Low Electronic Conductivity of Li7La3Zr2O12 (LLZO) Solid Electrolytes from First Principles

Alex Squires, Daniel Davies, Sunghyun Kim, David O Scanlon, Aron Walsh, Benjamin Morgan

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Lithium-rich garnets such as Li7La3Zr2O12(LLZO) are promising solid electrolytes with potential application in all-solid-state batteries that use lithium-metal anodes. The practical use of garnet electrolytes, however, is limited by pervasive lithium-dendrite growth, which leads to short-circuiting and cell failure. One possible mechanism for this lithium-dendrite growth is the direct reduction of lithium ions to lithium metal within the electrolyte, and lithium garnets have suggested to be particularly susceptible to this dendrite-growth mechanism due to high electronic conductivities relative to other solid electrolytes [Han et al. Nature Ener. 4 187, 2019]. The electronic conductivities of LLZO and other lithium-garnet solid electrolytes, however, are not yet well characterised. Here, we present a general scheme for calculating the intrinsic electronic conductivity of nominally insulating material under variable synthesis conditions from first principles and apply this to the prototypical lithium-garnet LLZO. Our model predicts that under typical battery operating conditions, electron and hole mobilities are low (<1 cmV-1 s-1), and bulk electron and hole carrier concentrations are negligible, irrespective of initial synthesis conditions or dopant levels. These results suggest that the bulk electronic conductivity of LLZO is not sufficiently high to cause bulk lithium-dendrite growth during cell operation, and that any non-negligible electronic conductivity in lithium garnet samples is likely due to extended defects or surface contributions.
Original languageEnglish
Article number085401
JournalPhysical Review Materials
Issue number8
Early online date1 Aug 2022
Publication statusPublished - 31 Dec 2022

Bibliographical note

The research was funded by the Royal Society (Grants No. UF100278, No. UF130329, and No. URF\R\191006), the Faraday Institution (Grant No. FIRG003), EPSRC (Grants No. EP/L01551X/1 and No. EP/N01572X/1), and the European Research Council, ERC (Grant No. 758345). This work used the Michael computing cluster. Additionally, this work used the ARCHER UK National Supercomputing Service [118] with access provided via our membership of the UK's HPC Materials Chemistry Consortium, which is funded by EPSRC Grants No. EP/L000202 and No. EP/R029431.


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