Porous materials, double-layer capacitance

High r factors are, however, not without some other complications since they imply porosity of materials. Porosity can lead to the following difficulties (a) impediment to disengagement of evolved gases or of diffusion of elec-trochemically consumable gases (as in fuel-cell electrodes 7i2) (b) expulsion of electrolyte from pores on gas evolution and (c) internal current distribution effects associated with pore resistance or interparticle resistance effects that can lead to anomalously high Tafel slopes (132, 477) and (d) difficulties in the use of impedance measurements for characterizing adsorption and the double-layer capacitance behavior of such materials. On the other hand, it is possible that finely porous materials, such as Raney nickels, can develop special catalytic properties associated with small atomic metal cluster structures, as known from the unusual catalytic activities of such synthetically produced polyatomic metal clusters (133). 

Double-layer properties of porous carbon materials have been widely investigated in relation to the development of the electrochemical capacitors. For detailed information the reader should consult specialized literature. For porous carbons materials, the double-layer capacitance depends on their specific snrface area [82,83], pore stmcture (notably, the pore size distribntion) [84-87], and their crystalline stmctnre and snrface chemistry [83,88,89], Shi [84] measnred the dc capacitance of varions carbons in a KOH electrolyte and noticed that the overall capacitance may reasonably be described as a sum of the capacitance of micro- and mesopores. Assuming that the electrical double layer propagates into micropores accessible for N2 adsorption, the author estimated the differential donble-layer capacitance per unit of micropore surface area as 15 to 20 p,F/cm. Lower values were reported by Vilinskaya... 

To increase the capacitance of ESs, some electrochemically active materials are explored for electrode use to provide much higher pseudocapacitance than double-layer capacitance. Pseudocapacitive charge storage fundamentally differs from the electrostatic mechanism that governs double-layer capacitance. For pseudocapacitance, a faradic charge transfer in the electrode porous layer occurs through a thermodynamically and kinetically favored electrochemical reduction-oxidation (redox) reaction [1]. 

The electrode layers formed using die physical loading method are usually relatively thicker (more than 10 pm in thickness), and the composite layers are composed of nanoparticles of the electrode material and the ionic polymer. These layers are both electronically and ionically conductive. The impedance for such electrodes is assumed to be similar to diat of porous electrodes. Levie (1963, 1964) was the first to develop a transmission line circuit (TLC) model of the porous electrode consisting of the electrolyte resistance and the double-layer capacitance. Subsequently, a number of authors proposed modified TLC models for the impedance of porous electrodes on the basis of Levie s model. Bisquert (2000) reviewed the various impedance models for porous electrodes. The composite electrode layers prepared by the physical loading method could be successfully represented by the impedance model for porous electrodes, as shown in Fig. 6d this model is composed of the double-layer capacitance, Cj, the Warburg diffusion capacitance, W and the electrolyte resistance, 7 (Liu et al. 2012 Cha and Porfiri 2013). 

A porous phase, exhibiting a pseudocapacitance charging due to a thin layer behavior of the film, a fast electron-transfer process confined to the pores in the film, and double-layer capacitance of a porous material. 

Dispersion — Frequency dispersion results from different frequencies propagating at different speeds through a material. For example, in the electrochemical impedance spectroscopy (EIS) of a crevice (or porous) electrode, the solution resistance, the charge transfer resistance, and the capacitance of the electric double layer often vary with position in the crevice (or pore). The impedance displays frequency dispersion in the high frequency range due to variations in the current distribution within the crevice (pore). Additionally, EIS measurements in thin layer cells (such as electro chromic... 

The most used materials for electrochemical double layer capacitors are activated carbons, because they are commercially available and cheap, and they can be produced with large specific surface area. In addition to the nanotextural properties, the chemical properties of carbons will determine their efficiency as electrodes. In the present section, an overview of the influence of the porous texture and surface chemistry of carbons on their electrochemical parameters, as capacitance or power density, is presented. 

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