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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics voltammograms [172-176]. These effects may explain the wide range (four orders of magnitude) in the reported standard heterogeneous rate constants obtained at carbon felt electrodes for the redox reactions that occur in vanadium redox flow batteries [177]. Recently, others have overcome these challenges by modelling carbon felt as a system of micro-cylinder electrodes to allow the rate constant to be determined using cyclic voltammetry at carbon felt electrodes [178]. While this approach is very promising, as the rate constant and felt void size distribution influence the voltammograms in a similar way, a manual fitting procedure was required in that work [178] and it was assumed that the rate constant was a fixed value throughout the felt. In this work, to quantify the influence of non-uniform kinetics at carbon felt electrodes, the electron transfer kinetics of the ferri/ferrocyanide redox couple are measured directly at 12 single carbon fibre electrodes extracted from a carbon felt sample. Ferri/ferrocyanide was used as a model redox couple for this work as has a standard redox potential which is far from the hydrogen and oxygen evolution potentials, and thus these reactions do not interfere with the data analysis. The advantage with using single fibre electrodes extracted from felt, is that the standard heterogeneous rate constant is determined at an electrode with the identical surface chemistry as found in the felt, without the complex mass transport behaviour. Importantly, for the first time, the distribution of rate constants for a felt sample is determined and then used along with the measured void size distribution to successfully model cyclic voltammograms at the carbon felt electrode. 52PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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