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

Abstract

6Li and 7Li MAS NMR spectra including 1D-EXSY (exchange spectroscopy) and inversion recovery experiments of fast ionic conducting Li2MgCl4, Li2–xCuxMgCl4, Li2–xNaxMgCl4, and Li2ZnCl4 have been recorded and discussed with respect to the dynamics and local structure of the lithium ions. The chemical shifts, intensities, and half-widths of the Li MAS NMR signals of the inverse spinel-type solid solutions Li2–xMIxMgCl4 (MI=Cu, Na) with the copper ions solely at tetrahedral sites and sodium ions at octahedral sites and the normal spinel-type zinc compound, respectively, confirm the assignment of the low-field signal to Litet of inverse spinel-type Li2MgCl4 and the high-field signal to Lioct as proposed by Nagel et al. (2000). In contrast to spinel-type Li2–2xMg1+xCl4 solid solutions with clustering of the vacancies and Mg2+ ions, the Cu+ and Na+ ions are randomly distributed on the tetrahedral and octahedral sites, respectively. The activation energies due to the various dynamic processes of the lithium ions in inverse spinel-type chlorides obtained by the NMR experiments are Ea=6.6–6.9 and ΔG*>79 KJ mol−1 (in addition to 23, 29, and 75 kJmol–1 obtained by other techniques), respectively. The largest activation energy of >79 KJ mol−1 corresponds to hopping exchange processes of Li ions between the tetrahedral 8a sites and the octahedral 16d sites. The smallest value of 6.6–6.9 KJ mol−1, which was derived from the temperature dependence of both the spin-lattice relaxation times T1 and the correlation times τC of Litet, reveals a dynamic process for the Litet ions inside the tetrahedral voids of the structure, probably between fourfold 32e split sites around the tetrahedral 8a site.