Enhanced chemical stability and H+/V4+ selectivity of microporous sulfonated polyimide via a triptycene-based crosslinker

Abstract

Long durability of sulfonated polyimide in vanadium redox flow battery (VRFB) is urgently required to be solved. Herein, we synthesize a triptycene-based crosslinker and use it as chemical crosslinking point to modify a linear sulfonated polyimide for promoting its antioxidative stability. The novel triptycene-based cross-linked sulfonated polyimide (TCSPI-X) membranes featuring covalently crosslinked network display lower water uptake and swelling ratio than the commercial perfluorinated ionomer membrane (Nafion 117) membrane. More importantly, unnoticeable proton conductivity loss is appeared. We speculate this is because of the covalently crosslinking structure provides stable proton transportation channels, and the formation of micropores induced by rigid triptycene unit decrease proton migration resistance. In which, the TCSPI-5 (with 5 % molar triptycene unit) exhibit higher voltage efficiency as compared with the pristine membrane TCSPI-0. Combined with the excellent vanadium ions resistance, the TCSPI-5 reaches energy efficiency of 78 % at the current density of 140 mA cm⁻². In addition, TCSPI-5 also shows high oxidation resistance even under strong acid and pentavalent vanadium ions (V⁵⁺) conditions. The above results suggest the potential of TCSPI-X membranes in VRFB application.