With a Little Help from 31P NMR: The Complete Picture on Localized and Long-Range Li+ Diffusion in Li6PS5I.

Li6PS5I acts as a perfect model substance to study length scale-dependent diffusion parameters in an ordered matrix. It provides Li-rich cages which offer rapid but localized Li+ translational jump processes. As jumps between these cages are assumed to be much less frequent, long-range ion transport is sluggish, resulting in ionic conductivities in the order of 10-6 S cm-1 at room temperature. In contrast, the site disordered analogues Li6PS5X (X = Br, Cl) are known as fast ion conductors because structural disorder facilities intercage dynamics. As yet, the two extremely distinct jump processes in Li6PS5I have not been visualized separately. Here, we used a combination of 31P and 7Li NMR relaxation measurements to probe this bimodal dynamic behavior, that is, ultrafast intracage Li+ hopping and the much slower Li+ intercage exchange process. While the first is to be characterized by an activation energy of ca. 0.2 eV as directly measured by 7Li NMR, the latter is best observed by 31P NMR and follows the Arrhenius law determined by 0.44 eV. This activation energy perfectly agrees with that seen by direct current conductivity spectroscopy being sensitive to long-range ion transport for which the intercage jumps are the rate limiting step. Moreover, quantitative agreement in terms of diffusion coefficients is also observed. The solid-state diffusion coefficient D σ obtained from conductivity spectroscopy agrees very well with that from 31P NMR (D NMR ≈ 4.6 × 10-15 cm2 s-1). D NMR was directly extracted from the pronounced diffusion-controlled 31P NMR spin-lock spin-lattice relaxation peak appearing at 366 K.