Recent Progress in Self-Powered Skin Sensors: History Edit

Introduction

Information, energy, and materials are the three pillars of the development of modern human society, among which information technology is the main driving force for development in recent decades. The collection and exchange of different information depends on sensors with different functions, which makes sensors play a vital role in many fields [1,2,3,4,5]. In the fields of health care, medical treatment, sports, human–machine interaction, and so on, sensors are required to obtain various signals from the human body. Obtaining information from the skin—the largest organ of human body in direct contact with the outside world—has always been a vital means in these fields. Skin sensors, as the kinds of devices that can be attached to human skin and collect signals from skin or detect external stimulation from around the environment, can well meet the above needs [6,7,8,9,10,11]. Under the current technological background, a majority of sensors need to be driven by external power sources and cannot work independently and sustainably, which has become one of the main factors restricting the development of skin sensors. One possible solution to address this challenge is to combine skin sensors with energy harvesting and storage components, which provides a feasible scheme for the sustainable operation of skin sensors [12,13,14,15]. Another way to effectively address such a challenge is to develop self-powered skin sensors. Physical movements, the heat emission of the human body, and human secretions are all sources of energy that can be converted into electrical outputs by energy harvesters, and the wave forms of their electrical signals reflect information of such energy sources [16,17,18,19,20,21,22,23]. Several technologies can convert these energy sources into electricity, including the piezoelectric effect, the triboelectric effect, the thermoelectric effect, and the spontaneous redox reaction [24,25,26,27,28,29,30,31]. Based on these principles, various energy harvesters with multiple functions have been developed. Among them, piezoelectric nanogenerators (PENGs) and triboelectric nanogenerators (TENGs) are mechanical energy harvesters that were first proposed in 2006 and 2012, respectively [32,33]. They can harvest mechanical energy from the human body and also work as self-powered skin sensors to detect body motion, touch/pressure, and acoustic sound [34,35,36,37,38,39,40,41,42,43,44]. In addition, non-motion-based energy harvesters, such as thermoelectric nanogenerators and biofuel cells, can serve as self-powered temperature and sweat skin sensors, respectively [45,46,47,48]. The use of new materials enables these devices to have good transparency, portability, flexibility, light weight, comfortability, and biocompatibility. All these advantages above have made self-powered skin sensors receive extensive attention in recent years, and they are undergoing fast development. Hence there is a great need to comprehensively review the recent progress of self-powered skin sensors.
In this review, the recent advances of self-powered skin sensors will be comprehensively reviewed. The self-powered skin sensors will be classified according to the different types of monitoring signals, with a focus on the working mechanism, device structure, and the sensing principle. Section 2Section 3 and Section 4 will review the self-powered skin sensors for detecting body motion, touch/pressure, and acoustic sound, respectively, which are all related to motion and based on PENGs and TENGs. Section 5 will review other types of self-powered skin sensors, including those used for sensing of body temperature and sweat. The working principle, device structure, device performance, and advantages and disadvantages of different types of self-powered skin sensors will be summarized. Finally, the challenges faced by self-powered skin sensors and the future prospects will be discussed.

Self-Powered Skin Sensors for Detecting Body Motion

Sensing body motion has a wide range of applications, such as automation, human–machine interaction, medical health, and sports. Current self-powered skin sensors to detect body motion can be mainly divided into two categories according to their working principles. One is based on TENGs and the other is based on PENGs. When mounted on the arms or legs, these sensors can detect human activities such as walking and jogging; when mounted onto fingers, wrists, elbows, or knees, they can monitor joint motion like the bending angle and frequency of joints [35,36,49,50,51,52,53,54,55]. In addition, the skin sensors for detecting body motion are also able to act as a breathing sensor to monitor people’s breathing state when placed on the chest [36,56].

Triboelectric Nanogenerators as Self-Powered Body Motion Skin Sensors

The basic working mechanism of skin TENGs as a body motion sensor is that body motion triggers relative displacement between the two triboelectric parts, which results in potential difference between the two working electrodes and drives electrons to flow across. The features, such as simple structure, easy fabrication, various working modes, multiple options regarding materials, high power density, and good flexibility, all make TENGs a good choice for self-powered skin sensors.
According to the triboelectric materials utilized, self-powered body motion skin sensors based on TENGs can be divided into several categories. The first kind is based on stretchable materials, such as rubber and silicone elastomers. Yi et al. reported a stretchable-rubber-based (SR-based) TENG which utilizes the triboelectricity between a stretchable rubber and an aluminum (Al) film, as shown in Figure 1a–c [35]. The SR-based TENG has a unique working principle. It uses the stretching rather than the position shift of rubber to induce in-plane charge separation between rubber and Al, which leads to the potential difference between the Al electrode and the ground. This SR-based TENG has a short-circuit current density of and an output power density of . Moreover, this SR-based TENG is able to detect the rates of diaphragmatic breathing and joint movements of a human body like the bending angle and frequency of the knee. Han et al. reported a soft and stretchable triboelectric band consisting of a rubber tube filled with physiological saline, as shown in Figure 1d–f [49]. When worn on different parts of the body, the band can detect changes in muscle volume during movements and can monitor six different types of human motion including swallowing, calf raising, jumping, squatting, breathing, and bicep curling. Furthermore, based on the unique gait patterns of different individuals, this band can be effectively used for identity recognition. Lim et al. fabricated a stretchable and durable TENG based on gold nanosheet embedded electrodes, as shown in Figure 2a,b [50]. With gold nanosheets embedded in PDMS matrix and micro-pyramid patterned PDMS, this type of electrode has excellent mechanical flexibility, tensile properties, and excellent output stability. The TENG can be mounted on the skin to detect the process of repeated bending and relaxation of joints.
 
Figure 1. (a) Device structure of the stretchable-rubber-based triboelectric nanogenerator (TENG). (b) Images and electrical outputs of the TENG on the abdomen during expiration and inspiration. (c) Optical images of the device on the knee at different bending angles and voltage responses when bending the knee at different angles and different rates [35]. Copyright 2015, Wiley. (d) Typical device structure of the TENG band. (e) Schematic illustration of the skin TENG band for body motion detection. (f) Schematic illustration of the skin TENG band for identification [49]. Copyright 2018, Elsevier.
 
Figure 2. (a) Schematic illustration of the structure of the stretchable TENG based on the gold-nanosheet (NS) electrodes. (b) Photographs and output-voltage responses to the repeated bending/relaxation of the TENG when installed on the index finger [50]. Copyright 2017, Elsevier. (c) Schematic diagram of the structure of PEDOT:PSS functionalized textile based TENG. (d) The photographs of the two-arch finger bending sensors installed on the index finger and the middle finger, and output voltages from the four arches when the hand repeats the gestures represented by ‘A’ [51]. Copyright 2018, Elsevier. (e) Device structure of the wavy-FTENG. (f) Relative changes in voltage versus time for monitoring elbow motion [52]. Copyright 2015, Wiley.
 
The second kind is based on textiles. He et al. reported a skin TENG based on a textile coated by a layer of PEDOT:PSS, which has a maximum output power of 3.26 mW and a power density of , as shown in Figure 2c,d [51]. This textile-based skin TENG can be applied to capture hand motion and detect finger bending angle. Zhu et al. reported a cotton-sock-based self-powered hybrid skin sensor with PEDOT:PSS coated fabric and PTFE film as the two triboelectric materials [54]. The device has a triboelectric power density of . This smart sock can realize multiple monitoring, including walking pattern recognition, motion tracking, and gait sensing. The third kind is based on flexible thin films. Yang et al. developed a skin TENG fabricated by assembling serpentine-patterned electrodes and a wavy-structured Kapton film which has an output power density of , as shown in Figure 2e,f [52]. The advantage of this skin TENG is to work stably under tensile strain or on a curved surface, at both the compressive and stretching mode. It can be attached onto human skin to detect motion of joints and muscles.

Piezoelectric Nanogenerators as Self-Powered Body Motion Skin Sensors

The piezoelectric effect of the materials used in PENGs can polarize the charge due to mechanical stimulation, and then generate electrical signals. PENGs have the advantages of high sensitivity, real-time sensing, and good flexibility, and can be used as self-powered skin sensors by using flexible materials. The reported skin PENGs are mostly based on conventional piezoelectric materials including zinc oxide (ZnO) nanowires, PVDF nanofibers, and lead zirconate titanate (PZT) powders [36,53,57,58,59,60,61,62]. In addition, some materials which have a piezoelectric effect at the nano scale but not in a bulk state have also been used in skin PENGs, such as boron nitride (BN) [63,64].
Among the traditional piezoelectric materials, ZnO nanowires have high sensitivity, while PVDF has relatively low sensitivity but good flexibility. Lee et al. reported a kind of skin PENG based on ZnO nanowires as a self-powered sensor to track tiny skin deformation, as shown in Figure 3a,b [36]. On the Al foil, anodic aluminum oxide (AAO) was grown to serve as the insulating layer between the Al electrode and the ZnO nanowire film to block electron transport. This skin PENG can track eye ball motion when attached to an eyelid. Deng at el. fabricated a PENG-based self-powered body motion skin sensor based on cowpea-structured PVDF/ZnO nanofibers which has a sandwich structure by electrospinning, as shown in Figure 3c,d [53]. Due to the synergistic piezoelectric effects of ZnO and PVDF, as well as the good flexibility of the polymer, the skin PENG has a bending sensitivity of , and can quantitatively measure the bending angle in a range from 44° to 122°. Placing this skin PENG on the joint of five fingers to capture human gestures and to transmit signals to the robotic palm can realize a timely self-powered human–machine interaction system.
 
Figure 3. (a) Schematic illustration of the structure of super-flexible PENG. (b) The PENG attached to the right eyelid as an active sensor for detecting the motion of a human eye ball. Output voltage measured under slow and rapid eye movement [36]. Copyright 2015, Wiley. (c) The structure design of the cowpea-structured PVDF/ZnO nanofibers based PENG. (d) The application of robot hand control based on the skin PENG [53]. Copyright 2018, Elsevier. (e) Schematic illustration of the device structure of the PENG. (f) The output voltage of the PENG working as a “smart wristband” under different wrist gestures [60]. Copyright 2018, Elsevier. (g) Schematic diagram of the structure of the boron nitride nanosheet based piezoelectric sensor. (h) Open-circuit voltage of the device during foot and neck motions [63]. Copyright 2018, Elsevier.
 
Skin PENGs to detect body motion based on piezoelectric ceramics and other materials have also been developed. Chou et al. reported a filler-elastomer-based stretchable PENG developed by incorporating high weight compositions of PZT particles and Ag-coated glass microspheres fillers into the solid-state silicone rubber, as shown in Figure 3e,f [60]. The PENG shows an output power density of 3.93 . This PENG can not only be mounted on the joint to capture the joint posture, but also to monitor the dynamic motion. Kim et al. reported a transparent and flexible piezoelectric sensor based on BN nanosheets which has an output power of 40 μW and a power density of 106 . The skin PENG based on BN nanosheets (1 wt%) dispersed into PDMS as the active layer can work under both tensile stress and compressive stress, as shown in Figure 3g,h [63]. When attached directly to human skin, this PENG can detect the movements of the human foot, neck, wrist, and knee.
Currently, self-powered motion skin sensors are mainly divided into TENG-based and PENG-based ones, which have their own advantages and disadvantages. Table 1 shows the comparison of self-powered skin sensors for detecting body motion in terms of mechanism, materials, motion detected, and output power density. TENG-based self-powered motion skin sensors have a simple fabrication process, multiple choice of materials, and high power density, but their performance is generally affected by environmental factors such as humidity. PENG-based self-powered motion skin sensors have high sensitivity and less environmental impact. However, materials used in these kinds of devices are limited, which must have the piezoelectric effect.
 
Table 1. Comparison of self-powered skin sensors for detecting body motion.
 
Mechanism Material Motion Detected Output Power Density Reference
TENG Rubber and Al Diaphragmatic breathing and joint movements 76.27 W m2 [35]
TENG Rubber and physiological saline Swallowing, calf raising, jumping, squatting, breathing, bicep curling, and gait patterns   [49]
TENG PDMS and Au nanosheets film Bending and relaxation of joints   [50]
TENG PEDOT:PSS coated textile and PTFE Hand motion and finger bending 2 W m2 [51]
TENG Kapton and Cu Motion of joints and muscles 5 W m2 [52]
TENG PTFE and Nylon Respiration   [56]
PENG ZnO Eye ball motion   [36]
PENG ZnO and PVDF Joint bending   [53]
PENG PZT Joint posture 3.93 μW cm3 [60]
PENG BN nanosheets Movements 106 μW cm3 [63]

Self-Powered Skin Sensors for Detecting Touch/Pressure

Human activities induce pressure, and physiological activity in different parts of the body, such as human voice, blood pressure wave, heartbeat, venous pulse, and respiratory movement, and these produce different pressures, which have a wide range from low pressure to high pressure (from 10 to 100 kPa) [65]. Detection of these pressures by pressure sensors is of great significance for the diagnosis and monitoring of various diseases of the human vocal cords, heart, respiratory system, and cardiovascular system [66]. At present, self-powered pressure and touch skin sensors are mainly based on TENGs and PENGs.

Triboelectric Nanogenerators as Self-Powered Touch/Pressure Skin Sensors

TENGs as self-powered touch/pressure skin sensors are mainly working in two kinds of modes: single-electrode mode and attached-electrode mode. The similarity between them is that the touch/pressure induced motion is in the vertical direction, and so is the contact/separation of the two triboelectric parts.
Dielectric materials with strong electron affinity are usually used as the negatively charged triboelectric layer for skin TENGs used for touch/pressure sensors working in the single-electrode mode [37,67,68,69,70]. Zhu et al. reported a TENG-based flexible tactile sensor which has a polymer-nanowire modified surface, as shown in Figure 4a–c [37]. As shown in Figure 4a, a layer of polyethylene terephthalate (PET) is sandwiched between two ITO electrodes, and a layer of fluorinated ethylene propylene (FEP) is applied as an electrification layer, which is modified by vertically aligned polymer nanowires (PNWs) on the surface. In the extremely low-pressure region (<0.15 kPa), this self-powered touch and pressure sensor which relies on contact electrification to generate voltage signals shows a pressure sensitivity of ( ) and a maximum touch sensitivity of ( ).
Figure 4. (a) Schematic illustration of the structural design of triboelectric sensor (TES). (b) Triggering a wireless alarm system by grasping the TES that is installed on a door handle. (c) Switching a panel light by a finger touching the TES that is applied on the surface of the light [37]. Copyright 2014, American Chemical Society. (d) Sketch of the layered structure of the sensor and SEM image of the patterned PDMS film with protruding triangular stripes. (e) A complete working cycle of the ionogel-based TENG sensor. (f) The output current of the sensor generated by human pulse beats [71]. Copyright 2016, Wiley.
 
For skin TENGs to detect touch/pressure working in the attached-electrode mode, an air gap between the two triboelectric layers is necessary so that the triboelectric charges on the two surfaces can contact and separate, which leads to electrical outputs [18,71,72,73,74]. Zhao et al. reported a skin TENG based self-powered tactile sensor with good pressure and tactile sensing performance, which has a maximum sensitivity of , as shown in Figure 4d–f [71]. The skin TENG has a double network ionogel and patterned polydimethylsiloxane (PDMS) with a dihedral stripes structure as the two triboelectric layers. A complete working cycle of the skin TENG is illustrated in Figure 4e to show the working principle of the sensor. This transparent and stretchable self-powered sensor has wide applications as wearable electronics to detect touching forces of different magnitudes, finger bending, human breathing, and pulse beating.

Piezoelectric Nanogenerators as Self-Powered Touch/Pressure Skin Sensors

With the use of piezoelectric materials, PENGs can directly convert the change of pressure into the change of electrical signals, which makes them a very good choice for monitoring touch/pressure. The piezoelectric materials used in PENG-based self-powered touch/pressure skin sensors include inorganic and organic materials. The inorganic piezoelectric materials are mainly nanomaterials of ZnO and piezoelectric ceramics [75,76,77,78], while organic piezoelectric materials are mainly PVDF-based materials [38,79,80,81,82].
The PENG-based self-powered touch/pressure skin sensor based on carbon nanotubes (CNTs)/piezoelectric ceramic composite have been reported to possess high sensitivity. For example, Kim et al. fabricated a flexible piezoelectric pressure skin sensor based on CNTs-doped 0–3 ceramic-epoxy nanocomposites, using ceramic powders and epoxy resin with the contents of 81 and 19 wt%, respectively, as shown in Figure 5a,b [75]. In this skin sensor, when the content of carbon nanotubes is 0.07 wt%, the piezoelectric coefficient of epoxy ceramic composite film reaches 68 pc/n. Additionally, it shows a linear response up to 150 kPa with a sensitivity of (67.6 mV/N). PENG-based self-powered touch/pressure skin sensors based on organic piezoelectric materials have also been reported. Wang et al. reported a PENG-based pressure skin sensor which consists of electrospinning-prepared PVDF nanofiber film with PDMS/Ag NWs and PET/ITO as the two electrodes, as shown in Figure 5c,d [38]. The PENG pressure skin sensor can capture tiny mechanical signals and have good flexibility and sensitivity. It also has the advantage of a simple preparation process. Spanu et al. reported a PENG-based tactile skin sensor based on an organic charge modulated FET coupled with a PVDF film, which is able to reliably transduce pressure as low as 300 Pa in a wide frequency range (20~500 Hz), as shown in Figure 5e,f [79].
 
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