Anion Exchange Membranes for Fuel Cells Based on Quaternized Polystyrene--poly(ethylene--butylene)--polystyrene Triblock Copolymers with Spacer-Sidechain Design.

This work studied the polystyrene--poly(ethylene--butylene)--polystyrene (SEBS) triblock copolymers functionalized by butyl quaternary ammonium (CQ) groups and alkyl side chains of different chain lengths (C, n = 0 to 24). The hydrated membrane morphology was modeled by dissipative particle dynamics simulation at hydration levels from 10 to 30. A hydroxide model was devised to characterize the diffusivity of anions under the coarse-grained framework. In general, the ionomers with alkyl side chains provided ion conductivity of a similar level at a lower ion exchange capacity. All hydrated SEBS-CQ-C ionomers showed clear phase separation of the hydrophobic and hydrophilic domains, featuring 18.6 mS/cm to 36.8 mS/cm ion conductivity. The hydrophilic channels expanded as the water content increased, forming more effective ion conductive pathways. Introducing excess alkyl side chains enhanced the nano-segregation, leading to more ordered structures and longer correlation lengths of the aqueous phase. The membrane morphology was controlled by the length of alkyl side-chains as well as their tethering positions. Ionomers with functionalized side chains tethered on the same block resulted in well-connective water networks and higher conductivities. The detailed structural analysis provides synthesis guidelines to fabricate anion exchange membranes with improved performances.