Construction of High-Performance, High-Temperature Proton Exchange Membranes through Incorporating SiO₂ Nanoparticles into Novel Cross-linked Polybenzimidazole Networks

The practical applications of phosphoric acid-doped polybenzimidazole (PA-PBI) as high-temperature proton exchange membranes (HT-PEMs) are mainly limited by their poor dimensional-mechanical stability at high acid doping levels (ADLs) and the leaching of PA from membranes during fuel cell operation. In this work, to overcome these issues, we fabricated novel cross-linked PBI networks with additional imidazole groups by employing a newly synthesized bibenzimidazole-containing dichloro compound as cross-linker and an arylether-type Ph-PBI as matrix. Ph-PBI featured by good solubility under high molecular weight offers satisfactory film-forming ability and mechanical strength using for the matrix. Importantly, the additional imidazole moieties in BIM-2Cl endow the cross-linked PBI membranes improved dimensional-mechanical stability with simultaneously enhanced ADLs and proton conductivity. Furthermore, superior acid retention capability is obtained by incorporating porous polyhydroxy SiO₂ nanoparticles into these cross-linked networks. As a result, the SiO₂/cross-linked PBI composite membranes are suitable to manufacture membrane electrode assemblies (MEAs), and an excellent H₂/O₂ cell performance with a peak power density of 497 mW cm^-2 at 160 °C under anhydrous conditions can be achieved.