The preferential solvation of sovents/ions around Li + ion in multicomponet mixtures is quite a complicated issue . In mixed carbonate systems such as EC/DMC, it was found that both EC and DMC participate in solvating Li + ion . There have been relatively fewer experimental attempts to determine the coordination number around the Li + ion. One such attempt was by Cazzanelli et al., who reported a CN of ∼2 in a mixture of EC and propylene carbonate (PC) at different concentrations . According to NMR experiments, EC preferentially solvates Li + ion over DMC in mixed EC/DMC systems, and that the carbonyl oxygen atoms were involved in solvation .Similarily, previous reported results using electrospray ionization and mass spectrometry (ESI-MS) techniques show that there is a stronger preference of Li + ion to bind with EC than with DMC in binary EC/DMC solvents. This preference has been attributed to the stronger ion dipole interactions between Li + ion and EC molecules. To date, theoretical works using classical force fields have also been performed to understand Li + ion transport and solvation in various carbonate electrolytes . These theoretical works indicated a coordination number of 4, where the Li + ion interacts with carbonyl oxygen atoms of the carbonate . Borodin and Smith performed MD simulation of a solution of LiPF 6 in an equimolar EC/DMC binary mixture using a polarizable potential model, and have shown that there was a slight preference for Li + ion to bind with DMC than EC molecules. In their study, the CN of DMC in the first solvation shell of Li + ion was found to be higher than the CN of EC. An opposite scenario for the results was reported by Tenney and Cygan , where the presence of EC was favoured in the first solvation shell of Li + ion in a low concentration LiPF 6 solution. Nevertheless, there has been a significant difference in the potential models employed in these two MD simulation studies. The potential model used by Borodin and Smith predicted a tetracoordinated Li + ion complexes inside its first solvation shell, whereas in the case of the simulation results reported by Tenney and Cygan the solvation shell of Li + ion involved five or six solvent molecules..Takeuchi et al. have come to similar conclusions about the Li + ion binding patterns to a [PF 6 ] -anion. Quantum chemical calculations based on DFT have predicted a preferential binding of Li + ion with EC rather than with DMC. However, MD simulations have predicted the existence of significant structural heterogeneities, extending up to a length scale which is several orders of magnitude larger than the size of the first shell radius. The structure around Li + ions in the mixed solvents was described in terms of a shortrange structure (up to 4-5 Å from Li + ), where the composition is rich in DMC, and by a longerrange structure where in the case of the binary solvent mixture, the composition was richer in EC . From an energetic point of view, the preference of Li + ion to bind with the highly polar EC molecules is favoured. From an entropic point of view, however, the addition of DMC molecules contributes to the decrease of the free energy of the clusters.