Dithiol cross-linked polynorbornene-based anion-exchange membranes with high hydroxide conductivity and alkaline stability

Vinylic-addition polynorbornenes possess high thermal stability, excellent mechanical integrity, and chemically inert backbones. Herein, we conveniently synthesize a series of vinylic-addition polynorbornene copolymers containing pendant alkenes from commercial vinyl-substituted norbornene (VNB) and alkyl-bromide-substituted norbornene (BrNB). Subsequently, the copolymers are photo-crosslinked with dithiol reagents through UV-initiated thiol-ene click reactions followed by quaternization to prepare the cross-linked anion-exchange membranes (AEMs). The extent of cross-linking and the hydrophobicity of the cross-linkers can be easily controlled, so that the absorption of excess water can be inhibited with enhanced membrane strength. The resultant AEMs have ultrahigh hydroxide conductivities (up to 199 mS/cm at 90 °C under humidified conditions) and excellent alkaline stability in 1 M KOH at 80 °C for 1200 h. The vinylic-addition AEMs are also successfully applied in alkaline anion-exchange membrane water electrolyzers with commercial noble-metal-free electrocatalysts.