Carbon materials have attracted intense interests as electrode materials for electrochemical capacitors, because of their high surface area, electrical conductivity, chemical stability and low cost. Activated carbons produced by different activation processes from various precursors are the most widely used electrodes. Recently, with the rapid growth of nanotechnology, nanostructured electrode materials, such as carbon nanotubes and template-synthesized porous carbons have been developed. Their unique electrical properties and well controlled pore sizes and structures facilitate fast ion and electron transportation. In order to further improve the power and energy densities of the capacitors, carbon-based composites combining electrical double layer capacitors (EDLC)-capacitance and pseudo-capacitance have been explored. They show not only enhanced capacitance, but as well good cyclability. In this review, recent progresses on carbon-based electrode materials are summarized, including activated carbons, carbon nanotubes, and template-synthesized porous carbons, in particular mesoporous carbons. Their advantages and disadvantages as electrochemical capacitors are discussed. At the end of this review, the future trends of electrochemical capacitors with high energy and power are proposed.

Carbon Materials for Chemical Capacitive Energy Storage

Because of their availability, adjustable microstructure, varieties of forms, and large specific surface area, porous carbon materials are of increasing interest for use in hydrogen storage adsorbents and electrode materials in supercapacitors and lithium–sulfur cells from the viewpoint of social sustainability and environmental friendliness. Therefore, much effort has been made to synthesize and tailor the microstructures of porous carbon materials via various activation procedures (physical and chemical activation). In particular, the chemical activation of various carbon sources using KOH as the activating reagent is very promising because of its lower activation temperature and higher yields, and well-defined micropore size distribution and ultrahigh specific surface area up to 3000 m2 g−1 of the resulting porous carbons. In this feature article, we will cover recent research progress since 2007 on the synthesis of KOH-activated carbons for hydrogen and electrical energy storage (supercapacitors and lithium–sulfur batteries). The textural properties and surface chemistry of KOH-activated carbons depend on not only the synthesis parameters, but also different carbon sources employed including fossil/biomass-derived materials, synthetic organic polymers, and various nanostructured carbons (e.g. carbon nanotubes, carbon nanofibers, carbon aerogels, carbide-derived carbons, graphene, etc.). Following the introduction to KOH activation mechanisms and processing technologies, the characteristics and performance of KOH-activated carbons as well as their relationships are summarized and discussed through the extensive analysis of the literature based on different energy storage systems.

KOH activation of carbon-based materials for energy storage

Supercapacitors (also known as ultracapacitors) are considered to be the most promising approach to meet the pressing requirements of energy storage. Supercapacitive electrode materials, which are closely related to the high-efficiency storage of energy, have provoked more interest. Herein, we present a high-capacity supercapacitor material based on the nitrogen-doped porous carbon nanofibers synthesized by carbonization of macroscopic-scale carbonaceous nanofibers (CNFs) coated with polypyrrole (CNFs@polypyrrole) at an appropriate temperature. The composite nanofibers exhibit a reversible specific capacitance of 202.0 F g–1 at the current density of 1.0 A g–1 in 6.0 mol L–1 aqueous KOH electrolyte, meanwhile maintaining a high-class capacitance retention capability and a maximum power density of 89.57 kW kg–1. This kind of nitrogen-doped carbon nanofiber represents an alternative promising candidate for an efficient electrode material for supercapacitors.

Synthesis of Nitrogen-Doped Porous Carbon Nanofibers as an Efficient Electrode Material for Supercapacitors

Heteroatom doped carbon materials represent one of the most prominent families of materials that are used in energy related applications, such as fuel cells, batteries, hydrogen storage or supercapacitors. While doping carbons with nitrogen atoms has experienced great progress throughout the past decades and yielded promising material concepts, also other doping candidates have gained the researchers' interest in the last few years. Boron is already relatively widely studied, and as its electronic situation is contrary to the one of nitrogen, codoping carbons with both heteroatoms can probably create synergistic effects. Sulphur and phosphorus have just recently entered the world of carbon synthesis, but already the first studies published prove their potential, especially as electrocatalysts in the cathodic compartment of fuel cells. Due to their size and their electronegativity being lower than those of carbon, structural distortions and changes of the charge densities are induced in the carbon materials. This article is to give a state of the art update on the most recent developments concerning the advanced heteroatom doping of carbon that goes beyond nitrogen. Doped carbon materials and their applications in energy devices are discussed with respect to their boron-, sulphur- and phosphorus-doping.

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Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications

Metal–organic frameworks (MOFs) have received a lot of attention because of their diverse structures, tunable properties and multiple applications such as gas storage, catalysis and magnetism. Recently, there has been a rapidly growing interest in developing MOF-based materials for electrochemical energy storage. MOFs have proved to be particularly suitable for electrochemical applications because of their tunable chemical composition that can be designed at the molecular level and their highly porous framework in which fast mass transportation of the related species is favorable. In this review, the recent progress in fabricating MOFs and MOF-derived nanostructures for electrochemical applications is presented. The review starts with an introduction of the principles and strategies for designing targeted MOFs followed by a discussion of some novel MOF-derived structures and their potential applications in electrochemical energy storage and conversion. Finally, major challenges in electrochemical energy storage are highlighted and prospective solutions from current progress in MOF-based nanostructure research are given.

Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion

Porous carbons prepared by using metal–organic framework as the precursor for supercapacitors

Boron and nitrogen co-doped porous carbon and its enhanced properties as supercapacitor

Ordered mesoporous Co3O4 has been synthesized by nanocasting from three-dimensional cubic KIT-6 template. The cobalt precursor is introduced into the silica pores by the “bi-solvent” method. The structure and textural characteristics are investigated by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, nitrogen sorption at 77 K. By changing the hydrothermal temperature of the KIT-6 template, two kinds of Co3O4 replicas with different mesostructured symmetries are obtained. Mesoporous Co3O4 oxides prepared from KIT-6 aged at low temperature have uncoupled sub-frameworks while mesoporous Co3O4 oxides prepared from KIT-6 aged at high temperature possess coupled sub-frameworks. CO oxidation is carried out as a model reaction to evaluate the catalytic activity. Co3O4 replicas with uncoupled sub-frameworks which possess higher surface area and more open pore system exhibit better performance than Co3O4 replicas with coupled sub-frameworks. The light-off temperature of CO oxidation reaches as low as 68 °C with a space velocity of 120,000 mL h − 1 g cat − 1 over the uncoupled Co3O4 replica. Calcination temperature of the cobalt precursor only has negligible or slight impact on the catalytic activity.

Hongliang Guo

Papers

Porous carbons prepared by using metal–organic framework as the precursor for supercapacitors

Boron and nitrogen co-doped porous carbon and its enhanced properties as supercapacitor

Influence of textural parameters on the catalytic behavior for CO oxidation over ordered mesoporous Co3O4

Hierarchical porous carbon obtained using the template of NaOH-treated zeolite β and its high performance as supercapacitor

Cryogenic hydrogen uptake of high surface area porous carbon materials activated by potassium hydroxide