Are NaTFSI and NaFSI Salt-Based Water-in-Salt Electrolytes Structurally Similar or Different?

Water-in-salt electrolytes (WiSEs) are a promising class of electrolytes due to their wide electrochemical stability window and nonflammability. In this study, we explore the structural organization of sodium bis(trifluoromethylsulfonyl)imide (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI) salt-based aqueous electrolytes, covering dilute to highly concentrated regions, by employing an all-atom molecular dynamics simulation. For the NaTFSI-based electrolyte, we observe that Na⁺ ions are mostly surrounded by water molecules at all the salt concentrations due to the very strong interaction between them. While TFSI anions weakly coordinate with Na⁺ ions and other TFSI anions, they also mostly prefer to be surrounded by water molecules. These interactions were found to have moderate dependence on the concentration of the NaTFSI salt. For the NaFSI-based electrolyte, while the Na⁺-water interaction is stronger at lower salt concentrations, the number of nearest neighbor FSI anions is found to be more than that of water at higher concentrations (≥20 m). This is because the increase in the salt concentration leads to expulsion of water molecules from the solvation shell of Na⁺ ions and enhances the interaction between Na⁺ ions and oxygen atoms of FSI. At the highest salt concentration (solubility limit), the bulk-like water structure is completely disrupted and dominated by an anionic network in the FSI-based electrolyte. In contrast, water-water hydrogen bonding network is still present even in the highly concentrated TFSI-based electrolyte. The simulated X-ray scattering pattern displays a low-q peak, revealing the presence of an intermediate range ordering due to alternating anion-rich and water/Na⁺-rich regions in both the electrolytes. However, the characteristic length scale corresponding to the low-q peak decreases with increasing the salt content in both the electrolytes.