Zwitterionic channels within covalent organic frameworks facilitate proton-selective transport for flow battery membrane

Abstract

Flow batteries demand for ion conductive membranes (ICMs) with high ion selectivity to achieve efficient energy conversion. Herein, we engineered a cysteine-modified covalent organic framework (Cys-COF) by a Thiol-ene click reaction. As a promising proton carrier, the incorporation of the Cys-COF with sulfonated poly(ether ketone) (SPEEK) yields advanced ICMs for vanadium flow batteries (VFBs). The zwitterionic cysteine groups anchored on the nanochannel walls simultaneously narrowed the pore size and ameliorated the protophilicity of Cys-COF, resulting in improved vanadium permeating resistance and proton conductivity. As a result, the optimal membrane demonstrated synchronized improvements in coulombic efficiency (95.01 %-98.84 %), voltage efficiency (95.15 %–77.84 %) and energy efficiency (90.41 %–76.94 %) with the current densities ranging from 40 to 200 mA cm−2. Regarding stability test, it achieved exceptional energy efficiency (∼84.3 %) over 1100 cycles and 550 h at the constant current density of 120 mA cm−2, outperforming pure polymer membrane and Nafion 212.