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

The large-scale practical application of fuel cells will be difficult to realize if the expensive platinum-based electrocatalysts for oxygen reduction reactions (ORRs) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, we report that vertically aligned nitrogen-containing carbon nanotubes (VA-NCNTs) can act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction in alkaline fuel cells. In air-saturated 0.1 molar potassium hydroxide, we observed a steady-state output potential of –80 millivolts and a current density of 4.1 milliamps per square centimeter at –0.22 volts, compared with –85 millivolts and 1.1 milliamps per square centimeter at –0.20 volts for a platinum-carbon electrode. The incorporation of electron-accepting nitrogen atoms in the conjugated nanotube carbon plane appears to impart a relatively high positive charge density on adjacent carbon atoms. This effect, coupled with aligning the NCNTs, provides a four-electron pathway for the ORR on VA-NCNTs with a superb performance.

http://science.sciencemag.org/content/sci/323/5915/760.full.pdf

Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction.

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

The Li-S battery has been under intense scrutiny for over two decades, as it offers the possibility of high gravimetric capacities and theoretical energy densities ranging up to a factor of five beyond conventional Li-ion systems. Herein, we report the feasibility to approach such capacities by creating highly ordered interwoven composites. The conductive mesoporous carbon framework precisely constrains sulphur nanofiller growth within its channels and generates essential electrical contact to the insulating sulphur. The structure provides access to Li+ ingress/egress for reactivity with the sulphur, and we speculate that the kinetic inhibition to diffusion within the framework and the sorption properties of the carbon aid in trapping the polysulphides formed during redox. Polymer modification of the carbon surface further provides a chemical gradient that retards diffusion of these large anions out of the electrode, thus facilitating more complete reaction. Reversible capacities up to 1,320 mA h g(-1) are attained. The assembly process is simple and broadly applicable, conceptually providing new opportunities for materials scientists for tailored design that can be extended to many different electrode materials.

http://dns2.asia.edu.tw/~ysho/YSHO-English/1000%20WC/PDF/Nat%20Mat8,%20500.pdf

A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries

Electrochemical energy conversion devices are pervasive in our daily lives. Batteries, fuel cells and supercapacitors belong to the same family of energy conversion devices. They are all based on the fundamentals of electrochemical thermodynamics and kinetics. All three are needed to service the wide energy requirements of various devices and systems. Neither batteries, fuel cells nor electrochemical capacitors, by themselves, can serve all applications.

Ralph J. Brodd

Papers

What Are Batteries, Fuel Cells, and Supercapacitors?

What Are Batteries, Fuel Cells, and Supercapacitors?

What Are Batteries, Fuel Cells, and Supercapacitors? (Chem. Rev. 2003, 104, 4245−4269. Published on the Web 09/28/2004.)