Home Journals Progress in Chemistry
Progress in Chemistry

Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

About  /  Aim & scope  /  Editorial board  /  Indexed  /  Contact  / 
Review

High-Sensitivity Flexible Pressure Sensor Based on Micro-Nano Structure

  • Yan Bao , 1, 2, * ,
  • Jiachen Xu 1 ,
  • Ruyue Guo 1 ,
  • Jianzhong Ma 1
Expand
  • 1 College of Bioresources Chemical and Materials Engineering (College of Flexible Electronics), Shaanxi University of Science & Technology,Xi’an 710021, China
  • 2 National Demonstration Center for Experinenced Light Chemical Engineering Education, Shaanxi University of Science & Technology,Xi’an 710021, China
* Corresponding author e-mail:

Received date: 2022-10-25

  Revised date: 2023-02-24

  Online published: 2023-04-30

Supported by

National Natural Science Foundation of China(22078188)

Xianyang City Qin Chuangyuan Science and Technology Innovation Special Project(2021ZDZX-GY-0007)

Abstract

In recent years, with the development and popularization of Internet and artificial intelligence, the flexible pressure sensor with light, convenience and excellent electronic performance, as the core device of wearable electronic equipment, has a increasingly broad market. Flexible pressure sensors have attracted extensive attention in electronic skin, motion detection, medical monitoring and man-machine interface because of its flexibility, folding and excellent sensing performance. The construction of micro-nano structures is the key to improve the sensitivity and sensing performance of pressure sensors. Based on this, the sensing mechanism (piezoresistive, capacitive, piezoelectric, triboelectric) and key performance parameters (sensitivity, pressure response range, detection limit, response/recovery time, stability of circulation and linearity, etc.) of the high-sensitivity pressure sensors were summarized. Then, research progress of flexible pressure sensors using substrates to construct surface micro-nano structures (micro-convex structure, bramble structure and fold structure) and using conductive materials to construct micro-nano structures (micro-sphere structure, urchin structure and cellular structure) were compared and concluded. Furthermore, the application status of high-sensitivity flexible pressure sensors based on micro-nano structure in pulse detection, electronic skin, motion detection and man-machine interface was concluded. Finally, from the perspective of future application, the challenges and development direction of high sensitivity flexible pressure sensor are summarized.

Contents

1 Introduction

2 Sensing mechanism and key performance parameters of high sensitivity flexible pressure sensor

2.1 Sensing mechanism

2.2 Key performance parameters

3 Construction of high sensitivity flexible pressure sensor based on micro-nano structure of substrate materials

3.1 Micro-convex structure

3.2 Bramble structure

3.3 Fold structure

4 Construction of high sensitivity flexible pressure sensor based on micro-nano structure of conductive materials

5 Application of high sensitivity flexible pressure sensor based on micro-nano structure

6 Summary and outlook

Cite this article

Yan Bao , Jiachen Xu , Ruyue Guo , Jianzhong Ma . High-Sensitivity Flexible Pressure Sensor Based on Micro-Nano Structure[J]. Progress in Chemistry, 2023 , 35(5) : 709 -720 . DOI: 10.7536/PC221014

1 Introduction

With the continuous development of intelligent and miniaturized technology, flexible pressure sensors have been widely studied. Flexible pressure sensor is a kind of sensor which can convert the input external force signal into electrical signal output through signal conversion and conduction, and has excellent external force sensing ability[1~3]. High-sensitivity pressure sensors can more accurately sense small human activities, such as breathing and heartbeat, so they can simulate real skin in the fields of new health care, electronic skin and multi-modal perception.In the field of soft robot, it can accurately sense the change of electrical signal caused by pressure, which is conducive to the realization of human-computer interaction function[4,5][6,7].
Micro-nano structures widely exist in nature, such as lotus leaves with the characteristics of "out of the mud but not stained", geckos with the ability to climb eaves and walls, water striders with micro-steps, and turtles with thousands of miles of knowledge, all of which are endowed by their special micro-nano structures in body structure[8,9]. The small size effect and large specific surface area brought by the micro-nano structuring of materials can not only improve the performance of materials, but also enrich the functions of materials, which is no exception for sensing materials[10]. For example, Wang et al., inspired by the fine micron-sized villi on spider legs, grew villous carbon nanotubes (CNTs) on the surface of carbon silk fabric in situ, and prepared an ultrasensitive all-textile flexible pressure sensor[11]. The fluffy CNT-modified fabric makes the sensor have a special micro-nano structure, which increases the contact area of the conductive material, thus endowing the sensor with excellent sensing performance. From the above, it can be seen that the construction of multi-scale micro-nano structure is the main way to improve the sensitivity of flexible pressure sensor[12~14].
Based on this, the research progress of high sensitivity flexible pressure sensors based on micro-nano structures is reviewed in this paper. Firstly, the sensing mechanism and key performance parameters of the high sensitivity pressure sensor are analyzed and summarized. Secondly, based on the two main ways to construct micro-nano structures, namely, using substrates to construct surface micro-nano structures and using conductive materials to construct micro-nano structures, the research progress, advantages and disadvantages of various methods are summarized and analyzed. Then, the application status of high sensitivity flexible pressure sensor based on micro-nano structure in pulse monitoring, electronic skin and motion detection is described. Finally, the challenges and future development directions of high-sensitivity flexible pressure sensors based on micro-nano structures are prospected.

2 Sensing Mechanism and Key Performance Parameters of High Sensitivity Flexible Pressure Transducer

2.1 Sensing mechanism

Flexible pressure sensor is a kind of sensor that can convert external force signals (such as bending, torsion, stretching and other stimuli) into resistance, current or capacitance signals. According to the different sensing mechanisms, it can be divided into four types: piezoresistive, capacitive, piezoelectric and triboelectric[15~18].
Piezoresistive pressure sensor is a kind of sensor that converts pressure change into resistance or current signal. Its resistance change formula is: R = ρL/A (ρ is the resistivity of the material, L and A are the length and surface area, respectively). The sensing mechanism is shown in Figure 1A. When external pressure is applied, the material will deform, which indirectly changes the distribution density and contact state of the conductive material inside the sensor, so that the electrical signal of the sensor changes regularly. Therefore, the piezoresistive pressure sensor has a simple structure and a wide detection range compared with other sensors, and is widely used in real-time health monitoring, intelligent robots, and artificial limbs[19,20]. For example, Zhou et al. Used electrospinning technology to prepare an ultra-thin sensing layer, which is a composite nanofiber film composed of poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) and polyamide 6, and connected electrodes on the upper and lower sides of the sensing layer.A flexible piezoresistive pressure sensor with high sensitivity (6554.6 kPa-1), fast response time (53 ms), wide detection range (0 ~ 60 kPa) and good cyclic stability (> 10 000 times) is obtained, which can detect human movements such as respiration, pulse, hand and wrist[21].
图1 不同压力传感器的传感机理:(a)压阻式;(b)电容式;(c)压电式;(d)摩擦电式

Fig. 1 The sensing mechanism of different pressure sensors: (a) piezoresistive; (b) capacitive; (c) piezoelectric; (d) triboelectric

Capacitive pressure sensor is a kind of sensor with parallel plate capacitor as the sensing element, which is usually composed of upper and lower electrode plates, insulator and substrate. The capacitance change formula is C=ε0εrA/d(C is the capacitance, ε0 is the vacuum permittivity, εr is the relative permittivity, and d is the plate spacing). The sensing mechanism is shown in Figure 1b. When subjected to pressure, the distance between the upper and lower electrode plates changes, resulting in a change in capacitance. Capacitive pressure sensor has the advantages of large detection range, high sensitivity, simple structure and low energy consumption. For example, Yu et al. Designed a multi-walled carbon nanotube/polydimethylsiloxane (MWCNTs/PDMS) electrode layer and a barium titanate/polydimethylsiloxane (BaTiO3/PDMS) dielectric layer with micro-convex structure embedded in the surface, and obtained a flexible capacitive pressure sensor with high sensitivity (2.39 kPa-1), wide pressure detection range (0 – 120 kPa), low detection limit (6.8 Pa) and fast response time (16 ms), which can identify postures such as sitting, standing, walking and running[22].
Piezoelectric pressure sensor is a kind of sensor based on pressure-sensitive effect, which can realize the conversion between mechanical energy and electrical energy. The conduction mechanism is shown in Figure 1C. When the material is deformed under pressure, the positive and negative charges inside the functional material are separated, and opposite charges are generated on the two surfaces, and a potential difference is formed inside. The pressure is determined by detecting the change of the potential difference. Compared with other sensors, piezoelectric pressure sensors can directly convert mechanical energy into electrical energy, which is of great significance to promote the realization of self-powered sensing technology. Park et al. Synthesized a lead zirconate titanate piezoelectric film and bonded it on a polyethylene terephthalate substrate to prepare a self-supplied voltage electric pulse sensor with high sensitivity (0.018 kPa-1), fast response time (60 ms) and good mechanical stability, which can be completely attached to the skin surface to respond to tiny pulse signals from the human body[23].
The triboelectric pressure sensor is a pressure sensor based on the coupling effect of triboelectrification and electrostatic induction, which is composed of two kinds of friction materials with opposite polarities. The sensing mechanism is shown in Figure 1 d. When pressure is applied, two different materials come into contact with each other, and opposite electrostatic charges are generated on the surface. As the pressure decreases, the two materials separate from each other, and the electrodes on the back of the two triboelectrically charged materials generate charges by electrostatic induction. This creates a potential difference that causes electrons to transfer through an external circuit until an equilibrium state is reached when the two materials are completely separated. Compared with piezoresistive and capacitive pressure sensors, triboelectric pressure sensors can work normally without power supply. Compared with piezoelectric pressure sensors, triboelectric pressure sensors have high sensitivity and many kinds of sensing materials to choose from[24]. Shlomy et al. Used PDMS as the negative electric layer, nylon and cellulose butyl acetate as the positive electric layer, and prepared a triboelectric pressure sensor by bonding metal electrodes. Implanted it under the skin, it can convert tactile pressure into potential, which can be transmitted to sensory nerves through electrodes to simulate tactile sensation and compensate for traumatic peripheral nerve injury[25]. The triboelectric pressure sensor-based triboelectric nanogenerator exhibits the advantages of high energy conversion efficiency, excellent performance, and easy processing, which brings new opportunities and challenges for self-powered wearable electronic devices.

2.2 Key performance parameter

Although different flexible pressure sensors have different sensing mechanisms and have their own advantages and disadvantages, the key performance indicators of flexible pressure sensors are the same.It mainly includes sensitivity, pressure detection range, detection limit, response/recovery time, cycle stability, etc. See Table 1 for the specific definition of performance indicators, the meaning expressed, and the way to improve.
表1 柔性压力传感器的关键性能参数

Table 1 Key performance parameters of flexible pressure sensor

It can be seen from Table 1 that a flexible pressure sensor with excellent performance requires a device with both high sensitivity and wide pressure response range. At the same time, low detection limit, short response/recovery time, high cycling stability and linearity are also the key indicators to be pursued for flexible pressure sensors, which are crucial for the reliable operation of sensors in new health care, pulse detection and electronic skin[30~33]. However, it is unrealistic to pursue all of the above properties to the extreme. Therefore, at present, the focus of attention in the development of flexible pressure sensors is first on the sensitivity, followed by the pressure response range, that is, to ensure the performance of the sensor before paying attention to its scope of application. According to the literature, the main factors affecting the sensitivity of the sensor are the substrate material and the microstructure of the sensing material.

3 High Sensitivity Flexible Pressure Sensor Based on Substrate Material Micro-nano Structure

In recent years, the fabrication of pressure sensors using substrate materials with surface microstructures has been shown to successfully achieve sensitivity improvement. The surface microstructure of existing substrate materials mainly includes micro-convex structure, thorn-like structure and wrinkle structure[34][35][36].

3.1 Micro-convex structure

Typical micro-convex structures mainly include micro-dome structure, micro-cone structure and micro-cylinder structure. Each micro-convex structure has its own characteristics, which can meet the needs of pressure sensors in different application directions. The micro-convex structure is easy to deform under small pressure, which can significantly increase the contact area of the active layer, thus producing a large electrical signal change and effectively improving the sensitivity of the pressure sensor. In addition, the deformation of the micro-convex structure can also broaden the pressure detection range.
Micro-dome structure is one of the most common surface micro-convex structures. Generally speaking, there are many smooth micro-bulges on the surface of the substrate material. Tang et al. Fabricated a graphene oxide (GO)/silicone rubber resistive pressure sensor based on a micro-dome structure using a one-step foaming strategy and a photolithography technique, as shown in Fig. 2[37]. By changing the foaming time to change the structural characteristics of the micro-dome, the sensitivity and linear working range of the pressure sensor can be adjusted. When the foaming time is 3 min, the sensitivity of the sensor is 0.19 kPa-1(0~4.2 kPa), which is much higher than that of the pressure sensor with flat surface (0.04 kPa-1). In addition, the sensor has a wide sensing range (0 ~ 100 kPa), short response time (75 ms) and recovery time (80 ms). The above results show that the flexible pressure sensor based on micro-dome structure has a good balance between sensitivity and linear sensing range, and can be applied in human body pulse detection, finger click detection, grip force sensing, etc. In order to further improve the sensitivity of the pressure sensor, Park et al. coated a mixture of CNT and PDMS on a silicon mold with a micro-dome structure, peeled it off from the mold after curing, prepared a conductive film with a uniform micro-dome array, and assembled it into a pressure sensor, as shown in Figure 3[38]. The sensor is based on the change of tunneling current between two microdome arrays. The external pressure causes stress concentration at small contact points and local deformation in the microdomain, which leads to the increase of contact area and tunneling current, and slows down the effect of hysteresis on the sensing performance. The sensor has a sensitivity of 15.1 kPa-1, a response time of 40 ms, and a detection limit of 0. 2 Pa, and has application prospects in health monitoring, motion detection, and so on. Although the sensitivity of the pressure sensor based on the micro-dome structure can be improved, and the response time and the sensing range can be improved, the improvement of the sensitivity of the structure is limited due to the smooth surface bulge.
图2 基于表面微穹顶结构的电阻式压力传感器:(a)微穹顶结构设计图;(b)受压时微穹顶结构顶点接触图;(c)灵敏度曲线图[37]

Fig. 2 Resistance pressure sensor based on surface micro dome structure: (a) design drawing of micro dome structure; (b) contact diagram of micro dome structure under compression; (c) sensitivity curve[37]

图3 基于微穹顶CNTs/PDMS薄膜的压力传感器:(a)微穹顶CNT/PDMS薄膜的制备过程;(b)传感机理图;(c)传感性能比较[38]

Fig. 3 Sensitivity curve of pressure sensor based on micro dome CNTs/PDMS film: (a) preparation process of CNT/PDMS thin films for micro dome; (b) preparation process of CNT/PDMS thin films for micro dome; (c) comparison of sensing performance[38]

The stress distribution of the micro-cone structure is not uniform, usually concentrated at the tip, so it shows the advantages of improving the sensitivity that the micro-dome structure does not have[39]. When pressure is applied, the tip of the micro-cone structure will be compressed more, resulting in higher mechanical deformation, greater electrical signal changes and improved sensitivity. Cao et al. First prepared a silicon mold with an inverted micro-cone structure, and sprayed single-walled carbon nanotubes (SWCNTs) on its surface. Finally, they spun the PDMS prepolymer and cured it to obtain a SWCNTs/PDMS composite film with a micro-cone structure, based on which they prepared a pressure sensor.The sensor has high sensitivity (3.26 kPa-1), short response/recovery time (200 ms/100 ms) and good cycling stability. It can recognize various textures like human fingerprint epidermis, such as textures of different fabrics, Braille, etc. It has great potential applications in robot skin and tactile perception[40]. As such,
Ma et al. Used the inverse template method to fabricate a flexible pressure sensor based on PDMS and CNT conductive micro-cone structure, as shown in Fig. 4[28]. A further improvement is that the sensor systematically adjusts the pressure sensing characteristics of the device by adjusting the spacing of the micro-cones and the length of the substrate. When the ratio of microcone spacing to substrate length is 1:1, the sensor has high sensitivity (0.34 kPa-1) in the range of 10 – 100 kPa, fast response time (48 ms), low hysteresis, low operating voltage (0.1 mV), and high mechanical robustness. The optimized sensor is integrated into a wearable pressure sensor system to realize the potential application in electronic skin. However, the tip of the micro-cone structure is easy to be worn during use, so its cyclic stability is not enough compared with the micro-dome structure.
图4 基于微锥结构的CNT/PDMS压力传感器等效电路及外观照片[28]

Fig. 4 Equivalent circuit and appearance photos of CNT/PDMS pressure sensor based on micro-cone structure[28]

The micro-cylinder structure has a larger contact area than the micro-dome structure, and has better structural stability than the micro-cone structure, so the advantages of the two structures can be integrated to better improve the sensing performance of the flexible pressure sensor. Lin et al. Prepared a PDMS film with a microcylinder array and a polyvinylidene fluoride (PVDF) fiber sensing electrode, and assembled them into a capacitive pressure sensor[41]. The high dielectric coefficient of PVDF and the voids generated by electrospinning are beneficial to the formation of a special expansion layer, and a novel double dielectric layer structure is obtained by combining the array micropillars. When pressure is applied on the sensor, the fiber layer releases air in the gap, and a slight pressure also changes the distance between the electrodes, thus improving the sensitivity of the sensor. When the pressure on the sensor is released, the cylinder pressed into the fiber quickly expands the distance between the electrodes, and the fiber layer compressed by the pressure quickly returns to its original bulky state. This microcylinder structure can respond quickly to changes in the distance between the electrodes and slow down the effects of hysteresis, thereby increasing the capacitance change and durability of the sensor. The sensor has a sensitivity of 0.6 kPa-1, a response time of 25 ms, a detection limit of 0. 06 Pa, and a good cyclic stability (> 10 000 cycles), and can be successfully applied to pulse, limb movement, respiration, and acoustic vibration. In addition, Lu et al. Prepared anodic aluminum oxide templates (t-AAO) with different heights by alternating oxidation and pre-broadening using phosphoric acid/oxalic acid as electrolyte, and used them as reaction vessels to polymerize pyrrole monomers into polypyrrole (PPy) on the pore walls of t-AAO templates through in-situ polymerization.Finally, a microcylinder structured film was prepared by coating a polymethylmethacrylate/N, N-dimethylformamide mixed solution, and the film was assembled together face to face to obtain a highly interlocked structure with interlocked nanoarrays (IOCA) pressure sensor, as shown in fig. 5[42]. The sensor has high sensitivity (268.36 kPa-1) in the pressure range of 0 to 200 Pa, fast response/recovery (48/56 ms) and good repeatability and continuity, and can accurately detect wind speed, wrist torsion and bending, which has a wide range of applications in wearable medical monitoring, electronic skin and so on.
图5 (a)基于微锥结构的IOCA压力传感器的制备过程示意图;(b)灵敏度拟合曲线图;(c)传感机理如图[42]

Fig. 5 IOCA pressure sensor based on micro cone structure. (a) Schematic diagram of preparation process; (b) sensitivity fitting curve; (c) the sensing mechanism is shown in figure[42]

3.2 Bramble texture

The small initial current and the significant change of current with pressure are the key to improve the sensitivity and linearity of the sensor[43,44]. The rough structure of the thorn-like conductive fibrous membrane can endow it with a large specific surface area and increase the contact between the sensitive layer and the electrode, thus effectively improving the sensing performance of the sensor. Hu et al. Prepared a carbon hybrid thorn-like fiber (CHF) with a fluffy structure by wet spinning. The skeleton of the fiber was composed of GO, and the entangled CNTs on the skeleton formed a thorn-like structure. Then the CHF and silver electrode were integrated on the PDMS substrate to obtain a flexible piezoresistive sensor, as shown in Figure 6[45]. The sensor's fluffy structure expands the internal space, allowing the fiber to deform, resulting in satisfactory sensitivity. When subjected to bending strain, the GO nanosheets begin to slide, and the CHF fibers deform to form conductive paths. With the increase of stress, the edge of GO nanosheets is disconnected, and the charge is transmitted through the thorn-like CNTs to ensure the integrity of the overall structure under strain loading. When the stress is removed, the sensor recovers the layered structure. The sensor has a sensitivity of 1127 kPa-1, a response time of 70 ms, and a cyclic stability of more than 2000 cycles, and can be used to record real-time sitting signals from the lumbar and cervical spines. Similarly, Sharma et al. Successfully prepared thorn-like P-CPCM fiber membranes by blending acrylonitrile, cellulose and MXene to prepare nanofiber membranes using electrospinning technology, followed by carbonization and in situ polymerization of polyaniline (PANI)[46]. A flexible piezoresistive sensor was successfully constructed by stacking two Cu electrodes and three layers of P-CPCM fiber membranes on a PDMS flexible substrate in turn. When pressure is applied, the thickness of the film decreases, the current passes through a large number of spine tip contacts, the conductive path increases, and the resistance decreases; The greater the pressure, the larger the contact area and the better the conductivity; After the pressure is released, the film thickness and the electrode are restored to the original state. The introduction of thorn-like nanofibers,
图6 基于海绵压力传感器的示意图和传感机理图[45]

Fig. 6 Schematic diagram and sensing mechanism diagram of sponge pressure sensor[45]

High sensitivity (179.1 kPa-1), low detection limit (1.2 Pa), wide pressure range (0 ~ 50 kPa) and high durability (> 10 000 cycles) of the piezoresistive sensor are achieved. It can be seen from the above that the bramble structure is mainly produced by attaching conductive materials to the fiber through spinning technology. Although the bramble structure can improve the sensitivity of the sensor, its preparation process is complex, and it is difficult to control the uniformity of the bristle structure, which may affect the sensing stability of the sensor.

3.3 Fold structure

Wrinkle structure is a special surface micropattern, which is usually formed under mechanical stress. Baek et al. Prepared silicone rubber with a wrinkled surface structure by mechanical stretching, and then placed gold-coated silicon electrodes on both sides of the silicone rubber to prepare a capacitive pressure sensor (Fig. 7)[47]. The wrinkle structure effectively increases the contact point density of the sensor, thereby improving the sensitivity of the sensor. Compared with the wrinkle-free sensor, the response and recovery time of the single-sided wrinkle sensor are improved by 9.7% and 17%, respectively, and the response and recovery time of the double-sided wrinkle sensor are improved by 42% and 25%, respectively.The results show that the introduction of wrinkled structure into the elastic matrix is an effective way to improve the sensing performance, and the degree of wrinkling has a significant impact on the response and recovery time of the sensor. In order to simplify the process, Luo et al. Prepared a PPy film with a wrinkled structure by electroplating, and then filled polyvinyl alcohol nanowires (PVANW) between the polyethylene terephthalate film sprayed with indium tin oxide and the wrinkled PPy film to prepare a capacitive pressure sensor[48]. When the sensor is subjected to external pressure, the wrinkled PPy film is deformed, the conductive path is increased, and the isolation function of PVANW is overcome, resulting in an ultra-high sensitivity (228.5 kPa-1), a low detection limit (2.97 Pa), and a fast response (66.8 ms). Compared with the surface micro-convex structure and the thorn structure, the wrinkle structure has the advantages of simple formation process, uniform wrinkle size, easy control, and relatively good stability in the use process, so it is an effective strategy to prepare a high-sensitivity flexible pressure sensor.
图7 基于褶皱结构的电容式压力传感器:(a~c)无褶皱、单侧褶皱和双侧褶皱压力传感器在5 kPa压力下的传感性能;(d~f)无褶皱、单侧褶皱和双侧褶皱压力传感器的响应时间;(g)传感器的制备过程示意图[47]

Fig. 7 Capacitive pressure sensor based on pleated structure. (a~c) Sensing performance of wrinkle free, unilateral wrinkle and bilateral wrinkle pressure sensors under 5 kPa pressure; (d~f) response time of non fold, unilateral fold and bilateral fold pressure sensors; (g) schematic diagram of sensor preparation process[47]

To sum up, the substrate material with surface microstructure is used to prepare the pressure sensor. Because the substrate material has good flexibility, the stability of the microstructure is relatively good, and the cycle stability is basically not affected while the sensitivity of the pressure sensor is improved. However, the contribution of different surface microstructures to the performance of the sensor is still different, as shown in Table 2, and the sensitivity of the pressure sensor formed by this strategy is limited, and the response/recovery time is longer.
表2 基于微纳结构的高灵敏度压力传感器的性能

Table 2 Performance of high sensitivity pressure sensor based on micro-nano structure

Micro-nano structure Sensitivity/ kPa-1 Detection range/kPa
(Detection limit/Pa)
Response (recovery) time/ms Cycle stability/
times
Application ref
Basal material None 5.24 0~16 40/380 > 3000 Bend the wrists, elbows, and knees 49
Micro dome structure 6.61 0~0.11(1) 100/100 > 3750 Finger click mouse, finger joint movement 50
0.19 0~100(500) 75/80 > 1000 Pulse, finger clicks, grip strength, and plantar pressure 37
15.1 0~59(0.2) 40/40 > 1000 Health testing, exercise monitoring 38
Micro vertebral structure 3.26 0~3 200/100 > 5000 Various textures, such as the texture of different fabrics, Braille, etc 40
2.51 0~10(2) 84/117 > 5000 Muscle activity and skipping rope 51
Micro cylindrical structure 419.6 0~0.1 31/15 > 1000 Swallowing and pulse 52
0.6 (0.06) 25/25 > 10000 Pulse, body movement, breathing, etc 41
Thorns structure 179.1 0~50(1.2) 400/400 > 10000 Heart rate and respiratory monitoring 46
1127 - 200/250 > 2000 Real-time posture signals were recorded at the lumbar and cervical spine 45
Fold structure 2.59 0~20(1) 10/20 > 3000 Clenching and joint movements 53
228.5 0~10(2.97) 66.8 > 10000 Pulse, finger movement 48
Conductive material Micro ball 924.37 0~220(0.83) - > 22000 Physiological signals such as arteries 59
Empty core ball 0.55 0~5 41 > 1200 Pulse and body movement 60
The sea
urchin shaped
680 0~150(83) 10/22 > 3500 Pulse, pronunciation, palm and finger movements, walking 64
Honeycomb 161.6 0~10(9) - > 200 Artificial skin 67

4 High Sensitivity Flexible Pressure Sensor Based on Conductive Material Micro-nano Structure

Conductive material is the main part of the sensor to sense the external pressure, and it is another key factor to determine the performance of the sensor. Common conductive materials include metal-based materials (such as metal nanoparticles, nanowires), carbon-based materials (such as graphene, CNT, carbon nanofibers, and carbon black), conductive polymers (such as polyaniline, polypyrrole, and polythiophene), and other materials (like MXene, zinc oxide, etc.). These materials have good mechanical properties, high electrical conductivity, and good mechanical flexibility, providing high sensitivity for pressure sensors[54,55]. On the one hand, designing the microstructure of conductive materials can improve the distribution of conductive materials in the sensor, on the other hand, it can change the contact mode of conductive materials when the sensor is subjected to external forces, so it is of great significance to improve the sensitivity of the sensor. At present, the common microstructures of conductive materials are mainly microsphere, echinoid and honeycomb.
The micro-spherical structure can detect the external force by the micro-structural deformation at the surface and interface of the micro-spherical structure, which is helpful to improve the sensitivity of the sensor[56,57]. Wu Suxin et al. Used the "grafting from" method to graft polyacrylic acid (PAA) on the surface of carbon spheres, and then polymerized polyaniline in situ to prepare the carbon spheres @ PAA/polyaniline conductive composite, whose conductivity was 7.9 S·cm-1, which was greatly improved compared with pure polyaniline (2.2 S·cm-1)[58]. Ji et al. Combined the micro-spherical conductive material with the micro-convex structure of the matrix to improve the sensitivity of the sensor[59]. Silver nanowires (AgNWs) were dip-coated/spin-coated on the PDMS film with microsphere structure, and then the solution composed of carbon black microspheres and PDMS precursor (CPDMS) was sprayed on the AgNWs film, and the CPDMS/AgNWs double conducting layer (DCL) was obtained by curing, and finally the piezoresistive pressure sensor was assembled with the flat electrode. Under external pressure, the thickness of CPDMS layer decreases, and the contact point and contact area between carbon black microspheres increase, forming a conductive path. As the amount of CPDMS and AgNWs increased, the DCL sensing layer obtained a higher current, thereby improving the sensitivity. The sensor has an operating range of 0 – 220 kPa and a sensitivity of 924.37 kPa-1, and can be used as a multifunctional wearable device to monitor physiological signals such as arteries.
Hollow carbon spheres are micro- or nano-sized carbon particles with hollow structure, which have high specific surface area, excellent electrical conductivity, good chemical stability and thermal stability. The spherical structure of hollow carbon spheres is extremely sensitive to external forces, which can cause changes in contact resistance and tunnel resistance under very small external forces. In addition, the existence of the hollow structure makes the carbon sphere have smaller density, and the number of the carbon sphere is greatly increased under the same dosage, so the hollow structure has great potential in the high-sensitivity piezoresistive sensor. Chu et al. Grafted nitroxyl compounds onto hollow carbon spheres, as shown in Fig. 8, and then formed a flexible piezoresistive strain sensor with PDMS[60]. The sensing of the sensor mainly depends on the contact between the carbon spheres. When an external force is applied, the hollow carbon spheres are compressed, the number of point contacts between the carbon spheres increases, and the conductive path increases. When the external force is released, the distance between the hollow carbon spheres is restored to the original distance, and the sensor is restored to the original state. The introduction of the hollow structure makes the piezoresistive sensor highly sensitive and versatile.
图8 导电空心碳球结构示意图[60]

Fig. 8 Schematic diagram of conductive hollow carbon ball structure[60]

The urchin-shaped conductive microsphere is composed of a one-dimensional nanorod and a zero-dimensional nanomicrosphere, the surface of the urchin-shaped structure contains a micro-spine structure, so that the surface area of the material is increased; under the action of pressure, the urchan-shaped microstructure is deformed due to extrusion, the micro-spine structures on the surfaces of adjacent units are contacted with each other, and contacts of the micro-spine structures form a conductive path[61]. The increased contact area of all urchin-like structures under pressure provides a more conductive path for electron transport, thereby reducing the total resistance in the circuit and greatly improving the sensing performance and responsiveness of the sensor[62,63]. Wang et al. Mixed carbon black, urchin-like Fe2O3 and SnO2 to prepare Fe2O3/C@SnO2 conductive composite by hydrothermal method, and then immersed the melamine sponge in the solution containing conductive composite, and after connecting the electrodes, the melamine sponge-based pressure sensor was obtained (Fig. 9)[64]. The urchin-like Fe2O3 promotes the conduction of signals, and carbon black and SnO2 improve the conductivity of Fe2O3. Under pressure, the internal conductive network structure of the sensor is deformed, and the Fe2O3/C@SnO2 are close to each other, resulting in the increase of contact points, the increase of contact area and the decrease of resistance, thus showing high sensitivity (680 kPa-1), fast response (10 ms) and good cycle stability (> 3500 cycles).
图9 基于Fe2O3/C@SnO2柔性海绵的压力传感机理示意图[64]

Fig. 9 Based on Fe2O3/C@SnO2 schematic diagram of pressure sensing mechanism of flexible sponge[64]

There are a large number of pores in the honeycomb conductive material, which has the characteristics of large surface area and easier deformation under pressure, and can achieve the purpose of improving the sensitivity of the sensor[65,66]. Sheng et al. Assembled multilayer GO nanosheets and evaporated the gas to obtain a honeycomb graphene film, which was then assembled into a pressure sensor[67]. At very low strain, the walls of the hole are in "point-to-point" and "face-to-face" contact, which greatly improves the sensitivity of the pressure sensor up to 161.6 kPa-1.
To sum up, changing the microstructure of the conductive material can not only improve the deformability of the conductive material under external force, but also increase the number of conductive materials in the flexible sensor.Therefore, under the action of a small external force, the contact point and the contact area between the conductive materials are rapidly increased, and the conductive path is increased, so that the sensitivity is greatly improved, and the response time is shortened. However, due to the brittleness of most conductive materials, the microstructure of conductive materials is easy to be damaged during long-term use, so the cycle stability of this kind of sensor is not as good as that of pressure sensors based on the surface microstructure of substrate materials.

5 Application of High Sensitivity Flexible Pressure Sensor Based on Micro-nano Structure

Flexible pressure sensors based on micro-nano structures are often used in pulse monitoring, electronic skin and motion detection because of their high sensitivity, short response time and low hysteresis, as well as their ability to respond quickly to small pressures or stresses.
Pulse is one of the key indicators reflecting human life and health status. The vibration frequency of pulse can be displayed in the form of visualization through sensing technology to monitor and predict early health risks. Wang et al. Prepared a wearable pressure sensor by using conductive fabric and silicone membrane. The special micro-nano structure on the surface of the silicone membrane and the plain structure on the surface of the conductive fabric provided a contact/separation area, which was conducive to signal transmission[68]. Attaching the sensor to the wrist can not only distinguish the pulse changes before and after exercise, but also distinguish the pulse signal differences between different positions. Song et al. Used high temperature carbonized masking paper as a carbon skeleton sensitive material, obtained a conductive fiber network with surface microstructure through simple heat treatment, and printed interdigital electrodes to prepare wearable pressure sensors[69]. The sensor can also monitor the wrist pulse, and can be placed in front of the mask to detect changes in respiratory rate and severity.
Electronic skin is a kind of flexible wearable electronic system which can imitate the function and mechanical characteristics of biological skin. It has a simple structure and can be processed into any shape. It can be attached to human skin like clothes and has certain tactile and perceptual abilities[70]. Chen et al. Prepared a porous CNTs-PDMS electrode layer under the action of formaldehyde, then prepared a helical CNTs-PDMS electrode layer by using a 3D printing mold with double helical grooves, and finally integrated the porous CNTs-PD electrode layer and the helical CNTs- PDMS electrode layers on the PDMS membrane to obtain a piezoresistive sensor based on micro-nano structure[71]. As an electronic skin, the rough surface of the helical CNT-PDMS electrode layer can be used for sliding detection, and the porous CNT-PDMS electrode layer can be used for pressure detection, both of which work together to significantly improve the sensitivity of the electronic skin, which can detect the pressure of fingertips and different fingerprint shapes through pressure and strain. Gao et al. Used polyurethane (PU) and MWCNTs to prepare a PU @ MWCNTs conductive layer with micro-nano structure, and used it as a self-healing electronic skin to achieve dual sensing of pressure and temperature[72].
The flexible pressure sensor can be attached to the human body to convert the motion signal into an electrical signal to realize the motion detection of the human body. Human motion detection is mainly divided into large-scale motion (such as joint motion, hand motion, etc.) and subtle motion (such as vocal cord vibration, breathing, etc.)[73,74]. Chen et al. Grown silver nanoparticles on the surface of PDMS and reduced graphene oxide to construct a sponge-based pressure sensor with a micro-spine structure[75]. The pressure sensor can be attached to the joints of the human body to detect the bending movement of the knee joint, and can also be placed between the thumb and the index finger to detect the pressure between the fingers. In addition, the sensor can be fixed on the mask to detect breathing behavior. Liu et al. Prepared a PDMS film with a wrinkled structure by an anti-template method, and closely adhered the protonated polyaniline film to the microstructure surface of the PDMS film to prepare a flexible pressure sensor[76]. The sensor can detect weak physiological behavior (breathing) and large body movements (finger bending and finger pressing, etc.), and can also identify the cyclic vibration of the engine, demonstrating the potential application of flexible pressure sensors in human motion detection.
In recent years, with the rapid development of the Internet and artificial intelligence, flexible pressure sensors are also widely used in human-computer interface and intelligent robots[77,78]. For example, Cha et al. Developed smart gloves with fabric-based pressure sensors, which input signals to the controller by bending fingers, and remotely control intelligent robots to perform medical surgery[79]. In addition, it is integrated into electronic devices to track and control through human-computer interaction, and then to guide the movement.

6 Conclusion and prospect

With the continuous development of flexible sensing technology, the performance of flexible sensors is no longer satisfied with simple sensing, but focuses more on the sensitive and rapid response of pressure sensors to small pressure or stress.Therefore, the microstructure design of the substrate material and conductive material for the sensor is a hot research topic. At present, researchers have done a lot of work in this area, but there is still a certain gap from the practical application, so we believe that it will mainly develop in the following five aspects in the future.
Firstly, the synthesis process and preparation process of high-sensitivity flexible pressure sensors with micro-nano structures are relatively complex, which requires a lot of time and energy to explore and practice, thus limiting the development and popularization of high-sensitivity pressure sensors. Therefore, the simplification and optimization of material selection, structural design and compounding methods are the focus of future development.
Secondly, there is often a contradiction between the sensitivity and cycle stability of flexible pressure sensors, and giving consideration to both the high sensitivity and cycle stability of flexible pressure sensors will also be the focus of future development.
Thirdly, in the process of wearing for a long time, the sensitivity, linearity and stability of the pressure sensor will be greatly reduced due to the combined effects of internal and external environments (such as sweat, temperature and humidity). Therefore, while ensuring the sensing performance and sensitivity, how to improve the environmental tolerance of high sensitivity pressure sensors based on micro-nano structures is a key problem restricting their development.
Fourthly, sensors used for body function detection should have the ability to monitor and predict risks in real time. However, most of the existing pressure sensors do not have self-powered and information storage functions.Therefore, the development of high-sensitivity pressure sensors with signal storage and analysis functions to predict and alarm dangerous signals is the development trend of future sensing technology.
Fifthly, the existing flexible pressure sensor can only sense the pressure, which limits its application range. How to combine pressure sensing with strain sensing to achieve 3D sensing will become the development trend in the future.
[1]
Li L, Zheng J H, Chen J, Luo Z B, Su Y, Tang W, Gao X, Li Y T, Cao C J, Liu Q H, Kang X Y, Wang L, Li H. Adv. Mater. Interfaces, 2020, 7(17): 2000743.

[2]
Zong Y, Tan S, Ma J Z. Macromol. Rapid Commun., 2022, 43(8): 2100873.

[3]
Guo R Y, Bao Y. Fine Chemicals, 2021, 38(04): 649.

(郭茹月, 鲍艳. 精细化工, 2021, 38(04): 649.).

[4]
Kang K, Park J, Kim K, Yu K J. Nano Res., 2021, 14(9): 3096.

[5]
Jason N N, Ho M D, Cheng W L. J. Mater. Chem. C, 2017, 5(24): 5845.

[6]
Guo R Y, Bao Y, Zheng X, Zhang W B, Liu C, Chen J, Xu J C, Wang L X, Ma J Z. Adv. Mater.Function., 2023, 33(12), 2213283.

[7]
Asghar W, Li F L, Zhou Y L, Wu Y Z, Yu Z, Li S B, Tang D X, Han X T, Shang J, Liu Y W, Li R W. Adv. Mater. Technol., 2020, 5(2): 1900934.

[8]
Wang Y J. Modern Chemical Research, 2018, (09): 122.

(王宇捷. 当代化工研究, 2018, (09): 122.).

[9]
Suresh Kumar N, Padma Suvarna R, Chandra Babu Naidu K, Banerjee P, Ratnamala A, Manjunatha H. Appl. Phys. A, 2020, 126(6): 445.

[10]
Lu G W, Chen F E, Wu X F, Qu L T, Zhang J X, Shi G Q. Chinese Science Bulletin, 2005, 50(15): 1545.

(鲁戈舞, 陈凤恩, 吴旭峰, 曲良体, 张家鑫, 石高全. 科学通报, 2005, 50(15): 1545.).

[11]
Wang H M, Li S, Wang Y L, Wang H M, Shen X Y, Zhang M C, Lu H J, He M S, Zhang Y Y. Adv. Mater., 2020, 32(11): 1908214.

[12]
Jian M Q, Wang C Y, Wang Q, Wang H M, Xia K L, Yin Z, Zhang M C, Liang X P, Zhang Y Y. Sci. China Mater., 2017, 60(11): 1026.

[13]
Gao Y Y, Yan C, Huang H C, Yang T, Tian G, Xiong D, Chen N J, Chu X, Zhong S, Deng W L, Fang Y, Yang W Q. Adv. Funct. Mater., 2020, 30(11): 1909603.

[14]
Lyu Y, Gan S Y, Bao Y, Zhong L J, Xu J N, Wang W, Liu Z B, Ma Y M, Yang G F, Niu L. Membranes, 2020, 10(6): 128.

[15]
Zhang J W, Zhang Y, Li Y Y, Wang P. Polym. Rev., 2022, 62(1): 65.

[16]
Zhang J W, Zhang Y, Li Y Y, Ye X, Wang P, Xu Y K. ACS Appl. Electron. Mater., 2021, 3(7): 3177.

[17]
Su M, Li P, Liu X Q, Wei D P, Yang J. Nanomaterials, 2022, 12(9): 1495.

[18]
Krause T, Meier M, Brunzendorf J. J. Loss Prev. Process. Ind., 2021, 71: 104523.

[19]
He J, Zhang Y F, Zhou R H, Meng L R, Chen T, Mai W J, Pan C F. J. Materiomics, 2020, 6(1): 86.

[20]
Wu Y Z, Liu Y W, Zhou Y L, Man Q K, Hu C, Asghar W, Li F L, Yu Z, Shang J, Liu G, Liao M Y, Li R W. Sci. Robot., 2018, 3(22): eaat0429.

[21]
Zhou Y, Zhao L P, Tao W, Wang T S, Sun P, Liu F M, Yan X, Lu G Y. ACS Appl. Mater. Interfaces, 2022, 14(17): 19949.

[22]
Yu Q Y, Zhang P, Chen Y C. Micromachines, 2021, 12(10): 1219.

[23]
Park D Y, Joe D J, Kim D H, Park H, Han J H, Jeong C K, Park H, Park J G, Joung B, Lee K J. Adv. Mater., 2017, 29(37): 1702308.

[24]
Pierre Claver U, Zhao G. Adv. Eng. Mater., 2021, 23(5): 2001187.

[25]
Shlomy I, Divald S, Tadmor K, Leichtmann-Bardoogo Y, Arami A, Maoz B M. ACS Nano, 2021, 15(7): 11087.

[26]
Shao T Y, Wu J N, Zhang Y H, Cheng Y R, Zuo Z Q, Lv H K, Ying M L, Wong C P, Li Z. Adv. Mater. Technol., 2020, 5(5): 2000032.

[27]
Peng S H, Blanloeuil P, Wu S Y, Wang C H. Adv. Mater. Interfaces, 2018, 5(18): 1800403.

[28]
Ma C, Xu D, Huang Y C, Wang P Q, Huang J, Zhou J Y, Liu W F, Li S T, Huang Y, Duan X F. ACS Nano, 2020, 14(10): 12866.

[29]
Dai H F. Master’s Dissertation of Changchun University of Technology, 2022.

(戴鸿飞. 长春工业大学硕士论文, 2022.).

[30]
Pan L M, Han L Y, Liu H X, Zhao J J, Dong Y, Wang X H. Chem. Eng. J., 2022, 450: 137929.

[31]
Lee S, Kim J, Roh H, Kim W, Chung S, Moon W, Cho K. Adv. Mater., 2022, 34(21): 2109545.

[32]
Formica D, Schena E. Sensors, 2021, 21(2): 543.

[33]
Samoei V K, Jayatissa A H. Sens. Actuat. A Phys., 2020, 303: 111816.

[34]
Ruth S R A, Feig V R, Tran H, Bao Z N. Adv. Funct. Mater., 2020, 30(39): 2003491.

[35]
Pan W W, Han Z Y, Chang Y, Duan X X. Biosens. Bioelectron., 2020, 167: 112504.

[36]
Weng M C, Sun L Q, Qu S X, Chen L Z. Extreme Mech. Lett., 2020, 37: 100714.

[37]
Tang Z H, Xue S S, Li Y Q, Zhu Z C, Huang P, Fu S Y. ACS Appl. Mater. Interfaces, 2021, 13(40): 48009.

[38]
Park J, Lee Y, Hong J, Ha M, Jung Y D, Lim H, Kim S Y, Ko H. ACS Nano, 2014, 8(5): 4689.

[39]
Khalili N, Shen X, Naguib H E. Soft Matter, 2018, 14(33): 6912.

[40]
Cao Y D, Li T, Gu Y, Luo H, Wang S Q, Zhang T. Small, 2018, 14(16): 1703902.

[41]
Lin M F, Cheng C, Yang C C, Hsiao W T, Yang C R. Org. Electron., 2021, 98: 106290.

[42]
Lu Y W, He Y, Qiao J T, Niu X, Li X J, Liu H, Liu L. ACS Appl. Mater. Interfaces, 2020, 12(49): 55169.

[43]
Lee S, Shin S, Lee S, Seo J, Lee J, Son S, Cho H J, Algadi H, Al-Sayari S, Kim D E, Lee T. Adv. Funct. Mater., 2015, 25(21): 3114.

[44]
Lu N S, Lu C, Yang S X, Rogers J. Adv. Funct. Mater., 2012, 22(19): 4044.

[45]
Hu Y F, Huang T Q, Zhang H J, Lin H J, Zhang Y, Ke L W, Cao W, Hu K, Ding Y, Wang X Y, Rui K, Zhu J X, Huang W. ACS Appl. Mater. Interfaces, 2021, 13(20): 23905.

[46]
Sharma S, Chhetry A, Maharjan P, Zhang S P, Shrestha K, Sharifuzzaman M, Bhatta T, Shin Y, Kim D, Lee S, Park J Y. Nano Energy, 2022, 95: 106970.

[47]
Baek S, Jang H, Kim S Y, Jeong H, Han S, Jang Y, Kim D H, Lee H S. RSC Adv., 2017, 7(63): 39420.

[48]
Luo C, Liu N S, Zhang H, Liu W J, Yue Y, Wang S L, Rao J Y, Yang C X, Su J, Jiang X L, Gao Y H. Nano Energy, 2017, 41: 527.

[49]
Peng Z Q, Zheng S J, Zhang X, Yang J L, Wu S Z, Ding C, Lei L, Chen L, Feng G Y. Micromachines, 2022, 13(5): 694.

[50]
Zhang Y, Han F, Hu Y G, Xiong Y X, Gu H, Zhang G Q, Zhu P L, Sun R, Wong C P. Macromol. Chem. Phys., 2020, 221(11): 2000073.

[51]
Zhang Z A, Gui X C, Hu Q M, Yang L L, Yang R L, Huang B F, Yang B R, Tang Z K. Adv. Electron. Mater., 2021, 7(7): 2100174.

[52]
Xia T C, Yu R, Yuan J, Yi C Q, Ma L J, Liu F, Cheng G J. Adv. Mater. Technol., 2021, 6(3): 2000984.

[53]
Du D W, Ma X Y, An W X, Yu S H. Measurement, 2022, 201: 111645.

[54]
Riazi H, Taghizadeh G, Soroush M. ACS Omega, 2021, 6(17): 11103.

[55]
Bao Y, Zheng X, Guo R Y. Chemical Industry and Engineering Progress, 2022, 41(07): 3624.

(鲍艳, 郑茜, 郭茹月. 化工进展, 2022, 41(07): 3624.).

[56]
Zou Z N, Zhu C P, Li Y, Lei X F, Zhang W, Xiao J L. Sci. Adv., 2018, 4(2): eaaq0508.

[57]
Le Y, Chen J F, Wang W C. Chemical Industry and Engineering Progress, 2004,(06): 595.

(乐园, 陈建峰, 汪文川. 化工进展, 2004,(06): 595.).

[58]
Wu S X, Zhang X Z, Yu Y. Chemistry & Bioengineering, 2021, 38(12): 41.

(吴素心, 张雄志, 喻尧. 化学与生物工程, 2021, 38(12): 41.).

[59]
Ji B, Zhou Q, Wu J B, Gao Y B, Wen W J, Zhou B P. ACS Appl. Mater. Interfaces, 2020, 12(27): 31021.

[60]
Chu J, Cai J P. Nanoscale, 2020, 12(17): 9375.

[61]
Bao Y, Li X Q. New Chem. Mater., 2018, 46(12): 42.

(鲍艳, 李欣倩. 化工新型材料, 2018, 46(12): 42.).

[62]
Wang Y J, Wang Y, Xu M T, Dai F Y, Li Z. ACS Sustainable Chem. Eng., 2022, 10(51): 17252.

[63]
Wang X M, Tao L Q, Yuan M, Wang Z P, Yu J B, Xie D L, Luo F, Chen X P, Wong C. Nat. Commun., 2021, 12: 1776.

[64]
Liu C, Cai J, Dang P Z, Li X H, Zhang D Y. ACS Appl. Mater. Interfaces, 2020, 12(10): 12101.

[65]
Wang G J, Lin Z H, Jin S H, Li M, Jing L Y. J. Energy Storage, 2022, 45: 103525.

[66]
Yang Y, Chen L, He J, Hou X J, Qiao X J, Xiong J J, Chou X J. Adv. Mater. Technol., 2022, 7(1): 2100702.

[67]
Wang X, Yang J, Feng Z P, Zhang G Q, Qiu J, Wu Y F, Yang J. ACS Appl. Mater. Interfaces, 2021, 13(46): 55747.

[68]
Chen S, Song Y J, Xu F. ACS Appl. Mater. Interfaces, 2018, 10(40): 34646.

[69]
Park J, Lee Y, Ha M, Cho S, Ko H. J. Mater. Chem. B, 2016, 4(18): 2999.

[70]
Chen H T, Miao L M, Su Z M, Song Y, Han M D, Chen X X, Cheng X L, Chen D M, Zhang H X. Nano Energy, 2017, 40: 65.

[71]
Gao Z Y, Lou Z, Han W, Shen G Z. ACS Appl. Mater. Interfaces, 2020, 12(21): 24339.

[72]
Lei P, Bao Y. Materials Reports, 2022, 36(14): 82.

(雷鹏, 鲍艳. 材料导报, 2022, 36(14): 82.).

[73]
Shi Z Y, Meng L X, Shi X L, Li H P, Zhang J Z, Sun Q Q, Liu X Y, Chen J Z, Liu S R. Nano Micro Lett., 2022, 14(1): 141.

[74]
Chen B D, Li H Q, Zhang S F, Lai X J, Zeng X R, Wu X R, Cheng X T, Liu H. Compos. A Appl. Sci. Manuf., 2022, 162: 107171.

[75]
Liu C, Xu L, Kong L Y, Xu Y Q, Zhou W, Qiang Q P, Tian L L, Chen W B, Cai M S, Lang T C, Han T, Liu B T. J. Mater. Chem. C, 2022, 10(36): 13064.

[76]
Zhao Z Q, Li Q J, Dong Y, Gong J X, Li Z, Qiao X R, Zhang J F. Energy Technol., 2021, 9(7): 2100166.

[77]
Liu J L, Yang Y N, Peng J, Wang H C, Chen D, Liu Y J, Yang L N, Chen H N. Soft Robotics, 2022, 9(3): 518.

[78]
Cha Y, Seo J, Kim J S, Park J M. Smart Mater. Struct., 2017, 26(5): 057002.

[79]
Lv Y H, Min L Z, Niu F X, Chen X Y, Zhao B, Liu Y, Pan K. Nanocomposites, 2022, 8(1): 81.

Outlines

/