Highly acidic protic ionic liquids (PILs) are promising materials for potential electrochemical applications due to their high proton conductivity and excellent thermal stability. Still, little is known about the correlation between charge transport and structural dynamics as well as the proton transport mechanism despite the large body of literature on this topic. Here, we have examined the charge transport and structural dynamics by employing broadband dielectric spectroscopy in two highly acidic PILs in their supercooled liquid and glassy states, which included the same anion [TfO]- and different cations, [Tau]+ vs [Ahs]+. Unlike many other ionic liquids, the conductivity relaxation time τe of two studied PILs is substantially faster than the structural relaxation time τα. The decoupling behavior between charge transport and structural dynamics of two materials, which is manifested by a decoupling index Rτ, varies between 0.3 and 2.3 over the temperature range above Tg. Moreover, "Walden" plots of the molar conductivity vs the viscosity qualify both compounds as "Super ILs." All findings support the physical picture of large, polar, and orientationally correlated ion clusters, where the slow α-relaxation can be identified as structural relaxation associated with cooperative reorientations of the cluster macrodipole. In contrast, the shortest timescale for diffusive charge transport, τe, is 1-2 decades shorter than τα, implying that proton hopping is triggered by "single particle" (ions or ion pair) rotations and jumps on a sub-length scale of the cluster size, a dynamics being present even in the glassy state as indicated by a strong β-relaxation. These results demonstrate the practicality of employing highly acidic PILs in electrochemical fields.
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