二维导电材料/柔性聚合物复合材料基可穿戴压阻式应变传感器的研究进展

可穿戴应变传感器在人体运动检测、健康监测、可穿戴电子设备和柔性电子皮肤等新兴领域具有极大的应用前景。近年来,由二维（2D）导电材料和柔性聚合物基体组成的可穿戴压阻式应变传感器具有较高的灵敏度、良好的拉伸性和柔韧性、优异的耐久性、可调的应变传感性和易加工等特点,受到广泛关注。基于此,本文对基于2D导电材料/柔性聚合物复合材料（2D-CPC）的可穿戴压阻式应变传感器的类型、传感机理、性能指标、影响因素及应用等进行了综述,并对其未来发展趋势进行了展望。     

A High–Performance Flexible Piezoresistive Pressure Sensor Features an Integrated Design of Conductive Fabric Electrode and Polyurethane Sponge

Due to its porous structure and good elasticity, conductive polyurethane (PU) sponge is used as the main substrate of the flexible piezoresistive pressure sensor. The effective combination of conductive PU sponge and electrode material is the foundation for the pressure sensor, but it needs to be bonded by expensive conductive silver paste or copper paste. In addition, the common electrode materials weaken the flexibility of the PU sponge pressure sensors because of their rigidity. Herein, PU sponge and polyester (PET) fabric are first bonded to produce (PET-PU) composite, which is then impregnated with graphene oxide (GO). The obtained reduced graphene oxide(rGO)@PET fabric and rGO@PU are used as electrode and piezoresistive material, respectively. Then rGO@(PET-PU) composite is assembled into a pressure sensor only by using wire connections in the rGO@PET fabric. Benefiting from excellent piezoresistive behavior, rGO@(PET-TPU) pressure sensor displays high sensitivity (0.255 kPa⁻¹ at below 2.6 kPa), wide detection limit (≈0–85.0%), and long durability (over 1800 cycles). Besides, the pressure sensor demonstrates good performance in monitoring human activities, including finger bending, clicking keyboard, breathing, elbow bending, and walking posture, thus providing a promising material for human activity monitoring.     

Durable and highly sensitive flexible sensors for wearable electronic devices with PDMS-MXene/TPU composite films

MXenes, as two-dimensional (2D) transition metal carbides, carbonitrides, and nitrides, have very excellent electrical properties and surface activity and are increasingly used in supercapacitors, batteries, electromagnetic interference shielding, and composite materials. Still, the poor stability of MXene when exposed to aqueous oxygen and the poor ability to interact with the polymer matrix have become important factors limiting its’ practical applications. To enhance stability, highly conductive and stretchable Ti₃C₂MXene/TPU sensing elements were prepared by a simple spraying process using thermoplastic polyurethane (TPU) as a substrate, and the sensing elements were encapsulated by polydimethylsiloxane (PDMS) to obtain MXene-TPU/PDMS constructed flexible strain sensors with excellent performance. This strain sensor features low detection limits (less than 0.005%, 0.5 μm), a wide sensing range (0–90%), a short response time (120.1 ms), and excellent durability (>3000 cycles). This strain sensor can be applied to a range of applications such as health detection, motion signals, detection of robot movements, and wearable electronic devices.     

Flexible piezoelectric sensor based on polyacrylonitrile/MWCNT/MXene composites films for human physiological health detection

Flexible piezoelectric sensors combine advantages including low-cost, flexibility, multi-functions, present a huge market prospect. In this research, multiwalled carbon nanotubes (MWCNT)/MXene/polyacrylonitrile (PAN) piezoelectric composites films for flexible piezoelectric sensors are fabricated by electrospinning technology, the planar zigzag conformation content of 97.98% in PAN composite fibers is achieved owing to the synergistic effect of MWCNT and MXene, the synergistic effect of MWCNT and MXene nanoparticles can also efficiently promote the mechanical performance and piezoelectric output. The piezoelectric sensor exhibits fast response time (10.21 ms), a possible mechanism is proposed to explain the improvement of piezoelectric effect. The sensor can measure human pulse, distinguish human movements, the fabricated sensor has broad practical value in the field of healthcare, its' use can contribute to stable and accurate measurements of physiological parameters, enabling applications in various healthcare and fitness monitoring scenarios.     

Double Network Hydrogel Sensors with High Sensitivity in Large Strain Range

Owing to their preferable flexibility and facilitation to integrate with various apparel products, flexible sensors with high sensitivity are highly favored in the fields of environmental monitoring, health diagnosis, and wearable electronics. However, great challenges still remain in integrating high sensitivity with wide sensing range in one single flexible strain sensor. Herein, a new stretchable conductive gel-based sensor exhibiting remarkable properties regarding stretchability and sensitivity is developed via improving the ionic conductivity of the PVA/P(AM-AANa) double network hydrogel. Specifically, the strain sensor developed exhibits an excellent elongation of 549%, good fatigue resistance, and recovery performance. Simultaneously, the hydrogel strain sensor shows a high conductivity of 25 mS cm⁻¹, fast response time of 360 ms, and a linear response (gauge factor = 4.75) to external strain (≈400%), which endow the sensor with accurate and reliable capacities to detect various human movements. Integrating the merits of flexibility, environment friendliness, and high sensitivity, the conductive gel-based sensor has promising application prospects in human–machine interfaces, touchpads, biosensors, electronic skin, wearable electronic devices, and so on.     

基于导电涂层微结构TPU柔性传感器的制备和性能

将具有表面微结构和平整的热塑性聚氨酯（TPU）传感基片封装成压阻型柔性压力传感器，其中前者（尺寸为10 mm×10 mm）的表面喷涂不同质量（0.02、0.05、0.1 g）的多壁碳纳米管（MWCNTs），并对微结构柔性传感基片表面形貌及传感器性能进行了表征和分析。结果表明，微结构传感基片表面上微柱顶面形成一定厚度的MWCNTs层，层内MWCNTs形成网络；喷涂较高MWCNTs质量时，传感器具有较高的灵敏度和较低的检测限，这归因于压力所致MWCNTs的网络搭接程度和传感基片间接触面积的增加量较大；喷涂0.1 g MWCNTs时，传感器的灵敏度为0.143 kPa^-1（0~3 kPa），检测限低至100 Pa，在较宽压力范围内（3~200 kPa）仍有一定的压阻响应，能在4 000次的循环压缩/释放测试（峰值压力约200 kPa）中保持稳定的压阻响应，且可准确检测典型人体运动所产生的压阻响应，具有应用于智能穿戴领域的潜能。     

A supersensitive wearable sensor constructed with PDMS porous foam and multi-integrated conductive pathways structure

In recent years, wearable multifunctional strain sensors have attracted attention for their promising applications in wearable electronics and portable devices. To achieve a high-performance wearable strain sensor with a wide sensing range and high gauge factor (GF), wisely choosing appropriate conductive materials and a rational structural design is essential. Herein, we develop a supersensitive sensor that contains one-dimensional conductive material CNT and two-dimensional material MXene built on a PDMS porous foam that is made based on a sugar template. The one-dimensional carbon nanotube (CNT) functionalizes as a conductive scale layer through solvent swelling and evaporation on the surface of the PDMS skeleton. The two-dimensional MXene is applied on top of the CNT layer to form final conductive pathways. The PDMS/CNT@MXene (PCM) sensor has a wide sensing range (150%), high sensitivity (GF = 26438), rapid response speed (response/recovery time of 60/71 ms), and exceptional durability (>1000 cycles) owing to its unique porous structure with scale layers and graded fracture of conductive pathways. Moreover, the PCM sensor is capable of monitoring subtle and significant human activities and is used for wireless sensing and medical diagnostics, even for solvent identification. The superior performance of the PCM sensor provides vast application potential in human movement, health monitoring, and warning devices.     

Preparation of multifunctional self-healing MXene/PVA double network hydrogel wearable strain sensor for monitoring human body and organ movement

In this work, a kind of conductive, self-healing hydrogel was prepared. Then it is assembled into a flexible wearable sensor for human motion detection and human-computer interaction. MXene/PVA-CBA hydrogel has super mechanical properties and excellent self-healing ability (1.8 s). It is assembled into a flexible sensor with high sensitivity, which can accurately detect various movements of the human body (ranging from frowning, speaking, and coughing on the face to bending of fingers and wrists, and body movements). Furthermore, it can be used for handwriting recognition. When it is installed on the artificial limb, it can realize the function of touching the capacitive screen. It solves the problem of using silicone prostheses to control the screen and has broad research potential in the field of intelligent robots. Therefore, the flexible wearable sensor composed of MXene/PVA-CBA hydrogel has great potential in human motion detection, bionic intelligent robot, and intelligent detection.     

MXene Reinforced PAA/PEDOT:PSS/MXene Conductive Hydrogel for Highly Sensitive Strain Sensors

Conductive hydrogel has a vital application prospect in flexible electronic fields such as electronic skin and force sensors. Developing conductive hydrogel with significant toughness and high sensitivity is urgently needed for application research. In this work, a strong and sensitive strain sensor based on conductive hydrogel is demonstrated by introducing MXene (Ti3C2Tx) into the micelle crosslinked polyacrylic acid (PAA)/poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate) (PEDOT:PSS) hydrogel network. The functional polymer micelle crosslinkers can dissipate external stress by deformation, endowing the hydrogel with high strength. The combination of MXene both improves the polymer network structure and the conductive pathways, further enhancing the mechanical properties and sensing performance. Resultantly, the flexible strain sensor base on PAA/PEDOT:PSS/MXene conductive hydrogel exhibits excellent sensing performance with a high gauge factor of 20.86, a large strain detection range of 1000%, as well as good adhesion on different interfaces. Thus, it can be used to monitor various movements of the human body and identify all kinds of handwriting, showing great potential into wearable electronics.     

Highly sensitive flexible strain sensor based on carbon nanotube/styrene butadiene styrene@ thermoplastic polyurethane fiber with a double percolated structure

The combination of a high sensitivity and a wide strain detection range in conductive polymer composites-based flexible strain sensors is still challenging to achieve. Herein, a double-percolation structural fiber strain sensor based on carbon nanotubes (CNT)/styrene butadiene styrene (SBS)@thermoplastic polyurethane (TPU) composite was fabricated by a simple melt mixing and fused filament fabrication strategy, in which the CNT/SBS and TPU were the conductive and insulating phases, respectively. Compared with the sensor without the double percolated structure, the CNT/SBS@TPU sensor achieved a lower percolation threshold (from 2.0 to 0.5 wt%, a reduction of 75%), and better electrical and sensing performance. It is shown that the strain detection range of the CNT/SBS@TPU sensor increases with increasing CNT loading. An opposite trend was observed for the sensitivity. The 1%-CNT/SBS@TPU sensor exhibited a high conductivity (1.08 × 10⁻³ S/m), high sensitivity (gauge factor of 2.65 × 10⁶ at 92% strain), wide strain detection range (0.2%–92% strain), high degree of linearity (R² = 0.954 at 0–10% strain), broad monitoring frequencies (0.05–0.5 Hz), and excellent stability (2000 cycles). Moreover, the CNT/SBS@TPU sensor was shown to successfully monitor a range of human physiological activities and to be capable of tactile perception and weight distribution sensing.     

Room temperature NH3 gas sensor based on PMMA/RGO/ZnO nanocomposite films fabricated by in-situ solution polymerization

Effective detection of ammonia gas is of great importance due to its detrimental effects on human health, environment, and ecosystem. High-performance composite gas sensors are vital in accomplishing this goal. Herein, we investigate the performance of an ammonia (NH₃) gas sensor fabricated via dip-coating the silver interdigitated electrode for PMMA/RGO/ZnO (PRZ) nanocomposite solution with acetone as a solvent. The PRZ ternary nanocomposite was synthesized using the in-situ solution polymerization method and the resistive properties of the films assembled on the interdigitated electrode were analyzed, with respect to the fixed and varying ammonia gas concentrations, using LCR meter. When the sensor is operated in the controlled chamber containing ammonia gas at room temperature, the sensor responds rapidly to ammonia with a fast recovery of 13.02 s at a gas concentration of 350 ppm. The PRZ sensor exhibits high sensing percentage response (527%), excellent repeatability (four times), high sensitivity at low concentrations (less than 10 ppm), swift response and recovery times (1.94 s/13.02 s), and long-term stability (up to 90 days) with fluctuation of 3.2%, which signifies PRZ composite as a potential material for ammonia gas sensor. Aspects such as simplicity of the synthesis process and fabrication, excellent sensing performance, as well as fast response-recovery time at a particular gas concentration are noteworthy in this study. These features can be utilized for the detection of ammonia gas in chemical and biological fields.     

Fabrication of 4H-SiC piezoresistive pressure sensor for high temperature using an integrated femtosecond laser-assisted plasma etching method

The processing, particularly, etching of brittle, hard, and anti-corrosion materials represented by the third-generation wide bandgap semiconductor silicon carbide (SiC), is a significant challenge. Although SiC has excellent electrical, mechanical, and chemical properties, the difficulty of processing limits its application in various sensor devices. To solve this problem, in this study, an integrated processing method of femtosecond laser-assisted SiC dry etching is proposed, which realizes high surface quality and high rate etching of the SiC microstructure. Specifically, the effects of different laser processing parameters on the processing effect were first studied through orthogonal experiments. Experiments indicate that compared with laser power and laser scan times, laser processing speed has a more obvious impact on the processing effect. Subsequently, considering the elastic modulus anisotropy of SiC, a 5 MPa piezoresistive pressure sensor chip was designed. Using the proposed composite processing method, a chip sensitive diaphragm was obtained. The diaphragm thickness and diameter are 76 μm and 1700 μm respectively. The overall sensor chip dimension was 4000 μm × 4000 μm × 350 μm. Static tests demonstrated that the sensor have excellent performance with sensitivity of 6.8 mV/MPa, linearity of 0.69% FS, and repeatability of 0.078% FS. In addition, by designing high-temperature packaging, the sensor achieved a pressure test at 400 °C. This study verifies the feasibility of the composite processing method, realizes the fabrication and measurement of high-temperature pressure sensors, and provides a reference for the micro-and nanostructure processing of various SiC sensors.     

Highly Stretchable and Sensitive SBS/Graphene Composite Fiber for Strain Sensors

Flexible strain sensors have attracted tremendous interests due to the emergence of intelligent wearable technology. Electrically conductive fibers are desirable candidates for flexible strain sensors, but up til now, there still exist enormous challenges to obtain conductive fibers exhibiting simultaneously high stretchability and high strain sensitivity. This paper introduces a poly (styrene‐butadiene‐styrene) (SBS)/graphene (Gr) composite fiber‐based flexible strain sensor fabricated by a facile and highly scalable wet spinning method. The results demonstrate that the graphene content has significant influence on the morphology, mechanical properties, and electromechanical properties of the composite fibers. The fibers with 5 wt% graphene have a wide response range of up to 100% strain, a high electrical sensitivity with the gauge factor of 10083.98 at 100% strain, and meanwhile, a high level of stability for 2100 stretching–releasing cycles under an applied strain of 20%. Furthermore, the SBS‐5%Gr composite fibers display excellent sensing performance in detecting human upper limb movements at different joints including hand joints, wrist joints, elbow joints, and shoulder joints.     

Low-Cost,Highly Sensitive,and Flexible Piezoresistive Pressure Sensor Characterized by Low-Temperature Interfacial Polymerization of Polypyrrole on Latex Sponge

Piezoresistive pressure sensors based on sponge are widely concerned because of their wide strain range, convenient signal acquisition, and good compressibility, yet it is still a challenge to acquire sponge-based pressure sensors with low cost and excellent sensing performance. Herein, low-priced FeCl₃^.6H₂O and pyrrole (Py) are dispersed in deionized water to form FeCl₃^.6H₂O/Py solution. Commercial latex sponge is impregnated into this solution to prepare conductive polypyrrole/latex (PPy/latex) sponge through low-temperature interfacial polymerization. The surface of latex sponge is covered by the micro-wrinkled PPy, which endows the PPy/latex sponge with a certain electrical conductivity. The specific porous structure and high elasticity of the latex sponge are the basic conditions for PPy/latex sponge excellent piezoresistive behaviors. PPy/latex sponge based piezoresistive pressure sensor shows high sensitivity (0.084 kPa⁻¹ at below 3.12 kPa), wider sensing range (0–85.0%) and long durability over 3800 s (1800 cycles). At the same time, the ability of the PPy/latex sponge based piezoresistive pressure sensor to monitor human movement has been successfully evaluated in some application scenarios, such as bending fingers, grabbing objects, tiptoe rising, and crouching.     

A Polyester/Polypyrrole Textile-Based Ultrasensitive Wearable Microdistance Sensor

Microdistance sensor, which can accurately detect the microdistance change, possesses significant applications in the cutting-edge technologies including biomedicine, energy storage, and info-communications. However, the high cost, complicated operation, and stringent testing requirements of the existing microdistance sensors limit their widespread application in the frontier fields, especially for the intelligent wearable electronics. Herein, a novel mechanism to detect microdistance change is developed, in which the external microdistance brings a change in the thickness of conductive textile and further converts into a distinguishable electrical signal. The polyester/polypyrrole (PET/PPy) conductive textile is fabricated via in situ solventless polymerization, and the derived microdistance sensor exhibits an ultrahigh sensitivity of 179 m⁻¹ within the detection region of 10–480 µm, a high resolution up to 5 µm, and good stability. The excellent sensing performance can be attributed to the high elasticity, deformation-recovery property, and 3D network structures of the PET/PPy conductive textile. Furthermore, the wearable sensor is applied to detect the microdistance changes in human and robot activities, providing an efficient and low-cost solution for microdistance detection in intelligent medical, health monitoring system, and biomimetic robot.     

A novel graphene-like titanium carbide MXene/Au–Ag nanoshuttles bifunctional nanosensor for electrochemical and SERS intelligent analysis of ultra-trace carbendazim coupled with machine learning

A new bifunctional intelligent nanosensing platform based on graphene-like titanium carbide MXene (Ti₂C MXene)/Au–Ag nanoshuttles (NSs) for both electrochemical and surface-enhanced Raman scattering (SERS) intelligent analysis of ultra-trace carbendazim (CBZ) residues in tea and rice coupled with machine learning (ML) was successfully designed. Ti₂C MXene was synthesized by selectively etching Al layers of Ti₂AlC with hydrofluoric acid and high-temperature calcination. Ti₂C MXene/Au–Ag NSs prepared by the ultrasonic dispersion of graphene-like Ti₂C MXene into Au–Ag NSs solution under dark conditions displayed large and rough surface, enhanced conductivity, excellent electrochemical response, prominent Raman enhancement, and high stability. The ML via different algorithms such as artificial neural network, support vector machine, and relevance vector machine (RVM) for the intelligent analysis of CBZ was contrasted and discussed. RVM displayed more superiority for the electrochemical analysis of CBZ in a wide linear range of 0.006 – 9.8 μM with low limit of detection (LOD) of 0.002 μM and SERS detection of CBZ in the wide linear range of 0.033 – 10 μM with low LOD of 0.01 μM. This will provide a new bifunctional intelligent sensing platform via different ML algorithms for improving accuracy of sensor via mutual verification of two or more methods of detection and a new bifunctional nanosensing platform based on the development of graphene-like nanohybrid for food and agro-products safety.     

Highly sensitive pressure sensor based on structurally modified tissue paper for human physiological activity monitoring

Pressure sensor has become an important part of physiological condition monitoring system because it can respond to small pressure in human activities. Tissue paper has been studied as a carrier of sensitive unit layer for pressure sensors in recent years due to its internal pore structure and wrinkle morphology of surface. In this work, the pore structure of the tissue paper is improved by the principle of hydration and destruction of hydrogen bonds. Based on flexible substrate of NaOH modified tissue paper (NMTP) with enhanced pore structure, combined with dip-coating composite conductive filler, the pressure sensor is fabricated by sandwiching the sensitive unit between the interdigital electrode and the microdome elastomer through layer-by-layer assembly method. Thanks to the excellent interfacial resistance effect of porous NMTP under pressure, the sensitivity of NMTP-based pressure sensor is as high as 37.5 kPa⁻¹ in a pressure range of 0–2 kPa. Finally, the follow-up studies on pressure sensors have been proven to be applicable to a variety of physiological activity such as pulse detection, respiration detection and voice recognition. The NMTP-based sensitive unit provides alternative strategy to improve performance of pressure sensors and extends potential applications in monitoring human physiological activities. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48973.     

Stretchable,Antifreezing, Non-Drying,and Fast-Response Sensors Based on Cellulose Nanocomposite Hydrogels for Signal Detection

Conductive hydrogels have received widespread attention in the applications of biosensors, human–machine interface, and health recording electrodes. Herein, the conductive hydrogels integrated with antifreezing, water retention, reusable, and sensing performances are fabricated by introducing polyvinyl alcohol, cellulose nanofibril, MXene nanosheets, and glycerol. The as-prepared hydrogels present prominent electrical conductivity (2.58 mS cm⁻¹) and flexibility even at −18 °C. In addition, the hydrogels have favorable water retention performance and can reuse after heating and cooling. When used as sensors, the hydrogels illustrate high sensitivity (gauge factor of 2.30), fast response time (0.165 s), wide working strain range (559%), favorable linearity (R² = 0.999), and wide operating temperature range (−18 to 60 °C). The hydrogels can detect not only large strains of 10–200%, but also small strains of 1–5%, making them promising candidates for wearable sensors to monitor large and subtle movements.     

3D-Printed Flexible Piezoresistive Sensors for Stretching and Out-of-Plane Forces

Conductive polymer composites (CPCs) of carbon nanotubes (CNTs) and graphite nanosheet (GNP)-filled thermoplastic polyurethane (TPU) are 3D-printed into flexible piezoresistive sensors via fused filament fabrication. The sensor, with a customized lever-cross structure, allows detection of stretching and out-of-plane forces of different magnitudes and frequencies. The out-of-plane force direction is obtained by combing the relative electrical resistance change in the cross section of the sensor with a force analysis. The 75-CNT/25-GNP sensor (CNT-to-GNP mass ratio of 75%-to-25%) demonstrates excellent sensing performance at a total nanoparticle loading of 3 wt%. The linearity of the 75-CNT/25-GNP sensor is 0.98, while those of the 100-CNT and 50-CNT/50-GNP sensors are 0.93 and 0.86, respectively. The gauge factor of the 75-CNT/25-GNP sensor is 52% higher than that of the 100-CNT sensor, and its sensing strain range is 79% above that of the 50-CNT/50-GNP sensor. Excellent sensing stability is demonstrated for the 75-CNT/25-GNP sensor after 1500 stretching (out-of-plane force) cycles. The synergistic effect of CNTs and GNPs on sensing performance of piezoresistive sensors is clearly shown in this study.     

A High Strength Hydrogel with a Core–Shell Structure Simultaneously Serving as Strain Sensor and Solar Water Evaporator

A super-strong poly (acrylic acid)- poly(3,4-ethylene dioxythiophene) (PAA-PEDOT) hydrogel with a unique core-shell structure is successfully constructed and studied. The shell composed of the conductive polymer PEDOT makes the composite hydrogel possess mechanical strength, electrical conductivity, and photothermal conversion properties, while the PAA hydrogel core ensures the flexibility, recovery, and water absorption of the composite hydrogel. The prepared PAA-PEDOT hydrogel displays outstanding tensile strength (up to 780 KPa) and satisfactory conductivity (6.6 S m⁻¹). Notably, the flexible strain sensor made of PAA-PEDOT composite hydrogel presents both high sensitivity (gauge factor up to 8.87) and short response time (<200 ms), demonstrating that the composite hydrogel can accurately and timely detect the movement of human joints. In addition, PAA-PEDOT composite hydrogel also has excellent photothermal conversion properties and can be used as a highly efficient solar water evaporator, which has a water evaporation efficiency of up to 3.05 kg m⁻² h and an excellent photothermal conversion efficiency of 95% under 1-sun irradiation (1kW m⁻²). These features make the composite hydrogel has great potential in many fields such as motion sensing, seawater desalination, and wastewater treatment.