Covalent triazine frameworks crosslinked microporous polymer membranes with fast and selective ion transport for ultra-stable vanadium redox flow batteries

Abstract

The vanadium redox flow batteries (VRFBs) are an essential pathway to long-duration energy storage with the merits of power and energy decoupling, long lifetime and safety. However, low coulombic efficiency stemming from vanadium crossover across the membrane together with notable ohmic loss originated from low proton conductivity of the membrane still limits high performance operation of the VRFBs. Herein, we proposed 2,2′-bipyridine-based covalent triazine frameworks (bipCTF) crosslinked sulfonated-poly (4,4′-diphenylether-5,5′-bibenzimidazole) (SOPBI) (bipCTF/SP-100) for use as the membrane in VRFBs, which synergistically prevents vanadium crossover and enhances proton conductivity. By delicately tuning the sulfonation degree and properly incorporate bipCTF, the bipCTF/SP-100 membrane is successfully synthesized based on OPBI polymers, which delivers a reduced area resistance of 0.3 Ω cm2 and a low VO2+ permeability of 19.05 × 10−9 cm2 s−1, affording an excellent trade-off between proton conductivity and ion selectivity. Theoretical calculation further corroborates that the high proton conductivity of bipCTF/SP-100 is attributed to the ionic channels formed by bipCTF, while the superior ion selectivity is assigned to protonated imidazole and pyridine. Benefiting from microporous bipCTF/SP-100 membrane, the VRFB exhibits a high CE of 99.8 % and an excellent EE of 78.3 % at 250 mA cm−2 and meanwhile yields a high capacity retention of 94.8 % after 200 cycles at 200 mA cm−2, which shows enormous potential for high power density operation of the VRFBs.