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3 Electrode modifications Metal Oxide Deposition Metal oxides have been deposited onto carbon surfaces to act as catalysts for the vanadium redox reactions. As with metal deposits, electrodeposition can be employed to deposit metal oxides [115, 116]. Hydrothermal and solvothermal processes for attachment of metal oxides have been studied [117, 118]. KMnO4 was co-reduced with graphene oxide in the presence of NH3 before the solution was drop cast onto a GC electrode [119]. Inherent Kinetics A solvothermal Mn3O4 / multi walled carbon nanotube (MWCNT) modified graphite felt electrode was credited with improving the electrocatalytic kinetics for the VO2+ / VO2+ redox reactions. However, no attempt was made to identify changes in electrically active surface area and therefore the improvements in electrochemical performance may have been due to an increased electrically active surface area not faster inherent kinetics [118]. Graphite felt modified by hydrothermal deposition of MnO2 was shown to have improved electrocatalytic activity towards the VO2+ / VO2+ redox couple. This was identified through a reduction in peak separation during cyclic voltammetry and a 12.5% increase in energy efficiency, at a current density of 150 mA cm−2. However, once again no mention of surface area or capacitance was made and thus it is possible improvements were solely from increased electrically active surface area [117]. Surface Area and Roughness Effects Electrochemical reduction of functionalized MWCNTs and W2O11-2 onto a graphite plate was shown to form a nanoporous structure with a large specific surface area. Subsequent cyclic voltammetry measurements showed a noticeable reduction in peak separation for the VO2 + / VO2+ redox couple, highlighting the importance of the electrically active surface area [116]. 31PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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