The diffusion behavior of Mg in electrolytes is not as readily accessible as that from Li or Na utilizing PFG NMR, due to the low sensitivity, poor resolution, and rapid relaxation encountered when attempting Mg NMR. In MgTFSI/DME solutions, "bound" DME (coordinating to Mg) and "free" DME (bulk) are distinguishable from H NMR. With the exchange rates between them obtained from 2D H EXSY NMR, we can extract the self-diffusivities of free DME and bound DME (which are equal to that of Mg) before the exchange occurs using PFG diffusion NMR measurements coupled with analytical formulas describing diffusion under two-site exchange. The high activation enthalpy for exhange (65-70 kJ/mol) can be explained by the structural change of bound DME as evidenced by its reduced C-H bond length. Comparison of the diffusion behaviors of Mg, TFSI, DME, and Li reveals a relative restriction to Mg diffusion that is caused by the long-range interaction between Mg and solvent molecules, especially those with suppressed motions at high concentrations and low temperatures.
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