Homogeneous Complexation Strategy to Manage Bromine for High‐Capacity Zinc–Bromine Flow Battery

Abstract Zinc–bromine flow batteries (ZBFBs) have received widespread attention as a transformative energy storage technology with a high theoretical energy density (430 Wh kg −1 ). However, its efficiency and stability have been long threatened as the positive active species of polybromide anions (Br 2 n +1 − ) are subject to severe crossover across the membrane at a high concentration. Herein, a novel highly hydrophilic complexing agent, N‐methyl‐N, N‐bis(2‐hydroxyethyl)‐1‐propanaminium bromide (PMDA), is developed to effectively manage bromine in a homogeneous posolyte, which realizes a low bromine crossover at a high operating concentration in ZBFBs. Both theoretical and experimental results suggest that the PMDA interacts with Br 2 n +1 − and forms a larger‐size complex PMDABr 2 n +1 . When adding 0.40 m PMDA, the bromine stays homogeneous at a high concentration up to 1.20 m , and its permeability is remarkably decreased by 74%. For demonstration, the ZBFB achieves a operating capacity record of 57.2 Ah L −1 in a homogeneous bromine posolyte with a high Coulombic efficiency of ≈90.0% and superior cycling stability (capacity retention rate of 100.0% per cycle). This work provides one innovative bromine management strategy to realize a high capacity and superior stability in ZBFBs.