A joint experimental-computational approach is being used to investigate the role of ion solvation environment on electrolyte properties, both in the electrolyte as well as the electrolyte-electrode interface for a glyme based electrolyte (sodium triflate in diglyme) relevant to sodium-air as well as sodium ion battery technologies. Despite the recent advances in computational chemistry, ab initio/quantum mechanics of the relevant length and time scales appropriate for realistic simulations of the glyme based electrolytes is intractable from a computational standpoint. However, ab initio MD simulations of the sub-systems of interest are indeed feasible. Classical empirical force-fields have been developed by parameterization to the data from these types of ab initio MD simulations. The solvation structure and dynamics of the sodium ion obtained from these simulations as a function of salt concentration as well as the presence of an electrode interface are being used to interpret the results on the structure from FTIR and neutron scattering experiments, conductivities from dielectric spectroscopy, as well as the dynamics from ultrafast 2DIR spectroscopy. The results of this synergistic investigation as well as the methodology will be presented.