Cross-Linked Sulfonated Poly(arylene ether sulfone) Membranes Formed by <i>in Situ</i> Casting and Click Reaction for Applications in Fuel Cells

Sulfonated poly­(arylene ether sulfone) membranes with cross-linked structures (C-SPAES) were simply prepared by simultaneously casting and heating the polymer solutions composed of sulfonated poly­(arylene ether sulfone) with azidomethyl side groups (SPAES-N₃), cross-linkers such as 1,4-diethynylbenzene and 4,4′-diazido-2,2′-stilbenedisulfonic acid disodium salt tetrahydrate, and a click reaction catalyst such as CuBr and <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>″,<i>N</i>″-pentamethyldiethylenetriamine in <i>N</i>,<i>N</i>-dimethylacetamide, where SPAES-N₃ were prepared by the substitution of sulfonated PAES (SPAES) through chloromethylation followed by azidation reaction. C-SPAES membranes obtained using the optimum amount of the cross-linkers showed much improved chemical and physical stabilities and mechanical strength compared with linear SPAES membrane. Since the cross-linked structures were formed by the cross-linker having sulfonic acid groups, C-SPAES membranes showed higher ion exchange capacity and proton conductivity than the linear SPAES membrane. Although the C-SPAES membrane can absorb more water than the linear SPAES membrane, less volume expansion was observed due to their physically stable cross-linked structures

Cross-Linked Benzoxazine–Benzimidazole Copolymer Electrolyte Membranes for Fuel Cells at Elevated Temperature

Here we report new H₃PO₄-doped cross-linked benzoxazine–benzimidazole copolymer membranes showing high proton conductivity and long-term durability for use in proton-exchange membrane fuel cells at elevated temperatures (>100 °C). The cross-linked copolymer membranes were prepared by mixing of poly­[2,2′-(<i>m</i>-phenylene)-5,5′-bibenzimidazole] (PBI) with 3-phenyl-3,4-dihydro-6-<i>tert</i>-butyl-2<i>H</i>-1,3-benzoxazine (<i>p</i>BUa) in <i><i>N,N</i></i>-dimethylacetamide, with subsequent stepwise heating to 220 °C, and even large-sized films (30 cm × 140 m) could be easily prepared. The membranes showed high proton conductivities of up to 0.12 S cm^–1 at 150 °C under anhydrous conditions. Membrane–electrode assemblies (MEAs) employing the membranes showed operating voltages of 0.71 V at 0.2 A cm^–2. Furthermore, the MEAs displayed long-term durability up to 1999 cycles, with much slower performance decay, −0.03 mV h^–1, than those prepared using the PBI membrane in <i>in situ</i> accelerated lifetime mode (load cycling testing)