Soft-hard zwitterionic additives for aqueous halide flow batteries

Aqueous redox flow batteries with halide-based catholytes (where the halogen atom (X) is Br or I) are promising for sustainable grid energy storage. However, the formation of polyhalides during electrochemical charging and the associated phase separation into X₂ limits the operable state of charge (SoC), results in vaporization and self-discharge inefficiencies, and spurs complete device failure^1-3. Here we introduce soft-hard zwitterionic trappers (SH-ZITs) as complexing agents composed of a polyhalide-complexing 'soft' cationic motif and a water-soluble 'hard' anionic motif to enable homogeneous halide cycling. More than 300 structures were designed and 13 were characterized, showcasing the ability to complex polyhalides in homogeneous aqueous solution, to deter cation-exchange membrane crossover and to alter the electrochemical electrode mechanism. In flow battery cycling at a standard catholyte SoC of 66.6 per cent (stoichiometrically X₃^-), an average coulombic efficiency of more than 99.9 per cent at 40 milliamperes per square centimetre with no apparent decay was observed after more than 1,000 cycles over 2 months, with stability at elevated temperatures also demonstrated. Interestingly, SH-ZITs enable homogeneous cycling of the halide catholyte up to 90 per cent SoC at 2 moles per litre (47.7 ampere-hours per litre) for bromide, revealing previously unknown polyhalide regimes to be studied. Ultimately, SH-ZIT enables ultrahigh catholyte capacity utilization up to over 120 ampere-hours per litre at 80 per cent SoC with homogeneous cycling as well as the ability to pair with a zinc anode in a hybrid flow battery.