Electrode Kinetics of Vanadium Flow Batteries: Contrasting Responses of V^II-V^IIIand V^IV-V^Vto Electrochemical Pretreatment of Carbon

Electrochemical impedance spectroscopy and cyclic voltammetry were used to investigate the electrode kinetics of VII-VIII and VIV-VV in H2SO4 on glassy carbon, carbon paper, carbon xerogel, and carbon fibers. It was shown that, for all carbon materials investigated, the kinetics of VII-VIII is enhanced by anodic, and inhibited by cathodic, treatment of the electrode; in contrast, the kinetics of VIV-VV is inhibited by anodic, and enhanced by cathodic, treatment. The potential region for each of these effects varied only slightly with carbon material. Rate constants were always greater for VIV-VV than for VII-VIII except when anodized electrodes were compared, which may explain discrepancies in the literature. The observed effects are attributed to oxygen-containing functional-groups on the electrode surface. The considerable differences between the potentials at which enhancement of VII-VIII and inhibition of VIV-VV occur indicates that they do not correspond to a common oxidized state of the electrode. Likewise inhibition of VII-VIII and enhancement of VIV-VV do not correspond to a common reduced state of the electrode. It is possible that enhancement of both VII-VIII and VIV-VV is due to the same (active) state of the electrode.