Spectral deconvolution in electrophoretic NMR to investigate the migration of neutral molecules in electrolytes

Electrophoretic nuclear magnetic resonance (eNMR) is a powerful tool in studies of nonaqueous electrolytes, such as ionic liquids. It delivers electrophoretic mobilities of the ionic constituents and thus sheds light on ion correlations. In applications of liquid electrolytes, uncharged additives are often employed, detectable via 1H NMR. Characterizing their mobility and coordination to charged entities is desirable; however, it is often hampered by small intensities and 1H signals overlapping with major constituents of the electrolyte. In this work, we evaluate methods of phase analysis of overlapping resonances to yield electrophoretic mobilities even for minor constituents. We use phase‐sensitive spectral deconvolution via a set of Lorentz distributions for the investigation of the migration behavior of additives in two different ionic liquid‐based lithium salt electrolytes. For vinylene carbonate as an additive, no field‐induced drift is observed; thus, its coordination to the Li+ ion does not induce a correlated drift with Li+. On the other hand, in a solvate ionic liquid with tetraglyme (G4) as an additive, a correlated migration of tetraglyme with lithium as a complex solvate cation is directly proven by eNMR. The phase evaluation procedure of superimposed resonances thus broadens the applicability of eNMR to application‐relevant complex electrolyte mixtures containing neutral additives with superimposed resonances. Spectral lines of small additive contributions overlapping with strong resonances are hard to analyze in eNMR. We propose a deconvolution method that allows precise phase analysis and thus yields the drift velocity of additives. A system without and with drift of neutral molecules in an electric field is demonstrated, respectively, shedding light on ion‐additive coordination and its relevance for transport properties.