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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics As the influence of void size on the cyclic voltammetry at a felt electrode decreases as the sweep rate increases, a felt electrode will approach the average single fibre electrode as the sweep rate increases. Therefore, the rate constant determined by fitting a model which assumes a single rate constant and a void size distribution should also approach the average rate constant determined from measurements at multiple single fibre electrodes. This is indeed found in this work, with the best fit single rate constant obtained for cyclic voltammograms measured at 1000 mV s-1 for the carbon felt electrode (0.0071 cm s-1, Table 5.2) agreeing very well with the average value calculated from 12 single fibre electrode measurements (0.0075 ± 0.0030 cm s-1, Table 5.1). The model used to describe the voltammograms at carbon felt assumes that the reaction occurring on the outer face of the electrode can be excluded from the calculation. To confirm that this assumption is reasonable, the charge transferred between the felt electrode and the redox couple within the felt was calculated based on the felt parameters and compared to the experimental results. For a total felt volume of 0.35 cm3, void volume fraction of 0.938 and with the felt initially containing 0.1 mM ferricyanide and 0.1 mM ferrocyanide, complete transformation between the two forms of the redox couple would result in 6.4 mC of charge passed. The anodic and cathodic charge was measured from cyclic voltammograms obtained at 50 mV s-1 as 6.2 and 5.9 mC respectively, suggesting that the voltammetric response of the felt is dominated by the redox reaction within the felt and that the model can safely exclude the contribution of the outer surface. 69PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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