Electrochemical capacitors (i.e. supercapacitors) include electrochemical double-layer capacitors that depend on the charge storage of ion adsorption and pseudo-capacitors that are based on charge storage involving fast surface redox reactions. The energy storage capacities of supercapacitors are several orders of magnitude higher than those of conventional dielectric capacitors, but are much lower than those of secondary batteries. They typically have high power density, long cyclic stability and high safety, and thus can be considered as an alternative or complement to rechargeable batteries in applications that require high power delivery or fast energy harvesting. This article reviews the latest progress in supercapacitors in charge storage mechanisms, electrode materials, electrolyte materials, systems, characterization methods, and applications. In particular, the newly developed charge storage mechanism for intercalative pseudocapacitive behaviour, which bridges the gap between battery behaviour and conventional pseudocapacitive behaviour, is also clarified for comparison. Finally, the prospects and challenges associated with supercapacitors in practical applications are also discussed.

Electrochemical capacitors: mechanism, materials, systems, characterization and applications

There are an increasing number of studies regarding active electrode materials that undergo faradaic reactions but are used for electrochemical capacitor applications. Unfortunately, some of these materials are described as “pseudocapacitive” materials despite the fact that their electrochemical signature (e.g., cyclic voltammogram and charge/discharge curve) is analogous to that of a “battery” material, as commonly observed for Ni(OH)2 and cobalt oxides in KOH electrolyte. Conversely, true pseudocapacitive electrode materials such as MnO2 display electrochemical behavior typical of that observed for a capacitive carbon electrode. The difference between these two classes of materials will be explained, and we demonstrate why it is inappropriate to describe nickel oxide or hydroxide and cobalt oxide/hydroxide as pseudocapacitive electrode materials. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0201505jes] All rights reserved.

https://iopscience.iop.org/article/10.1149/2.0201505jes/pdf

To Be or Not To Be Pseudocapacitive

Supercapacitors have gained a lot of attention due to their unique features like high power, long cycle life and environment-friendly nature. They act as a link for energy-power difference between a traditional capacitor (having high power) and fuel cells/batteries (having high energy storage). In this perspective, a worldwide research has been reported to address this and rapid progress has been achieved in the advancement of fundamental as well as the applied aspects of supercapacitors. Here, a concise description of technologies and working principles of different materials utilized for supercapacitors has been provided. The main focus has been on materials like carbon-based nanomaterials, metal oxides, conducting polymers and their nanocomposites along with some novel materials like metal-organic frameworks, MXenes, metal nitrides, covalent organic frameworks and black phosphorus. The performance of nanocomposites has been analysed by parameters like energy, capacitance, power, cyclic performance and rate capability. Some of the latest supercapacitors such as electrochromic supercapacitor, battery-supercapacitor hybrid device, electrochemical flow capacitor, alternating current line filtering capacitor, micro-supercapacitor, photo-supercapacitor, thermally chargeable supercapacitor, self-healing supercapacitor, piezoelectric and shape memory supercapacitor have also been discussed. This review covers the up-to-date progress achieved in novel materials for supercapacitor electrodes. The latest fabricated symmetric/asymmetric supercapacitors have also been reported.

Review of supercapacitors: Materials and devices

The world is recently witnessing an explosive development of novel electronic and optoelectronic devices that demand more-reliable power sources that combine higher energy density and longer-term durability. Supercapacitors have become one of the most promising energy-storage systems, as they present multifold advantages of high power density, fast charging-discharging, and long cyclic stability. However, the intrinsically low energy density inherent to traditional supercapacitors severely limits their widespread applications, triggering researchers to explore new types of supercapacitors with improved performance. Asymmetric supercapacitors (ASCs) assembled using two dissimilar electrode materials offer a distinct advantage of wide operational voltage window, and thereby significantly enhance the energy density. Recent progress made in the field of ASCs is critically reviewed, with the main focus on an extensive survey of the materials developed for ASC electrodes, as well as covering the progress made in the fabrication of ASC devices over the last few decades. Current challenges and a future outlook of the field of ASCs are also discussed.

Asymmetric Supercapacitor Electrodes and Devices.

It is of great interest to develop new carbon-based materials as electrodes for supercapacitors because the conventional electrodes of activated carbons in supercapacitors cannot meet the ever-increasing demands for high energy and power densities for electronic devices. Due to their high electronic conductivity and improved hydrophilic properties, together with their easy syntheses and functionalization, N-doped carbons have shown a great potential in energy storage and conversion applications. In this review, after a brief introduction of electrochemical capacitors, we summarize the advances, in the recent six years, in the preparation methods of N-doped carbons for applications in supercapacitors. We also discuss and predict futuristic research trends towards the design and syntheses of N-doped carbons with unique properties for electrochemical energy storage.

Review on recent advances in nitrogen-doped carbons: preparations and applications in supercapacitors

One-step preparation of single-crystalline Fe2O3 particles/graphene composite hydrogels as high performance anode materials for supercapacitors

Asymmetric supercapacitors based on carbon nanotubes@NiO ultrathin nanosheets core-shell composites and MOF-derived porous carbon polyhedrons with super-long cycle life

A pulsed laser deposition process using ozone as an oxidant is developed to grow NiO nanoparticles on highly conductive three-dimensional (3D) graphene foam (GF). The excellent electrical conductivity and interconnected pore structure of the hybrid NiO/GF electrode facilitate fast electron and ion transportation. The NiO/GF electrode displays a high specific capacitance (1225 F g−1 at 2 A g−1) and a superb rate capability (68% capacity retention at 100 A g−1). A novel asymmetric supercapacitor with high power and energy densities is successfully fabricated using NiO/GF as the positive electrode and hierarchical porous nitrogen-doped carbon nanotubes (HPNCNTs) as the negative electrode in aqueous KOH solution. Because of the high individual capacitive performance of NiO/GF and HPNCNTs, as well as the synergistic effect between the two electrodes, the asymmetric capacitor exhibits an excellent energy storage performance. At a voltage range from 0.0 to 1.4 V, an energy density of 32 W h kg−1 is achieved at a power density of 700 W kg−1. Even at a 2.8 s charge–discharge rate (42 kW kg−1), an energy density as high as 17 W h kg−1 is retained. Additionally, the NiO/GF//HPNCNT asymmetric supercapacitor exhibits excellent cycling durability, with 94% specific capacitance retained after 2000 cycles.

Asymmetric supercapacitors based on nano-architectured nickel oxide/graphene foam and hierarchical porous nitrogen-doped carbon nanotubes with ultrahigh-rate performance

A facile one-step strategy has been developed to prepare 3D graphene/VO2 nanobelt composite hydrogels, which can be readily scaled-up for mass production by using commercial V2O5 and graphene oxide as precursors. During the formation of the graphene/VO2 architecture, 1D VO2 nanobelts and 2D flexible graphene sheets are self-assembled to form interconnected porous microstructures through hydrogen bonding, which facilitates charge and ion transport in the electrode. Due to the hierarchical network framework and the pseudocapacitance contribution from VO2 nanobelts, the hybrid electrode demonstrates excellent capacitive performances. In the two-electrode configuration, the graphene/VO2 nanobelt composite hydrogel exhibits a specific capacitance of 426 F g−1 at 1 A g−1 in the potential range of −0.6 to 0.6 V, which greatly surpasses that of each individual counterpart (191 F g−1 and 243 F g−1 at 1 A g−1 for VO2 nanobelt and graphene hydrogel, respectively). The hybrid electrode also shows an improved rate capability and cycling stability, which is indicative of a positive synergistic effect of VO2 and graphene on the improvement of electrochemical performance. These findings reveal the importance and great potential of graphene composite hydrogels in the development of energy storage devices with high power and energy densities.

One-step strategy to three-dimensional graphene/VO2 nanobelt composite hydrogels for high performance supercapacitors

The ethyl celluloses (ECs) modified with 5.0, 10.0, and 20.0 wt % polyaniline (PANI) (PANI/ECs) prepared by homogeneously mixing the EC and PANI formic acid solutions have demonstrated a superior hexavalent chromium (Cr(VI)) removal performance to that of pure EC. Having an increased Cr(VI) removal percentage with increased PANI loading, the PANI/ECs with 20.0% PANI loading were noticed to remove 2.0 mg/L Cr(VI) completely within 5 min, much faster than the pristine EC (>1 h). A chemical redox of Cr(VI) to Cr(III) by the active functional groups of PANI/ECs was revealed from the kinetic study. Meanwhile, isothermal study demonstrated a monolayer adsorption behavior following the Langmuir model with a calculated maximum absorption capacity of 19.49, 26.11, and 38.76 mg/g for the 5.0, 10.0, and 20.0 wt % PANI/ECs, much higher than that of EC (12.2 mg/g). The Cr(VI) removal mechanisms were interpreted considering the functional groups of both PANI and EC, the valence state fates of Cr(VI), and the variation ...

Huan Yi

Papers

One-step preparation of single-crystalline Fe2O3 particles/graphene composite hydrogels as high performance anode materials for supercapacitors

Asymmetric supercapacitors based on carbon nanotubes@NiO ultrathin nanosheets core-shell composites and MOF-derived porous carbon polyhedrons with super-long cycle life

Asymmetric supercapacitors based on nano-architectured nickel oxide/graphene foam and hierarchical porous nitrogen-doped carbon nanotubes with ultrahigh-rate performance

One-step strategy to three-dimensional graphene/VO2 nanobelt composite hydrogels for high performance supercapacitors

Polyaniline Coated Ethyl Cellulose with Improved Hexavalent Chromium Removal