Cu3(HHTP)2 c-MOF/ZnO Ultrafast Ultraviolet Photodetector for Wearable Optoelectronics

Two-dimensional conductive metal–organic frameworks (2D c-MOFs) are a family of highly tunable and electrically conducting materials that can be utilized in optoelectronics. A major issue of 2D c-MOFs for photodetection is their poor charge separation and recombination dynamics upon illumination. This study demonstrates a Cu₃(HHTP)₂/ZnO type-II heterojunction ultraviolet (UV) photodetector fabricated by layer-by-layer (LbL) deposition, in which the charge separation of photogenerated carriers is enhanced. At optimized MOF layer cycles, the device achieves a responsivity of 78.2 A/W and detectivity of 3.8×10⁹ Jones at 1 V. Particularly, the device can be operated in the self-powered mode with an ultrafast response time of 70 μs, which is the record value for MOF-based photodetectors. In addition, even after 1000-time bending of 180°, the flexible device maintains stable performance. This flexible MOF-based UV photodetector with anti-fatigue and anti-bending properties provides strong implication to wearable optoelectronics.     

Non‐oxidized graphene/elastomer composite films for wearable strain and pressure sensors with ultra‐high flexibility and sensitivity

It remains challenging to prepare wearable strain and pressure sensors with excellent mechanical properties, ultra‐high flexibility and sensitivity. Electrically conductive graphene platelets (GnPs) with high structural integrity are used in making a composite film fabricated using robust fabrication techniques. The gauge factor for the strain is up to 100 at 0%‐5% strain and 50 at 5%‐30% strain, and the sensitivity to pressure is 2.7×10^‐2 kPa^‐1 between 0 and 10 kPa and 1.5×10^‐4 kPa^‐1 between 300 and 1000 kPa. In addition, the flexible sensor demonstrates good repeatability and durability after 1000 cycles of tensile and compression tests. The flexible sensor has fast response ability and a wide operating temperature range, suggesting the excellent response to temperature. The flexible sensor is applied in monitoring several human motions as a wearable device with high accuracy. The ability to detect strain, pressure and temperature of the flexible sensor extends its applications to multifunctional wearable devices.     

Fiber-shaped Supercapacitors: Advanced Strategies toward High-performances and Multi-functions

Fiber-shaped supercapacitors(FSSCs) show great potential in portable and wearable electronics due to their unique advantages of high safety, environmental friendliness, high performances, outstanding flexibility and integrability. They can directly act as the power sources or be easily integrated with other flexible devices to constitute self-powered and sustainable energy suppliers, providing excellent adaptability to irregular surfaces. This review mainly summarizes the recently reported works of FSSCs including preparation methods of various fiber electrodes,construction strategies of FSSCs and multi-functional device integrations, exploration of reaction mechanisms and strategies to improve the electrochemical performance and provision of suggestions on further designing and optimization of FSSCs. Meanwhile, it shares our perspectives on challenges and opportunities in this field, shedding light on the development of high-performance fiber-shaped supercapacitors with multifunctions.     

Self-powered Biosensor Big Data Intelligent Information Processing System for Real-time Motion Monitoring

A portable self-powered biosensor big data information processing system has been designed to help coaches monitor athlete training performance in real-time. The material system is composed of tetrapod-shaped ZnO nanowires and common textiles. Based on the piezoelectric effect, the device can convert weak shape variables into electrical signals, and the output piezoelectric signal obviously depends on the shape variable, the surrounding humidity and temperature. After attaching the device to the athlete, it can monitor the speed, frequency, angle of an athlete, and surrounding humidity and temperature in real-time without external power supply. API data collected by information processing end, server behavior simulated by Web service, turns the host of integrated web services into a data server, shares to other terminals via LAN to implement the visual charts summary for data-driven views, summarize and analyze charts. This multidisciplinary research can point out the new development direction of sport science and may promote the development of flexible self-powered multifunctional nano-systems.     

Dual nanocatalysts co-decorated three-dimensional,laser-induced graphene hybrid nanomaterials integrated with a smartphone portable electrochemical system for point-of-care non-enzymatic glucose diagnosis

Non-enzymatic biosensors based on various nanomaterials with large surface-volume ratios and high catalytic efficiencies have been proposed to compensate for the non-stability and high cost of enzymatic biosensors. However, the construction of a stable, highly sensitive, flexible, three-dimensional (3D), microstructured, non-enzymatic biosensor integrated with a smartphone-based portable system has been challenging. Herein, highly conductive laser-induced graphene (LIG) array with a honeycomb-like 3D microstructure co-decorated with copper(I) oxide and gold nanocatalysts was developed via simple and green electro-deposition and chemical reduction approaches for a miniaturized electrochemical flexible non-enzymatic biosensor. SEM, XRD, Raman and XPS analyzations indicated that the Cu₂O and Au nanocatalysts co-decorated three-dimensional, laser-induced graphene hybrid nanomaterials were developed successfully. The signal of the biosensor was improved by more than 10 fold compared to the LIG alone due to the co-decorated with copper(I) oxide and gold nanocatalysts. The fabricated electrochemical biochip was integrated with a smartphone-based microstation for glucose monitoring, presenting a larger linear interval of 1–20 mM with an excellent sensitivity of 236 μA/mM/cm² and a relatively low detection limit of 0.31 μM. Noticeably, the biochip could measure blood sugar on curved surfaces and still deliver stable sensing signals after being bent back-and-forth 25 times. The novel biosensor is a potentially valuable flexible electronic device. The hybrid nanomaterials developed in this work may be applicable to other biosensing, catalytic, and energy devices (supercapacitors and batteries).     

Freestanding film formed with Sb-nanoplates embedded in flexible porous carbon nanofibers as a binder-free anode for high-performance wearable potassium-ion battery

Antimony-based materials are considered as promising anodes for potassium ion batteries due to their high theoretical capacity and low electrode potential. However, the aggregation and bulk expansion of Sb particles in cycling will cause capacity attenuation and poor rate performance. In this paper, Sb nanoplates were designed to be embedded in flexible porous N-dopped carbon nanofibers (Sb@PCNFs) by a simple electrospinning deposition (ESD) method. In this structural design, Sb nanoplates of high capacity were employed as active materials, N-dopped carbon nanofibers were used to improve conductivity and structural stability. The introduction of pore-forming agent enables the nanofibers to possess porous structure, thus buffering the huge volume change and promoting the transfer of electrolyte/ions. More importantly, the freestanding film can be directly used as a working electrode, reducing the redundancy in the battery and the cost. Benefitting from the favorable structure, the freestanding flexible Sb@PCNFs electrode shows excellent potassium storage performance with a capacity of 314 mAh/g after 2000 cycles at 500 mA/g. This strategy of employing active material with high capacity in porous and conductive flexible nanofibers represents an effective method of achieving binder-free electrode with good electrochemical performance towards wearable energy storage devices.     

Skin‐worn Soft Microfluidic Potentiometric Detection System

A flexible skin‐mounted microfluidic potentiometric device for simultaneous electrochemical monitoring of sodium and potassium in sweat is presented. The wearable device allows efficient natural sweat pumping to the potentiometric detection chamber, containing solid‐contact ion‐selective Na⁺ and K⁺ electrodes, during exercise activity. The fabricated microchip electrolyte‐sensing device displays good analytical performance and addresses sweat mixing and carry‐over issues of early epidermal potentiometric sensors. Such soft skin‐worn microchip platform integrates potentiometric measurement, microfluidic technologies with flexible electronics for real‐time wireless data transmission to mobile devices. The new fully integrated microfluidic electrolyte‐detection device paves the way for practical fitness and health monitoring applications.     

3D nanoporous gold scaffold supported on graphene paper: Freestanding and flexible electrode with high loading of ultrafine PtCo alloy nanoparticles for electrochemical glucose sensing

Recent advances in on-body wearable medical apparatus and implantable devices drive the development of light-weight and bendable electrochemical sensors, which require the design of high-performance flexible electrode system. In this work, we reported a new type of freestanding and flexible electrode based on graphene paper (GP) supported 3D monolithic nanoporous gold (NPG) scaffold (NPG/GP), which was further modified by a layer of highly dense, well dispersed and ultrafine binary PtCo alloy nanoparticles via a facile and effective ultrasonic electrodeposition method. Our results demonstrated that benefited from the synergistic effect of the electrocatalytically active PtCo alloy nanoparticles, the large-active-area and highly conductive 3D NPG scaffold, and the mechanically strong and stable GP electrode substrate, the resultant PtCo alloy nanoparticles modified NPG/GP (PtCo/NPG/GP) exhibited high mechanical strength and good electrochemical sensing performances toward nonenzymatic detection of glucose, including a wide linear range from 35 μM– to 30 mM, a low detection limit of 5 μM (S/N = 3) and a high sensitivity of 7.84 μA cm⁻² mM⁻¹ as well as good selectivity, long-term stability and reproducibility. The practical application of the proposed PtCo/NPG/GP has also been demonstrated in in vitro detection of blood glucose in real clinic samples.     

Recent progress of unconventional and multifunctional integrated supercapacitors

We summary the latest works of multifunctional integrated supercapacitors which were combined with photodetectors, gas sensors, electrochromic or physiological/mechanical activities monitors.     

一种高透明、可拉伸导电水凝胶的制备及其在电容传感器中的应用

导电水凝胶由于具备良好的电学特性、可调节的机械性能、易于加工性和生物相容性等,是制备柔性电子设备的理想基材。本文使用马来酸与丙烯酰胺作为共聚单体,氯化锂作为导电离子,N,N'-二甲基双丙烯酰胺作为交联剂,使用光引发剂,采用原位光聚合的方式制备了一种导电水凝胶。制得的水凝胶可见光透过率高达93%,最大拉伸形变~380%,导电率最大为12 S/m。鉴于其优异的综合性能,实验中使用导电水凝胶制备了电容传感器并应用于人体活动监测。结果表明,制备的导电水凝胶电容传感器对不同程度的手指弯曲形变和不同力度的手指触碰均表现出灵敏的响应行为,为未来可穿戴柔性电子产品的发展起到了一定的推动作用。     

Theoretical investigation of polymer molecular structure influence on dielectric properties and mechanical properties

Triboelectric nanogenerator (TENG) technologies have explosive development in the field of energy harvesting and self-powered sensing. As the key element of triboelectric devices, dielectric polymers have obtained much attention in recent years. The dielectric properties of polymer determine the output performance of TENG. In this paper, we take silicone rubber as an example of dielectric polymers, to study the properties of molecular structure influence on the dielectric properties and mechanical properties by the molecular dynamics simulation method. The free volume fraction, dielectric constant, and mechanical properties of silicone rubbers with different branch chains were calculated. The dielectric constant is highly related to the free volume distribution and the dipole moments of silicone rubbers with different amounts of branch chains. For fewer branch chains silicone rubber, the free volume distribution contributes most to the dielectric constant; for more branch chains silicone rubber, the dipole moment dominates the dielectric constant. Therefore, the silicone rubber ratio has a great influence on the dielectric constant of silicone rubber. With the increase of temperature, the dielectric constant of 2-chain silicone rubber increases at first and then decreases, and the maximum value is obtained near 300 K. Therefore, it is necessary to control the temperature when silicone rubber is used as a dielectric material. This work can be a guide for improving the dielectric properties of silicone rubber, and it provides a new approach to the optimal design of high-performance triboelectric nanogenerators.     

柔性复合热电材料及器件的研究进展

热电材料能够将热能与电能直接相互转化,在废热回收及绿色制冷领域中具有巨大的应用潜力。相比无机块体热电材料,柔性热电材料具有可弯折、体积小、质量轻等优点,还适用于制备可穿戴电子设备。近10年来,基于导电高分子、碳材料和无机纳米材料等的柔性复合热电材料及器件逐渐成为炙手可热的研究领域,受到了业内广泛的关注。本文综述了近年来基于不同材料体系的柔性热电材料及器件的研究进展、存在的亟待解决的问题和未来的发展方向。大量研究结果表明,材料的热电性能可以通过化学合成和分子设计战略、形貌控制及掺杂技术等进行有效的调控。研发满足实际应用需要的先进柔性热电材料仍然极具挑战性。     

Improving the performances of direct-current triboelectric nanogenerators with surface chemistry

Over the past decade, triboelectric nanogenerators (TENGs) – small and portable devices designed to harvest electricity from mechanical vibrations and friction – have matured from a niche theme of electrical engineering research into multidisciplinary research encompassing materials science, physics, and chemistry. Recent advances in both the fundamental understanding and performances of TENGs have been made possible by surface chemistry, electrochemistry, and theoretical chemistry research entering this active and promising field. This short review focuses on the recent developments of direct-current (DC) TENGs, where sliding friction or repetitive contact–separation cycles between the surface of polymers, metals, chemically modified semiconductors, and more recently even by the simple contact of surfaces with water solutions, can output DC suitable to power electronic devices without the need of additional rectification. We critically analyze the role of surface chemistry toward maximizing DC TENG outputs and device longevity. The major current hypotheses about their working mechanism(s) are also discussed.     

Wearable self-powered biosensors

Wearable self-powered biosensors are devices that operate without an external electronic power source or onboard battery and that use a biorecognition detection element to relay sensing information. Such devices are becoming more widespread following the larger trend of more ubiquitous wearable devices in general. Self-powering can be a particularly important characteristic in situations where replacing/recharging a battery is either impossible or impractical. Most wearable self-powered biosensors rely primarily on enzymatic reactions to supply the energy required for operation, but there are also other innovative approaches that combine multiple signal transduction techniques to simultaneously provide power and produce a detection signal. Areas of needed research include developing higher power energy harvesting techniques and more wearable self-powered biosensor devices that have integrated low-power wireless electronics.     

Printing graphene-carbon nanotube-ionic liquid gel on graphene paper: Towards flexible electrodes with efficient loading of PtAu alloy nanoparticles for electrochemical sensing of blood glucose

The increasing demands for portable, wearable, and implantable sensing devices have stimulated growing interest in innovative electrode materials. In this work, we have demonstrated that printing a conductive ink formulated by blending three-dimensional (3D) porous graphene–carbon nanotube (CNT) assembly with ionic liquid (IL) on two-dimensional (2D) graphene paper (GP), leads to a freestanding GP supported graphene–CNT–IL nanocomposite (graphene–CNT–IL/GP). The incorporation of highly conductive CNTs into graphene assembly effectively increases its surface area and improves its electrical and mechanical properties. The graphene–CNT–IL/GP, as freestanding and flexible substrates, allows for efficient loading of PtAu alloy nanoparticles by means of ultrasonic-electrochemical deposition. Owing to the synergistic effect of PtAu alloy nanoparticles, 3D porous graphene–CNT scaffold, IL binder and 2D flexible GP substrate, the resultant lightweight nanohybrid paper electrode exhibits excellent sensing performances in nonenzymatic electrochemical detection of glucose in terms of sensitivity, selectivity, reproducibility and mechanical properties.     

Flexible asymmetric supercapacitor with high energy density based on optimized MnO2 cathode and Fe2O3 anode

A flexible asymmetric supercapacitor is assembled using MnO₂ nanosheets/carbon fabric and Fe₂O₃/carbon fabric electrodes. By optimizing the reaction condition of the two electrodes, the device shows high energy densities and excellent flexibility.     

3D braided yarns to create electrochemical cells

The demands for new configurations of electrochemical cells continue to grow and novel approaches are being enabled by the advent of new electromaterials and novel fabrication strategies. Wearable energy storage devices that can be seamlessly integrated into garments are a critical component of the wearable electronics genre. Recently, flexible yarn supercapacitors have attracted significant attention due to their ability to be integrated into fabrics, or stitched into existing textiles. Large-scale production of yarn supercapacitors using conventional manufacturing processes, however, is still a challenge. Here, we introduce the use of braiding technology to achieve a predetermined arrangement of fibre electrodes, the basis of a mass fabrication protocol to produce specific electrochemical cells: wearable supercapacitors. The resultant supercapacitors show a high capacitance of 1.71 mF cm^− 1. The structure is highly flexible with a 25% capacitance loss recorded after 1000 bending cycles.     

Highly Stretchable Supercapacitors Based on Aligned Carbon Nanotube/Molybdenum Disulfide Composites

Stretchable supercapacitors that can sustain their performance under unpredictable tensile force are important elements for practical applications of various portable and wearable electronics. However, the stretchability of most reported supercapacitors was often lower than 100 % because of the limitation of the electrodes used. Herein we developed all‐solid‐state supercapacitors with a stretchability as high as 240 % by using aligned carbon nanotube composites with compact structure as electrodes. By combined with pseudocapacitive molybdenum disulfide nanosheets, the newly developed supercapacitor showed a specific capacitance of 13.16 F cm^?3, and also showed excellent cycling retention (98 %) after 10 000 charge–discharge cycles. This work also presents a general and effective approach in developing high‐performance electrodes for flexible and stretchable electronics.     

Paper test strip for silver ions detection in drinking water samples based on combined fluorometric and colorimetric methods

In this study, a portable silver ion (Ag⁺) sensor was fabricated based on a dual signal output system using black phosphorus quantum dots (BPQDs) as probes. It is the first work for Ag⁺ detection using paper test strip based on BPQDs. The color change of BPQDs paper sensor for the determination of Ag⁺ was easily identified by naked eye. BPQDs were synthesized from bulk black phosphorus (BP) by mechanical exfoliation combined with a solvothermal method. BPQDs exhibited blue fluorescence with a quantum yield of 8.82 %. The fluorescence of BPQDs can be quenched by Ag⁺, and the absorbance of BPQDs is increased with increasing Ag⁺ concentration. The mechanism of the interaction between BPQDs and Ag⁺ involving fluorescence quenching and bonding was investigated by experimental and computational methods. The detection limit of Ag⁺ was 1.56 μg/mL and 0.19 μg/mL using fluorometry and colorimetry methods, respectively. A portable visual sensor based on paper test strip was constructed for Ag⁺ detection using the colorimetric approach. The strategy was employed to determine Ag⁺ successfully in drinking water samples. Therefore, the proposed portable Ag⁺ sensor can be potentially utilized for the lab-free analysis of drinking water and even dietary samples.     

Robust cellulose-carbon nanotube conductive fibers for electrical heating and humidity sensing

Multifunctional fibers have attracted widespread attention due to applications in flexible smart wearable devices. However, simultaneously obtaining a strong and functional woven fiber is still a great challenge owing to the conflict between the properties mentioned above. Herein, mechanically strong and highly conductive cellulose/carbon nanotube (CNT) composite fibers were spun using an aqueous alkaline/urea solution. The microstructure as well as physical properties of the resulting fibers were characterized via scanning electron microscopy, infrared spectroscopy, mechanical and electrical measurement. We demonstrated that carboxylic CNTs can be well dispersed in alkali/urea aqueous systems which also dissolved cellulose well. The subsequent wet spinning process aligned the CNTs and cellulose molecules inside the regenerated composite fiber well, enhancing the interaction between these two components and endowing the composite fiber having a 20% CNT loading with an excellent mechanical strength of 185 MPa. Benefiting from the formation of conductive paths, the composite fiber with the diameter of about 50 μm possessed an electrical conductivity value in the range of 64–1274 S/m for 5–20 wt% CNT loading. This excellent mechanical strength and high electrical conductivity enable the composite fiber to exhibit a great potential in joule heating; the heating temperature of cellulose/CNT-20 fiber reached more than 55 °C within 15 s at 9 V. In addition, the multifunctional filaments are further manufactured as a water sensor to measure humidity. This work provides a potential material that can be applied in the fields of wearable electronics and smart flexible fabrics.

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