Development of high-voltage bipolar redox-active organic molecules through the electronic coupling of catholyte and anolyte structures.

All-organic non-aqueous redox flow batteries (O-NRFBs) are a promising technology for grid-scale energy storage. However, most examples of high-voltage (>2 V) O-NRFBs rely upon the use of distinct anolytes and catholytes separated by a membrane or porous separator which can result in crossover of redox active material from one side of the battery to the other. The resulting electrolyte mixing leads to irreversible reductions in energy density and capacity. A potentially attractive solution to overcome this crossover issue is the implementation of symmetric flow batteries where a single bipolar molecule functions as both an anolyte and a catholyte. Herein, we report the development of a new class of bipolar redox active materials for use in such symmetric flow batteries through the electronic coupling of phenothiazine catholytes and phthalimide anolytes. Such a strategy results in hybrid molecules possessing higher cell voltages than what could be obtained together by their uncoupled building blocks. Performance in flow batteries is demonstrated for two members of this new class of molecules, with the highest performing candidate featuring a ΔE of 2.31 V and demonstrating 93.6% average coulombic efficiency, 86.8% energy efficiency, and 68.6% capacity retention over the course of 275 charge-discharge cycles and 5 cell polarity reversals. Finally, the superior performance of symmetric O-NRFBs is experimentally confirmed by comparing these results to an asymmetric flow battery constructed with a distinct phenothiazine catholyte and a distinct phthalimide anolyte on opposing sides of the cell.