Enhanced decoupling of conductivity relaxation from structural relaxation in non-stoichiometric protic ionic liquids involving triflic acid and 2-aminoethyl hydrogen sulfate

The glass transition dynamics and conductivity relaxation are studied for a series of non-stoichiometric protic ionic liquids (PILs) based on 2-aminoethyl hydrogen sulfate and triflic acid with varying molar ratios (denoted as AT-55, AT-46, AT-37, AT-28, and AT-19) by broadband dielectric spectroscopy in a wide frequency (10−1–107 Hz) and temperature range (173–353 K). The results indicate that the addition of acid lowers the glass transition temperature, as confirmed by the activation energy fine structure analysis and a crossover in the conductivity relaxation time. Notably, samples with higher acid content deliver markedly increased conductivity. In addition, detailed analysis of the permittivity and modulus spectra reveals enhanced decoupling between the structural (α-process) and conductivity relaxation in samples with a higher acid content. Remarkably, nano-phase separation in AT-28 and AT-19 samples is observed, resulting in a second glass transition temperature indicating a more mobile phase. Based on the above-mentioned findings, we infer that increased acid content disrupts strong ionic interactions within the IL fraction, resulting in a decrease in the glass transition temperature and leading to nano-phase separation into distinct acid-rich and IL-rich phases with varying Tg values. This phase separation alters the long-range ionic pathways, shifting from being solely governed by IL cluster dynamics to a scenario where charge transport becomes largely decoupled from the dynamics of IL-rich clusters. Hence, modulating the stoichiometry of PILs appears a promising approach to enhance the conductivity together with widening the usable temperature range for applications.