High‐Performance Fiber‐Shaped All‐Solid‐State Asymmetric Supercapacitors Based on Ultrathin MnO2 Nanosheet/Carbon Fiber Cathodes for Wearable Electronics

Flexible fiber‐shaped supercapacitors have shown great potential in portable and wearable electronics. However, small specific capacitance and low operating voltage limit the practical application of fiber‐shaped supercapacitors in high energy density devices. Herein, direct growth of ultrathin MnO₂ nanosheet arrays on conductive carbon fibers with robust adhesion is exhibited, which exhibit a high specific capacitance of 634.5 F g^?1 at a current density of 2.5 A g^?1 and possess superior cycle stability. When MnO₂ nanosheet arrays on carbon fibers and graphene on carbon fibers are used as a positive electrode and a negative electrode, respectively, in an all‐solid‐state asymmetric supercapacitor (ASC), the ASC displays a high specific capacitance of 87.1 F g^?1 and an exceptional energy density of 27.2 Wh kg^?1. In addition, its capacitance retention reaches 95.2% over 3000 cycles, representing the excellent cyclic ability. The flexibility and mechanical stability of these ASCs are highlighted by the negligible degradation of their electrochemical performance even under severely bending states. Impressively, as‐prepared fiber‐shaped ASCs could successfully power a photodetector based on CdS nanowires without applying any external bias voltage. The excellent performance of all‐solid‐state ASCs opens up new opportunity for development of wearable and self‐powered nanodevices in near future.     

Large‐Scale Conductive Yarns Based on Twistable Korean Traditional Paper (Hanji) for Supercapacitor Applications: Toward High‐Performance Paper Supercapacitors

A simple and scalable method to fabricate a yarn‐type supercapacitor with a large specific capacitance without the aid of traditional pseudocapacitive electrode materials such as conducting polymers and metal oxides is reported. The yarn‐type supercapacitors are made from twisting reduced graphene oxide (rGO) or/and single‐walled carbon nanotubes (SWNTs)‐coated Korean traditional paper (KTP). The yarn‐type paper supercapacitor displays surprisingly enhanced electrochemical capacitance values, showing synergistic effect between rGO and SWNTs (500 times larger than performance of yarn‐type rGO‐coated paper supercapacitors). Coating rGO or/and SWNTs on KTP gives good morphology to the composite film, in which porosity increases and mean pore diameter decreases. The yarn‐type rGO/SWNT paper supercapacitor shows good mechanical strength, high flexibility, excellent electrochemical performance, and long‐life operation. The yarn‐type supercapacitor has an excellent electrochemical performance with a specific capacitance of 366 F g^?1 at scan rate of 25 mV s^?1 and high stability without any degradation in electrical performance up to 10 000 charge–discharge cycles. The average capacitance of rGO/SWNT@KTP yarn‐type supercapacitors is seven times higher than that of sheet‐type supercapacitors at scan rate of 500 mV s^?1. The lighting of a red light‐emitting diode (LED) is demonstrated by the yarn‐type paper supercapacitor without connecting supercapacitors in series.     

Quantifying the Volumetric Performance Metrics of Supercapacitors

Nanostructured materials have greatly improved the performance of electrochemical energy storage devices because of the increased activity and surface area. However, nanomaterials (e.g., nanocarbons) normally possess low packing density, and thus occupy more space which restricts their suitability for making electrochemical devices as compact as possible. This has resulted in their low volumetric performance (capacitance, energy density, and power density), which is a practical obstacle for the application of nanomaterials in mobile and on‐board energy storage devices. While rating electrode materials for supercapacitors, their volumetric performance is equally important as the gravimetric metrics and more reliable in particular for systems with limited space. However, the adopted criteria for measuring the volumetric performance of supercapacitors vary in the literature. Identifying the appropriate performance criteria for the volumetric values will set a universal ground for valid comparison. Here, the authors discuss the rationale for quantifying the volumetric performance metrics of supercapacitors from the three progressive levels of materials, electrodes, and devices. It is hoped that these thoughts will be of value for the general community in energy storage research.     

Flexible and Wearable All‐Solid‐State Supercapacitors with Ultrahigh Energy Density Based on a Carbon Fiber Fabric Electrode

Wearable textile energy storage systems are rapidly growing, but obtaining carbon fiber fabric electrodes with both high capacitances to provide a high energy density and mechanical strength to allow the material to be weaved or knitted into desired devices remains challenging. In this work, N/O‐enriched carbon cloth with a large surface area and the desired pore volume is fabricated. An electrochemical oxidation method is used to modify the surface chemistry through incorporation of electrochemical active functional groups to the carbon surface and to further increase the specific surface area and the pore volume of the carbon cloth. The resulting carbon cloth electrode presents excellent electrochemical properties, including ultrahigh areal capacitance with good rate ability and cycling stability. Furthermore, the fabricated symmetric supercapacitors with a 2 V stable voltage window deliver ultrahigh energy densities (6.8 mW h cm^?3 for fiber‐shaped samples and 9.4 mW h cm^?3 for fabric samples) and exhibit excellent flexibility. The fabric supercapacitors are further tested in a belt‐shaped device as a watchband to power an electronic watch for ≈9 h, in a heart‐shaped logo to supply power for ≈1 h and in a safety light that functions for ≈1 h, indicating various promising applications of these supercapacitors.     

Development of easy made low cost bindless monolithic electrodes from biomass with controlled properties to be used as electrochemical capacitors

The aim of the work now reported is the development of low cost electrodes in the monolithic shape without the need for a pos-production step with potential to be used in supercapacitors. The tested materials were activated carbon fibres prepared and activated carbons made from coffee endocarp. The main functional groups identified were quinone, lactone, Si-H, phenol, hydroxyl, carbonyl and ether for activated carbon samples and amine, amide, pyrone, lactone, carbonyl and hydroxyl for activated carbon fibres samples. The nanostructure of the materials is predominantly microporous but with a significant variety of porosity development with BET surface area and pore volume given by α(s) method range from 89 to 1050 m(2) g(-1) and 0.04 to 0.50 cm(3) g(-1), respectively. The electrochemical properties of the materials were investigated using classic cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. The higher specific capacitance achieved was 176 F g(-1).     

Structure‐Controlled,Vertical Graphene‐Based,Binder‐Free Electrodes from Plasma‐Reformed Butter Enhance Supercapacitor Performance

Vertical graphene nanosheets (VGNS) hold great promise for high‐performance supercapacitors owing to their excellent electrical transport property, large surface area and in particular, an inherent three‐dimensional, open network structure. However, it remains challenging to materialise the VGNS‐based supercapacitors due to their poor specific capacitance, high temperature processing, poor binding to electrode support materials, uncontrollable microstructure, and non‐cost effective way of fabrication. Here we use a single‐step, fast, scalable, and environmentally‐benign plasma‐enabled method to fabricate VGNS using cheap and spreadable natural fatty precursor butter, and demonstrate the controllability over the degree of graphitization and the density of VGNS edge planes. Our VGNS employed as binder‐free supercapacitor electrodes exhibit high specific capacitance up to 230 F g^?1 at a scan rate of 10 mV s^?1 and >99% capacitance retention after 1,500 charge‐discharge cycles at a high current density, when the optimum combination of graphitic structure and edge plane effects is utilised. The energy storage performance can be further enhanced by forming stable hybrid MnO₂/VGNS nano‐architectures which synergistically combine the advantages from both VGNS and MnO₂. This deterministic and plasma‐unique way of fabricating VGNS may open a new avenue for producing functional nanomaterials for advanced energy storage devices.     

Electrochemical Capacitors: Performance Metrics and Evaluation by Testing and Analysis

Electrochemical capacitors (i.e., supercapacitors) as energy storage technologies have attracted a lot of attention because of the increasing demand for efficient high-power delivery. Over the past decades, various advanced electrode materials and cell design have been developed to improve the performance of electrochemical capacitors. Hybrid capacitors and pseudocapacitors achieve much higher energy density due to their fast surface redox reactions. However, although all of them can be classified as electrochemical capacitors, different charge storage mechanisms alter their electrochemical characteristics. All the speculation and potential uncertainties, in the absence of standard performance metrics and test method, make it rather challenging to reliably evaluate the performance of various electrochemical systems, which hinder the development of advanced energy storage technologies and make the comparison between different energy storage systems (batteries, electrochemical capacitors, and hybrid devices) not so meaningful. In this regard, the uncertainties related to the performance metrics and evaluation of electrochemical capacitors are summarized and the ways in which the uncertainties can be minimized for both electric double layer capacitors (EDLCs) and hybrid supercapacitors is analyzed. It is hoped this effort will provide an accurate assessment method for determining the device properties to a high level of confidence and promote the standardization process of performance evaluation for the electrochemical energy storage systems.     

Anatase TiO2 Confined in Carbon Nanopores for High‐Energy Li‐Ion Hybrid Supercapacitors Operating at High Rates and Subzero Temperatures

Li‐ion hybrid supercapacitors (Li‐HSCs) hold great promise in future electrical energy storage due to their relatively high power and energy density. However, a major challenge lies in the slow kinetics of Li‐ion intercalation/extraction within metal‐oxide electrodes. Here, it is shown that ultrafast charge storage is realized by confining anatase TiO₂ nanoparticles in carbon nanopores to enable a high‐rate anode for Li‐HSCs. The porous carbon with interconnected pore walls and open channels not only works as a conductive host to protect TiO₂ from structural degradation but also provides fast pathways for ion/electron transport. As a result, the assembled cells exhibit remarkable rate capabilities with a specific capacity of ≈140 mAh g^?1 at a slow charge and ≈60 mAh g^?1 at a 3.5 s fast charge. While the charge/discharge process can be completed as fast as that of state‐of‐the‐art electrical double‐layer capacitors (EDLCs), the produced nanocomposites show three to seven times higher volumetric capacitance than activated carbons used in commercial EDLCs with acetonitrile‐based electrolytes. Equally important for some applications in cold climates or the space, the Li‐HSCs can operate at subzero temperatures as low as ?40 °C, which is likely only limited by thermal properties of the acetonitrile (melting point of ?45 °C).     

Highly Stretchable Supercapacitors via Crumpled Vertically Aligned Carbon Nanotube Forests

Stretchable supercapacitors have received increasing attention due to their broad applications in developing self‐powered stretchable electronics for wearable electronics, epidermal and implantable electronics, and biomedical devices that are capable of sustaining large deformations and conforming to complicated surfaces. In this work, a new type of highly stretchable and reliable supercapacitor is developed based on crumpled vertically aligned carbon nanotube (CNT) forests transferred onto an elastomer substrate with the assistance of a thermal annealing process in atmosphere environment. The crumpled CNT‐forest electrodes demonstrated good electrochemical performance and stability under either uniaxial (300%) or biaxial strains (300% × 300%) for thousands of stretching–relaxing cycles. The resulting supercapacitors can sustain a stretchability of 800% and possess a specific capacitance of 5 mF cm^?2 at the scan rate of 50 mV s^?1. Furthermore, the crumpled CNT‐forest electrodes can be easily decorated with impregnated metal oxide nanoparticles to improve the specific capacitance and energy density of the supercapacitors. The approach developed in this work offers an alternative strategy for developing novel stretchable energy devices with vertically aligned nanotubes or nanowires for advanced applications in stretchable, flexible, and wearable electronic systems.     

Metalorganic Quantum Dots and Their Graphene‐Like Derivative Porous Graphitic Carbon for Advanced Lithium‐Ion Hybrid Supercapacitor

Lithium‐ion hybrid supercapacitors (LICs) are considered as a promising candidate in energy storage systems. Taking the factor of sluggish kinetics behavior, battery‐type anode plays a significant role in improving the performance of LICs. Here, onion‐shaped graphene‐like derivatives are synthesized via carbonization of metalorganic quantum dots (MQDs) accompanied with in situ catalytic graphitization by reduced metal. Notably MQDs, exhibiting water‐soluble character and ultrafine particles (2.5–5.5 nm) morphology, are prepared by the amidation reaction. The carbonized sample exhibits highly graphitic tendency with graphitization degree up to 95.6%, and shows graphene‐like porous structure, appropriate amorphous carbon decoration characteristic, as well as N‐doping and defective nature. When employed as anode material in LICs, it shows high energy density of 83.7 Wh kg^–1 and high power density of 6527 W kg^–1 when the mass ratio of cathode to anode is 1:1 and the operating voltage ranges from 2.0 to 4.0 V. It also possesses the long cyclic stability with the energy density retention maintains at 97.3% after 10 000 cycles at 5.0 A g^–1. In addition, the energy density is further increased by altering cathode/anode mass ratio and extending working voltage. This work provides a novel strategy to develop unique carbon materials for energy storage.     

Preparation of capacitor’s electrode from sunflower seed shell

Series of nanoporous carbons are prepared from sunflower seed shell (SSS) by two different strategies and used as electrode material for electrochemical double-layer capacitor (EDLC). The surface area and pore-structure of the nanoporous carbons are characterized intensively using N₂ adsorption technique. The results show that the pore-structure of the carbons is closely related to activation temperature and dosage of KOH. Electrochemical measurements show that the carbons made by impregnation-activation process have better capacitive behavior and higher capacitance retention ratio at high drain current than the carbons made by carbonization-activation process, which is due to that there are abundant macroscopic pores and less interior micropore surface in the texture of the former. More importantly, the capacitive performances of these carbons are much better than ordered mesoporous carbons and commercial wood-based active carbon, thus highlighting the success of preparing high performance electrode material for EDLC from SSS.     

Boron Element Nanowires Electrode for Supercapacitors

The pursuit of new categories of active materials as electrodes of supercapacitors remains a great challenge. Herein, for the first time, elemental boron as a superior electrode material of supercapacitors is reported, which exhibits significantly high capacitances and excellent rate performance in all alkaline, neutral, and acidic electrolytes. Notably, boron nanowire‐carbon fiber cloth (BNWs‐CFC) electrodes achieve a capacitance up to 42.8 mF cm^?2 at a scan rate of 5 mV s^?1 and 60.2 mF cm^?2 at a current density of 0.2 mA cm^?2 in the acidic electrolyte. Moreover, in all these three kinds of electrolytes, BNWs‐CFC electrodes demonstrate a decent cycling stability with >80% capacitance retention after 8000 charging/discharging cycles. The Dominating energy storage mechanism of BNWs in the different electrolytes is analyzed by looking into the kinetics of the electrochemical process. Subsequently, the BNWs‐CFC electrode is used to fabricate a flexible solid‐state supercapacitor, which reveals a specific capacitance up to 22.73 mF cm^?2 and good mechanical performance after 1000 bending cycles. This study opens a new avenue to explore elemental boron‐based new nanomaterials for the application of energy storage with superior electrochemical performance.     

All Pseudocapacitive MXene‐RuO2 Asymmetric Supercapacitors

2D transition metal carbides and nitrides, known as MXenes, are an emerging class of 2D materials with a wide spectrum of potential applications, in particular in electrochemical energy storage. The hydrophilicity of MXenes combined with their metallic conductivity and surface redox reactions is the key for high‐rate pseudocapacitive energy storage in MXene electrodes. However, symmetric MXene supercapacitors have a limited voltage window of around 0.6 V due to possible oxidation at high anodic potentials. In this study, the fact that titanium carbide MXene (Ti₃C₂T_x) can operate at negative potentials in acidic electrolyte is exploited, to design an all‐pseudocapacitive asymmetric device by combining it with a ruthenium oxide (RuO₂) positive electrode. This asymmetric device operates at a voltage window of 1.5 V, which is about two times wider than the operating voltage window of symmetric MXene supercapacitors, and is the widest voltage window reported to date for MXene‐based supercapacitors. The complementary working potential windows of MXene and RuO₂, along with proton‐induced pseudocapacitance, significantly enhance the device performance. As a result, the asymmetric devices can deliver an energy density of 37 µW h cm^?2 at a power density of 40 mW cm^?2, with 86% capacitance retention after 20 000 charge–discharge cycles. These results show that pseudocapacitive negative MXene electrodes can potentially replace carbon‐based materials in asymmetric electrochemical capacitors, leading to an increased energy density.     

Correlation Between Microstructure and Na Storage Behavior in Hard Carbon

Hard carbons are considered among the most promising anode materials for Na‐ion batteries. Understanding their structure is of great importance for optimizing their Na storage capabilities and therefore achieving high performance. Herein, carbon nanofibers (CNFs) are prepared by electrospinning and their microstructure, texture, and surface functionality are tailored through carbonization at various temperatures ranging from 650 to 2800 °C. Stepwise carbonization gradually removes the heteroatoms and increases the graphitization degree, enabling us to monitor the corresponding electrochemical performance for establishing a correlation between the CNFs characteristics and Na storage behavior. Outstandingly, it is found that for CNFs carbonized at above 2000 °C, a single voltage Na uptake plateau at ≈0.1 V with a capacity of ≈200 mAh g^‐1. This specific performance may be nested in the higher degree of graphitization, lower active surface area, and different porous texture of the CNFs at such temperatures. It is demonstrated via the assembly of a CNF/Na₂Fe₂(SO₄)₃ cell the benefit of such CNFs electrode for enhancing the energy density of full Na‐ion cells. This finding sheds new insights in the quest for high performance carbon based anode materials.     

A High Performance Stretchable Asymmetric Fiber‐Shaped Supercapacitor with a Core‐Sheath Helical Structure

The emerging fiber‐shaped supercapacitors (FSSs) have motivated tremendous research interest in energy storage devices. However, challenges still exist in the pursuit of combination of excellent electrochemical performance and mechanical stretchability. Here, a core‐sheath asymmetric FSS is first made by wrapping gel electrolyte coated carbon nanotube (CNT)@MnO₂ core fiber with CNT@PPy composite film. Then a stretchable helical structure is formed by over‐twisting the FSS. The resulted stretchable asymmetric FSS exhibits a specific capacitance of 60.435 mF cm^?2 at the scan rate of 10 mV s^?1 and the capacitance performance is well maintained during repeated stretching to 20% strain. Furthermore, a high energy density of 18.88 μW h cm^?2 is achieved for the stretchable FSS due to its high specific capacitance and extended potential window of 1.5 V.     

Controlled Growth of NiMoO4 Nanosheet and Nanorod Arrays on Various Conductive Substrates as Advanced Electrodes for Asymmetric Supercapacitors

Hierarchical NiMoO₄ architectures assembled from well‐aligned uniform nanosheets or nanorods are successfully grown on various conductive substrates using a facile and effective general approach. Importantly, the nanostructures of NiMoO₄ can be easily controlled to be nanosheets or nanorods by using different solvents. By virtue of their intriguing structure features, NiMoO₄ nanosheets as integrated additive‐free electrodes for supercapacitors manifest higher Faradaic capacitance than NiMoO₄ nanorods. Moreover, an asymmetric supercapacitor (ASC) is constructed using the as‐prepared NiMoO₄ nanosheets as the positive electrode and activated carbon (AC) as the negative electrode. The optimized ASC with an extended operating voltage range of 0–1.7 V displays excellent electrochemical performance with a high energy density of 60.9 Wh kg^?1 at a power density of 850 W kg^?1 in addition to superior rate capability. Furthermore, the NiMoO₄//AC ASC device exhibits remarkable cycling stability with 85.7% specific capacitance retention after 10 000 cycles. The results show that these NiMoO₄‐based nanostructures are promising for high‐energy supercapacitors.     

Systematic Study of Effect on Enhancing Specific Capacity and Electrochemical Behaviors of Lithium–Sulfur Batteries

Herein, a flexible method is designed to engineer nitrogen‐doped carbon materials (NC) with different functional and structural specialties involving N‐doping level, graphitization, and surface area via tuning the carbonization temperature of the pre‐prepared zeolitic imidazolate framework‐8 (ZIF‐8 ) crystals. With the aim to unveil the effect of these features on the electrochemical performance of sulfur cathode, these samples are evaluated as sulfur host and comprehensively investigated. NC‐800 (800 °C, 10.45%N, 1032.4 m² g^?1) exhibits the best electrochemical capability comparing with NC‐700 (700 °C, 16.59%N, 891.4 m² g^?1) and NC‐900 (900 °C, 7.59%N, 987.6 m² g^?1). High surface area and N‐doping can work together to well increase the capacity of sulfur cathode, thanks to the improved transportation of charge carriers and effective anchoring of active sulfur, while the latter specialty just makes sulfur cathode have decent capacity in case of low surface area. Graphitization and quaternary nitrogen favorably improve the electric conductivity of the electrode, empowering the improvement of discharge capacity initially and rendering the good cyclability cooperatively relying on the effective immobilization of active materials. The related results suggest the significance of rational design of carbon maxtrix for sulfur to improve the performance of Li‐S batteries.     

A High‐Performance Supercapacitor Based on KOH Activated 1D C70 Microstructures

Fullerenes are of tremendous interest from fundamental researches to applied perspectives in the past decades. However, their application in supercapacitors has been underdeveloped for a long time. Here, the KOH activation of C₇₀ microtubes is reported at high temperatures, which provides activated samples exhibiting excellent capacitive properties. The improved capacitive performance can be attributed to three aspects: the generation of macropores and micropores, the introduction of oxygen functionalities, and the formation of graphitic carbons from ellipsoidal fullerenes. The optimum activated state for supercapacitor application is achieved at 600 °C, at which the product exhibits the best electrochemical behavior with a gravimetric capacitance of 362.0 F g^?1 at 0.1 A g^?1 and excellent cycling stability with capacitance retention of 92.5% over 5000 cycles at 1 A g^?1.     

High Volumetric Capacitance,Ultralong Life Supercapacitors Enabled by Waxberry‐Derived Hierarchical Porous Carbon Materials

Supercapacitors with fast charge/discharge rate and long cycling stability (>50 000 cycles) are attractive for energy storage and mobile power supply. In this paper, a facile strategy is developed to fabricate an Fe₂O₃/FeS‐decorated N, S‐codoped hierarchical porous carbon hybrid. Its microstructure and compositions can be readily controlled through adjusting the hydrothermal reaction between waxberry and iron sulfate. The constructed supercapacitors with the as‐prepared carbon materials from this reaction are able to exhibit outstanding capacitive performance with a superfast charge/discharge rate (<1 s), ultralong cycle life (>50 000 cycles, 80 A g⁻¹), ultrahigh volumetric capacitance (1320.4 F cm⁻³, 0.1 A g⁻¹), and high energy density (100.9 W h kg⁻¹, 221.9 W h L⁻¹). The outstanding performance makes it one of the best biomass‐derived supercapacitors. The superior capacitive behavior is likely to arise from the N and S codoping on the surface/edge/skeleton of the carbon microspheres and nanosheet composites coupled with the fast redox reaction of Fe₂O₃/FeS. Overall, this research presents a new avenue for developing the next generation of sustainable high‐performance energy storage device.     

Recent Progress in Flexible Electrochemical Capacitors: Electrode Materials,Device Configuration,and Functions

With increasing demand for portable, flexible, and even wearable electronic devices, flexible energy storage systems have received increasing attention as a key component in this emerging field. Among the options, supercapacitors, commonly referred to as ultracapacitors or electrochemical capacitors, are widely recognized as a potential energy storage system due to their high power, fast charge/discharge rate, long cycling life‐time, and low cost. To date, considerable effort has been dedicated to developing high‐performance flexible supercapacitors based on various electrode materials; including carbon nanomaterials (e.g., carbon nanotubes, graphene, porous carbon materials, carbon paper, and textile), conducting polymers (e.g., polyaniline, polypyrrole, polythiophene), and hybrid materials. A brief introduction to the field is provided and the state‐of‐the‐art is reviewed with special emphasis on electrode materials and device configurations.