Dynamics of Interlayer Na-Ions in Ga-Substituted Na2Zn2TeO6 (NZTO) Studied by Variable-Temperature Solid-State 23Na NMR Spectroscopy and DFT Modeling

Local Na-coordination and dynamics of Na_2–xZn_2–xGa_xTeO₆; x = 0.00 (NZTO), 0.05, 0.10, 0.15, 0.20, were studied by variable-temperature, ²³Na NMR methods and DFT AIMD simulations. Structure and dynamics were probed by NMR in the temperature ranges of 100–293 K in a magnetic field of 18.8 T and from 293 up to 500 K in a magnetic field of 11.7 T. Line shapes and T₁ relaxation constants were analyzed. At 100 K, the otherwise dynamic Na-ions are frozen out on the NMR time scale, and a local structure characterization was performed for Na-ions at three interlayer sites. On increasing the temperature, complex peak shape coalescences occurred, and at 293 K, the Na NMR spectra showed some averaging due to Na-ion dynamics. A further increase to 500 K did not reveal any new peak shape variations until the highest temperatures, where an apparent peak splitting was observed, similar to what was observed in the 18.8 T experiments at lower temperatures. A three-site exchange model coupled with reduced quadrupolar couplings due to dynamics appear to explain these peak shape observations. The Ga substitution increases the Na-jumping rate, as proved by relaxation measurements and by a decrease in temperature for peak coalescence. The estimated activation energy for Na dynamics in the NZTO sample, from relaxation measurements, corresponds well to results from DFT AIMD simulations. Upon Ga substitution, measured activation energies are reduced, which is supported, in part, by DFT calculations. Addressing the correlated motion of Na-ions appears important for solid-state ion conductors since benefits can be gained from the decrease in activation energy upon Ga substitution, for example.