Toward Understanding of the Li-Ion Migration Pathways in the Lithium Aluminum Sulfides Li(3)AlS(3) and Li(4.3)AlS(3.3)Cl(0.7) via (6,7)Li Solid-State Nuclear Magnetic Resonance Spectroscopy

[Image: see text] Li-containing materials providing fast ion transport pathways are fundamental in Li solid electrolytes and the future of all-solid-state batteries. Understanding these pathways, which usually benefit from structural disorder and cation/anion substitution, is paramount for further developments in next-generation Li solid electrolytes. Here, we exploit a range of variable temperature (6)Li and (7)Li nuclear magnetic resonance approaches to determine Li-ion mobility pathways, quantify Li-ion jump rates, and subsequently identify the limiting factors for Li-ion diffusion in Li(3)AlS(3) and chlorine-doped analogue Li(4.3)AlS(3.3)Cl(0.7). Static (7)Li NMR line narrowing spectra of Li(3)AlS(3) show the existence of both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion, while in Li(4.3)AlS(3.3)Cl(0.7), a single type of fast-moving ion is present and responsible for the higher conductivity of this phase. (6)Li–(6)Li exchange spectroscopy spectra of Li(3)AlS(3) reveal that the slower moving ions hop between non-equivalent Li positions in different structural layers. The absence of the immobile ions in Li(4.3)AlS(3.3)Cl(0.7), as revealed from (7)Li line narrowing experiments, suggests an increased rate of ion exchange between the layers in this phase compared with Li(3)AlS(3). Detailed analysis of spin–lattice relaxation data allows extraction of Li-ion jump rates that are significantly increased for the doped material and identify Li mobility pathways in both materials to be three-dimensional. The identification of factors limiting long-range translational Li diffusion and understanding the effects of structural modification (such as anion substitution) on Li-ion mobility provide a framework for the further development of more highly conductive Li solid electrolytes.