Solid-Like Nano-Anion Cluster Constructs a Free Lithium-Ion-Conducting Superfluid Framework in a Water-in-Salt Electrolyte

The ion transportation mechanism in a high-concentration solution remains unclear due to the complexity of the strong ion–ion/ion–solvent interaction, resulting in the invalidation of most ionic conducting theories based on diluted solutions. Here, a superconcentrated electrolyte (water-in-salt) is investigated by multiple experimental techniques, including advanced tools (NMR, synchrotron X-ray diffraction, and spallation neutron scattering), combined with molecular dynamics (MD) simulation to draw out its unique microstructure and uncover its intrinsic relationship with the ionic transportation. Based on the results, we firstly proposed the ionic transport model for the water-in-salt electrolyte, where the solid-like nano-anion clusters construct a superfluid framework and the lithium ion is able to move freely like in an ionic atmosphere. Our model gives a unified explanation to the unique phenomena previously discovered in water-in-salt electrolytes, including the decoupling of conductivity–viscosity and the nanophase separation between the anion and water. Our findings on the microstructure of the super-high-concentrated electrolyte and the involved unique Li-conducting mechanism can fill in the gap between a solid-state conductor and a dilute liquid electrolytic solution.