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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics The simulation results clearly show that the void size distribution has a significant effect on the cyclic voltammetry of the porous carbon felt electrode, (compare Figure 5.5a to Figure 5.5b and Figure 5.5c to Figure 5.5d). This is because the carbon fibres in the felt which are spaced furthest apart behave like single carbon fibre electrodes with semi-infinite cylindrical diffusion, and thus these fibres give a relatively large ΞπΈπ (Figure 6a, red lines). Conversely, the fibres which are spaced closer together, behave more like thin-layer electrodes, with a smaller ΞπΈπ (Figure 5.6a, black lines). When these effects are combined with the measured void size distribution, the peaks on the simulated cyclic voltammogram broaden, and the peak separation is dominated by the fibres located within voids of diameter around 20 to 40 ΞΌm (Figure 5.6b, black lines). Figure 5.6: Simulated cyclic voltammograms at felt electrodes, using the average rate constant (0.0075 cm s-1) with different void diameters in a solution of 0.1 mM ferricyanide and 0.1 mM ferrocyanide, at a sweep rate of 100 mV s-1. a) Cyclic voltammograms for felts with different void sizes but equal electroactive surface areas. b) Cyclic voltammograms for felts with different void sizes weighted by the fractional surface area calculated from the void size distribution. 66PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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