Enhanced Performance of a Sulfonated Poly(arylene ether ketone) Block Copolymer Bearing Pendant Sulfonic Acid Groups for Polymer Electrolyte Membrane Fuel Cells Operating at 80% Relative Humidity

The series of sulfonated poly(arylene ether ketone) (SPAEK) block copolymers with controlled F-oligomer length bearing pendant diphenyl unit were synthesized via a polycondensation reaction. Sulfonation was verified by ¹H NMR analysis to introduce sulfonic acid group selectively and intensively on the pendant diphenyl unit of polymer backbones. The SPAEK membranes fabricated by the solution casting approach were very transparent and flexible with the thickness of ∼50 μm. These membranes with different F-oligomer lengths were investigated to the physiochemical properties such as water absorption, dimensional stability, ion exchange capacity, and proton conductivity. As a result, the SPAEK membranes (X4.8Y8.8, X7.5Y8.8, and X9.1Y8.8) in accordance to increasing the length of hydrophilic oligomer showed excellent proton conductivity in range of 131-154 mS cm^-1 compared to Nafion-115 (131 mS cm^-1) at 90 °C under 100% relative humidity (RH). Among the SPAEK membranes, proton conductivity of SPAEK X9.1Y8.8 (140.7 mS cm^-1) is higher than that of Nafion-115 (102 mS cm^-1) at 90 °C under 80% RH. The atomic force microscopy image demonstrated that number of ion transport channels is increased with increase in the length of hydrophilic oligomer in the main chains, and the morphology is proved to be related to the proton conductivity. The synthesized SPAEK membrane exhibited a maximum power density of 324 mW cm^-2, which is higher than that of Nafion-115 (291 mW cm^-2) at 60 °C under 100% RH.