Vehicular Motions Dominate the Ion Transport in Concentrated LiTFSI Aqueous Solutions?

Water-in-salt electrolytes (WiSEs) show great promise for applications in grid-scale energy storage. The design of high-performance WiSEs requires a comprehensive understanding of their microstructures and ion transport properties. In the present work, based on the CL&Pol force field, we have developed a polarizable force field (PFF) tailored for high-concentration LiTFSI aqueous solutions, which accurately reproduces the structural and dynamical properties. Unlike the literature, we do not observe the presence of bulk-like water in LiTFSI solutions exceeding 19 mol/kg. Furthermore, we find that the vast majority of Li(H20)n+ are short-lived, and thus, the structural motion rather than the vehicular motion is the main mode of ion transport. Our results have significant implications for understanding the ion dynamics in WiSEs. Additionally, further in-depth experimental analyses are imperative.