Hierarchically Plied Mechano-Electrochemical Energy Harvesting Using a Scalable Kinematic Sensing Textile Woven from a Graphene-Coated Commercial Cotton Yarn.

Wearable sensing systems are suitable for monitoring human motion. To realize a cost-effective and self-powered strain-sensing fiber, we developed a mechano-electrochemical harvesting yarn and textile using hierarchically arranged plied yarns composed of meter-long graphene-coated cotton yarns. Such a fiber relies on the principle of electrochemical capacity change to convert mechanical energy to electric energy. Further, this harvester can be used as a self-powered strain sensor because its output depends on mechanical stimuli. Additionally, the yarn can be woven into a kinematic sensing textile that measures the strength and direction of the applied force. The textile-type harvester can successfully detect various human movements such as pressing, bending, and stretching. The proposed sensing fiber will pave the way for the development of advanced wearable systems for ubiquitous healthcare in the future.

Microbuckled Mechano-electrochemical Harvesting Fiber for Self-Powered Organ Motion Sensors.

Mechanical harvesters have attracted tremendous attention as self-powered strain sensors; previous harvesters required high stress to stretch the fiber because of their high Young's modulus and low elasticity. We report on a mechano-electrochemical harvesting (MECH) fiber based on the new buckle structure, which has a low Young's modulus (2 MPa) with high elasticity (up to 100%) in a similar physiological fluid. MECH converts mechanical energy into electrical energy by changing the capacitance due to changing the surface area caused by the microbuckle on the surface. The damage to the cells can be minimized by their softness; the fiber was stitched on the tissue of the pig stomach while maintaining the performance like a suture fiber. Additionally, the fiber successfully operated in an organ-similar system, which is composed of the stomach or bladder of a pig. The fiber has a high potential to be applied in wearable energy sources and self-powered strain sensors.

Stretchy Electrochemical Harvesters for Binarized Self-Powered Strain Gauge-Based Static Motion Sensors.

The human monitoring system has motivated the search for new technology, leading to the development of a self-powered strain sensor. We report on the stretchable and soft stretchy electrochemical harvester (SECH) bilayer for a binarized self-powered strain gauge in dynamic and static motion. The active surface area participating in the electrochemical reaction was enhanced after stretching the SECH in the electrolyte, leading to an increase in the electrochemical double-layer capacitance. A change in the capacitance induced a change in the electrical potential of the bilayer, generating electrical energy. The SECH overcomes several challenges of the previous mechano-electrochemical harvester: The harvester had high elasticity (50%), which satisfied the required strain during human motion. The harvester was highly soft (modulus of 5.8 MPa), 103 times lower than that of the previous harvester. The SECH can be applied to a self-powered strain gauge, capable of measuring stationary deformation and low-speed motion. The SECH created a system to examine the configuration of the human body, as demonstrated by the human monitoring sensor from five independent SECH assembled on the hand. Furthermore, the sensing information was simplified through the binarized signal. It can be used to assess the hand configuration for hand signals and sign language.

Integrated Mechano-Electrochemical Harvesting Fiber and Thermally Responsive Artificial Muscle for Self-Powered Temperature-Strain Dual-Parameter Sensor.

Significant progress in healthcare fields around the world has inspired us to develop a wearable strain−temperature sensor that can monitor biomedical signals in daily life. This novel self-powered temperature−strain dual-parameter sensor comprises a mechano-electrochemical harvester (MEH) and a thermally responsive artificial muscle (TAM). The MEHTAM system generates electricity from strain and thermal fluctuations. In addition, the sensor is comfortable to wear, owing to its stretchability (>100%), softness (<3 MPa), and one-dimensional fibers (diameter 230 µm). The MEH induces a change in the electrochemical capacitance, resulting in an electrical signal under applied strain (34 µA/m) and stress (20 µA/(m·MPa)). The TAM can be used as a mechanical temperature sensor, because the tensile stroke responds linearly to changes in temperature. As the harvester and artificial muscle are combined, the MEHTAM system generates electricity, owing to external and internal mechanical stimuli caused by muscle contractions as a response to temperature changes. The MEHTAM system that we have developed­a self-powered, strain−temperature dual-parameter sensor that is soft, stretchable, and fiber-shaped­is an interesting candidate for the production of comfortable, wearable, dual-parameter sensors.

Stretchable Fiber Biofuel Cell by Rewrapping Multiwalled Carbon Nanotube Sheets.

The fiber-type biofuel cell is attractive as an implantable energy source because the fiber can modify various structures and the wound can be stitched like a suture. In addition, in daily life, the biofuel cell is forced by human motion, and stretchability is a critical requirement for real applications. Therefore, we introduce a new type of highly stretchable, stable, soft fiber biofuel cell with microdiameter dimensions as an energy harvester. The completed biofuel cell operated well in fluids similar to human fluids, such as 20 mM phosphate-buffered 0.14 M NaCl solution (39.5 mW/cm2) and human serum (36.6 µW/cm2). The fiber-type biofuel cell can be reversibly stretched up to 100% in tensile direction while producing sustainable electrical power. In addition, the unique rewrapping structure, which traps the enzyme between multiwalled carbon nanotube sheets, enormously enhanced the stability of the biofuel cell when the biofuel cell was repeatedly stretched (the power density retention increased from 63 to 99%) and operated in human serum (the power density retention increased from 29 to 86%). The fiber can be easily woven into various structures, such as McKibben braid yarn, and scaled up by series and parallel connections.

Twist-Stabilized, Coiled Carbon Nanotube Yarns with Enhanced Capacitance.

Coil-structured carbon nanotube (CNT) yarns have recently attracted considerable attention. However, structural instability due to heavy twist insertion, and inherent hydrophobicity restrict its wider application. We report a twist-stable and hydrophilic coiled CNT yarn produced by the facile electrochemical oxidation (ECO) method. The ECO-treated coiled CNT yarn is prepared by applying low potentiostatic voltages (3.0-4.5 V vs Ag/AgCl) between the coiled CNT yarn and a counter electrode immersed in an electrolyte for 10-30 s. Notably, a large volume expansion of the coiled CNT yarns prepared by electrochemical charge injection produces morphological changes, such as surface microbuckling and large reductions in the yarn bias angle and diameter, resulting in the twist-stability of the dried ECO-treated coiled CNT yarns with increased yarn density. The resulting yarns are well functionalized with oxygen-containing groups; they exhibit extrinsic hydrophilicity and significantly improved capacitance (approximately 17-fold). We quantitatively explain the origin of the capacitance improvement using theoretical simulations and experimental observations. Stretchable supercapacitors fabricated with the ECO-treated coiled CNT yarns show high capacitance (12.48 mF/cm and 172.93 mF/cm2, respectively) and great stretchability (80%). Moreover, the ECO-treated coiled CNT yarns are strong enough to be woven into a mask as wearable supercapacitors.

Self-Helical Fiber for Glucose-Responsive Artificial Muscle.

A helical configuration confers a great advantage in artificial muscle due to great movement potential. However, most helical fibers are exposed to a high temperature to produce the coiled helical structure. Hence, thermoset polymer-composed hydrogels are difficult to fabricate as helical fibers due to their thermal degeneration. Here, we describe a self-helical hydrogel fiber that is produced without thermal exposure as a glucose-responsive artificial muscle. The sheath-core fiber was spontaneously transformed into the helical structure during the swelling state by balancing the forces between the untwisting force of the twisted nylon fiber core and the recovery force of the hydrogel sheath. To induce controllable actuation, we also applied a reversible interaction between phenylboronic acid and glucose to the self-helical hydrogel. Consequently, the maximum tensile stroke was 2.3%, and the performance was six times greater than that of the nonhelical fiber. The fiber also exhibited tensile stroke with load and a maximum work density of 130 kJ/m3. Furthermore, we showed a reversible tensile stroke in response to the change in glucose level. Therefore, these results indicate that the self-helical hydrogel fiber has a high potential for use in artificial muscles, glucose sensors, and drug delivery systems.

Electrical energy harvesting from ferritin biscrolled carbon nanotube yarn.

Various studies about harvesting energy for future energy production have been conducted. In particular, replacing batteries in implantable medical devices with electrical harvesting is a great challenge. Here, we have improved the electrical harvesting performance of twisted carbon nanotube yarn, which was previously reported to be an electrical energy harvester, by biscrolling positively charged ferritin protein in a biofluid environment. The harvester electrodes are made by biscrolling ferritin (40 wt%) in carbon nanotube yarn and twisting it into a coiled structure, which provides stretchability. The coiled ferritin/carbon nanotube yarn generated a 2.8-fold higher peak-to-peak open circuit voltage (OCV) and a 1.5-fold higher peak power than that generated by bare carbon nanotube yarn in phosphate-buffered saline (PBS) buffer. The improved performance is the result of the increased capacitance change and the shifting of the potential of zero charges that are induced by the electrochemically capacitive, positively charged ferritin. As a result, we confirm that the electrical performance of the carbon nanotube harvester can be improved using biomaterials. This carbon nanotube yarn harvester, which contains protein, has the potential to replace batteries in implantable devices.

Self-Healing Electrode with High Electrical Conductivity and Mechanical Strength for Artificial Electronic Skin.

A self-healing electrode is an electrical conductor that can repair internal damage by itself, similar to human skin. Since self-healing electrodes are based on polymers and hydrogels, these components are still limited by low electrical conductivity and mechanical strength. In this study, we designed an electrically conductive, mechanically strong, and printable self-healing electrode using liquid crystal graphene oxide (LCGO) and silver nanowires (AgNWs). The conductive ink was easily prepared by simply mixing LCGO and AgNWs solutions. The ultrathin (3 µm thick) electrode can be printed in various shapes, such as a butterfly, in a freestanding state. The maximum conductivity and strength of the LCGO/AgNW composite were 17 800 S/cm and 4.2 MPa, respectively; these values are 24 and 4 times higher, respectively, than those of a previously developed self-healing electrode. The LCGO/AgNW composite self-healed internal damage in ambient conditions with moisture and consequently recovered 96.8% electrical conductivity and 95% mechanical toughness compared with the undamaged state. The electrical properties of the composite exhibited metallic tendencies. Therefore, these results suggest that the composite can be used as an artificial electronic skin that detects environmental conditions, such as compression and temperature. This self-healing artificial electronic skin could be applied to human condition monitoring and robotic sensing systems.

Self-Powered Coiled Carbon-Nanotube Yarn Sensor for Gastric Electronics.

The strong peristaltic contraction of the stomach facilitates mixing and emptying of ingested food, which occurs rhythmically at approximately 3 cycles/min (cpm) in humans. Generally, most patients with gastroparesis show gastric electrical dysrhythmia that is disrupted electrical signals controlling gastric contractions. For treatment of gastric electrical dysrhythmia, in vivo electrical impulses to the stomach via an implanted gastric stimulator have been known to restore these gastric deformations. Nevertheless, improved sensors to monitor gastric contractions are still needed in current gastric stimulators. Recently, we have developed a new technology converting mechanical motion to electrical energy by using stretch-induced capacitance changes of a coiled carbon-nanotube (CNT) yarn. For its potential use as a gastric deformation sensor, the performance of a coiled CNT yarn was evaluated in several biological fluids. For a sinusoidal stretch to 30%, the peak-to-peak open-circuit voltage (OCV) was consistently generated at frequencies below 0.1 Hz. This sinusoidal variation in OCV augmented as the strain increased from 10 to 30%. In an in vitro artificial gastric system, the OCV was approximately linearly proportional to the balloon volume, which can monitor periodic deformations of the balloon at 2, 3, and 4 cpm as shown for human gastric deformations. Moreover, stretchy coiled yarns generate the peak electrical voltage and power when deformed. The present study shows that a self-powered CNT yarn sensor can not only monitor the changes in frequency and amplitude of volumetric change but also generate electrical power by periodic deformations of the balloon. Therefore, it seems possible to automatically deliver accurate electrical impulses according to real-time evaluation of a patient's gastric deformation based on information on the frequency, amplitude, and rate of the OCV from CNT yarn.

Sheath-run artificial muscles.

Although guest-filled carbon nanotube yarns provide record performance as torsional and tensile artificial muscles, they are expensive, and only part of the muscle effectively contributes to actuation. We describe a muscle type that provides higher performance, in which the guest that drives actuation is a sheath on a twisted or coiled core that can be an inexpensive yarn. This change from guest-filled to sheath-run artificial muscles increases the maximum work capacity by factors of 1.70 to 2.15 for tensile muscles driven electrothermally or by vapor absorption. A sheath-run electrochemical muscle generates 1.98 watts per gram of average contractile power-40 times that for human muscle and 9.0 times that of the highest power alternative electrochemical muscle. Theory predicts the observed performance advantages of sheath-run muscles.

Harvesting electrical energy from torsional thermal actuation driven by natural convection.

The development of practical, cost-effective systems for the conversion of low-grade waste heat to electrical energy is an important area of renewable energy research. We here demonstrate a thermal energy harvester that is driven by the small temperature fluctuations provided by natural convection. This harvester uses coiled yarn artificial muscles, comprising well-aligned shape memory polyurethane (SMPU) microfibers, to convert thermal energy to torsional mechanical energy, which is then electromagnetically converted to electrical energy. Temperature fluctuations in a yarn muscle, having a maximum hot-to-cold temperature difference of about 13 °C, were used to spin a magnetic rotor to a peak torsional rotation speed of 3,000 rpm. The electromagnetic energy generator converted the torsional energy to electrical energy, thereby producing an oscillating output voltage of up to 0.81 V and peak power of 4 W/kg, based on SMPU mass.

Temperature-Responsive Tensile Actuator Based on Multi-walled Carbon Nanotube Yarn.

Many temperature indicators or sensors show color changes for materials used in food and medical fields. However, they are not helpful for a color-blind person or children who lack judgment. In this paper, we introduce simply fabricated and more useful low-temperature indicator (~30 °C) for devices that actuates using paraffin-infiltrated multi-walled carbon nanotube (MWCNT) coiled yarn. The density difference of MWCNT yarn provides large strain (~330 %) when heat causes the melted polymer to move. Furthermore, the MWCNT yarn decreases the melting point of paraffin. These properties allow control of the actuating temperature. In addition, mechanical strength was enhanced by MWCNT than previously reported temperature-responsive actuators based on shape memory polymers. This simply fabricated temperature indicator can be applied in latching devices for medical and biological fields.

Stretchable Triboelectric Fiber for Self-powered Kinematic Sensing Textile.

Stretchable fiber and yarn triboelectric nanogenerator are sought for such applications as wearable sensing system such as cloth communication devices, electronic textiles, and robotic sensory skin. Unfortunately, previously reported triboelectric fiber and yarn are difficult to have stretchable property. We introduce here a new type of stretchable and weavable triboelectric fibers with microdiameter dimensions. The stretchable triboelectric fibers can be reversibly stretched up to 50% in tensile direction while generating voltage output proportional to the applied tensile strain. The reversible distance change induced by the Poisson's ratio difference between the core fiber (silver-coated nylon/polyurethane) and the shell (wrinkled polyvinylidene fluoride-co-trifluoroethylene/carbon nanotube layer) during tensile deformation is the key working principle for electrical generation. Owing to exceptional structural stability, the stretchable triboelectric fibers show high performance retention after 10,000 times repeated stretching/releasing cycle. Furthermore, the stretchable triboelectric fibers are mechanically strong to be woven into a commercial textile for textile based sensors, which can detect magnitude as well as direction of the motion.

Shape-engineerable composite fibers and their supercapacitor application.

Due to excellent electrical and mechanical properties of carbon nano materials, it is of great interest to fabricate flexible, high conductive, and shape engineered carbon based fibers. As part of these approaches, hollow, twist, ribbon, and other various shapes of carbon based fibers have been researched for various functionality and application. In this paper, we suggest simple and effective method to control the fiber shape. We fabricate the three different shapes of hollow, twisted, and ribbon shaped fibers from wet spun giant graphene oxide (GGO)/single walled-nanotubes (SWNTs)/poly(vinyl alcohol) (PVA) gels. Each shaped fibers exhibit different mechanical properties. The average specific strengthes of the hollow, twist, and ribbon fibers presented here are 126.5, 106.9, and 38.0 MPa while strain are 9.3, 13.5, and 5%, respectively. Especially, the ribbon fiber shows high electrical conductivity (524 ± 64 S cm(-1)) and areal capacitance (2.38 mF cm(-2)).

Woven-Yarn Thermoelectric Textiles.

The fabrication and characterization of highly flexible textiles are reported. These textiles can harvest thermal energy from temperature gradients in the desirable through-thickness direction. The tiger yarns containing n- and p-type segments are woven to provide textiles containing n-p junctions. A high power output of up to 8.6 W m(-2) is obtained for a temperature difference of 200 °C.

Stretchable, weavable coiled carbon nanotube/MnO2/polymer fiber solid-state supercapacitors.

Fiber and yarn supercapacitors that are elastomerically deformable without performance loss are sought for such applications as power sources for wearable electronics, micro-devices, and implantable medical devices. Previously reported yarn and fiber supercapacitors are expensive to fabricate, difficult to upscale, or non-stretchable, which limits possible use. The elastomeric electrodes of the present solid-state supercapacitors are made by using giant inserted twist to coil a nylon sewing thread that is helically wrapped with a carbon nanotube sheet, and then electrochemically depositing pseudocapacitive MnO2 nanofibers. These solid-state supercapacitors decrease capacitance by less than 15% when reversibly stretched by 150% in the fiber direction, and largely retain capacitance while being cyclically stretched during charge and discharge. The maximum linear and areal capacitances (based on active materials) and areal energy storage and power densities (based on overall supercapacitor dimensions) are high (5.4 mF/cm, 40.9 mF/cm(2), 2.6 µWh/cm(2) and 66.9 µW/cm(2), respectively), despite the engineered superelasticity of the fiber supercapacitor. Retention of supercapacitor performance during large strain (50%) elastic deformation is demonstrated for supercapacitors incorporated into the wristband of a glove.