Fibrous Conductive Metallogels with Hybrid Electron/Ion Networks for Boosted Extreme Sensitivity and High Linearity Strain Sensor.

Fibrous strain sensing materials with both high sensitivity and high linearity are of significant importance for wearable sensors, yet they still face great challenges. Herein, a photo-spun reaction encapsulation strategy is proposed for the continuous fabrication of fibrous strain sensor materials (AMGF) with a core-sheath structure. Metallogels (MOGs) formed by bacterial cellulose (BC) nanofibers and Ag nanoparticles (AgNPs), and thermoplastic elastomers (TPE) are employed as the core and sheath, respectively. The in situ ultraviolet light reduction of Ag+ ensured AgNPs to maintain the interconnections between the BC nanofibers and form electron conductive networks (0.31 S m-1 ). Under applied strain, the BC nanofibers experience separation, bringing AMGF a high sensitivity (gauge factor 4.36). The concentration of free ions in the MOGs uniformly varies with applied deformation, endowing AMGF with high linearity and a goodness-of-fit of 0.98. The sheath TPE provided AMGF sensor with stable working life (>10 000 s). Furthermore, the AMGF sensors are demonstrated to monitor complex deformations of the dummy joints in real-time as a wearable sensor. Therefore, the fibrous hybrid conductive network fibers fabricated via the photo-spun reaction encapsulation strategy provide a new route for addressing the challenge of achieving both high sensitivity and high linearity.

Toward Self-Powered Sensing and Thermal Energy Harvesting in High-Performance Composites via Self-Folded Carbon Nanotube Honeycomb Structures.

The development of high-performance self-powered sensors in advanced composites addresses the increasing demands of various fields such as aerospace, wearable electronics, healthcare devices, and the Internet-of-Things. Among different energy sources, the thermoelectric (TE) effect which converts ambient temperature gradients to electric energy is of particular interest. However, challenges remain on how to increase the power output as well as how to harvest thermal energy at the out-of-plane direction in high-performance fiber-reinforced composite laminates, greatly limiting the pace of advance in this evolving field. Herein, we utilize a temperature-induced self-folding process together with continuous carbon nanotube veils to overcome these two challenges simultaneously, achieving a high TE output (21 mV and 812 nW at a temperature difference of 17 °C only) in structural composites with the capability to harvest the thermal energy from out-of-plane direction. Real-time self-powered deformation and damage sensing is achieved in fabricated composite laminates based on a thermal gradient of 17 °C only, without the need of any external power supply, opening up new areas of autonomous self-powered sensing in high-performance applications based on TE materials.

Optimization of thermoelectric properties of carbon nanotube veils by defect engineering.

Carbon nanotubes (CNTs), with their combination of excellent electrical conductivity, Seebeck coefficient, mechanical robustness and environmental stability are highly desired as thermoelectric (TE) materials for a wide range of fields including Internet of Things, health monitoring and environmental remediation solutions. However, their high thermal conductivity (κ) is an obstacle to practical TE applications. Herein, we present a novel method to reduce the κ of CNT veils, by introducing defects, while preserving their Seebeck coefficient and electrical conductivity. Solid-state drawing of a CNT veil embedded within two polycarbonate films generates CNT veil fragments of reducing size with increasing draw ratio. A successive heat treatment, at above the polycarbonate glass-to-rubber transition temperature, spontaneously reconnects the CNT veils fragments electrically but not thermally. Stretching to a draw ratio of 1.5 and heat repairing at 170 °C leads to a dramatic 3.5-fold decrease in κ (from 46 to 13 W m-1 K-1), in contrast with a decrease in electrical conductivity of only 26% and an increase in Seebeck coefficient of 10%. To clarify the mechanism of reduction in thermal conductivity, a large-scale mesoscopic simulation of CNT veils under uniaxial stretching has also been used. This work shows that defect engineering can be a valuable strategy to optimize TE properties of CNT veils and, potentially, other thermoelectric materials.

Stretchable, Environment-Stable, and Knittable Ionic Conducting Fibers Based on Metallogels for Wearable Wide-Range and Durable Strain Sensors.

The construction of fibrous ionic conductors and sensors with large stretchability, low-temperature tolerance, and environmental stability is highly desired for practical wearable devices yet is challenging. Herein, metallogels (MOGs) with a rapidly reversible force-stimulated sol-gel transition were employed and encapsulated into a hollow thermoplastic elastomer (TPE) microfiber through a simple coaxial spinning. The resultant MOG@TPE coaxial fiber exhibited a high stretchability (>100%) in a broad temperature range (-50 to 50 °C). The MOG@TPE fibrous strain sensor demonstrated a high-yet-linear working curve, fast response time (<100 ms), highly stable conductivity under large deformation, and excellent cycling stability (>3000 cycles). The MOG@TPE fibrous sensors were demonstrated to be directly attached to the human skin to monitor the real-time movements of large/facet joints of the elbow, wrist, finger, and knee. It is believed that the present work for preparing the stretchable ionic conductive fibers holds great promise for applications in fibrous wearable sensors with broad temperature range, large stretchability, stable conductivity, and high wearing comfort.

Self-powered ultrasensitive and highly stretchable temperature-strain sensing composite yarns.

With the emergence of stretchable/wearable devices, functions, such as sensing, energy storage/harvesting, and electrical conduction, should ideally be carried out by a single material, while retaining its ability to withstand large elastic deformations, to create compact, functionally-integrated and autonomous systems. A new class of trimodal, stretchable yarn-based transducer formed by coating commercially available Lycra® yarns with PEDOT:PSS is presented. The material developed can sense strain (first mode), and temperature (second mode) and can power itself thermoelectrically (third mode), eliminating the need for an external power-supply. The yarns were extensively characterized and obtained an ultrahigh (gauge factor ∼3.6 × 105, at 10-20% strain) and tunable (up to about 2 orders of magnitude) strain sensitivity together with a very high strain-at-break point (up to ∼1000%). These PEDOT:PSS-Lycra yarns also exhibited stable thermoelectric behavior (Seebeck coefficient of 15 µV K-1), which was exploited both for temperature sensing and self-powering (∼0.5 µW, for a 10-couple module at ΔT ∼ 95 K). The produced material has potential to be interfaced with microcontroller-based systems to create internet-enabled, internet-of-things type devices in a variety of form factors.

Dense Hydrogen-Bonding Network Boosts Ionic Conductive Hydrogels with Extremely High Toughness, Rapid Self-Recovery, and Autonomous Adhesion for Human-Motion Detection.

The construction of ionic conductive hydrogels with high transparency, excellent mechanical robustness, high toughness, and rapid self-recovery is highly desired yet challenging. Herein, a hydrogen-bonding network densification strategy is presented for preparing a highly stretchable and transparent poly(ionic liquid) hydrogel (PAM-r-MVIC) from the perspective of random copolymerization of 1-methyl-3-(4-vinylbenzyl) imidazolium chloride and acrylamide in water. Ascribing to the formation of a dense hydrogen-bonding network, the resultant PAM-r-MVIC exhibited an intrinsically high stretchability (>1000%) and compressibility (90%), fast self-recovery with high toughness (2950 kJ m-3), and excellent fatigue resistance with no deviation for 100 cycles. Dissipative particle dynamics simulations revealed that the orientation of hydrogen bonds along the stretching direction boosted mechanical strength and toughness, which were further proved by the restriction of molecular chain movements ascribing to the formation of a dense hydrogen-bonding network from mean square displacement calculations. Combining with high ionic conductivity over a wide temperature range and autonomous adhesion on various surfaces with tailored adhesive strength, the PAM-r-MVIC can readily work as a highly stretchable and healable ionic conductor for a capacitive/resistive bimodal sensor with self-adhesion, high sensitivity, excellent linearity, and great durability. This study might provide a new path of designing and fabricating ionic conductive hydrogels with high mechanical elasticity, high toughness, and excellent fatigue resilience for skin-inspired ionic sensors in detecting complex human motions.

Superelastic, Fatigue-Resistant, and Flame-Retardant Spongy Conductor for Human Motion Detection against a Harsh High-Temperature Condition.

The construction of wearable piezoresistive sensors with high elasticity, large gauge factor, and excellent durability in a harsh high-temperature environment is highly desired yet challenging. Here, a lightweight, superelastic, and fatigue-resistant spongy conductor was fabricated via a sponge-constrained network assembly, during which highly conductive graphene and flame-retardant montmorillonite were alternatively deposited on a three-dimensional melamine scaffold. The as-obtained spongy conductor exhibited a highly deformation-tolerant conductivity up to 80% strain and excellent fatigue resistance of 10,000 compressive cycles at 70% strain. As a result, the spongy conductor can readily work as a piezoresistive sensor and exhibited a high gauge factor value of ∼2.3 in a strain range of 60-80% and excellent durability under 60% strain for 10,000 cycles without sacrificing its piezoresistive performance. Additionally, the piezoresistive sensor showed great thermal stability up to 250 °C for more than 7 days and sufficient flame-retardant performance for at least 20 s. This lightweight, superelastic, and flame-retardant spongy conductor reveals tremendous potential in human motion detection against a harsh high-temperature environment.

Static and Dynamic Postannealing Strategies for Roll-to-Roll Fabrication of DC Magnetron Sputtered Bismuth Telluride Thin Films onto Polymer Webs.

High-throughput roll-to-roll processes are desirable to scale up the manufacture of flexible thermoelectric generators. While vacuum deposition onto a heated dynamic substrate presents a considerable engineering challenge, viable postdeposition in-line annealing processes are considered as an alternative to improve the functional performance of as-deposited films. The effect of infrared and electron-beam irradiations of 1 µm thick bismuth telluride thin films, produced by a vacuum roll-to-roll process for use as thermoelectric materials, was examined. A static vacuum oven and pulsed high-energy electron beam were also studied as control groups. All annealing strategies increased the crystallite size and decreased the Te content. Only the static vacuum oven treatment was shown to significantly improve the film's crystallinity. After 1 h annealing, the power factor improved by 400% (from 2.8 to 14 × 10-4 W/mK2), which, to the knowledge of the authors, is the highest reported thermoelectric performance of postannealed or hot-deposited Bi-Te films. As for in-line annealing, infrared and electron-beam post treatments improved the power factor by 146% (from 2.8 to 6.9 × 10-4 W/mK2) and 64% (from 2.8 to 4.6 × 10-4 W/mK2), respectively.