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Cyclic voltammetry of four different carbon fiber electrodes before and after thermal treatment at 450 oC for 1 hour, showed that the rate constant for the Fe(CN) 3− / Fe(CN) 4− increased with thermal treatment. The capacitance of the carbon fiber electrodes also increased significantly, indicating that in part the increased kinetic performance was due to an increase in the wetted area of the electrodes, likely caused by the formation of pores at the carbon fiber surface. However, the magnitude of the apparent rate constant increase was significantly different to the increased capacitance at three of the four fiber types tested, indicating that functional groups at the surface strongly influence the kinetic performance. Thermal treatment of three different felts showed a clear increase in the electrical double layer capacitance and physical area measured by BET. Therefore, the surface area and hence roughness of the fibers also increased. Cyclic voltammetry of the VO2+ / VO2+ redox couple showed improved kinetics and thus the increase in capacitance was linked to an increase in apparent kinetics for the VO2+ / VO2+ redox couple. As with the Fe(CN) 3− / Fe(CN) 4− , the 66 magnitude of the surface area increase was not consistent with the increase in the apparent rate constants. Therefore, the presence of different functional groups at the surface alters the kinetics of the reaction. The apparent rate constants calculated from cyclic voltammetry of carbon felt electrodes were validated with half-cell polarization curve and charge / discharge measurements. With very close agreement observed between the rate constants calculated from cyclic voltammetry and polarization curve measurements. Finally, the charge / discharge measurements demonstrated that carbon felts with higher apparent rate constants for the VO2+ / VO2+ redox couple had higher energy efficiency. iv 66PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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