Isotropic Anhydrous Superprotonic Conductivity Cooperated with Installed Imidazolium Molecular Motions in a 3D Hydrogen-Bonded Phosphate Network

Utilizing molecular motion is essential for the use of anhydrous superprotonic molecular proton conductors (sigma beyond 10(-4) S cm(-1)) as electrolytes in hydrogen fuel cells. However, molecular motion contributing to the improvement of intrinsic proton conduction has been limited and little clarified in relation to the proton conduction mechanism, limiting the development of material design guidelines. Here, a salt with a three-dimensional (3D) hydrogen-bonded (H-bonded) phosphate network with imidazolium cations installed inside was studied, whose components are known to exhibit molecular motions that contribute to proton conduction. Despite its anisotropic H-bonded network, the salt exhibits isotropic anhydrous superprotonic conductivity exceeding 10(-3) S cm(-1) at approximate to 351 K, which is the first example for organic molecular crystal. Variable-temperature X-ray structural analysis and solid-state H-2 NMR measurements revealed significant 3D molecular motion of imidazolium cations, which accelerate proton conduction via the 3D H-bonded phosphate network.

Automated summary

A salt with a three-dimensional hydrogen-bonded phosphate network and imidazolium cations was found to exhibit isotropic anhydrous superprotonic conductivity exceeding 10(-3) S cm(-1), which is achieved through the accelerated molecular motion along the proton conduction pathway.