Sulfonated Styrene‐Grafted Polyvinylidene Fluoride Copolymers for Proton Exchange Membranes for AQDS/Bromine Redox Flow Batteries

This study presents the preparation and electrochemical testing of sulfonated styrene-grafted poly(vinylidene fluoride) (pVDF) copolymers as proton exchange membranes (PEMs) for semi-organic redox flow batteries (RFBs) based on 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/bromine. The copolymers are synthesized via a two-step procedure, involving i) atom transfer radical polymerization of styrene (Sty) for the grafting to the pVDF backbone and ii) the sulfonation of the polystyrene grafted side chains. Copolymers with different amounts of sulfonated styrene (SSty) in the side chains (i.e., degree of sulfonation (DS)) are obtained and used for the preparation of PEMs by solution casting. The PEMs are characterized to assess their thermal, mechanical, water absorption, and ion exchange properties, to evaluate the effect of DS on membrane properties, and to select the membrane with the best overall performance for application in single cell tests. Electrochemical testing reveals that the pVDF-g-(Sty26-co-SSty14) membrane exhibits low crossover of redox species, favorable ohmic resistance, and energy efficiency. Results from single cell tests, as compared with commercial benchmarks such as Nafion 115 and Aquivion E87-12s, highlight the potential of such copolymers as alternative membranes for RFBs.