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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics For some porous electrodes, it is possible to find two distinct pairs of peaks from a redox couple with only a single electron transfer process due to the differing transport behaviour within the porous electrode and between the outer electrode surface and the bulk electrolyte [175]. However, as the felt electrode is thick in this case (3.5 mm), the voltammetric response of the felt electrode is dominated by the redox reaction within the felt, with diffusion between the outer surface of the felt and the bulk electrolyte expected to have only a minor contribution, as seen later in this work. The complex mass transport behaviour within felt electrodes can be avoided by performing cyclic voltammetry at a number of single carbon fibres extracted from the felt. Others have shown that kinetics of redox reactions can be measured and the cyclic voltammetry simulated at micro cylindrical electrodes [142, 181, 185-187]. Aoki et al. [142] originally demonstrated that the peak separation from cyclic voltammetry can be related to the rate constant at a cylindrical electrode, however they determined that the relationship between peak separation and experimental conditions for quasi-reversible cases was too complex to be expressed with simple equations. Neudeck et al. [181] showed that using non-linear regression approximate values for the rate constant and diffusion coefficient can be calculated from experimental cyclic voltammograms at cylindrical electrodes. 60PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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