Abstract
Lithium garnets are promising solid-state electrolytes for next generation lithium-ion batteries. These materials have high ionic conductivity, a wide electrochemical window and stability with Li metal. However, lithium garnets have a maximum limit of 7 lithium atoms per formula unit (e.g. La3Zr2Li7O12), before the system transitions from a cubic to a tetragonal phase with poor ionic mobility. This arises from full occupation of the Li sites. Hence, the most conductive lithium garnets have Li between 6-6.55 Li per formula unit, which maintains the cubic symmetry and the disordered Li sub-lattice. The tetragonal phase, however, forms the highly conducting cubic phase at higher temperatures, thought to arise from increased cell volume and entropic stabilisation permitting Li disorder. However, little work has been undertaken in understanding the controlling factors of this phase transition, which could enable enhanced dopant strategies to maintain room temperature cubic garnet at higher Li contents. Here, a series of nine tetragonal garnets were synthesised and analysed via variable temperature XRD to understand the dependence of site substitution on the phase transition temperature. Interestingly the octahedral site cation radius was identified as the key parameter for the transition temperature with larger or smaller dopants altering the transition temperature noticeably. A site substitution was, however, found to make little difference irrespective of significant changes to cell volume.
Original language | English |
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Journal | Chemistry: A European Journal |
Early online date | 1 Dec 2021 |
DOIs | |
Publication status | E-pub ahead of print - 1 Dec 2021 |
Bibliographical note
Publisher Copyright:© 2021 Wiley-VCH GmbH
Keywords
- lithium
- lithium garnets
- phase transition
- solid-state structures
- tetragonal phases
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry