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Physically reinforced short-side-chain perfluorinated sulfonic acid electrolyte membranes were fabricated by annealing and using a porous support. Five types of solution-cast membranes were produced from commercial perfluorinated ionomers (3M and Aquivion (AQ)) with different equivalent weights, annealed at different temperatures, and characterized in terms of ion conductivity, water uptake, and in-plane/through-plane swelling, while the effect of annealing on physical structure of membranes was evaluated by small-angle X-ray scattering and dynamic mechanical analysis. To create a reinforced composite membrane (RCM), we impregnated a polytetrafluoroethylene porous support with 3M 729 and AQ 720 electrolytes exhibiting excellent proton conductivity and water uptake. The electrolyte impregnation stability for the porous support was evaluated using a solvent resistance test, and the best performance was observed for the 3M 729 RCM annealed at 200 °C. Both annealed and nonannealed 3M 729 RCMs were used to produce membrane electrode assemblies, the durability of which was evaluated by open-circuit voltage combined wet-dry cycling tests. The nonannealed 3M 729 RCM survived 5800 cycles, while the 3M 729 RCM annealed at 200 °C survived 16 600 cycles and thus exhibited improved mechanical durability.

Improving the Mechanical Durability of Short-Side-Chain Perfluorinated Polymer Electrolyte Membranes by Annealing and Physical Reinforcement