Self-Assembled Construction of Ion-Selective Nanobarriers in Electrolyte Membranes for Redox Flow Batteries

Ion-conducting membranes (ICMs) with high selectivity are important components in redox flow batteries. However it is still a challenge to break the trade-off between ion conductivity and ion selectivity, which can be resolved by the regulation of their nanostructures. Here, polyoxometalate (POM)-hybridized block copolymers (BCPs) are used as self-assembled additives to construct proton-selective nanobarriers in the ICM matrix to improve the microscopic structures and macroscopic properties of ICMs. Benefiting from the co-assembly behavior of BCPs and POMs and their cooperative noncovalent interactions with the polymer matrix, ∼50 nm ellipsoidal functional nanoassemblies with hydrophobic vanadium-shielding cores and hydrophilic proton-conducting shells are constructed in the sulfonated poly(ether ether ketone) matrix, which leads to an overall enhancement of proton conductivity, proton selectivity, and cell performance. These results present a self-assembly route to construct functional nanostructures for the modification of polymer electrolyte membranes toward emerging energy technologies.