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


Duff, Benjamin B ORCID: 0000-0002-7398-5002, 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.

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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 <sup>6</sup>Li and <sup>7</sup>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<sub>3</sub>AlS<sub>3</sub> and chlorine-doped analogue Li<sub>4.3</sub>AlS<sub>3.3</sub>Cl<sub>0.7</sub>. Static <sup>7</sup>Li NMR line narrowing spectra of Li<sub>3</sub>AlS<sub>3</sub> show the existence of both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion, while in Li<sub>4.3</sub>AlS<sub>3.3</sub>Cl<sub>0.7</sub>, a single type of fast-moving ion is present and responsible for the higher conductivity of this phase. <sup>6</sup>Li-<sup>6</sup>Li exchange spectroscopy spectra of Li<sub>3</sub>AlS<sub>3</sub> reveal that the slower moving ions hop between non-equivalent Li positions in different structural layers. The absence of the immobile ions in Li<sub>4.3</sub>AlS<sub>3.3</sub>Cl<sub>0.7</sub>, as revealed from <sup>7</sup>Li line narrowing experiments, suggests an increased rate of ion exchange between the layers in this phase compared with Li<sub>3</sub>AlS<sub>3</sub>. 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
Uncontrolled Keywords: Rare Diseases
Depositing User: Symplectic Admin
Date Deposited: 20 Dec 2022 08:35
Last Modified: 15 Mar 2024 01:25
DOI: 10.1021/acs.chemmater.2c02101
Open Access URL: https://pubs.acs.org/doi/full/10.1021/acs.chemmate...
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3166728
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