Why Lithium Ions Stick to Some Anions and Not Others.

Designing battery electrolytes for lithium-ion batteries has been a topic of extensive research for decades. The ideal electrolyte must have a large conductivity as well as high Li+ transference number. The conductivity is very sensitive to the nature of the anions and dynamical correlations between ions. For example, lithium bis(trifluoromethane)sulfonimide (LiTFSI) has a large conductivity, but the chemically similar lithium trifluoromethanesulfonate (LiOTf) shows poor conductivity. In this work, we study the binding of Li+ to these anions in an ethylene carbonate (EC) solvent using enhanced sampling metadynamics. The evaluated free energies display a large dissociation barrier for LiOTf compared to LiTFSI, suggesting long-lived ion-pair formation in the former but not the latter. We probe these observations via unbiased molecular dynamics simulations and metadynamics simulations of TFSI with a hypothetical OTF-like partial charge model indicating an electrostatic origin for those differences. Our results highlight the deleterious impact of sulfonate groups in lithium-ion battery electrolytes and provide a new basis for the assessment of electrolyte designs.