Ab initio molecular dynamics study of proton transport in imidazolium-based ionic liquids with added imidazole

Development of efficient anhydrous proton-conducting materials would expand the operational temperature ranges of hydrogen fuels cells (HFCs) and eliminate their dependence on maintaining sufficient hydration levels to function efficiently. Protic ionic liquids (PILs), which have high ionic densities and low vapor pressures, have emerged as a potential material for proton conducting layers in HFCs. In this work, we investigate proton transport via the Grotthuss mechanism in 1-ethylimidazolium bis-(trifluoromethanesulfonyl)imide ([C₂HIm][TFSI]) protic ionic liquids with added imidazole (Im⁰) using ab initio molecular dynamics. In particular, we vary the composition of the systems studied from pure [C₂HIm][TFSI] to those where the mole fraction of Im⁰ is 0.67. Given the large difference in pK_a between C₂HIm⁺ and HTFSI, TFSI^- does not accept acidic protons from C₂HIm⁺; conversely, imidazolium (HIm⁺) and C₂HIm⁺ have very similar pK_a values, and thus Im⁰ can readily accept protons. We find that the unprotonated nitrogen on Im⁰ dominates solvation of the labile protons on C₂HIm⁺ and other Im⁰ species, resulting in formation of robust imidazole wires. Given the amphoteric nature of Im⁰, i.e. its ability to accept and donate protons, these wires provide conduits along which protons can rapidly traverse via the Grotthuss mechanism, thereby greatly increasing the proton coefficient of self-diffusion. We find that the average length of the wires increases with added Im⁰, and thus as the mole fraction of Im⁰ increases so too does the proton diffusion constant. Lastly, we analyze our trajectories to determine the energy and time scales associated with proton transfer.