Heterogeneity and Nanostructure of Superconcentrated LiTFSI-EmimTFSI Hybrid Aqueous Electrolytes: Beyond the 21 m Limit of Water-in-Salt Electrolyte.

Ionic liquids such as EmimTFSI (1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide) have been found to improve the solubility of LiTFSI salt in water-in-salt electrolyte (WiSE) from 21 to 60 m. However, the molecular origin of such enhancement in the solubility is still unknown. In the present work, we elucidate the microscopic structures of LiTFSI-EmimTFSI-based hybrid aqueous electrolytes and compare them with the structure of LiTFSI-based WiSE using molecular dynamics simulations. Our analysis reveals the presence of alternating water-rich clusters and TFSI-rich extended domains in the WiSE. In these clusters and domains, the Li ions reside such that the total number of oxygen atoms around them is conserved to four, where water contributes about three oxygen atoms. The addition of EmimTFSI in the WiSE results in removal of water from the nearest-neighbor solvation shell of TFSI ions but not from the Li ions. Significant structural changes are observed when LiTFSI salt is further added to LiTFSI-EmimTFSI aqueous solution. In both the hybrid electrolytes, water and Emim cations are found to avoid each other. The simulated X-ray scattering structure factor reveals the presence of larger length-scale heterogeneity in the most concentrated solution of the hybrid aqueous electrolyte. We observe that this nanoscale heterogeneity originates from a water-TFSI-Emim-TFSI-water-TFSI-Emim-TFSI-like arrangement in which Li ions are dispersed such that the coordination number of oxygen atoms around them is enhanced to five, wherein the major contribution comes from the TFSI ions. We envision that the enhanced LiTFSI solubility originates from the replacement of water molecules with TFSI ions in the first solvation shell of Li ions.