Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

https://hal.archives-ouvertes.fr/hal-02417326/document

Materials for electrochemical capacitors

Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

http://pubs.acs.org/doi/pdf/10.1021/cr1002326

Solar Water Splitting Cells

We present a method for calculating the stability of reaction intermediates of electrochemical processes on the basis of electronic structure calculations. We used that method in combination with detailed density functional calculations to develop a detailed description of the free-energy landscape of the electrochemical oxygen reduction reaction over Pt(111) as a function of applied bias. This allowed us to identify the origin of the overpotential found for this reaction. Adsorbed oxygen and hydroxyl are found to be very stable intermediates at potentials close to equilibrium, and the calculated rate constant for the activated proton/electron transfer to adsorbed oxygen or hydroxyl can account quantitatively for the observed kinetics. On the basis of a database of calculated oxygen and hydroxyl adsorption energies, the trends in the oxygen reduction rate for a large number of different transition and noble metals can be accounted for. Alternative reaction mechanisms involving proton/electron transfer to ...

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Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode

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

The surface area of a single graphene sheet is 2630 m2/g, substantially higher than values derived from BET surface area measurements of activated carbons used in current electrochemical double layer capacitors. Our group has pioneered a new carbon material that we call chemically modified graphene (CMG). CMG materials are made from 1-atom thick sheets of carbon, functionalized as needed, and here we demonstrate in an ultracapacitor cell their performance. Specific capacitances of 135 and 99 F/g in aqueous and organic electrolytes, respectively, have been measured. In addition, high electrical conductivity gives these materials consistently good performance over a wide range of voltage scan rates. These encouraging results illustrate the exciting potential for high performance, electrical energy storage devices based on this new class of carbon material.

Graphene-Based Ultracapacitors

This book focuses on topics at the forefront of electrochemical research. Splitting water by electrolysis; splitting water by visible light; the recent development of lithium batteries; theoretical approaches to intercalation; and fundamental concepts of electrode kinetics, particularly as applied to semiconductors are discussed. It is recommended for electrochemists, physical chemists, corrosion scientists, and those working in the fields of analytical chemistry, surface and colloid science, materials science, electrical engineering, and chemical engineering.

/pdf/modern-aspects-of-electrochemistry-51qnvn2czv.pdf

Modern Aspects of Electrochemistry

Modern aspects of electrochemistry

1 Introduction and Historical Perspective 2 Similarities and Differences between Supercapacitors and Batteries for Electrical Energy Storage 3 Energetics and Elements of Kinetics of Electrode Processes 4 Elements of Electrostatics Involved in Treatment of Double-Layers and Ions at Capacitors Electrode Interfaces 5 Behavior of Dielectrics in Capacitors and Theories of Dielectric Polarization 6 The Double-Layer at Capacitor Electrode Interfaces: Its Structure and Capacitance 7 Theoretical Treatment and Modeling of the Double-Layer at Electrode Interfaces 8 Behavior of the Double-Layer in Non-Aqueous Electrolytes and Non-Aqueous Electrolyte Capacitors 9 The Double-Layer and Surface Functionalities at Carbon 10 Electrochemical Capacitors Based on Pseudocapacitance 11 The Electrochemical Behavior of Ruthenium Oxide (RuO2) as a Material for Electrochemical Capacitors 12 Capacitance Behavior of Films Conducting, Electrochemically Reactive Polymers 13 The Electrolyte Factor in Supercapacitor Design and Performance: Conductivity, Ion-Pairing and Solvation 14 Electrochemical Behavior at Porous Electrodes Applications to Capacitors 15 Energy-Density and Power-Density of Electrical Energy Storage Devices 16 AC Impedance Behavior of Electrochemical Capacitors and Other Electrochemical Systems 17 Treatments of Impedance Behavior of Various Circuits and Modeling of Double-Layer Capacitor Frequency Response 18 Self-Discharge of Electrochemical Capacitors in Relation to that of at Batteries 19 Technology Development 20 Patent Survey

Electrochemical Supercapacitors : Scientific Fundamentals and Technological Applications

Comprehensive Treatise of Electrochemistry

The storage of electrochemical energy in battery, "supercapacitor," and double‐layer capacitor devices is considered. A comparison of the mechanisms and performance of such systems enables their essential features to be recognized and distinguished, and the conditions for transition between supercapacitor and "battery" behavior to be characterized. Supercapacitor systems based on two‐dimensional underpotential deposition reactions are highly reversible and their behavior arises from the pseudocapacitance associated with potential‐dependence of two‐dimensional coverage of electroactive adatoms on an electrode substrate surface. Such capacitance can be 10–100 times the double‐layer capacitance of the same electrode area. An essential fundamental difference from battery behavior arises because, in such systems, the chemical and associated electrode potentials are a continuous function of degree of charge, unlike the thermodynamic behavior of single‐phase battery reactants. Quasi‐two‐dimensional systems, such as hyperextended hydrous , also exhibit large pseudocapacitance which, in this case, is associated with a sequence of redox processes that are highly reversible. Such oxide redox systems give rise to the best supercapacitor behavior and capacitances of farads per gram can be achieved. Other examples are the conducting polymer electrodes and Li intercalate systems. These systems provide examples of the transition between battery and supercapacitor behavior arising from a range of degrees of oxidation/ reduction that arise over an appreciable range of potentials. The impedance behavior of an supercapacitor is illustrated but is far from that expected for an electrostatic capacitor.

https://iopscience.iop.org/article/10.1149/1.2085829/pdf

Brian E. Conway

Papers

Modern Aspects of Electrochemistry

Modern aspects of electrochemistry

Electrochemical Supercapacitors : Scientific Fundamentals and Technological Applications

Comprehensive Treatise of Electrochemistry

Transition from “Supercapacitor” to “Battery” Behavior in Electrochemical Energy Storage