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 H-1,H-2, Li-6,Li-7, F-19, Na-23 NMR helps throw light on the origins of rapid self-diffusion in materials being relevant for energy storage. It is well accepted that Li+ 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 ( Ba, Ca) F-2, Li-bearing garnets (Li7La3Zr2O12) and thiophosphates such as LiTi2(PS4)(3). 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 (Me, Ca)F-2 (Me=Ba, Pb) cation mixing influences F anion dynamics, in Li6PS5X (X=Br, Cl, I) the potential landscape can be manipulated by anion site disorder. On the other hand, in the mixed conductor Li4+xTi5O12 cation-cation repulsions immediately lead to a boost in Li+ 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 RbSn2F5 or MeSnF4. 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'.

Automated summary

Nuclear magnetic resonance is a valuable tool for analyzing ionic jump processes in solids and shedding light on rapid diffusion in materials relevant for energy storage. Processes involving Li+ ions in compounds with strong site preferences may lead to slow diffusion, while the loss of site preference can result in rapid cation diffusion, similar to glassy materials. This effect is also seen in other materials such as cation-mixed fluorides and garnets.