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Abstract
The Li-stuffed garnets Li xM 2M3′O 12 are promising Li-ion solid electrolytes with potential use in solid-state batteries. One strategy for optimizing ionic conductivities in these materials is to tune lithium stoichiometries through aliovalent doping, which is often assumed to produce proportionate numbers of charge-compensating Li vacancies. The native defect chemistry of the Li-stuffed garnets and their response to doping, however, are not well understood, and it is unknown to what degree a simple vacancy-compensation model is valid. Here, we report hybrid density functional theory calculations of a broad range of native defects in the prototypical Li garnet Li 7La 3Zr 2O 12. We calculate equilibrium defect concentrations as a function of synthesis conditions and model the response of these defect populations to extrinsic doping. We predict a rich defect chemistry that includes Li and O vacancies and interstitials, and significant numbers of cation-antisite defects. Under reducing conditions, O vacancies act as color centers by trapping electrons. We find that supervalent (donor) doping does not produce charge compensating Li vacancies under all synthesis conditions; under Li-rich/Zr-poor conditions the dominant compensating defects are Li Zr antisites, and Li stoichiometries strongly deviate from those predicted by simple "vacancy compensation" models.
Original language | English |
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Pages (from-to) | 1876-1886 |
Number of pages | 11 |
Journal | Chemistry of Materials |
Volume | 32 |
Issue number | 5 |
Early online date | 23 Dec 2019 |
DOIs | |
Publication status | Published - 10 Mar 2020 |
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
- Materials Chemistry
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Dive into the research topics of 'Native Defects and their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12'. Together they form a unique fingerprint.Projects
- 1 Finished
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Dr B Morgan URF - Modelling Collective Lithium-Ion Dynamics in Battery Materials
1/10/14 → 30/09/19
Project: Research council
Datasets
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Dataset for "Native Defects and their Doping Response in the Lithium Solid Electrolyte Li7La3Zr2O12"
Squires, A. G. (Creator), Scanlon, D. O. (Creator) & Morgan, B. (Creator), University of Bath, 23 Dec 2019
DOI: 10.15125/BATH-00691
Dataset