Influence of the Oxygen Surface Functionalities Introduced by Electrochemical Treatment on the Behavior of Graphite Felts as Electrodes in VRFBs

Abstract

Graphite felts act as electrodes in VRFBs thanks to their properties such as chemical strength and electrical conductivity or 3D-structure. However, there are significant drawbacks to be overcome, such as their low wettability, sluggish kinetic reversibility and electroactivity towards faradaic processes related to vanadium electroactive species. As a consequence, it is key to alter the fibres to enhance their electrochemical performance during battery operation. Most of the previously reported modifications have been focused on incorporating surface oxygenated functional groups, even though the role of those groups on the electrocatalytic activity towards vanadium faradaic processes is still not clear. Aiming to gain knowledge on this issue, this work investigates the influence of electro-oxidation and electro-reduction treatments, performed in different acidic media (H2SO4 or HNO3 solutions), on their subsequent electrochemical response towards VO2+/VO2+ and V3+/V2+ faradaic processes. The chemical and electrochemical properties of the modified felts were analyzed to understand two key parameters that affect the vanadium reaction catalysis: the depth and oxidation degree of the fibres. A treatment with HNO3, a strong oxidizing agent, leads to a deep oxidation of the fibre and the development of a high density of oxygenated functional groups, mainly C=O, which hinder the redox reactions of vanadium, especially for the faradaic reactions from the catholyte.