Cross-linked polybenzimidazole with enhanced stability for high temperature proton exchange membrane fuel cells

Cross-linked polybenzimidazole membranes were obtained by heating at 160 °C, using 4,4′-diglycidyl(3,3′,5,5′-tetramethylbiphenyl) epoxy resin (TMBP) as the cross-linker. The cross-linking reaction temperature was determined by DSC and the successful completion of the cross-linking reaction was shown by FTIR and solubility tests. The cross-linked membranes showed high proton conductivity and strong mechanical properties, as well as low swelling after immersion in 85% phosphoric acid at 90 °C. For instance, the membrane with a cross-linker content weight percent of 20% (PBI-TMBP 20%) with a PA doping level of 4.1 exhibited a proton conductivity of 0.010 S cm ^-1 and a low swelling volume of 50%. Moreover, the cross-linked membranes showed excellent oxidative stability. The PBI-TMBP 20% cross-linked membrane tested in Fenton's reagent (3% H₂O₂ solution, 4 ppm Fe²⁺, 70 °C) kept its shape for more than 480 h and did not break. In particular, the proton conductivity of the PA-PBI-TMBP 20% membrane after Fenton's test (30% H₂O₂, 20 ppm Fe²⁺, 85 °C) remained at a high level of 0.009 S cm^-1. This investigation proved that cross-linking is a very effective approach for improving the performance of proton exchange membranes.