Dumbbell‐Shaped, Block‐Graft Copolymer with Aligned Domains for High‐performance Hydrocarbon Polymer Electrolyte Membranes

Abstract

Given the environmental concerns surrounding fluoromaterials, the use of high‐cost perfluorinated sulfonic acids (PFSAs) in fuel cells and water electrolysis contradicts the pursuit of clean energy systems. Herein, we present a fluorine‐free dumbbell‐shaped block‐graft copolymer, derived from the cost‐effective triblock copolymer poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), for polymer electrolyte membranes (PEMs). This unique polymer shape led to the alignment of the hydrophobic‐hydrophilic domains along a preferred orientation, resulting in the construction of interconnected proton channels across the membrane. A bicontinuous network allowed efficient proton transport with reduced tortuosity, leading to an exceptional ionic conductivity (249 mS cm‐1 at 80 °C and 90% relative humidity (RH)), despite a low ion exchange capacity (IEC; 1.41). Furthermore, membrane‐electrode assembly (MEA) prepared with our membrane exhibited stable performance over a period of 150 h at 80 °C and 30% RH. This study demonstrates a novel polymer structure design and highlights a promising outlook for hydrocarbon PEMs as alternatives to PFSAs.