From Networked to Isolated: Observing Water Hydrogen Bonds in Concentrated Electrolytes with Two-Dimensional Infrared Spectroscopy.

Superconcentrated electrolytes have emerged as a promising class of materials for energy storage devices, with evidence that high voltage performance is possible even with water as the solvent. Here, we study the changes in the water hydrogen bonding network induced by the dissolution of lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in concentrations ranging from the dilute to the superconcentrated regimes. Using time-resolved two-dimensional infrared spectroscopy, we observe the progressive disruption of the water-water hydrogen bond network and the appearance of isolated water molecules interacting only with ions, which can be identified and spectroscopically isolated through the intermolecular cross-peaks between the water and the TFSI ions. Analyzing the vibrational relaxation of excitations of the HO stretching mode, we observe a transition in the dominant relaxation path as the bulk-like water vanishes and is replaced by ion-solvation water with the rapid single-step relaxation of delocalized stretching vibrations into the low frequency modes being replaced by multistep relaxation through the intramolecular HO bend and into the TFSI high frequency modes prior to relaxing to the low frequency structural degrees of freedom. These results definitively demonstrate the absence of vibrationally bulk-like water in the presence of high concentrations of LiTFSI and especially in the superconcentrated regime, while additionally revealing aspects of the water hydrogen bond network that have been difficult to discern from the vibrational spectroscopy of the neat liquid.