Nuclear magnetic resonance (NMR) has been productively employed to investigate ion transport and solvation in standard carbonate-based Li ion battery electrolytes. Future electrochemical power sources require new electrolytes to adapt to disruptive changes in the basic working chemistry, such as moving from Li to Na. This work extends the application of some of the NMR tools developed by our lab and others to study the standard electrolytes to the new electrolytes. Using a combination of ²³Na, ¹⁹F and natural abundance ¹⁷O NMR, and pulsed field gradient diffusion, we have examined NaPF₆ solutions in binary solvent mixtures ethylene carbonate (EC) and ethylmethyl carbonate (EMC) for possible cation solvation preference as a function of EC/EMC ratio. Using similar methods, we also investigate the transport properties of newly discovered highly conductive ultra-concentrated aqueous solutions of LiTFSI.