Channel electrodes theoretical models

In order to see how the electrode thickness might be optimized in order to provide the lowest electrode resistivity, we have developed a theoretical model to describe the charge/discharge processes in porous carbon electrodes. As a first approximation, let us consider an electrode having two sets of cylindrical pores, namely, nanopores (NP) of less than 3 nm in diameter and transport channels (TC) of more than 20 nm in diameter, with each nanopore having an exit to only one TC. ... 

The study of the electric field strength effect on the shape of the density gradient formed in the TLF cell indicated an important difference compared with the first approximation theoretical model. A series of experimental data and the theoretically calculated curves are shown in Figure 6. The difference can be caused by the interactions between the colloidal particles of the binary density forming carrier liquid. Moreover, the electric field strength across the cell or channel thickness was estimated from the electric potential measured between the electrodes, but the electrochemical processes at both electrodes can contribute to this difference. 

This section provides a brief review of both the available theoretical models and the experiments relating to pitting corrosion at channel electrodes. A thorough coverage of pitting corrosion per se is beyond the scope of this chapter and the reader is referred to ref. 182 for further detail. 

Consider an electrode covered with a film that has continuous pores or channels from the solution to the electrode (Figure 14.4.1, process 6). We can ask how the electrolysis of a species in solution at such an electrode differs from that at the bare (unfilmed) electrode. The answer depends upon the extent of coverage of the electrode by the film, the size and distribution of the pores, and the time scale of the experiment. The situation is complicated, because the pores can have different dimensions and degrees of tortuosity, and their distribution within the film may not be uniform. Thus, theoretical treatments of such films often use idealized models. The theory for electrodes of this type is closely related to that for ultramicroelectrode arrays (Section 5.9.3), which, however, often involve a better-defined geometry and uniform distribution of active sites (81, 82). 

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