Coordination of lithium ion with ethylene carbonate electrolyte solvent: A computational study

The coordination and energetics of low‐lying structures of [Li(EC) n ] + have been analyzed by density functional theory (DFT) and polarizable continuum model (PCM) at the B3LYP/6‐311+G (d, p) level. The results show that the first shell around the lithium ion is fully occupied with four ethylene carbonate (EC) molecules in both gas phase and solvent. The examination on the contribution of vibration entropy to free energy of isomers of [Li(EC) n ] + reveals that the stability of the best candidates at zero‐temperature cannot be maintained at finite temperatures due to the effects of their vibration entropy. In addition, structural transitions between the most stable four‐coordinated and the metastable three‐coordinated structure demand a very low energy barrier, suggesting that at a finite temperature the four‐coordinated and three‐coordinated isomers of [Li(EC) n ] + can coexist in the EC organic solvent lithium salt electrolyte.