Water-in-Salt LiTFSI Aqueous Electrolytes. 1. Liquid Structure from Combined Molecular Dynamics Simulation and Experimental Studies

The concept of water-in-salt electrolytes was introduced recently, and these systems have been successfully applied to yield extended operation voltage and hence significantly improved energy density in aqueous Li-ion batteries. In the present work, results of X-ray scattering and Fourier-transform infrared spectra measurements over a wide range of temperatures and salt concentrations are reported for the LiTFSI (lithium bis­(trifluoro­methane sulfonyl)­imide)-based water-in-salt electrolyte. Classical molecular dynamics simulations are validated against the experiments and used to gain additional information about the electrolyte structure. Based on our analyses, a new model for the liquid structure is proposed. Specifically, we demonstrate that at the highest LiTFSI concentration of 20 m the water network is disrupted, and the majority of water molecules exist in the form of isolated monomers, clusters, or small aggregates with chain-like configurations. On the other hand, TFSI– anions are connected to each other and form a network. This description is fundamentally different from those proposed in earlier studies of this system.