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

The increasing interest in energy storage for the grid can be attributed to multiple factors, including the capital costs of managing peak demands, the investments needed for grid reliability, and the integration of renewable energy sources. Although existing energy storage is dominated by pumped hydroelectric, there is the recognition that battery systems can offer a number of high-value opportunities, provided that lower costs can be obtained. The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.

Electrical Energy Storage for the Grid: A Battery of Choices

Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.

Li-O2 and Li-S batteries with high energy storage.

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

This tutorial review provides a brief summary of recent research progress on carbon-based electrode materials for supercapacitors, as well as the importance of electrolytes in the development of supercapacitor technology. The basic principles of supercapacitors, the characteristics and performances of various nanostructured carbon-based electrode materials are discussed. Aqueous and non-aqueous electrolyte solutions used in supercapacitors are compared. The trend on future development of high-power and high-energy supercapacitors is analyzed.

Carbon-based materials as supercapacitor electrodes

Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution. The development of new materials for Li-ion batteries is the focus of research in prominent groups in the field of materials science throughout the world. Li-ion batteries can be considered to be the most impressive success story of modern electrochemistry in the last two decades. They power most of today's portable devices, and seem to overcome the psychological barriers against the use of such high energy density devices on a larger scale for more demanding applications, such as EV. Since this field is advancing rapidly and attracting an increasing number of researchers, it is important to provide current and timely updates of this constantly changing technology. In this review, we describe the key aspects of Li-ion batteries: the basic science behind their operation, the most relevant components, anodes, cathodes, electrolyte solutions, as well as important future directions for R&D of advanced Li-ion batteries for demanding use, such as EV and load-leveling applications.

Challenges in the development of advanced Li-ion batteries: a review

Li(metal)-sulfur (Li-S) systems are among the rechargeable batteries of the highest possible energy density due to the high capacity of both electrodes. The surface chemistry developed on Li electrodes in electrolyte solutions for Li-S batteries was rigorously studied using Fourier transform infrared and X-ray photoelectron spectroscopies. A special methodology was developed for handling the highly reactive Li samples. It was possible to analyze the contribution of solvents such as 1-3 dioxolane, the electrolyte LiN(SO 2 CF 3 ) 2 , polysulfide (Li 2 S n ), and LiNO 3 additives to protective surface films that are formed on the Li electrodes. The role of LiNO 3 as a critical component whose presence in solutions prevents a shuttle mechanism that limits the capacity of the sulfur electrodes is discussed and explained herein.

https://iopscience.iop.org/article/10.1149/1.3148721/pdf

On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries

A route for the preparation of binder-free sulfur-carbon cathodes is developed for lithium sulfur batteries. The method is based on the impregnation of elemental sulfur into the micropores of activated carbon fibers. These electrodes demonstrate good electrochemical performance at high current density attributed to the uniform dispersion of sulfur inside the carbon fiber.

Sulfur‐Impregnated Activated Carbon Fiber Cloth as a Binder‐Free Cathode for Rechargeable Li‐S Batteries

This paper compares the electroanalytical behavior of lithiated graphite, , , and spinel electrodes. Slow scan rate cyclic voltammetry (SSCV), potentiostatic intermittent titration (PITT), and electrochemical impedance spectroscopy (EIS) were applied in order to study the potentiodynamic behavior, the variation of the solid‐state diffusion coefficient, and the impedance of these electrodes. In addition, X‐ray diffractometry and Fourier transform infrared (FTIR) spectroscopy were used in order to follow structural and surface chemical changes of these electrodes upon cycling. It was found that all four types of electrodes behave very similarly. Their SSCV are characterized by narrow peaks which may reflect phase transition between intercalation stages, and the potential‐dependent Li chemical diffusion coefficient is a function with sharp minima in the vicinity of the CV peak potentials, in which the differential electrode capacity is maximal. The impedance spectra of these electrodes reflect an overall process of various steps in series. These include ion migration through surface films, charge transfer which depends strongly on the potential, solid‐state diffusion and, finally, accumulation of the intercalants in their sites in the bulk of the active mass, which appears as a strongly potential‐dependent, low‐frequency capacitive element. It is demonstrated that the above electro‐analytical response, which can be considered as the electrochemical fingerprint of these electrodes, may serve as a good in situ tool for the study of capacity fading mechanisms.

Common Electroanalytical Behavior of Li Intercalation Processes into Graphite and Transition Metal Oxides

The development and commercialization of Li ion batteries during recent decades is one of the great successes of modern electrochemistry The increasing reliability of Li ion batteries makes them natural candidates as power sources for electric vehicles However, their current energy density, which can reach an average of 200 Wh kg−1 on the single cell level, limits the possible driving range of electric cars propelled by Li-ion batteries Thereby, there is a strong driving force to develop power sources technologies beyond Li-ion batteries that will mark breakthroughs in energy density capabilities Li-sulfur batteries have high theoretical energy density that can revolutionize electrochemical propulsion capability Consequently, in recent years there has been much work throughout the world related to these systems The scope of work on this topic justifies frequent publications of review articles that summarize recent extensive work and provide guidelines and direction for focused future work Here, a comprehensive, systematic work related to Li-sulfur battery systems is described, beginning with the Li anode challenges, carbon-encapsulated sulfur cathodes, and various kinds of relevant electrolyte solutions Based on the work described and parallel recent studies by other groups, important and comprehensive guidelines for further research and development efforts in this field are provided

Gregory Salitra

Papers

Challenges in the development of advanced Li-ion batteries: a review

On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries

Sulfur‐Impregnated Activated Carbon Fiber Cloth as a Binder‐Free Cathode for Rechargeable Li‐S Batteries

Common Electroanalytical Behavior of Li Intercalation Processes into Graphite and Transition Metal Oxides

Review on Li-Sulfur Battery Systems: an Integral Perspective