Formation of Polymer-like Nanochains with Short Lithium–Lithium Distances in a Water-in-Salt Electrolyte

Water-in-salts (WiSs) have recently emerged as promising electrolytes for energy storage applications ranging from aqueous batteries to supercapacitors. Here, ab initio molecular dynamics is used to study the structure of a 21 m LiTFSI WiS. The simulation reveals a new feature, in which the lithium ions form polymer-like nanochains that involve up to 10 ions. Despite the strong Coulombic interaction between them, the ions in the chains are found at a distance of 2.5 Å. They show a drastically different solvation shell compared to that of the isolated ions, in which they share on average two water molecules. The nanochains have a highly transient character due to the low free energy barrier for forming/breaking them. Providing new insights into the nanostructure of WiS electrolytes, our work calls for reevaluating our current knowledge of highly concentrated electrolytes and the impact of the modification of the solvation of active species on their electrochemical performances.