Ultrafast Proton Conduction in an Aqueous Electrolyte Confined in Adamantane-like Micropores of a Sulfonated,...

Sulfonated, cross-linked porous polymers are promising frameworks for aqueous high-performance electrolyte-host systems for electrochemical energy storage and conversion. The systems offer high proton conductivities, excellent chemical and mechanical stabilities, and straightforward water management. However, little is known about mass transport mechanisms in such nanostructured hosts. We report on the synthesis and postsynthetic sulfonation of an aromatic framework (SPAF-2) with a 3D-interconnected nanoporosity and varying sulfonation degrees. Water adsorption produces the system SPAF-2^H. It features proton exchange capacities up to 6 mequiv g^-1 and exceptional proton conductivities of about 1 S cm^-1. Two contributions are essential for the highly efficient transport. First, the nanometer-sized pores link the charge transport to the diffusion of adsorbed water molecules, which is almost as fast as bulk water. Second, continuous exchange between interface-bound and mobile species enhances the conductivities at elevated temperatures. SPAF-2^H showcases how to tailor nanostructured electrolyte-host systems with liquid-like conductivities.