Nanoheterogeneity of LiTFSI Solutions Transitions Close to a Surface and with Concentration

Water-in-salt (WIS) electrolytes composed of 21 m LiTFSI have recently emerged as a safe and environmentally friendly alternative to conventional organic electrolytes in Li-ion batteries. Several studies have emphasized the relation between the high conductivity of WIS electrolytes and their nanoscale structure. Combining force measurements with a surface forces apparatus and atomic force microscopy, this study describes the nanoheterogeneity of LiTFSI solutions as a function of concentration and distance from a negatively charged (mica) surface. We report various nanostructures coexisting in the WIS electrolyte, whose size increases with concentration and is influenced by the proximity of the mica surface. Two key concentration thresholds are identified, beyond which a transition of behavior is observed. The careful scrutinization on the concentration-dependent nanostructures lays groundwork for designing novel electrolytes in future energy storage devices.