Proton-Exchange Membranes with Stabilized Conductivity

Proton-exchange membranes are crucial for water electrolyzers and fuel cells, but their performance declines under low humidity due to dehydration. Existing reviews mainly list experimental results without analyzing the mechanisms of proton conductivity stabilization. This review systematically summarizes approaches to enhance moisture-independent proton conductivity and evaluates their prospects. Key factors governing conductivity include microstructure, sulfonic group concentration, and hydration level. Stability under dry conditions depends on water retention and thermal resistance. Main strategies involve hybrid composite membranes, ionomer structure control via pre-treatments, and novel proton-conducting polymers. Promising directions include oriented channel structures, MOFs, and graphene-based materials. The stabilization mechanism relies on retaining water through hydrophilic additives that form stable hydrates, enabling proton transport even under harsh conditions (up to 120 °C and 50% RH, per US DOE targets). Among Nafion alternatives, sulfonated aromatic polymers and phosphoric-acid-doped polybenzimidazole demonstrate good performance at elevated temperatures (100–200 °C), though durability remains a challenge for the latter. Despite ongoing research, Nafion-based composites still offer one of the best overall balances of conductivity, stability, and processability. A significant research gap persists: long-term membrane performance is poorly studied, and many additives degrade over time or block proton transport sites due to ion exchange with metal cations.