Quantum chemical calculations have been employed to investigate the solvation of Lithium cations in ethylene carbonate / propylene carbonate and propylene carbonate / dimethyl carbonate mixed electrolytes. The impact of the presence of the counter anion on the solvation of Li + in pure propylene carbonate and dimethyl carbonate was also studied. The calculations revealed small free energy changes for the transitions between different preferred structures in mixed solvents. This implies that transitions between distinct local arrangements can take place in the mixtures. The addition of dimethyl carbonate causes a significant increase of the dipole moment of solvation clusters, indicating important molecular-scale modifications when dimethyl carbonate is used as co-solvent. The presence of an anion in the solvation shell of Li$^+$ modifies the intermolecular structure comprising four carbonate molecules in dilute solutions, allowing only two carbonate molecules to coordinate to Li$^+$. The bidentate complexation of Li$^+$ with the anion's electron donor atoms, however, maintains the local tetrahedral structure on interatomic length scales. The neutralization of the solvation shell of Li$^+$ due to contact ion-pair formation, and the consequent implications on the underlying mechanisms, provide a rational explanation for the ionic conductivity drop of electrolyte solutions at high salt concentrations.