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

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

A review of electrolyte materials and compositions for electrochemical supercapacitors

The science and technology of ultracapacitors are reviewed for a number of electrode materials, including carbon, mixed metal oxides, and conducting polymers. More work has been done using microporous carbons than with the other materials and most of the commercially available devices use carbon electrodes and an organic electrolytes. The energy density of these devices is 3¯5 Wh/kg with a power density of 300¯500 W/kg for high efficiency (90¯95%) charge/discharges. Projections of future developments using carbon indicate that energy densities of 10 Wh/kg or higher are likely with power densities of 1¯2 kW/kg. A key problem in the fabrication of these advanced devices is the bonding of the thin electrodes to a current collector such the contact resistance is less than 0.1 cm2. Special attention is given in the paper to comparing the power density characteristics of ultracapacitors and batteries. The comparisons should be made at the same charge/discharge efficiency.

Ultracapacitors: Why, How, and Where is the Technology

Electrical energy storage (EES) is one of the most critical areas of technological research around the world. Storing and efficiently using electricity generated by intermittent sources and the transition of our transportation fleet to electric drive depend fundamentally on the development of EES systems with high energy and power densities. Supercapacitors are promising devices for highly efficient energy storage and power management, yet they still suffer from moderate energy densities compared to batteries. To establish a detailed understanding of the science and technology of carbon/carbon supercapacitors, this review discusses the basic principles of the electrical double-layer (EDL), especially regarding the correlation between ion size/ion solvation and the pore size of porous carbon electrodes. We summarize the key aspects of various carbon materials synthesized for use in supercapacitors. With the objective of improving the energy density, the last two sections are dedicated to strategies to increase the capacitance by either introducing pseudocapacitive materials or by using novel electrolytes that allow to increasing the cell voltage. In particular, advances in ionic liquids, but also in the field of organic electrolytes, are discussed and electrode mass balancing is expanded because of its importance to create higher performance asymmetric electrochemical capacitors.

Carbons and Electrolytes for Advanced Supercapacitors

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

This paper is focused on neutral aqueous medium, i.e.lithium, sodium and potassium sulfate solutions in a wide range of concentrations (0.1–2.5 mol L−1) as promising electrolytes for electrochemical capacitors because they are cheap, non-corrosive and allow applying diverse current collectors. These properties make the capacitor assembling process much easier and cheaper. Additionally, such electrolytes are electrochemically stable and environmentally friendly. Electrochemical investigations carried out especially for 1 mol L−1Li2SO4 aqueous solution confirmed the possibility of efficient capacitor work in a wider voltage range, i.e. even at 2.2 V without any significant capacitance fade during 15 000 cycles. The physicochemical properties of ions (i.e. solvation, diffusion or mobility) and their influence on the capacitor electrochemical behaviour are considered.

Novel insight into neutral medium as electrolyte for high-voltage supercapacitors

This paper presents various applications of carbon nanotubes as components of electrode materials for such electrochemical use as electrochemical capacitors, fuel cells, hydrogen electrosorption and accumulators. Generally, carbon nanotubes give exceptional improvement of electrode performance due to their mesoporous and well conducting networks. The cell resistance is drastically reduced and the transport of ions is greatly enhanced. In addition to their good conductivity, carbon nanotubes can be flexible and stretchable which is crucial for cyclability of electrodes, especially if volumetric changes of electrode material occur during operation. Consequently, they serve as excellent support for conducting polymers (e.g. polyaniline, polypyrrole) and metal oxides (e.g. MnO2) giving attractive capacitor electrodes. The presence of nanotubes in carbon precursor rich in heteroatoms, e.g. nitrogen from melamine or oxygen, also supplies an interesting carbonized composite with a good charge propagation for supercapacitor use. Furthermore, carbon nanotubes have been tested for hydrogen electrosorption giving a very moderate hydrogen capacity (0.27 wt.%). However, modification of nanotubes can enhance hydrogen storage. On the other hand, carbon nanotubes can serve as an excellent additive to many electrode materials for improvement of conductivity and cell performance. They could be a good support of the catalytic particles for fuel cell application as well.

Carbon nanotubes and their composites in electrochemical applications

Sustainable materials for electrochemical capacitors

High-voltage aqueous electrolyte based supercapacitors (U > 1.23 V) attract significant attention for next-generation high power, low cost and environmentally friendly energy storage applications. Cell ageing is however markedly pronounced at elevated voltages and results in accelerated overall performance fade and increased safety concerns. Online electrochemical mass spectrometry, combined with cell pressure analysis, is for the first time shown to provide a powerful means for in situ investigation of degradation mechanisms in aqueous electrolyte/carbon based supercapacitors. The activated carbon electrodes possess high specific surface area and oxygen-based surface functionalities (mainly phenol, lactone and anhydride groups), which are oxidized already at a cell voltage of 0.6 V to provoke the evolution of minor amounts of CO and CO2. Noticeable water decomposition starts at a high voltage of 1.6 V with the evolution of H2 on the negative electrode and carbon corrosion on the positive electrode with the generation of predominantly CO. In this paper we also report that short-term cycling leads to partly reversible gas evolution/consumption side-reactions giving negligible capacitance. On the other hand, long-term cycling causes irreversible side-reactions, deteriorates the electrochemical performance, and increases the internal pressure of the cell. Repeated cycling (U < 2 V) is confirmed as a more harmful technique for the electrode integrity compared to the voltage holding in a floating test. In situ gas analysis is shown to provide valuable insights into the electrochemical cell ageing aspects, such as the nature and potential onsets of side-reactions, hence paving the way for fundamental understanding and mitigating the performance and safety loss of high-energy aqueous supercapacitors.

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Ageing phenomena in high-voltage aqueous supercapacitors investigated by in situ gas analysis

This paper reports the electrochemical behaviour of supercapacitor carbon electrodes operating in different aqueous solutions modified by various redox-active species (hydroxybenzenes, bromine derivatives and iodide). Three dihydroxybenzenes with varying stereochemistry, i.e., –OH substitution, have been considered as electrolyte additives (0.38 mol L−1) in acidic, alkaline and neutral solutions. High capacitance values have been obtained, especially for the acidic and alkaline solutions containing 1,4-dihydroxybenzene (hydroquinone). Bromine derivatives of dihydroxybenzenes were also considered as the additive in alkaline solution for use as a supercapacitor electrolyte, and a significant increase in capacitance value was observed. The redox couple investigated next was an iodide/iodine system, where 2 mol L−1 NaI aqueous electrolyte was utilized. In this case, the most promising faradaic contribution during capacitor operation was achieved. In particular, stable capacitance values from 300–400 F g−1 have been confirmed by long-term galvanostatic cycling (over 100 000 cycles), cycling voltammetry and floating. The mechanism of pseudocapacitance phenomena was discussed and supported by electrochemical and physicochemical measurements, e.g., in situ Raman spectroscopy.

Krzysztof Fic

Papers

Novel insight into neutral medium as electrolyte for high-voltage supercapacitors

Carbon nanotubes and their composites in electrochemical applications

Sustainable materials for electrochemical capacitors

Ageing phenomena in high-voltage aqueous supercapacitors investigated by in situ gas analysis

Redox-active electrolyte for supercapacitor application