Morscher, A 
ORCID: 0000-0001-9850-1222, Dyer, MS ORCID: 0000-0002-4923-3003, Duff, BB ORCID: 0000-0002-7398-5002, Han, G ORCID: 0000-0003-3861-5396, Gamon, J, Daniels, LM ORCID: 0000-0002-7077-6125, Dang, Y ORCID: 0000-0002-0140-0140, Surta, TW ORCID: 0000-0002-2882-6483, Robertson, CM ORCID: 0000-0002-4789-7607, Blanc, F ORCID: 0000-0001-9171-1454 et al (show 2 more authors)
(2021)
Li6SiO4Cl2: A Hexagonal Argyrodite Based on Antiperovskite Layer Stacking
Chemistry of Materials, 33 (6).
pp. 2206-2217.
ISSN 0897-4756, 1520-5002
Abstract
A hexagonal analogue, Li6SiO4Cl2, of the cubic lithium argyrodite family of solid electrolytes is isolated by a computation-experiment approach. We show that the argyrodite structure is equivalent to the cubic antiperovskite solid electrolyte structure through anion site and vacancy ordering within a cubic stacking of two close-packed layers. Construction of models that assemble these layers with the combination of hexagonal and cubic stacking motifs, both well known in the large family of perovskite structural variants, followed by energy minimization identifies Li6SiO4Cl2 as a stable candidate composition. Synthesis and structure determination demonstrate that the material adopts the predicted lithium site-ordered structure with a low lithium conductivity of ∼10-10 S cm-1 at room temperature and the predicted hexagonal argyrodite structure above an order-disorder transition at 469.3(1) K. This transition establishes dynamic Li site disorder analogous to that of cubic argyrodite solid electrolytes in hexagonal argyrodite Li6SiO4Cl2 and increases Li-ion mobility observed via NMR and AC impedance spectroscopy. The compositional flexibility of both argyrodite and perovskite alongside this newly established structural connection, which enables the use of hexagonal and cubic stacking motifs, identifies a wealth of unexplored chemistry significant to the field of solid electrolytes.
| Item Type: | Article |
|---|---|
| Additional Information: | No access restrictions, data can be made immediately available. |
| Uncontrolled Keywords: | 3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences, 3406 Physical Chemistry, 40 Engineering, 4016 Materials Engineering |
| Divisions: | Faculty of Science & Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 25 Mar 2021 10:25 |
| Last Modified: | 01 Mar 2026 09:51 |
| DOI: | 10.1021/acs.chemmater.1c00157 |
| Open Access URL: | https://doi.org/10.1021/acs.chemmater.1c00157 |
| Related Websites: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3118149 |
| 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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