Conductive Polymer Coatings Control Reaction Selectivity in All‐Iron Redox Flow Batteries

Abstract Aqueous all‐iron redox flow batteries are an attractive and economic technology for grid‐scale energy storage owing to their use of abundant and environmentally benign iron as the redox active material and water as solvent. However, the battery operation is challenged by the plating/stripping reactions of iron and the competing hydrogen evolution reaction at the negative electrode, which hinder performance and durability. Here, the reaction selectivity of the negative electrode is tailored by introducing conductive polymer coatings onto porous carbonaceous electrodes. Two conductive polymers, poly(3,4‐ethylenedioxythiophene) (PEDOT) and poly(pyrrole) (PPy) are conformally coated with the dopant poly(4‐styrenesulfonate) (PSS) and the resulting electrochemistry is studied on model electroanalytical platforms and redox flow batteries. Both polymers decrease the hydrogen evolution current on rotating disc electrodes, with PPy/PSS strongly inhibiting the reaction at high overpotentials. In full all‐iron redox flow cells, PPy/PSS coating extends cyclability and significantly reduces hydrogen evolution, while PEDOT/PSS coating improves the round‐trip efficiency, possibly acting as a redox shuttle for the iron stripping reaction. These findings motivate broader investigation and implementation of conductive polymers to engineer reaction selectivity for flow batteries and other electrochemical technologies.