Assessing the importance of cation size in the tetragonal-cubic phase transition in lithium garnet electrolytes

Mark Stockham, Alice Griffiths, Bo Dong, Peter Slater

Research output: Contribution to journalArticlepeer-review

19 Downloads (Pure)


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 languageEnglish
JournalChemistry: A European Journal
Early online date1 Dec 2021
Publication statusE-pub ahead of print - 1 Dec 2021

Bibliographical note

Publisher Copyright:
© 2021 Wiley-VCH GmbH


  • lithium
  • lithium garnets
  • phase transition
  • solid-state structures
  • tetragonal phases

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry


Dive into the research topics of 'Assessing the importance of cation size in the tetragonal-cubic phase transition in lithium garnet electrolytes'. Together they form a unique fingerprint.

Cite this