Anhydrous protic conduction of mechanochemically synthesized CsHSO4–Azole-derived composites

Solid inorganic–organic composites were synthesized for the application as an electrolyte in fuel cells. CsHSO4 (CHS) was mechanochemically treated with Azole, which has a five-membered nitrogen heterocyclic ring such as imidazole (Iz), 1,2,4-triazole (Tz) and benzimidazole (Bz), in dry nitrogen atmosphere to obtain composites with xCHS·(100 − x)Azole (x = 90–50 mol%). Chemical interactions between CHS and Azoles after solid-state mechanochemical treatment were confirmed from structural observation. The proton conductivity of the composites was largely increased by introduction of Azoles, particularly in the lower temperature region than a superprotic phase-transition temperature of CHS and melting points of Azoles. Proton conductivities of 80CHS·20Iz and 80CHS·20Tz composites ranged from 7 × 10−4 to 2 × 10−3 S cm−1 over a wide temperature range (60–160 °C). However, CHS–Bz composites showed lower conductivities due to the lower reactivity of Bz. Proton transfer in CHS–Azole composite systems includes the proton-hopping mechanism and self-dissociation, which probably supports protic diffusion, especially in low temperature regions.

► Mechanochemical synthesis of CsHSO4–Azole (CHS–Azole) composites as an electrolyte. ► Anhydrous proton conductive electrolytes for the intermediate-temperature dry fuel cells. ► A development of acid–base complex cluster via hydrogen bond and NO bond between CHS and Azole.