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5 Single fibre electrode measurements - a versatile strategy for assessing the non-uniform kinetics To investigate the importance of the measured rate constant distribution, an average rate constant which provides the best fit between the model and measured voltammograms at carbon felt electrodes was determined as a function of sweep rate (Table 5.2). Table 5.2: Rate constants found by fitting the carbon felt electrode model to measured voltammograms, assuming a single rate constant and the previously shown void size distribution. Sweep Rate (mV s-1) 20 50 100 200 500 1000 Fitted Rate Constant (cm s-1) 0.0045 ± 0.0005 0.0057 ± 0.0005 0.0060 ± 0.0005 0.0063 ± 0.0004 0.0068 ± 0.0003 0.0071 ± 0.0002 The values in Table 5.2 were obtained by fitting the peak potential separation from a felt electrode, with only one rate constant. The fitting method was the same as that used for the single fibres, with the fitting procedure (bisection method) minimizing the difference between the experimental and simulated peak separation by varying k0. The fits show that the calculated average rate constant increases as a function of sweep rate. However, as the rate constant should be independent of sweep rate, we conclude that rather than an average rate constant, a rate constant distribution is required to account for behaviour over a wide range of sweep rates. 67PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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