Duff, Benjamin B, Elliott, Stuart J, Gamon, Jacinthe, Daniels, Luke M 
ORCID: 0000-0002-7077-6125, Rosseinsky, Matthew J ORCID: 0000-0002-1910-2483 and Blanc, Frederic ORCID: 0000-0001-9171-1454
(2023)
Toward Understanding of the Li-Ion Migration Pathways in the Lithium Aluminum Sulfides Li3AlS3 and Li4.3AlS3.3Cl0.7 via 6,7Li Solid- State Nuclear Magnetic Resonance Spectroscopy
CHEMISTRY OF MATERIALS, 35 (1).
pp. 27-40.
ISSN 0897-4756, 1520-5002
Abstract
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 6Li and 7Li 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<inf>3</inf>AlS<inf>3</inf> and chlorine-doped analogue Li<inf>4.3</inf>AlS<inf>3.3</inf>Cl<inf>0.7</inf>. Static 7Li NMR line narrowing spectra of Li<inf>3</inf>AlS<inf>3</inf> show the existence of both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion, while in Li<inf>4.3</inf>AlS<inf>3.3</inf>Cl<inf>0.7</inf>, a single type of fast-moving ion is present and responsible for the higher conductivity of this phase. 6Li-6Li exchange spectroscopy spectra of Li<inf>3</inf>AlS<inf>3</inf> reveal that the slower moving ions hop between non-equivalent Li positions in different structural layers. The absence of the immobile ions in Li<inf>4.3</inf>AlS<inf>3.3</inf>Cl<inf>0.7</inf>, as revealed from 7Li line narrowing experiments, suggests an increased rate of ion exchange between the layers in this phase compared with Li<inf>3</inf>AlS<inf>3</inf>. 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.
| Item Type: | Article |
|---|---|
| Additional Information: | No access restrictions: data can be made immediately available. |
| Uncontrolled Keywords: | 34 Chemical Sciences, 3406 Physical Chemistry |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 20 Dec 2022 08:35 |
| Last Modified: | 16 Jun 2026 11:49 |
| DOI: | 10.1021/acs.chemmater.2c02101 |
| Open Access URL: | https://pubs.acs.org/doi/full/10.1021/acs.chemmate... |
| Related Websites: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3166728 |
| Disclaimer: | The University of Liverpool is not responsible for content contained on other websites from links within repository metadata. Please contact us if you notice anything that appears incorrect or inappropriate. |
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