Integrated Construction Improving Electrochemical Performance of Stretchable Supercapacitors Based on Ant-Nest Amphiphilic Gel Electrolytes.

Aqueous integrated stretchable supercapacitors (ISSCs) have attracted extensive attention due to the intrinsic safety in future wearable electronics. However, aqueous ISSCs usually suffer from low energy density and poor dynamic deformation stability owing to the conventional hydrogel electrolytes' narrow electrochemical stability window (ESW) and dissatisfied interface bonding. Herein, an ant-nest amphiphilic polyurethane hydro/organogel electrolyte (sAPUGE) with a wide ESW (≈2.2 V) and superb self-adhesion is prepared by electrospinning, which interacts with carbon-based stretchable electrodes for the construction of flame-retardant PU-based sAPUGE-ISSC. Benefitting from the synergistic effect of chemical bonding and mechanical meshing between the electrode and gel electrolyte interface, as-assembled sAPUGE-ISSC delivers a high energy density of 13.7 mWh cm-3 (at a power density of 0.126 W cm-3 ) and outstanding dynamic deformation stability (98.3% capacitance retention after 500 stretching cycles under 100% strain). This unique hydro/organogel electrolyte provides a pathway toward the next generation of wearable energy products in modern electronics.

Mini Review of Reliable Fabrication of Electrode under Stretching for Supercapacitor Application.

Currently, there is an increasing demand for portable and wearable electronics. This has necessitated the development of stretchable energy storage devices, while simultaneously maintaining performance. Hence, the electrodes and electrolyte materials used in stretchable supercapacitors should be robust under severe mechanical deformation. Polymers are widely used in the fabrication of stretchable supercapacitors. It is not only crucial to choose good polymer candidates with inherent advantages, but it is also important to design suitable polymer materials for both electrodes and electrolytes. This mini-review explains the concept of stretchable supercapacitors, the theoretical background of polymer-based electrodes for supercapacitors, and the fabrication strategies of stretchable electrodes for supercapacitors. Finally, we present the drawbacks and areas that still need to be developed.

Autonomous Self-Healing of Highly Stretchable Supercapacitors at All Climates.

Realizing autonomous self-healing and high stretchability of flexible supercapacitors over a wide temperature range remains a big challenge because of simultaneous incorporation of self-healing, stretchable and temperature-tolerant elements into a device as well as unfavorable electrochemical kinetics in harsh conditions. Here, we demonstrate for the first time an autonomous self-healing and intrinsically stretchable supercapacitor that can work at all-climate environments assembled by universally self-healing and highly stretchable organohydrogel electrodes with record-high temperature-invariant conductivity of ∼965 S/cm. Benefiting from multiple hydrogen bonding and dynamic metal coordination combined with electrochemistry-favorable components and integrated device configuration, the supercapacitor exhibits outstanding long-term stability, high stretchability, instantaneous and complete capacitive self-healability, and real-time mechanical healing at harsh temperatures from -35 to 80 °C. The superiorities in stretchability, self-healability, and all-climate tolerance enable the supercapacitor presented here as the best performer among the flexible supercapacitors reported to date.

High-Performance-Integrated Stretchable Supercapacitors Based on a Polyurethane Organo/Hydrogel Electrolyte.

Stretchable supercapacitors (SSCs) are promising energy storage devices for emerging wearable electronics. However, the low-energy density and poor deformation performance are still a challenge. Herein, an amphiphilic polyurethane-based organo/hydrogel electrolyte (APUGE) with a H2O/AN-in-salt (H2O/AN-NaClO4) is prepared for the first time. The as-prepared APUGE shows a wide voltage window (∼2.3 V), good adhesion, and excellent resilience. In addition, the intrinsically stretchable electrodes are prepared by coating the activated carbon slurry onto the PU/carbon black/MWCNT conductive elastic substrate. Based on the strong interface adhesion of the PU matrix, the as-assembled SSC delivers high-energy density (5.65 mW h cm-3 when the power density is 0.0256 W cm-3) and excellent deformation stability with 94.5% capacitance retention after 500 stretching cycles at 100% strain. This fully integrated construction concept is expected to be extended to multisystem stretchable metal ion batteries, stretchable lithium-sulfur batteries, and other stretchable energy storage devices.

MnOx-Electrodeposited Fabric-Based Stretchable Supercapacitors with Intrinsic Strain Sensing.

The increasing number of devices needed by wearable systems to bring radical advances in healthcare, robotics, and human-machine interfaces is a threat to their growth if the integration and energy-related challenges are not managed. A natural solution is to reduce the number of devices while retaining the functionality or simply using multifunctional devices, as demonstrated here through a stretchable supercapacitor (SSC) with intrinsic strain sensing. The presented SSC was obtained by electrodeposition of nanoflower MnOx on fabric (as a pseudocapacitive electrode) and three-dimensional conductive wrapping of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) to boost the performance. Among fabricated devices, the stretchable PEDOT:PSS/MnOx/PEDOT:PSS supercapacitor (SPMP-SC) showed the best performance (specific capacitance of 580 mF·cm-2 (108.1 F·g-1); energy density of 51.4 µWh·cm-2 at 0.5 mA). The stretchability (0-100%; 1000 cycles) analysis of SPMP-SC with Ecoflex encapsulation showed high capacitance retention (>90% for 40% stretch). The intrinsic strain sensing of the SSC was confirmed by the linear variation of capacitance (sensitivity -0.4%) during stretching. Finally, as a proof-of-concept, the application of SSC with intrinsic sensing was demonstrated for health monitoring through volumetric expansion of a manikin during ventilator operation and in robotics and by measuring the joint angle of a robotic hand.

Recent Development of Flexible and Stretchable Supercapacitors Using Transition Metal Compounds as Electrode Materials.

Flexible and stretchable supercapacitors (FS-SCs) are promising energy storage devices for wearable electronics due to their versatile flexibility/stretchability, long cycle life, high power density, and safety. Transition metal compounds (TMCs) can deliver a high capacitance and energy density when applied as pseudocapacitive or battery-like electrode materials owing to their large theoretical capacitance and faradaic charge-storage mechanism. The recent development of TMCs (metal oxides/hydroxides, phosphides, sulfides, nitrides, and selenides) as electrode materials for FS-SCs are discussed here. First, fundamental energy-storage mechanisms of distinct TMCs, various flexible and stretchable substrates, and electrolytes for FS-SCs are presented. Then, the electrochemical performance and features of TMC-based electrodes for FS-SCs are categorically analyzed. The gravimetric, areal, and volumetric energy density of SC using TMC electrodes are summarized in Ragone plots. More importantly, several recent design strategies for achieving high-performance TMC-based electrodes are highlighted, including material composition, current collector design, nanostructure design, doping/intercalation, defect engineering, phase control, valence tuning, and surface coating. Integrated systems that combine wearable electronics with FS-SCs are introduced. Finally, a summary and outlook on TMCs as electrodes for FS-SCs are provided.

Stretchable Energy Storage Devices Based on Carbon Materials.

Stretchable energy storage devices are essential for developing stretchable electronics and have thus attracted extensive attention in a variety of fields including wearable devices and bioelectronics. Carbon materials, e.g., carbon nanotube and graphene, are widely investigated as electrode materials for energy storage devices due to their large specific surface areas and combined remarkable electrical and electrochemical properties. They can also be effectively composited with many other functional materials or designed into different microstructures for fabricating stretchable energy storage devices. This review summarizes recent advances toward the development of carbon-material-based stretchable energy storage devices. An overview of common carbon materials' fundamental properties and general strategies to enable the stretchability of carbon-material-based electrodes are presented. The performances of the as-fabricated stretchable energy storage devices including supercapacitors, lithium-ion batteries, metal-air batteries, and other batteries are then carefully discussed. Challenges and perspectives in this emerging field are finally highlighted for future studies.

Highly Elastic Slide-Ring Hydrogel with Good Recovery as Stretchable Supercapacitor.

As a new material with excellent mechanical properties and good stability, slide-ring gels have attracted attention and research. However, they cannot be widely used due to their relatively complicated synthesis. Herein, we use 6-acrylamidomethylether-modified α-cyclodextrin (αCDAAmMe) and PEG20000 diacrylate (PEG20000 DA) to construct a polypseudorotaxane. Then, the polypseudorotaxane reacts with acrylamide via a photo-initiated polymerization in situ to conveniently obtain a slide-ring hydrogel with good elastic property and high recovery property. The hydrogel can be easily stretched to 22.5 times of its original length but recovered rapidly and almost reversibly. These results enable the application of hydrogel to make an intrinsically stretchable and compressible supercapacitor after doping ions and the adhesion of commercially available carbon nanotube (CNT) paper as electrodes, giving the ionic conductivity of 17.0 mS cm-1 (comparable to that of the commercial PVA/H3 PO4 electrolyte) and the capacitance of 0.87 µF cm-2 (at the scan speed of 100 mV s-1 ), and its capacitance can be further enhanced under stretching.

Ti3C2Tx MXene-Reduced Graphene Oxide Composite Electrodes for Stretchable Supercapacitors.

The development of stretchable electronics requires the invention of compatible high-performance power sources, such as stretchable supercapacitors and batteries. In this work, two-dimensional (2D) titanium carbide (Ti3C2Tx) MXene is being explored for flexible and printed energy storage devices by fabrication of a robust, stretchable high-performance supercapacitor with reduced graphene oxide (RGO) to create a composite electrode. The Ti3C2Tx/RGO composite electrode combines the superior electrochemical and mechanical properties of Ti3C2Tx and the mechanical robustness of RGO resulting from strong nanosheet interactions, larger nanoflake size, and mechanical flexibility. It is found that the Ti3C2Tx/RGO composite electrodes with 50 wt % RGO incorporated prove to mitigate cracks generated under large strains. The composite electrodes exhibit a large capacitance of 49 mF/cm2 (∼490 F/cm3 and ∼140 F/g) and good electrochemical and mechanical stability when subjected to cyclic uniaxial (300%) or biaxial (200% × 200%) strains. The as-assembled symmetric supercapacitor demonstrates a specific capacitance of 18.6 mF/cm2 (∼90 F/cm3 and ∼29 F/g) and a stretchability of up to 300%. The developed approach offers an alternative strategy to fabricate stretchable MXene-based energy storage devices and can be extended to other members of the large MXene family.

Dynamically Stretchable Supercapacitor for Powering an Integrated Biosensor in an All-in-One Textile System.

Textile-based electronics have attracted much attention as they can perfectly combine the functionality of wearable devices with the soft and comfortable properties of flexible textile fibers. In this work, we report a dynamically stretchable high-performance supercapacitor for powering an integrated sensor in an all-in-one textile system to detect various biosignals. The supercapacitor fabricated with MWCNT/MoO3 nanocomposite electrodes and nonaqueous gel electrolyte, along the course direction of the fabric, exhibits stable and high electrochemical performance under dynamic and static deformation, including stretching in real time, regardless of the strain rate. The strain sensor created along the wale direction of the fabric shows a high sensitivity of 46.3 under an applied strain up to 60%, a fast response time of 50 ms, and high stability over 10 000 cycles of stretching/releasing. Finally, the supercapacitor and strain sensor are integrated into an all-in-one textile system via liquid-metal interconnections, and the sensor is powered by the stored energy in the supercapacitor. This system sewed into cloth successfully detects strain due to joint movement and the wrist pulse. This work demonstrates the high feasibility of utilizing the fabricated stretchable all-in-one textile system for real-time health monitoring in everyday wearable devices.

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.

Skin-Like, Dynamically Stretchable, Planar Supercapacitors with Buckled Carbon Nanotube/Mn-Mo Mixed Oxide Electrodes and Air-Stable Organic Electrolyte.

For practical applications of high-performance supercapacitors as wearable energy storage devices attached to skin or clothes, the supercapacitors are recommended to have stable mechanical and electrochemical performances during dynamic deformations, including stretching, due to real-time movements of the human body. In this work, we demonstrate a skin-like, dynamically stretchable, planar supercapacitor (SPS). The SPS consists of buckled manganese/molybdenum (Mn/Mo) mixed oxide@multiwalled carbon nanotube (MWCNT) electrodes; organic gel polymer electrolyte of adiponitrile, succinonitrile, lithium bis(trifluoromethanesulfonyl)imide, and poly(methyl methacrylate); and a porous, elastomeric substrate. The addition of an Mn/Mo mixed oxide to the MWCNT film produces an 8-fold increase in the areal capacitance. The use of an organic solvent-based electrolyte enhances the operation cell voltage to 2 V and air stability to one month under ambient air conditions. The fabricated planar supercapacitors are biaxially stretchable up to 50% strain and maintain ∼90% of their initial capacitance after 1000 repetitive stretching/releasing cycles. Furthermore, the SPS exhibits stable electrochemical performance under dynamic stretching in real time regardless of the strain rate and performs reliably during repetitive bending/spreading motions of an index finger while attached to skin.

Recent Advances in Stretchable Supercapacitors Enabled by Low-Dimensional Nanomaterials.

Supercapacitors (SCs) have shown great potential for mobile energy storage technology owing to their long-term durability, electrochemical stability, structural simplicity, as well as exceptional power density without much compromise in the energy density and cycle life parameters. As a result, stretchable SC devices have been incorporated in a variety of emerging electronics applications ranging from wearable electronic textiles to microrobots to integrated energy systems. In this review, the recent progress and achievements in the field of stretchable SCs enabled by low-dimensional nanomaterials such as polypyrrole, carbon nanotubes, and graphene are presented. First, the three major categories of stretchable supercapacitors are discussed: double-layer supercapacitors, pseudo-supercapacitors, and hybrid supercapacitors. Then, the representative progress in developing stretchable electrodes with low-dimensional (0D, 1D, and 2D) nanomaterials is described. Next, the design strategies enabling the stretchability of the devices, including the wavy-shape design, wire-shape design, textile-shape design, kirigami-shape design, origami-shape design, and serpentine bridge-island design are emphasized, with the aim of improving the electrochemical performance under the complex stretchability conditions that may be encountered in practical applications. Finally, the newest developments, major challenges, and outlook in the field of stretchable SC development and manufacturing are discussed.

Recent Advances in Flexible/Stretchable Supercapacitors for Wearable Electronics.

The popularization of personalized wearable devices has accelerated the development of flexible/stretchable supercapacitors (SCs) that possess remarkable features of miniaturization, high security, and easy integration to build an all-in-one integrated system, and realize the functions of comfortable, noninvasive and continuous health monitoring, motion records, and information acquisition, etc. This Review presents a brief phylogeny of flexible/stretchable SCs, represented by planar micro-supercapacitors (MSCs) and 1D fibrous SCs. The latest progress and advantages of different flexible/stretchable/self-healing substrate, solid-state electrolyte and electrode materials for the fabrication of wearable SCs devices are summarized. The various configurations used in planar MSCs and 1D fibrous SCs aiming at the improvement of performance are also discussed. In addition, from the viewpoint of practical value and large-scale production, a survey of integrated systems, from different types of SC powered wearable sensing (gas, pressure, tactile…) systems, wearable all-in-one systems (including energy harvest, storage, and functional groups), to device packaging is presented. Finally, the challenges and future perspectives of wearable SCs are also considered.

Flexible, Stretchable, and Transparent Planar Microsupercapacitors Based on 3D Porous Laser-Induced Graphene.

The graphene with 3D porous network structure is directly laser-induced on polyimide sheets at room temperature in ambient environment by an inexpensive and one-step method, then transferred to silicon rubber substrate to obtain highly stretchable, transparent, and flexible electrode of the all-solid-state planar microsupercapacitors. The electrochemical capacitance properties of the graphene electrodes are further enhanced by nitrogen doping and with conductive poly(3,4-ethylenedioxythiophene) coating. With excellent flexibility, stretchability, and capacitance properties, the planar microsupercapacitors present a great potential in fashionable and comfortable designs for wearable electronics.

Enhanced tolerance to stretch-induced performance degradation of stretchable MnO2-based supercapacitors.

The performance of many stretchable electronics, such as energy storage devices and strain sensors, is highly limited by the structural breakdown arising from the stretch imposed. In this article, we focus on a detailed study on materials matching between functional materials and their conductive substrate, as well as enhancement of the tolerance to stretch-induced performance degradation of stretchable supercapacitors, which are essential for the design of a stretchable device. It is revealed that, being widely utilized as the electrode material of the stretchable supercapacitor, metal oxides such as MnO2 nanosheets have serious strain-induced performance degradation due to their rigid structure. In comparison, with conducting polymers like a polypyrrole (PPy) film as the electrochemically active material, the performance of stretchable supercapacitors can be well preserved under strain. Therefore, a smart design is to combine PPy with MnO2 nanosheets to achieve enhanced tolerance to strain-induced performance degradation of MnO2-based supercapacitors, which is realized by fabricating an electrode of PPy-penetrated MnO2 nanosheets. The composite electrodes exhibit a remarkable enhanced tolerance to strain-induced performance degradation with well-preserved performance over 93% under strain. The detailed morphology and electrochemical impedance variations are investigated for the mechanism analyses. Our work presents a systematic investigation on the selection and matching of electrode materials for stretchable supercapacitors to achieve high performance and great tolerance to strain, which may guide the selection of functional materials and their substrate materials for the next-generation of stretchable electronics.