Fast Li Ion Dynamics in Defect-Rich Nanocrystalline Li₄PS₄I─The Effect of Disorder on Activation Energies and Attempt Frequencies

Abstract

High Resolution Image Download MS PowerPoint Slide Solid-state electrolytes with fast ionic transport properties will play a crucial role in future energy storage applications that rely on electrochemical reactions. The group of lithium thiophosphates appears to be especially promising as it includes compounds such as Li 10 GeP 2 S 12, already exceeding the conductivity of conventional liquid electrolytes. Recently, the I-containing thiophosphate, Li 4 PS 4 I, belonging also to this group attracted great interest due to its theoretically high ionic conductivity that is assumed from the favorable 3D percolation pathways. However, earlier studies showed that ionic conductivity is lower than expected from these structural considerations. Here, we reinvestigated both long-range and short-range ion dynamics through nuclear magnetic resonance (NMR) measurements as well as by conductivity spectroscopy to gain more insights into the conduction mechanism. It turned out that by changing the morphology of Li 4 PS 4 I, that is, by going from the coarse-grained to the nanocrystalline form, a significant increase in ion dynamics is seen that is accompanied by a change in the Arrhenius prefactor and a clear decrease in activation energy [0.35 eV (nano) and 0.49 eV (micro)] for ionic conduction. We assume that the smaller energy barrier for the nanostructured sample, which was prepared by ball milling, originates form the increased number of defects introduced through mechanical treatment. In line with the reduction in activation energy, we clearly observed an increase in room-temperature conductivity from 2.9 × 10 –2 mS cm –1 (micro) to 0.47 mS cm –1 (nano), that is, by almost two orders of magnitude. Diffusion-induced spin–lattice relaxation 7 Li NMR measurements reveal two distinct Li ion diffusion processes. While the slower process shows similar activation energies for both micro- and nanocrystalline Li 4 PS 4 I, the faster relaxation process displays, however, activation energies of 0.32 and 0.13 eV for the microcrystalline and the nanocrystalline sample, respectively. Additional spin-lock NMR measurements sense long-range ion transport (0.34–0.36 eV) and point to anisotropic ion conduction for both samples. Taken together, the combination of nuclear and non-nuclear methods operating on different time scales help characterize the relevant diffusion pathways in Li 4 PS 4 I finally leading to the superior behavior of nano-Li 4 PS 4 I in terms of through-going ionic conduction.

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