Coupled Transport, Plasticization, and Retention Mechanisms in Phosphoric Acid-Doped PBI Membranes

Phosphoric acid-doped polybenzimidazole membranes are a leading fluorine-free electrolyte platform for high-temperature proton exchange membrane fuel cells, enabling proton transport under anhydrous conditions. However, recent evidence shows that conductivity, mechanical stability, and acid retention are intrinsically coupled, preventing independent optimization of these properties. This review establishes a unified framework in which membrane performance is governed by a multidimensional design space defined by acid doping level, activation energy (Ea), hydrogen-bond network topology, and mechanical confinement. Conductivity is shown to scale with both carrier density and hopping energetics, while mechanical stability decays with increasing ADL due to acid-induced plasticization, described through a semi-empirical relationship. Analysis across molecular architectures, including molecular weight control, crosslinking, backbone modification, topological design, and free-volume engineering, demonstrates that performance emerges from a balance between transport efficiency and structural stability. Device-level benchmarking further reveals that similar conductivity values can correspond to orders-of-magnitude differences in voltage decay rate, confirming that durability is governed primarily by mechanical confinement and acid mobility rather than σ alone. A multivariate stability corridor is identified, within which phosphoric acid-doped polybenzimidazole membranes achieve σ ≈ 0.14–0.20 S·cm−1 while maintaining low degradation rates under realistic high temperature proton exchange membrane conditions. Based on this framework, quantitative design rules are derived linking acid doping level, activation, topology, and mechanical properties. This work shifts membrane design from conductivity-driven optimization toward predictive structure–property–durability engineering, providing a basis for the development of next-generation HT-PEM fuel cells with sustained long-term performance.