Tale of a “Non-interacting” Additive in a Lithium-Ion Electrolyte: Effect on Ionic Speciation and Electrochemical Properties

/DMC electrolyte, the addition of a co-solvent (PFB) with a larger dielectric constant results in the strengthening of the lithium-anion interaction and the formation of aggregate species since PFB does not interact with the anion. Conversely, in the LiTFSI/DMC electrolyte, the co-solvent appears to interact with the anion via hydrogen bonds, which leads to the dissociation of contact ion pairs. The change in ionic speciation of the electrolytes upon addition of PFB provides a reasonable framework to explain the different trends in both the bulk and interfacial macroscopic properties, such as conductivity, viscosity, and electrochemical stability. Overall, our findings demonstrate that the interactions between the anion and the co-solvent must be taken into consideration when adding a co-solvent because they play a major role in determining the final electrolyte properties.