Perfluorocyclobutyl-containing multiblock copolymers to induce enhanced hydrophilic/hydrophobic phase separation and high proton conductivity at low humidity

A multiblock copolymer containing a highly sulfonated poly(phenylene sulfide sulfone) (sPPSS) hydrophilic oligomer and a partially fluorinated perfluorocyclobutyl (PFCB)-containing hydrophobic oligomer was synthesized. The sharp contrast between the hydrophilic and hydrophobic moieties induced a well-developed phase separation, which was observed in the transmission electron microscopy (TEM) images within the polymer electrolyte membrane (PEM). The increased chain mobility from the flexible ether and PFCB groups afforded facile thermal annealing of the membrane. Thermal annealing induced polymer chain packing of the hydrophobic moieties, enhancing the hydrophilic/hydrophobic phase separation. The fabricated membranes exhibited higher proton conductivity compared with those of conventional hydrocarbon PEM possessing a random copolymer architecture, while their dimensional swelling was suppressed. Additionally, under low humidification (a relative humidity (RH) of 50%), the sulfonated–fluorinated membrane achieved a high proton conductivity of up to 41.9 mScm−1. A high adhesion strength of 32.7 mNcm−1 was also observed, indicating strong interfacial compatibility in the membrane electrode assembly (MEA) due to its structural affinity for the contacting perfluorosulfonated binder. The enhanced hydrophilic/hydrophobic phase separations facilitated fuel cell performances of 1.13 and 0.61 Acm−2 at 0.6 V and 65 °C under 100% and 50% RH conditions, respectively, in addition to achieving stable chemical and physical durabilities.