Fig. 4: Solvation structures and localized environment near the positive electrode during discharge in the bare DMF electrolyte and 3G7F decoupled electrolyte.

Snapshots and typical Li⁺ clusters of the a bare DMF and c 3G7F electrolytes obtained from MD simulations. Distribution of possible solvation structures, structures of the most probable inner solvation shells of Li⁺ ions for the b bare DMF and d 3G7F electrolytes, obtained by MD simulations. The structures of the Li⁺ solvation cluster are provided in Supplementary Data 1. In the 3G7F electrolyte, Li⁺ clusters solvated with TEGDME demonstrate relatively more positive ESP maps. Interfacial cumulated density profiles of Li⁺, FSI⁻, and solvent molecules (DMF and TEGDME) and schematic snapshots (side view) of the localized environment near the positive electrode during discharge in the e bare DMF and f 3G7F electrolytes, respectively. Z: distance from the positive electrode surface. Density: the ratio of the number of molecules to that near neutrally charged positive electrodes (Supplementary Fig. 23). Color scheme of molecules: Li, green; C, light blue; O, red; S, yellow; N, navy; H, white; F, pink.