Robust Chalcogenophene Viologens as Anolytes for Long-Life Aqueous Organic Redox Flow Batteries with High Battery Voltage.

A series of chalcogenophene viologens ( [(NPr) 2 FV]Cl 4 , [(NPr) 2 TV]Cl 4 , and [(NPr) 2 SeV]Cl 4 ) as anolytes for neutral aqueous organic redox flow batteries (AORFBs) via a combination of chalcogenophenes (furan, thiophene, and selenophene) and viologens are reported. The chalcogenophene viologens showed narrow HOMO-LUMO energy gap, high solubility, and stable electrochemical properties. Compared with the parent [(NPr) 2 V]Cl 4 , the introduction of π-conjugated chalcogenophene groups reduced the redox potential and enhanced the stability of their free radical state, which endowed the chalcogenophene viologens/FcNCl -based AORFBs with a higher theoretical battery voltage of 1.20 V and enhanced stability for one-electron storage. In particular, the [(NPr) 2 FV]Cl 4 /FcNCl -based AORFB exhibited excellent long-cycle stability for 3000 cycles with 0.0006% capacity decay per cycle for one-electron storage and 300 cycles with 0.06% capacity decay per cycle for two-electron storage at a charge voltage of 1.9 V (1.42 V theoretical battery voltage). This work provided a new strategy for regulating the voltage and improving the performance of neutral AORFBs.