Tracking Ions the Direct Way: Long-Range Li⁺ Dynamics in the Thio-LISICON Family Li₄MCh₄ (M = Sn, Ge; Ch = S, Se) as Probed by ⁷Li NMR Relaxometry and ⁷Li Spin-Alignment Echo NMR.

ABSTRACT: Solid electrolytes are key elements for next-generation energy storage systems. To design powerful electrolytes with high ionic conductivity, we need to improve our understanding of the mechanisms that are at the heart of the rapid ion exchange processes in solids. Such an understanding also requires evaluation and testing of methods not routinely used to characterize ion conductors. Here, the ternary Li₄MCh₄ system (M = Ge, Sn; Ch = Se, S) provides model compounds to study the applicability of ⁷Li nuclear magnetic resonance (NMR) spin-alignment echo (SAE) spectroscopy to probe slow Li⁺ exchange processes. Whereas the exact interpretation of conventional spin-lattice relaxation data depends on models, SAE NMR offers a model-independent, direct access to motional correlation rates. Indeed, the jump rates and activation energies deduced from time-domain relaxometry data perfectly agree with results from ⁷Li SAE NMR. In particular, long-range Li⁺ diffusion in polycrystalline Li₄SnS₄ as seen by NMR in a dynamic range covering 6 orders of magnitude is determined by an activation energy of E _a = 0.55 eV and a pre-exponential factor of 3 × 10¹³ s^-1. The variation in E _a and 1/?₀ is related to the LiCh₄ volume that changes within the four Li₄MCh₄ compounds studied. The corresponding volume of Li₄SnS₄ seems to be close to optimum for Li⁺ diffusivity.

SUBMITTER: Hogrefe K 

PROVIDER: S-EPMC7876753 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature