Assessing the Importance of Cation Size in the Tetragonal‐Cubic Phase Transition in Lithium‐Garnet Electrolytes

• Published in: Chemistry : a European journal Vol. 28; no. 6; pp. e202103442 - n/a
• Main Authors: Stockham, Mark P., Griffiths, Alice, Dong, Bo, Slater, Peter R.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 27.01.2022
• Subjects: Batteries; Cations; Cell size; Chemistry; Cubic lattice; Dopants; Electrochemistry; Electrolytes; Garnets; Ion currents; Ionic mobility; Lithium; lithium garnets; Lithium-ion batteries; Molten salt electrolytes; Parameter identification; phase transition; Phase transitions; Room temperature; Solid electrolytes; solid-state structures; Substitutes; Temperature; tetragonal phases; Transition temperature; Transition temperatures; lithium; phase transition; lithium garnets; solid-state structures; tetragonal phases
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202103442

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 seven 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 by 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. The high temperature tetragonal‐cubic phase in lithium garnet electrolytes (A3B2Li7O12) is not fully understood. Herein, the transition temperature dependence based on site substitution is investigated, surprisingly it was found a direct relationship to cell volume is perhaps too simplistic. We show that the B site plays an important role, whereas A site substitution (which alters the cell volume noticeably) has minimal difference. The octahedral site ionic radius required to stabilise a room temperature A3B2Li7O12 cubic phase is then suggested.