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The compound AgI crystallizes, depending on temperature and pressure, with various crystal structures. While α-AgI is the stable form at elevated temperatures, the βand the γforms exist at lower temperatures. Variants with stacking sequences different than in pure β-AgI and γ-AgI enrich the complex crystallographic situation for AgI. In the study presented here, we converted a mixture of β-AgI and γ-AgI into nanostructured γ-AgI by mechanical treatment, that is, by high-energy ball milling of such a mixture under ambient conditions. Our work extends an earlier study by Ahmad (Z. Naturforsch. 2015, 70b, 17). We used variable-temperature, potentiostatic conductivity spectroscopy as well as electric modulus measurements to characterize the electric transport parameters. For the case that the sample is heated to temperatures near and above 420 K, preliminary information on the “resistance” of the electric conductivity against healing of defects are also collected. As compared to the unmilled but mixed sample, whose Ag+ionic transport is dominated by those ions residing in the γ-phase of AgI (0.25 eV vs. 0.46 eV in β-AgI), ball milling only leads to a small increase in overall electric conductivity (by a factor of 3–4) for nanocrystalline γ-AgI (0.25 eV). This observation is perfectly in line with a recent observation for the fast ion conductor Li10GeP2S12(Hogrefe et al., J. Am. Chem. Soc. 2022, 144, 9597): In materials with already rapid diffusion pathways, nanostructuring and the introduction of defects and distortions do not lead to significantly enhanced ion transport. Here, a careful analysis of data from conductivity and modulus spectroscopy helps identify which dynamic parameters are mainly responsible for the change in the overall conductivity upon mechanical treatment of coarse-grained γ-AgI.

Understanding the origins of fast ion transport in solids is important to develop new ionic conductors for batteries and sensors. Nature offers a rich assortment of rather inspiring structures to elucidate these origins. In particular, layer-structured materials are prone to show facile Li+transport along their inner surfaces. Here, synthetic hectorite-type Li0.5[Mg2.5Li0.5]Si4O10F2, being a phyllosilicate, served as a model substance to investigate Li+translational ion dynamics by both broadband conductivity spectroscopy and diffusion-induced 7Li nuclear magnetic resonance (NMR) spin–lattice relaxation experiments. It turned out that conductivity spectroscopy, electric modulus data, and NMR are indeed able to detect a rapid 2D Li+exchange process governed by an activation energy as low as 0.35 eV. At room temperature, the bulk conductivity turned out to be in the order of 0.1 mS cm–1. Thus, the silicate represents a promising starting point for further improvements by crystal chemical engineering. To the best of our knowledge, such a high Li+ionic conductivity has not been observed for any silicate yet.