Lithium ion Speciation in Cyclic Solvents: Impact of Anion Charge Delocalization and Solvent Polarizability

The increasing demand for lithium batteries has triggered the search for safer and more efficient electrolytes. Insights into the atomistic description of electrolytes are critical for relating microscopic and macroscopic (physicochemical) properties. Previous studies have shown that the type of lithium salt and solvent used in the electrolyte influences its performance by dictating the speciation of the ionic components in the system. Here, we investigate the molecular origins of ion association in lithium-based electrolytes as a function of anion charge delocalization and solvent chemical identity. To this end, a family of cyano-based lithium salts in organic solvents, having a cyclic structure and containing carbonyl groups, was investigated using a combination of linear infrared spectroscopy and ab initio computations. Our results show that the formation of contact-ion pairs (CIPs) is more favorable in organic solvents containing either ester or carbonate groups and in lithium salts with an anion having low charge delocalization than in an amide/urea solvent and an anion with large charge delocalization. Ab initio computations attribute the degree of CIP formation to the energetics of the process, which is largely influenced by the chemical nature of the lithium ion solvation shell. At the molecular level, atomic charge analysis reveals that CIP formation is directly related to the ability of the solvent molecule to rearrange its electronic density upon coordination to the lithium ion. Overall, these findings emphasize the importance of local interactions in determining the nature of ion-molecule interactions and provide a molecular framework for explaining lithium ion speciation in the design of new electrolytes.