Spatial structure regulation towards armor-clad five-membered pyrroline nitroxides catholyte for long-life aqueous organic redox flow batteries

Abstract

Five-membered pyrroline nitroxides with high-potential is fascinating as catholyte for aqueous organic redox flow batteries (AORFBs), however, it suffers from a primary deficiency of insufficient stability due to ring-opening side reaction. Herein we report a spatial structure regulation strategy by host-guest chemistry, encapsulating 3-carbamoyl-2,2,5,5-tetramethylpyrroline-1-oxyl (CPL) into hydrosoluble cyclodextrins (CDs) with an inclusion structure of N–O· head towards cavity bottom, to boost the solubility and cyclability of pyrroline nitroxides significantly. The armor-clad CPL (CPL⊂HP-β-CD) catholyte in 0.05–0.5 ​M presents a battery capacity fade rate as low as 0.002 ​%/cycle (0.233 ​%/day) compared to the sole CPL in 0.05 ​M (0.039 ​%/cycle or 5.23 ​%/day) over 500 cycles in assembled AORFBs. The optimized reclining spatial structure with N–O· head towards CD cavity bottom effectively inhibits the attack of Lewis base species on the hydrogen abstraction site in pyrroline ring, and thus avoids the ring-opening side reaction of pyrroline nitroxides.