In this critical review, metal oxides-based materials for electrochemical supercapacitor (ES) electrodes are reviewed in detail together with a brief review of carbon materials and conducting polymers. Their advantages, disadvantages, and performance in ES electrodes are discussed through extensive analysis of the literature, and new trends in material development are also reviewed. Two important future research directions are indicated and summarized, based on results published in the literature: the development of composite and nanostructured ES materials to overcome the major challenge posed by the low energy density of ES (476 references).

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A review of electrode materials for electrochemical supercapacitors

Electrochemical energy storage technology is based on devices capable of exhibiting high energy density (batteries) or high power density (electrochemical capacitors). There is a growing need, for current and near-future applications, where both high energy and high power densities are required in the same material. Pseudocapacitance, a faradaic process involving surface or near surface redox reactions, offers a means of achieving high energy density at high charge–discharge rates. Here, we focus on the pseudocapacitive properties of transition metal oxides. First, we introduce pseudocapacitance and describe its electrochemical features. Then, we review the most relevant pseudocapacitive materials in aqueous and non-aqueous electrolytes. The major challenges for pseudocapacitive materials along with a future outlook are detailed at the end.

https://hal.archives-ouvertes.fr/hal-01171774/document

Pseudocapacitive oxide materials for high-rate electrochemical energy storage

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

Supercapacitors have drawn considerable attention in recent years due to their high specific power, long cycle life, and ability to bridge the power/energy gap between conventional capacitors and batteries/fuel cells. Nanostructured electrode materials have demonstrated superior electrochemical properties in producing high-performance supercapacitors. In this review article, we describe the recent progress and advances in designing nanostructured supercapacitor electrode materials based on various dimensions ranging from zero to three. We highlight the effect of nanostructures on the properties of supercapacitors including specific capacitance, rate capability and cycle stability, which may serve as a guideline for the next generation of supercapacitor electrode design.

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Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions

A promising family of mixed transition-metal oxides (MTMOs) (designated as Ax B3-x O4 ; A, B=Co, Ni, Zn, Mn, Fe, etc.) with stoichiometric or even non-stoichiometric compositions, typically in a spinel structure, has recently attracted increasing research interest worldwide. Benefiting from their remarkable electrochemical properties, these MTMOs will play significant roles for low-cost and environmentally friendly energy storage/conversion technologies. In this Review, we summarize recent research advances in the rational design and efficient synthesis of MTMOs with controlled shapes, sizes, compositions, and micro-/nanostructures, along with their applications as electrode materials for lithium-ion batteries and electrochemical capacitors, and efficient electrocatalysts for the oxygen reduction reaction in metal-air batteries and fuel cells. Some future trends and prospects to further develop advanced MTMOs for next-generation electrochemical energy storage/conversion systems are also presented.

Mixed transition-metal oxides: design, synthesis, and energy-related applications.

Adv. Mater. 2010, 22, 347–351 2010 WILEY-VCH Verlag Gm The ever worsening energy depletion and global warming issues call for not only urgent development of clean alternative energies and emission control of global warming gases, but also more advanced energy storage and management devices. Supercapacitors, offering transient but extremely high powers, are probably the most important next generation energy storage device. To boost the specific capacitance of supercapacitors, the specific surface area of the electrode materials needs to be as high as possible to promote the electric double-layer capacitances and to accommodate a large amount of superficial electroactive species to participate in faradaic redox reactions. In addition, suitable pore sizes, 2–5 nm, of the porous electrode materials are critical to ease the mass transfer of electrolytes within the pores for fast redox reactions and double-layer charging/discharging. Aerogels are a class of mesoporous materials possessing highly specific surface areas and porosities, from which promising applications in a wide range of areas have been investigated. They are composed of 3D networks of nanoparticles with an average pore size of several nanometers, adjustably falling within the optimal pore sizes of 2–5 nm. Consequently, aerogels are a promising candidate for supercapacitor applications. As to the electrode material, electroactive materials possessing multiple oxidation states/structures that enable rich redox reactions for pseudocapacitance generation are desirable for supercapacitors. Transition metal oxides are such a class of materials that have drawn extensive and intensive research attention in recent years. Among them, RuO2 is themost prominent one with a specific capacitance as high as 1580F g , probably the highest ever reported. The commercialization of RuO2 based supercapacitors, however, is not promising because of the high cost and rareness of Ru. Spinel nickel cobaltite (NiCo2O4) is a low-cost, environmentally friendly transition metal oxide, which has been employed in electrocatalytic water splitting (oxygen evolution) and lithium ion batteries. Its application in supercapacitors, however, received much less attention. Nickel cobaltite has been reported to possess a much better electronic conductivity, at least two orders of magnitude higher, and higher electrochemical activity than those of nickel oxides and cobalt oxides. It is expected to offer richer redox reactions, including contributions from both nickel and cobalt ions, than the two corresponding single component oxides and is a potential cost-effective alternative for RuO2. Based on the above considerations, one would expect nickel cobaltite aerogels, with anticipated good electronic conductivity, low diffusion resistance to protons/cations, easy electrolyte penetration, and high electroactive areas to be a promising candidate for the construction of next-generation, ultrahighperformance supercapacitors. Traditionally, aerogels are prepared with sol–gel processes by taking corresponding alkoxides as the precursors. Alkoxides are generally expensive and sensitive to moisture and heat, requiring careful handling. Recently, to tackle these drawbacks, the epoxide synthetic route, enabling the use of low-cost and stable metal salts as the precursors, was successfully developed to prepare metal oxide aerogels. In this work, we reported the first successful preparation of nickel cobaltite aerogels with the epoxide-driven sol–gel process. The effects of the post-gel-drying calcination temperature on the critical properties of the product aerogels were investigated. At a starting Ni/Co ratio of 0.5 and a post-gel-drying calcination temperature of 200 8C, an optimal combination of composition, crystallinity, specific surface area, pore volume, and pore size was achieved to afford the nickel cobaltite aerogels that showed an extremely high-specific capacitance of 1400 F g 1 under a mass loading of 0.4 mg cm 2 at a sweep rate of 25mV s 1 within a potential window of 0.04 to 0.52V in a 1 M NaOH solution. The excellent reversibility and cycle stability of the product aerogels were also demonstrated. A stoichiometric mixture of nickel and cobalt chlorides was used as the precursor for the preparation of the nickel cobaltite aerogels. After the gel is dried in supercritical carbon dioxide, a post-gel-drying calcination is generally required to acquire preferred composition and/or better crystallinity of the products. The post-gel-drying calcination temperature is thus an important processing parameter to be studied. For referring convenience, we term the product aerogels as Ni–Co–O–T, with Tdenoting the calcination temperature. The T block is omitted for as-prepared samples. Also, for comparison purposes, NiO and Co3O4 aerogels were prepared, termed as Ni–O–T and Co–O–T, respectively. Figure 1a shows the X-ray diffraction (XRD) patterns of the as-prepared product aerogels and those samples calcined at 200 and 300 8C. Surprisingly, nickel cobaltite was formed even at the as-prepared condition. The diffraction peak located at the 2u value

A Cost-Effective Supercapacitor Material of Ultrahigh Specific Capacitances: Spinel Nickel Cobaltite Aerogels from an Epoxide-Driven Sol–Gel Process

Mesoporous structures of high specific surface areas and high porosities, such as aerogels, are ideal for supercapacitor applications. This idea was successfully demonstrated for the first time by taking cobalt oxide aerogels as an example. Cobalt oxide aerogels of excellent supercapacitive properties, including high specific capacitances (the highest ever reported for cobalt oxides, >600 F/g at a high mass loading of 1 mg/cm2) and onset frequencies, and excellent reversibility and cycle stability, were successfully synthesized with an epoxide addition procedure by using cobalt nitrate as the precursor. The present development makes possible the low cost production of high performance supercapacitors of the asymmetric type.

Chun-Hung Chen

Papers

A Cost-Effective Supercapacitor Material of Ultrahigh Specific Capacitances: Spinel Nickel Cobaltite Aerogels from an Epoxide-Driven Sol–Gel Process

Cobalt Oxide Aerogels of Ideal Supercapacitive Properties Prepared with an Epoxide Synthetic Route