Redox electrochemical capacitors

Pseudocapacitance is used to describe electrical storage devices that have capacitor-like characteristics but that are based on redox (reduction and oxidation) reactions. Examples of pseudocapacitance are the overlapping redox reactions observed with metal oxides (e.g., RuO,) and the p- and n-dopings of polymer electrodes that occur at different voltages (e.g. polythiophene). Devices based on these charge storage mechanisms are included in electrochemical capacitors because of their energy and power profiles. 

Figure 2. Representation of (A, top) an electrochemical capacitor (supercapacitor), illustrating the energy storage in the electric double layers at the electrode—electrolyte interfaces, and (B, bottom) a fuel cell showing the continuous supply of reactants (hydrogen at the anode and oxygen at the cathode) and redox reactions in the cell.

In electrochemical capacitors (or supercapacitors), energy may not be delivered via redox reactions and, thus the use of the terms anode and cathode may not be appropriate but are in common usage. By orientation of electrolyte ions at the electrolyte/electrolyte interface, so-called electrical double layers (EDLs) are formed and released, which results in a parallel movement of electrons in the external wire, that is, in the energy-delivering process. 

In the second type of supercapacitor, sometimes termed pseudocapacitors, redox capacitors or electrochemical capacitors, the non-Faradaic doublelayer charging process is accompanied by charge transfer. This Faradaic process must be characterized by extremely fast kinetics in order to allow device operation with high current density discharge pulses. 

In general, two modes of energy storage are combined in electrochemical capacitors (1) the electrostatic attraction between the surface charges and the ions of opposite charge (EDL) and (2) a pseudocapacitive contribution which is related with quick faradic charge transfer reactions between the electrolyte and the electrode [7,8], Whereas the redox process occurs at almost constant potential in an accumulator, the electrode potential varies proportionally to the charge utilized dr/ in a pseudocapacitor, which can be summarized by Equation 8.5 ... 

Recently, we have explored the use of anodic Ti02 nanotube layers as electrodes for electrochemical capacitors [94], Nickel oxide was incorporated into the Ti02 nanotubes, with nickel-to-titanium atom ratio being 9.6 at% and 36.4 at%, respectively, for redox capacitance application. The experimental results showed that the corresponding specific redox capacitance was 26 and 85 mF/cm2 with highly reversible charge-discharge stability,... 

Pseudocapacitors store charge based on reversible (faradaic) charge transfer reactions with ions in the electrolyte. For example, in a metal oxide (such as RUO2 or I1O2) electrode, charge storage results from a sequence of redox reactions. Electrochemical capacitors (ECs) based on such pseudocapacitive materials will have both faradaic and nonfaradaic contributions. The optimization of both EDLCs and pseudocapacitors depends on understanding how features at the nanoscale (e.g. pore size distribution, crystaUite or particle size) affect ion and electron transport and the fundamental properties of electrochemical interfaces. 

Yamazaki, S., T. Ito, M. Yamagata, and M. Ishikawa. 2012. Non-aqneons electrochemical capacitor utilizing electrolytic redox reactions of bromide species in ionic liquid. 

Batteries store and deliver energy on the basis of chemical reactions, and hence their capacities depend on the redox reactions. In contrast, the energy storage or the charging-discharging mechanism by electrochemical capacitors are based on... 

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