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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics The largest influence of the rate constant distribution on the cyclic voltammetry occurs at high sweep rates where the void size distribution becomes less important. This can be seen by simulating cyclic voltammetry at 1000 mV s-1 at single fibre electrodes contained within cylindrical voids. Figure 5.7: Simulated results of cyclic voltammograms at fibres in a solution of 0.1 mM ferricyanide and 0.1 mM ferrocyanide, at a sweep rate of 1000 mVs-1. a) using the average rate constant (0.0075 cm s-1) with different void diameters. b) 60 μm void modelled with a selection rate constants (in cm s-1) from Table 1. These simulations show that the voltammetric response starts to become independent from the void diameter at diameters greater than 40 μm (Figure 5.7a). This is because the diffusion layer thickness only grows to around 20 μm from the fibre surface and thus fibres in voids with diameters greater than around 40 μm are not affected by the no-flux condition at the void boundary. However, as expected, the cyclic voltammograms of fibres in voids with large diameters are still clearly influenced by the rate constant (Figure 5.7b); thus including the rate constant distribution when modelling carbon felt electrodes is most important at high sweep rates. 68PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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