Rational design of conductive metal-organic frameworks and aligned carbon nanofibers for enhancing the performance of flexible supercapacitors.

Carbonaceous materials are attractive active materials for the manufacture of flexible electrochemical double-layer capacitors (EDLCs) because of their high electrical conductivity, large surface area, and inherent resilience against deformation. However, compared to pseudocapacitors, which store electrochemical energy via faradaic redox reactions, EDLCs generally exhibit inferior energy density. One potential approach to addressing this issue is to incorporate highly porous and electrically conductive materials into carbonaceous material-based EDLCs. In this paper, we present a hybrid electrode consisting of a conductive metal-organic framework (c-MOF) with high electrical conductivity and unique porous structure combined with a mat of aligned carbon nanofibers (ACNFs). Its highly ordered structure facilitates electronic/ionic transport, increasing the areal capacitance by up to 3.9 times compared to randomly-oriented carbon nanofibers (RCNFs). An additional increase in areal capacitance (+64%) is achieved by introducing c-MOF (RCNFs: 25.4 mF cm-2; ACNFs: 98.7 mF cm-2; c-MOF/ACNF: 161.8 mF cm-2). Additionally, an ACNF mat exhibits excellent mechanical flexibility and electrochemical reliability, making it highly suitable for the assembly of freestanding flexible supercapacitors. By optimizing the electrochemical performance of c-MOF/ACNF and its suitability for utilization in flexible energy storage systems, this study presents a promising avenue for the practical implementation of c-MOF-based supercapacitors.

Hydrovoltaic Electricity Generator with Hygroscopic Materials: A Review and New Perspective.

The global energy crisis caused by the overconsumption of nonrenewable fuels has prompted researchers to develop alternative strategies for producing electrical energy. In this review, a fascinating strategy that simply utilizes water, an abundant natural substance throughout the globe and even in air as moisture, as a power source is introduced. The concept of the hydrovoltaic electricity generator (HEG) proposed herein involves generating an electrical potential gradient by exposing the two ends of the HEG device to dissimilar physicochemical environments, which leads to the production of an electrical current through the active material. HEGs, with a large variety of viable active materials, have much potential for expansion toward diverse applications including permanent and/or emergency power sources. In this review, representative HEGs that generate electricity by the mechanisms of diffusion, streaming, and capacitance as case studies for building a fundamental understanding of the electricity generation process are discussed. In particular, by comparing the use and absence of hygroscopic materials, HEG mechanism studies to establish active material design principles are meticulously elucidated. The review with future perspectives on electrode design using conducting nanomaterials, considerations for high performance device construction, and potential impacts of the HEG technology in improving the livelihoods are reviewed.

A π-Bridge Spacer Embedded Electron Donor-Acceptor Polymer for Flexible Electrochromic Zn-Ion Batteries.

Zinc-ion batteries (ZIBs) have drawn much attention for next-generation energy storage for smart and wearable electronics due to their high theoretical gravimetric/volumetric energy capacities, safety from explosive hazards, and cost-effectiveness. However, current state-of-the-art ZIBs lack the energy capacity necessary to facilitate smart functionalities for intelligent electronics. In this work, a "π-bridge spacer"-embedded electron donor-acceptor polymer cathode combined with a Zn2+ -ion-conducting electrolyte is proposed for a smart and flexible ZIB to provide high electrochromic-electrochemical performances. The π-bridge spacer endows the polymeric skeleton with improved physical ion accessibility and sensitive charge transfer through the cycles, providing extremely stable cyclability with high specific capacity (110 mAh g-1 ) at very fast rates (8 A g-1 ) and large coloration efficiency (79.8 cm2  C-1 ) under severe mechanical deformation over a long period. These results are markedly outstanding compared to the topological analogue without the π-bridge spacer (80 mAh g-1 at current density of 8 A g-1 , 63.0 cm2  C-1 ). The design to incorporate a π-bridge spacer realizes notable electrochromism behaviors and high electrochemical performance, which sheds light on the rational development of multifunctional flexible-ZIBs with color visualization properties for widespread usage in powering smart electronics.

Bidirectional Water-Stream Behavior on a Multifunctional Membrane for Simultaneous Energy Generation and Water Purification.

Hydroelectric nanogenerators have been previously proposed to recycle various water resources and polluted water. However, as conventional hydroelectric nanogenerators only utilize water resources, they cannot provide a fundamental solution for water recycling. In this study, a water purification membrane is proposed that can simultaneously generate electricity during the purification process (electricity generation and purification membrane (EPM)) for water recycling. As polluted water passes through the EPM, the water is purified in the perpendicular direction, while electricity is simultaneously produced in the horizontal direction by the movement of ions. Notably, the EPM exhibits high energy generation performance (maximum power 16.44 µW and energy 15.16 mJ) by the streaming effect of water-streaming carbon nanotubes (CNTs). Moreover, by using a poly(acrylic acid)/carboxymethyl cellulose (PAA/CMC) binder to EPM, the energy-generation performance and long-term stability are substantially improved and outstanding mechanical stability is provided, regardless of the acidity of the water source (pH 1-10). More importantly, the EPM exhibits the water purification characteristics of >90% rejection of sub-10 nm pollutants and potentiality of ångstrom level cation rejection, with simultaneous and continuous energy generation. Overall, this study proposes an efficient EPM model, which can be potentially used as a next-generation renewable energy generation approach, thus laying the foundation for effective utilization of polluted water resources.

Transpiration Driven Electrokinetic Power Generator.

Transpiration is the process by which water is carried in plants from the roots to the leaves where evaporation takes place. Here, we report a transpiration driven electrokinetic power generator (TEPG) that exploits capillary flow of water in an asymmetrically wetted cotton fabric coated with carbon black. Accumulation of protons induced by the electrical double layer formed at the solid (carbon black)/liquid (water) interface gives rise to potential difference between the wet and dry sides. The conductive carbon black coating channels electrical current driven by the pseudostreaming mechanism. A TEPG of 90 mm × 30 mm × 0.12 mm yields a maximum voltage of 0.53 V, maximum current of 3.91 µA, and maximum energy density of 1.14 mWh cm-3, depending on the loading of the carbon black. Multiple TEPGs generate enough power to light up a light-emitting diode (20 mA × 2.2 V) or charge a 1 F supercapacitor.

All-Transparent Stretchable Electrochromic Supercapacitor Wearable Patch Device.

Flexible and stretchable electrochromic supercapacitor systems are widely considered as promising multifunctional energy storage devices that eliminate the need for an external power source. Nevertheless, the performance of conventional designs deteriorates significantly as a result of electrode/electrolyte exposure to atmosphere as well as mechanical deformations for the case of flexible systems. In this study, we suggest an all-transparent stretchable electrochromic supercapacitor device with ultrastable performance, which consists of Au/Ag core-shell nanowire-embedded polydimethylsiloxane (PDMS), bistacked WO3 nanotube/PEDOT:PSS, and polyacrylamide (PAAm)-based hydrogel electrolyte. Au/Ag core-shell nanowire-embedded PDMS integrated with PAAm-based hydrogel electrolyte prevents Ag oxidation and dehydration while maintaining ionic and electrical conductivity at high voltage even after 16 days of exposure to ambient conditions and under application of mechanical strains in both tensile and bending conditions. WO3 nanotube/PEDOT:PSS bistacked active materials maintain high electrochemical-electrochromic performance even under mechanical deformations. Maximum specific capacitance of 471.0 F g-1 was obtained with a 92.9% capacity retention even after 50 000 charge-discharge cycles. In addition, high coloration efficiency of 83.9 cm2 C-1 was shown to be due to the dual coloration and pseudocapacitor characteristics of the WO3 nanotube and PEDOT:PSS thin layer.

Three-Dimensional Nanofibrous Air Electrode Assembled With Carbon Nanotubes-Bridged Hollow Fe2O3 Nanoparticles for High-Performance Lithium-Oxygen Batteries.

Lithium-oxygen batteries have been considered as one of the most viable energy source options for electric vehicles due to their high energy density. However, they are still faced with technical challenges, such as low round-trip efficiency and short cycle life, which mainly originate from the cathode part of the battery. In this work, we designed a three-dimensional nanofibrous air electrode consisted of hierarchically structured carbon nanotube-bridged hollow Fe2O3 nanoparticles (H-Fe2O3/CNT NFs). Composite nanofibers consisted of hollow Fe2O3 NPs anchored by multiple CNTs offered enhanced catalytic sites (interconnected hollow Fe2O3 NPs) and fast charge-transport highway (bridged CNTs) for facile formation and decomposition of Li2O2, leading to outstanding cell performance: (1) Swagelok cell exhibited highly reversible cycling characteristics for 250 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 500 mA g-1. (2) A module composed of two pouch-type cells stably powered an light-emitting diode lamp operated at 5.0 V.

Photoresponsive Smart Coloration Electrochromic Supercapacitor.

Electrochromic devices have been widely adopted in energy saving applications by taking advantage of the electrode coloration, but it is critical to develop a new electrochromic device that can undergo smart coloration and can have a wide spectrum in transmittance in response to input light intensity while also functioning as a rechargeable energy storage system. In this study, a photoresponsive electrochromic supercapacitor based on cellulose-nanofiber/Ag-nanowire/reduced-graphene-oxide/WO3 -composite electrode that is capable of undergoing "smart" reversible coloration while simultaneously functioning as a reliable energy-storage device is developed. The fabricated device exhibits a high coloration efficiency of 64.8 cm2 C-1 and electrochemical performance with specific capacitance of 406.0 F g-1 , energy/power densities of 40.6-47.8 Wh kg-1 and 6.8-16.9 kW kg-1 . The electrochromic supercapacitor exhibits excellent cycle reliability, where 75.0% and 94.1% of its coloration efficiency and electrochemical performance is retained, respectively, beyond 10 000 charge-discharge cycles. Cyclic fatigue tests show that the developed device is mechanically durable and suitable for wearable electronics applications. The smart electrochromic supercapacitor system is then integrated with a solar sensor to enable photoresponsive coloration where the transmittance changes in response to varying light intensity.

Vertically aligned P(VDF-TrFE) core-shell structures on flexible pillar arrays.

PVDF and P(VDF-TrFE) nano- and micro- structures have been widely used due to their potential applications in several fields, including sensors, actuators, vital sign transducers, and energy harvesters. In this study, we developed vertically aligned P(VDF-TrFE) core-shell structures using high modulus polyurethane acrylate (PUA) pillars as the support structure to maintain the structural integrity. In addition, we were able to improve the piezoelectric effect by 1.85 times from 40 ± 2 to 74 ± 2 pm/V when compared to the thin film counterpart, which contributes to the more efficient current generation under a given stress, by making an effective use of the P(VDF-TrFE) thin top layer as well as the side walls. We attribute the enhancement of piezoelectric effects to the contributions from the shell component and the strain confinement effect, which was supported by our modeling results. We envision that these organic-based P(VDF-TrFE) core-shell structures will be used widely as 3D sensors and power generators because they are optimized for current generations by utilizing all surface areas, including the side walls of core-shell structures.

Time-dependent mechanical-electrical coupled behavior in single crystal ZnO nanorods.

Nanoscale time-dependent mechanical-electrical coupled behavior of single crystal ZnO nanorods was systematically explored, which is essential for accessing the long-term reliability of the ZnO nanorod-based flexible devices. A series of compression creep tests combined with in-situ electrical measurement was performed on vertically-grown single crystal ZnO nanorods. Continuous measurement of the current (I)-voltage (V) curves before, during, after the creep tests revealed that I is non-negligibly increased as a result of the time-dependent deformation. Analysis of the I-V curves based on the thermionic emission-diffusion theory allowed extraction of nanorod resistance, which was shown to decrease as time-dependent deformation. Finally, based on the observations in this study, a simple analytical model for predicting the reduction in nanorod resistance as a function of creep strain that is induced from diffusional mechanisms is proposed, and this model was demonstrated to be in an excellent agreement with the experimental results.

Polypyrrole-MnO2-Coated Textile-Based Flexible-Stretchable Supercapacitor with High Electrochemical and Mechanical Reliability.

Carbon-nanotube (CNT)-based textile supercapacitors with MnO2 nanoparticles have excellent power and energy densities, but MnO2 nanoparticles can be delaminated during charge-discharge cycles, which results in significant degradation in capacitance. In this study, polypyrrole conductive polymer was coated on top of MnO2 nanoparticles that are deposited on CNT textile supercapacitor to prevent delamination of MnO2 nanoparticles. An increase of 38% in electrochemical energy capacity to 461 F/g was observed, while cyclic reliability also improved, as 93.8% of energy capacity was retained over 10 000 cycles. Energy density and power density were measured to be 31.1 Wh/kg and 22.1 kW/kg, respectively. An in situ electrochemical-mechanical study revealed that polypyrrole-MnO2-coated CNT textile supercapacitor can retain 98.5% of its initial energy capacity upon application of 21% tensile strain and showed no observable energy storage capacity change upon application of 13% bending strain. After imposing cyclic bending of 750 000 cycles, the capacitance was retained to 96.3%. Therefore, the results from this study confirmed for the first time that the polypyrrole-MnO2-coated CNT textile can reliably operate with high energy and power densities with in situ application of both tensile and bending strains.