6Li and 7Li MAS-NMR studies on fast ionic conducting inverse spinel-type Li2−2xMg1+xCl4 and normal spinel-type Li2ZnCl4

6Li and 7Li MAS NMR Studies on Fast Ionic Conducting Spinel-Type Li2MgCl4, Li2–xCuxMgCl4, Li2–xNaxMgCl4, and Li2ZnCl4

“…The Li MAS NMR spectra of the spinel-type solid solutions under investigation are, in general, very similar to those of ternary Li MgCl (7,8). Thus, the chemical shifts of the two NMR signals 1 and 2, which we assign to the tetrahedral and the octahedral position, respectively (see below), are 1.2 and 0.2 ppm, as found for Li MgCl .…”

“…The intensity relations of the two NMR signals of the spinel-type solid solutions under investigation, however, di!er from those of Li MgCl and of Li \V Mg >V Cl solid solutions (7,8) as expected. Thus, even if one considers the experimental uncertainties in the obtained data, in the case of the copper-containing compounds, the relative intensity of the low-,eld signal 1 decreases with increasing copper content while the high-,eld signal 2 is not signi"cantly a!ected (see Fig.…”

“…Thus, the chemical shifts of the two NMR signals 1 and 2, which we assign to the tetrahedral and the octahedral position, respectively (see below), are 1.2 and 0.2 ppm, as found for Li MgCl . These chemical shifts, however, do not change with decreasing lithium content in contrast to the behavior of Li \V Mg >V Cl solid solutions (7,8). In the latter case, the high-"eld shift of the two signals observed with decreasing lithium content was ascribed to clustering of the lithium and magnesium ions in these metal ion de"cient compounds (8).…”

“…These chemical shifts, however, do not change with decreasing lithium content in contrast to the behavior of Li \V Mg >V Cl solid solutions (7,8). In the latter case, the high-"eld shift of the two signals observed with decreasing lithium content was ascribed to clustering of the lithium and magnesium ions in these metal ion de"cient compounds (8). If this interpretation holds, the di!erent behavior of the chemical shifts means that there is a random distribution of the sodium and copper ions at the respective lattice sites of the spinel-type solid solutions.…”

“…Very recently, we performed Li and Li MAS NMR experiments on Li ZnCl and Li MgCl including Li \V Mg >V Cl solid solutions (7,8). The latter display an increased ionic conductivity compared to stoichiometric Li MgCl (9,10).…”