Ultraslow Relaxation in Aprotic Double Salt Ionic Liquids

A mixture of two pure ionic liquids (ILs) or double salt ILs (DSILs) can push the limits of ILs in terms of unraveling their unique physicochemical properties and potential in clean technology. While the correlated ion dynamics and heterogeneity in the bulk of pure ILs have been reported, such a phenomenon at longer timescales in DSILs has never been elucidated. Here, a combination of temperature-dependent polarized dynamic light scattering and rheological measurements has been employed to reveal the presence of structural and ultraslow relaxation in three DSILs, each containing a 1-ethyl-3-methylimidazolium cation and two different anions. The slow relaxation caused by Brownian diffusion of cluster-like arrangements occurs at a timescale of a few to several hundred milliseconds; both the relaxation processes, nevertheless, are Arrhenius in nature. Notably, slow relaxation in the DSILs is much different compared to that in the pure ILs. The decay of intensity correlation functions (ICFs) and average hydrodynamic correlation length of the clusters and their response to temperature markedly vary with the nature of the two anions present in the DSILs. Stretched exponential analyses of the ICFs disclose the cluster-to-cluster transfer of ionic species as well as percolation dynamics among clusters. The identity of anions also governs whether the DSILs follow or violate the Stokes-Einstein relationship or not.