MeTFSI (Me = Li, Na) Solvation in Ethylene Carbonate and Fluorinated Ethylene Carbonate: A Molecular Dynamics Study

Classical and ab initio molecular dynamics (MD) simulations have been performed for electrolytes based on LiTFSI and NaTFSI solutions in ethylene carbonate and its mono- and difluoro derivatives. Differences between electrolytes with Li⁺ or Na⁺ ions and the effect of fluorination on the structure and transport properties have been analyzed. The observed differences are related to the strength of Me⁺-carbonate binding, which is weaker for the Na⁺ cation and/or fluorinated solvents. Infrared spectra have been computed from ab initio MD and density functional tight binding (DFTB) MD trajectories. The changes of vibrational frequencies have been related to the local structure of the electrolyte and to interactions between salt cations and solvent molecules. The frequency shifts obtained from the AIMD simulations agree with experimental data, whereas DFTB underestimates Na⁺-carbonate interactions.