Bi2Te3气凝胶材料的制备工艺流程图

Fig. S1 Preparation process flow chart of the WPU-CNT@Bi2Te3 aerogel

图S2 不同CNT@Bi2Te3质量分数气凝胶的电阻率与塞贝克系数

Fig. S2 Electrical resistivities and Seebeck coefficients of aerogels with different mass percentages of CNT@Bi2Te3

图S3 WPU-CNT@Bi2Te3气凝胶的压缩力学性能

Fig. S3 Compression performance of WPU-CNT@Bi2Te3 aerogel (a) Optical image of practical recovering status under a strain of 50%; Stress-strain behaviors under (b) various compression strains of 10%-60% and (c) different compression speeds of 20-300 mm/min; (d) Cyclic test under a strain of 30%

表S1 基于WPU-CNT@Bi2Te3气凝胶柔性触觉传感器与文献报道传感器性能对比

Table S1 Comparison of performance between WPU-CNT@Bi2Te3 aerogel-based flexible tactile sensor and relevant studies

Sensitive material system	Sensor device structure	Multifunctional parameters	Sensing mechanism	Decoupling capability	Integration difficulty/Cost	Pressure sensitivity	Temperature sensitivity	Ref.
WPU-CNT@Bi₂Te₃	Aerogel monolith	Temperature, pressure	Thermoelectric piezoresistive	√	√ General	-19.9%/N (1.28 kPa^-1)	12.8 μV/K (1.2 K^-1)	This work
Ag nanoparticle/PDMS	Aerogel monolith	Temperature, pressure	Thermoelectric	×	× Relatively high	\	0.0017 K^-1	[15]
MWCNTs	Conventional membrane	Temperature, pressure	Thermoelectric piezoresistive	√	× General	0.74 kPa^-1	0.95 K^-1	[16]
PEDOT: PSS	Aerogel monolith	Temperature, pressure	Thermoelectric piezoresistive	√	× General	28.9 kPa^-1	<0.1 K^-1	[20]
PTFE	Conventional membrane	Pressure	Triboelectric	×	√ General	\	\	[24]
PEDOT:PSS/CNT	Conventional membrane	Static pressure, dynamic pressure	Triboelectric piezoresistive	×	× Relatively high	291699.6 kPa^-1	\	[25]
Liquid metal	Conventional membrane	Static pressure, dynamic pressure	Triboelectric	×	× Relatively high	\	\	[S1]
GO-PDMS/PTFE	Conventional monolith	Temperature, pressure	Triboelectric piezoresistive	√	× General	15.22 kPa^-1	1 K^-1	[S2]
Ag nanowires	Conventional membrane	Temperature, pressure	Thermal conductivity piezoresistive	×	× Relatively high	\	0.05 K^-1	[S3]
PDMS/liquid metal/NdFeB	Conventional monolith	Non-contact pressure	Magnetoelastic piezoresistive	√	× Relatively high	0.27 kPa^-1	\	[S4]
PDMS/ionic liquid	Conventional membrane	Non-contact pressure	Piezoresistive capacitance	√	× Relatively high	0.93 kPa^-1	\	[S5]

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聚氨酯-碳纳米管@碲化铋复合气凝胶的制备及传感性能

Polyurethane-carbon Nanotubes@Bismuth Telluride Hybrid Aerogel: Preparation and Sensing Properties

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