Design Strategies and Challenges of Proton-Exchange Membranes for Medium- and High-Temperature Fuel Cell Applications

Perfluorosulfonic acid (PFSA) membranes, exemplified by Nafion, suffer dehydration-induced degradation at elevated temperatures, although modifications enhance their conductivity and performance. Sulfonated aromatic polymers (SAPs) exhibit weaker phase separation, yielding narrow, tortuous ion channels and lower conductivity than their PFSA membrane counterparts at equivalent ion exchange capacity; however, excessive sulfonation causes swelling and mechanical instability, offset by cost advantages. Phosphoric acid-doped polybenzimidazole (PBI) offers superior thermal stability and high conductivity, with recent advances in polybenzimidazole derivatives and composites driving medium-to-high temperature proton-exchange membrane fuel cell innovation. This review summarizes progress in three major medium-to-high temperature proton-exchange membrane fuel cell categories—perfluorosulfonic acid, sulfonated polymers, and PBI-based membranes—while addressing challenges and future goals for enhanced performance.