Double crosslinked polyetheretherketone-based polymer electrolyte membranes prepared by radiation and thermal crosslinking techniques

Novel one-step preparation of polymer electrolyte membranes without a membrane casting process is achieved by radiation crosslinking of a polyetheretherketone (PEEK) film to prevent dissolution and deformation of the original film in sulfonating solutions. The films crosslinked with doses more than 33 MGy can be effectively sulfonated in a chlorosulfonic solution, resulting in a crosslinked sulfonated PEEK (sPEEK) electrolyte membrane with high proton conductivity comparable to Nafion. Nevertheless, its water uptake was high for application in fuel cells. The thermal treatment was effective for further crosslinking of the membrane; as a result, the water uptake and methanol permeability of the double crosslinked sPEEK membranes drastically decreased, compensating for a slight decrease of proton conductivity. In addition, unlike the traditional cast sPEEK membrane showing the irreversible swelling in hot water, the double crosslinked sPEEK membranes exhibited excellent stability toward 100 °C hot water for more than 200 h without any decrease in proton conductivity, and had the mechanical and thermal properties superior to those of Nafion.