Proton transfer efficiency enhanced over wide relative humidity: Etidronic acid-modified polyphosphazenes cross-linked polybenzimidazoles membranes

To enhance the proton conductivity and oxidative stability of the proton exchange membrane, an effective strategy to construct robust high-temperature PEMs (HT-PEMs) is proposed. The polyoxy(etidronic acid)phazenes cross-linked m-polybenzimidazole membranes (POHP-mPBI) are prepared by solution casting, thermal-crosslinking and acidification. Polyoxy(etidronic acid sodium)phazenes (Na–POHP) is cross-linkable proton conductors by partially phosphonic acid functionalized polyphosphazenes, which ensures proton transport while retaining the cross-linked groups. After covalent cross-linking between Na–POHP and mPBI, the cross-linked macromolecular structure stably locks the proton conductor in the polymer matrix , which ensures the construction of the proton transfer pathway at wide relative humidity (RH). The molecular dynamics simulation was conducted to verify the hydrogen bonds network with the POHP-mPBI membrane. The POHP-mPBI cross-linked membranes exhibit good oxidative stability, mechanical strength , proton conductivity and low fuel transmembrane permeability. At 180 °C and different RH (100% RH, 50% RH, 30% RH and 0 RH), the proton conductivity of POHP(50)-mPBI membrane is 0.150, 0.076, 0.055 and 0.048 S cm −1 , respectively. After the water washing for 96 h, the durability of proton conductivity and weight loss shows a rare decline. The incorporation of proton conductors (POHP) into the PBI matrix by cross-linking is a perspective method to enhance the comprehensive performance of HT-PEM.