Spin-alignment echo NMR: probing Li⁺hopping motion in the solid electrolyte Li₇La₃Zr₂O₁₂with garnet-type tetragonal structure

Abstract

(7)Li spin-alignment echo (SAE) nuclear magnetic resonance (NMR) spectroscopy has been used to measure single-spin hopping correlation functions of polycrystalline Li(7)La(3)Zr(2)O(12). Damping of the echo amplitude S(2)(t(m),t(p)), recorded at variable mixing time t(m) but fixed preparation time t(p), turns out to be solely controlled by slow Li jump processes taking place in the garnet-like structure. The decay rates τ(SAE)(-1) directly obtained by parametrizing the curves S(2)(t(m),t(p)) with stretched exponential functions show Arrhenius behaviour pointing to an activation energy of approximately 0.5 eV. This value, probed by employing an atomic-scale NMR method, is in very good agreement with that deduced from impedance spectroscopy used to measure macroscopic Li transport parameters. Most likely, the two methods are sensitive to the same hopping correlation function although Li dynamics are probed in a quite different manner.