Editable Supercapacitors with Customizable Stretchability Based on Mechanically Strengthened Ultralong MnO2 Nanowire Composite

Although some progress has been made on stretchable supercapacitors, traditional stretchable supercapacitors fabricated by predesigning structured electrodes for device assembling still lack the device‐level editability and programmability. To adapt to wearable electronics with arbitrary configurations, it is highly desirable to develop editable supercapacitors that can be directly transferred into desirable shapes and stretchability. In this work, editable supercapacitors for customizable shapes and stretchability using electrodes based on mechanically strengthened ultralong MnO₂ nanowire composites are developed. A supercapacitor edited with honeycomb‐like structure shows a specific capacitance of 227.2 mF cm^?2 and can be stretched up to 500% without degradation of electrochemical performance, which is superior to most of the state‐of‐the‐art stretchable supercapacitors. In addition, it maintains nearly 98% of the initial capacitance after 10 000 stretch‐and‐release cycles under 400% tensile strain. As a representative of concept for system integration, the editable supercapacitors are integrated with a strain sensor, and the system exhibits a stable sensing performance even under arm swing. Being highly stretchable, easily programmable, as well as connectable in series and parallel, an editable supercapacitor with customizable stretchability is promising to produce stylish energy storage devices to power various portable, stretchable, and wearable devices.     

Self-healing flexible/stretchable energy storage devices

During the past decade, flexible/stretchable energy storage devices have garnered increasing attention, with the successful development of wearable electronics. However, due to the repeated deformation accompanied with the electrochemical depletion process, these devices suffer from unavoidable damage, including cracks, crazing, puncture and delamination, which can lead to serious performance degradation or even safety issues. Simultaneously, inspired by biological organs, self-healing capability is found to be a promising approach to address these issues by restoring the mechanical and electrochemical performance. This review first summarizes the structural design and features of various flexible/stretchable energy storage devices, from 1D to 3D configurations. Then, basic concepts and three self-healing mechanisms, including capsule-based systems, vascular-based systems, and intrinsic healing systems are analyzed along with a brief look at existing applications. Then we review all the important parts of state-of-art flexible/stretchable self-healing supercapacitors and batteries including electrodes, electrolytes, substrates and encapsulation. Moreover, a detailed evaluation of methodologies for flexibility, stretchability and self-healing capabilities are described in detail. Finally, the critical challenges and prospects of future promising solutions for self-healing flexible/stretchable energy storage devices or even electronics are provided.     

Recent Advances in 1D Stretchable Electrodes and Devices for Textile and Wearable Electronics: Materials,Fabrications, and Applications

Research on wearable electronic devices that can be directly integrated into daily textiles or clothes has been explosively grown holding great potential for various practical wearable applications. These wearable electronic devices strongly demand 1D electronic devices that are light–weight, weavable, highly flexible, stretchable, and adaptable to comport to frequent deformations during usage in daily life. To this end, the development of 1D electrodes with high stretchability and electrical performance is fundamentally essential. Herein, the recent process of 1D stretchable electrodes for wearable and textile electronics is described, focusing on representative conductive materials, fabrication techniques for 1D stretchable electrodes with high performance, and designs and applications of various 1D stretchable electronic devices. To conclude, discussions are presented regarding limitations and perspectives of current materials and devices in terms of performance and scientific understanding that should be considered for further advances.     

超级电容器电极材料及器件的柔性化与微型化

随着可穿戴式电子设备的快速发展,各类柔性储能器件也相继出现。柔性超级电容器因其稳定性高、体积小、电化学性能优越等特点受到研究人员的广泛关注。开发一种工艺简单、电化学性能和柔性良好的电极材料对制备性能优越的柔性超级电容器具有重要意义。材料的选取、电极的制备及器件的微型化将是未来的主要研究方向。本文主要综述了柔性超级电容器电极材料的分类、具体的制备方法以及器件的主要构型,并探讨了柔性超级电容器电极材料及器件的主要发展方向和研究重点。     

A Highly Stretchable and Real‐Time Healable Supercapacitor

In addition to a high specific capacitance, a large stretchability and self‐healing properties are also essential to improve the practicality and reliability of supercapacitors in portable and wearable electronics. However, the integration of multiple functions into one device remains challenging. Here, the construction of a highly stretchable and real‐time omni‐healable supercapacitor is demonstrated by sandwiching the polypyrrole‐incorporated gold nanoparticle/carbon nanotube (CNT)/poly(acrylamide) (GCP@PPy) hydrogel electrodes with a CNT‐free GCP (GP) hydrogel as the electrolyte and chemically soldering an Ag nanowire film to the hydrogel electrode as the current collector. The newly developed dynamic metal‐thiolate (M‐SR, M = Au, Ag) bond‐induced integrated configuration, with an intrinsically powerful electrode and electrolyte, enables the assembled supercapacitor to deliver an areal capacitance of 885 mF cm^?2 and an energy density of 123 µWh cm^?2, which are among the highest‐reported values for stretchable supercapacitors. Notably, the device exhibits a superhigh stretching strain of 800%, rapid optical healing capability, and significant real‐time healability during the charge–discharge process. The exceptional performance combined with the facile assembly method confirms this multifunctional device as the best performer among all the flexible supercapacitors reported to date.     

Ultrathin ZnS nanosheet/carbon nanotube hybrid electrode for high-performance flexible all-solid-state supercapacitor

Flexible and easily reconfigurable supercapacitors show great promise for application in wearable electronics.In this study,multiwall C nanotubes (CNTs) decorated with hierarchical ultrathin zinc sulfide (ZnS) nanosheets (ZnS@CNT) are synthesized via a facile method.The resulting ZnS@CNT electrode,which delivers a high specific capacitance of 347.3 F·g-1 and an excellent cycling stability,can function as a high-performance electrode for a flexible all-solid-state supercapacitor using a polymer gel electrolyte.Our device exhibits a remarkable specific capacitance of 159.6 F·g-1,a high energy density of 22.3 W·h·kg-1 and a power density of 5 kW·kg-1.It also has high electrochemical performance even under bending or twisting.The all-solid-state supercapacitors can be easily integrated in series to power different commercial light-emitting diodes without an external bias voltage.     

An All‐Freeze‐Casting Strategy to Design Typographical Supercapacitors with Integrated Architectures

The emergence of flexible and wearable electronics has raised the demand for flexible supercapacitors with accurate sizes and aesthetic shapes. Here, a strategy is developed to prepare flexible all‐in‐one integrated supercapacitors by combining all‐freeze‐casting with typography technique. The continuous seamless connection of all‐in‐one supercapacitor devices enhances the load and/or electron transfer capacity and avoids displacing and detaching between their neighboring components at bending status. Therefore, such a unique structure of all‐in‐one integrated devices is beneficial for retaining stable electrochemical performance at different bending levels. More importantly, the sizes and aesthetic shapes of integrated supercapacitors could be controlled by the designed molds, like type matrices of typography. The molds could be assembled together and typeset randomly, achieving the controllable construction and series and/or parallel connection of several supercapacitor devices. The preparation of flexible integrated supercapacitors will pave the way for assembling programmable all‐in‐one energy storage devices into highly flexible electronics.     

Energy Harvesters for Wearable and Stretchable Electronics: From Flexibility to Stretchability

The rapid advancements of wearable electronics have caused a paradigm shift in consumer electronics, and the emerging development of stretchable electronics opens a new spectrum of applications for electronic systems. Playing a critical role as the power sources for independent electronic systems, energy harvesters with high flexibility or stretchability have been the focus of research efforts over the past decade. A large number of the flexible energy harvesters developed can only operate at very low strain level (≈0.1%), and their limited flexibility impedes their application in wearable or stretchable electronics. Here, the development of highly flexible and stretchable (stretchability >15% strain) energy harvesters is reviewed with emphasis on strategies of materials synthesis, device fabrication, and integration schemes for enhanced flexibility and stretchability. Due to their particular potential applications in wearable and stretchable electronics, energy‐harvesting devices based on piezoelectricity, triboelectricity, thermoelectricity, and dielectric elastomers have been largely developed and the progress is summarized. The challenges and opportunities of assembly and integration of energy harvesters into stretchable systems are also discussed.     

Fabric Organic Electrochemical Transistors for Biosensors

Flexible fabric biosensors can find promising applications in wearable electronics. However, high‐performance fabric biosensors have been rarely reported due to many special requirements in device fabrication. Here, the preparation of organic electrochemical transistors (OECTs) on Nylon fibers is reported. By introducing metal/conductive polymer multilayer electrodes on the fibers, the OECTs show very stable performance during bending tests. The devices with functionalized gates are successfully used as various biosensors with high sensitivity and selectivity. The fiber‐based OECTs are woven together with cotton yarns successfully by using a conventional weaving machine, resulting in flexible and stretchable fabric biosensors with high performance. The fabric sensors show much more stable signals in the analysis of moving aqueous solutions than planar devices due to a capillary effect in fabrics. The fabric devices are integrated in a diaper and remotely operated by using a mobile phone, offering a unique platform for convenient wearable healthcare monitoring.     

Flexible Energy‐Storage Devices: Design Consideration and Recent Progress

Flexible energy‐storage devices are attracting increasing attention as they show unique promising advantages, such as flexibility, shape diversity, light weight, and so on; these properties enable applications in portable, flexible, and even wearable electronic devices, including soft electronic products, roll‐up displays, and wearable devices. Consequently, considerable effort has been made in recent years to fulfill the requirements of future flexible energy‐storage devices, and much progress has been witnessed. This review describes the most recent advances in flexible energy‐storage devices, including flexible lithium‐ion batteries and flexible supercapacitors. The latest successful examples in flexible lithium‐ion batteries and their technological innovations and challenges are reviewed first. This is followed by a detailed overview of the recent progress in flexible supercapacitors based on carbon materials and a number of composites and flexible micro‐supercapacitors. Some of the latest achievements regarding interesting integrated energy‐storage systems are also reviewed. Further research direction is also proposed to surpass existing technological bottle‐necks and realize idealized flexible energy‐storage devices.     

Design of Novel Wearable,Stretchable, and Waterproof Cable‐Type Supercapacitors Based on High‐Performance Nickel Cobalt Sulfide‐Coated Etching‐Annealed Yarn Electrodes

Rapid advances in functional electronics bring tremendous demands on innovation toward effective designs of device structures. Yarn supercapacitors (SCs) show advantages of flexibility, knittability, and small size, and can be integrated into various electronic devices with low cost and high efficiency for energy storage. In this work, functionalized stainless steel yarns are developed to support active materials of positive and negative electrodes, which not only enhance capacitance of both electrodes but can also be designed into stretchable configurations. The as‐made asymmetric yarn SCs show a high energy density of 0.0487 mWh cm^?2 (10.19 mWh cm^?3) at a power density of 0.553 mW cm^?2 (129.1 mW cm^?3) and a specific capacitance of 127.2 mF cm^?2 under an operating voltage window of 1.7 V. The fabricated SC is then made into a stretchable configuration by a prestraining‐then‐releasing approach using polydimethylsiloxane (PDMS) tube, and its electrochemical performance can be well maintained when stretching up to a high strain of 100%. Moreover, the stretchable cable‐type SCs are stably workable under water‐immersed condition. The method opens up new ways for fabricating flexible, stretchable, and waterproof devices.     

Design and integration of flexible planar micro-supercapacitors

As promising candidates for energy-storage devices,supercapacitors (SCs) have attracted considerable attention because of their unique features,such as their high power density,outstanding rate capability,excellent cycling performance,and safety.The recent boom in portable electronic devices requires high-performance SCs that are flexible,simplified,thin,and integrated.Tremendous efforts have been directed towards the design and integration of planar microSCs (MSCs) based on different active electrode materials by various methods.This review highlights the recent developments in the device design of flexible planar MSCs and their integration with other electronic devices.The current challenges and future prospects for the development of flexible MSCs are also discussed.     

A review on structures,materials and applications of stretchable electrodes

With the rapid development of wearable smart devices,many researchershave carried out in-depth research on the stretchable electrodes.As one of the corecomponents for electronics,the electrode mainly transfers the electrons,which plays animportant role in driving the various electrical devices.The key to the research for thestretchable electrode is to maintain the excellent electrical properties or exhibit theregular conductive change when subjected to large tensile deformation.This articleoutlines the recent progress of stretchable electrodes and gives a comprehensiveintroduction to the structures,materials,and applications,including supercapacitors,lithium-ion batteries,organic light-emitting diodes,smart sensors,and heaters.Theperformance comparison of various stretchable electrodes was proposed to clearly showthe development challenges in this field.We hope that it can provide a meaningfulreference for realizing more sensitive,smart,and low-cost wearable electrical devices inthe near future.     

Printable Fabrication of a Fully Integrated and Self‐Powered Sensor System on Plastic Substrates

Wearable and portable devices with desirable flexibility, operational safety, and long cruising time, are in urgent demand for applications in wireless communications, multifunctional entertainments, personal healthcare monitoring, etc. Herein, a monolithically integrated self‐powered smart sensor system with printed interconnects, printed gas sensor for ethanol and acetone detection, and printable supercapacitors and embedded solar cells as energy sources, is successfully demonstrated in a wearable wristband fashion by utilizing inkjet printing as a proof‐of‐concept. In such a “wearable wristband”, the harvested solar energy can either directly drive the sensor and power up a light‐emitting diode as a warning signal, or can be stored in the supercapacitors in a standby mode, and the energy released from supercapacitors can compensate the intermittency of light illumination. To the best of our knowledge, the demonstration of such a self‐powered sensor system integrated onto a single piece of flexible substrate in a printable and additive manner has not previously been reported. Particularly, the printable supercapacitors deliver an areal capacitance of 12.9 mF cm^?2 and the printed SnO₂ gas sensor shows remarkable detection sensitivity under room temperature. The printable strategies for device fabrication and system integration developed here show great potency for scalable and facile fabrication of a variety of wearable devices.     

Toward Wearable Self‐Charging Power Systems: The Integration of Energy‐Harvesting and Storage Devices

One major challenge for wearable electronics is that the state‐of‐the‐art batteries are inadequate to provide sufficient energy for long‐term operations, leading to inconvenient battery replacement or frequent recharging. Other than the pursuit of high energy density of secondary batteries, an alternative approach recently drawing intensive attention from the research community, is to integrate energy‐generation and energy‐storage devices into self‐charging power systems (SCPSs), so that the scavenged energy can be simultaneously stored for sustainable power supply. This paper reviews recent developments in SCPSs with the integration of various energy‐harvesting devices (including piezoelectric nanogenerators, triboelectric nanogenerators, solar cells, and thermoelectric nanogenerators) and energy‐storage devices, such as batteries and supercapacitors. SCPSs with multiple energy‐harvesting devices are also included. Emphasis is placed on integrated flexible or wearable SCPSs. Remaining challenges and perspectives are also examined to suggest how to bring the appealing SCPSs into practical applications in the near future.     

Printable Fabrication of Nanocoral‐Structured Electrodes for High‐Performance Flexible and Planar Supercapacitor with Artistic Design

Planar supercapacitors with high flexibility, desirable operation safety, and high performance are considered as attractive candidates to serve as energy‐storage devices for portable and wearable electronics. Here, a scalable and printable technique is adopted to construct novel and unique hierarchical nanocoral structures as the interdigitated electrodes on flexible substrates. The as‐fabricated flexible all‐solid‐state planar supercapacitors with nanocoral structures achieve areal capacitance up to 52.9 mF cm^?2, which is 2.5 times that of devices without nanocoral structures, and this figure‐of‐merit is among the highest in the literature for the same category of devices. More interestingly, due to utilization of the inkjet‐printing technique, excellent versatility on electrode‐pattern artistic design is achieved. Particularly, working supercapacitors with artistically designed patterns are demonstrated. Meanwhile, the high scalability of such a printable method is also demonstrated by fabrication of large‐sized artistic supercapacitors serving as energy‐storage devices in a wearable self‐powered system as a proof of concept.     

A Flexible Stretchable Hydrogel Electrolyte for Healable All‐in‐One Configured Supercapacitors

The development of integrated high‐performance supercapacitors with all‐in‐one configuration, excellent flexibility and autonomously intrinsic self‐healability, and without the extra healable film layers, is still tremendously challenging. Compared to the sandwich‐like laminated structures of supercapacitors with augmented interfacial contact resistance, the flexible healable integrated supercapacitor with all‐in‐one structure could theoretically improve their interfacial contact resistance and energy densities, simplify the tedious device assembly process, prolong the lifetime, and avoid the displacement and delamination of multilayered configurations under deformations. Herein, a flexible healable all‐in‐one configured supercapacitor with excellent flexibility and reliable self‐healing ability by avoiding the extra healable film substrates and the postassembled sandwich‐like laminated structures is developed. The healable all‐in‐one configured supercapacitor is prepared from in situ polymerization and deposition of nanocomposites electrode materials onto the two‐sided faces of the self‐healing hydrogel electrolyte separator. The self‐healing hydrogel film is obtained from the physically crosslinked hydrogel with enormous hydrogen bonds, which can endow the healable capability through dynamic hydrogen bonding. The assembled all‐in‐one configured supercapacitor exhibits enhanced capacitive performance, good cycling stability, reliable self‐healing capability, and excellent flexibility. It holds broad prospects for obtaining various flexible healable all‐in‐one configured supercapacitors for working as portable energy storage devices in wearable electronics.     

An All‐Stretchable‐Component Sodium‐Ion Full Battery

Stretchable energy‐storage devices receive considerable attention due to their promising applications in future wearable technologies. However, they currently suffer from many problems, including low utility of active materials, limited multidirectional stretchability, and poor stability under stretched conditions. In addition, most proposed designs use one or more rigid components that fail to meet the stretchability requirement for the entire device. Here, an all‐stretchable‐component sodium‐ion full battery based on graphene‐modified poly(dimethylsiloxane) sponge electrodes and an elastic gel membrane is developed for the first time. The battery exhibits reasonable electrochemical performance and robust mechanical deformability; its electrochemical characteristics can be well‐maintained under many different stretched conditions and after hundreds of stretching–release cycles. This novel design integrating all stretchable components provides a pathway toward the next generation of wearable energy devices in modern electronics.     

Recent Advances in Fiber-Shaped Supercapacitors and Lithium-Ion Batteries

The rapid development in wearable electronics has spurred a great deal of interest in flexible energy storage devices, particularly fiber-shaped energy storage devices (FSESDs), such as fiber-shaped supercapacitors (FSSCs) and fiber-shaped batteries (FSBs). Depending on their electrode configurations, FSESDs can contain five differently structured electrodes, including parallel fiber electrodes (PFEs), twisted fiber electrodes (TFDs), wrapped fiber electrodes (WFEs), coaxial fiber devices (CFEs), and rolled electrodes (REs). Various rational methods have been devised to incorporate these fiber-shaped electrodes into multifunctional FSESDs, including fiber-shaped supercapacitors, lithium-ion batteries, lithium–sulfur batteries, lithium–air batteries, zinc–air batteries, and aluminum–air batteries. Although significant progress has been made in FSESDs, it remains a major challenge to make high-performance fiber-shaped devices at low cost. A focused and critical review of the recent advancements in fiber-shaped supercapacitors and lithium-ion batteries is provided here. The pros and cons for each of the aforementioned electrode configurations and FSESDs are discussed, along with current challenges and future opportunities for FSESDs.     

Recent progress on printable power supply devices and systems with nanomaterials

In recent years, tremendous research interest has been triggered in the fields of flexible, wearable and miniaturized power supply devices and self-powered energy sources, in which energy harvesting/conversion devices are integrated with energy storage devices into an infinitely self-powered energy system. As opposed to conventional fabrication methods, printing techniques hold promising potency for fabrication of power supply devices with practical scalability and versatility, especially for applications in wearable and portable electronics. To further enhance the performance of the as-fabricated devices, the utilization of nanomaterials is one of the promising strategies, owing to their unique properties. In this review, an overview on the progress of printable strategies to revolutionize the fabrication of power supply devices and integrated system with attractive form factors is provided. The advantages and limitations of the commonly adopted printing techniques for power supply device fabrication are first summarized. Thereafter, the research progress on novel developed printable energy harvesting and conversion devices, including solar cells, nanogenerators and biofuel cells, and the research advances on printable energy storage devices, namely, supercapacitors and rechargeable batteries, are presented, respectively. Although exciting advances on printable material modification, innovative fabrication methods and device performance improvement have been witnessed, there are still several challenges to be addressed to realize fully printable fabrication of integrated self-powered energy sources.

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