How to Harvest Grotthuss Diffusion in Protic Ionic Liquid Electrolyte Systems.

Hydrogen is often regarded as fuel of the future, and there is an increasing demand for the development of anhydrous proton-conducting electrolytes to enable fuel-cell operation at elevated temperatures exceeding 120 °C. Much attention has been directed at protic ionic liquids as promising candidates, but in the search for highly conductive systems the possibility of designing Grotthuss diffusion-enabled protic ionic liquids has been widely overlooked. Herein, the mechanics of proton-transfer mechanism in the equimolar mixture of N-methylimidazole and acetic acid was explored using ab initio molecular dynamics simulations. The ionicity of the system is approximated with good agreement to experiments. This system consists mostly of neutral species but exhibits a high ionic conductivity through Grotthuss-like proton conduction. Chains of acetic-acid molecules and other species participating in the proton-transfer mechanisms resembling Grotthuss diffusion could be directly observed. Furthermore, based on these findings, a series of static quantum chemical calculations was conducted to investigate the effect of substituting the anion and cation with different functional groups. We predict whether a given combination of cation and anion will be a true ionic liquid or a molecular mixture and propose some systems as candidates for Grotthuss diffusion-enabled protic ionic liquids.