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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics To simulate the cyclic voltammetry of the carbon felt electrodes, the approach of treating the carbon felt electrode as an array of micro-cylinders was adopted [178]. This model treats the carbon felt as an array of micro-cylinders with a no-flux boundary condition imposed at a set distance from the fibre surface, with the distance chosen to reflect the inter-fibre spacing within the felt. Here each carbon fibre within the felt is modelled in the same way as the single fibres in a bulk solution, but with a no-flux boundary condition imposed at a set distance from the fibre surface instead of a constant concentration boundary condition. In practice the Neumann- Boundary equations are the same, but as the radii of the void size distribution measured by x- ray computed tomography are much smaller than the arbitrarily large radius imposed for the single fibre simulations. The concentration of redox species at the boundary changes during the cyclic voltammetry simulation. In our work the cyclic voltammograms were simulated at 10 discrete void sizes, with the 12 discrete rate constants found from experimental results on single fibres. In total 120 different cyclic voltammograms were computed at each sweep rate, each with a unique combination of void size and rate constant. The voltammetry of the felt was taken as the sum of these voltammograms, where the current was weighted by the fraction of the felt represented by each void size. The void size distribution was calculated from micro-CT imaging measurements of the felt (see section 5.2). 58PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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