Fuzzy logic: about the origins of fast ion dynamics in crystalline solids

Nuclear magnetic resonance offers a wide range of tools to analyse ionic jump processes in crystalline and amorphous solids. Both high-resolution and time-domain [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] NMR helps throw light on the origins of rapid self-diffusion in materials being relevant for energy storage. It is well accepted that [Formula: see text] ions are subjected to extremely slow exchange processes in compounds with strong site preferences. The loss of this site preference may lead to rapid cation diffusion, as is also well known for glassy materials. Further examples that benefit from this effect include, e.g. cation-mixed, high-entropy fluorides [Formula: see text], Li-bearing garnets ([Formula: see text]) and thiophosphates such as [Formula: see text]. In non-equilibrium phases site disorder, polyhedra distortions, strain and the various types of defects will affect both the activation energy and the corresponding attempt frequencies. Whereas in [Formula: see text] ([Formula: see text]) cation mixing influences F anion dynamics, in [Formula: see text] ([Formula: see text]) the potential landscape can be manipulated by anion site disorder. On the other hand, in the mixed conductor [Formula: see text] cation-cation repulsions immediately lead to a boost in [Formula: see text] diffusivity at the early stages of chemical lithiation. Finally, rapid diffusion is also expected for materials that are able to guide the ions along (macroscopic) pathways with confined (or low-dimensional) dimensions, as is the case in layer-structured [Formula: see text] or [Formula: see text]. Diffusion on fractal systems complements this type of diffusion. This article is part of the Theo Murphy meeting issue 'Understanding fast-ion conduction in solid electrolytes'.