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Mechanism of Li nucleation at graphite anodes and mitigation strategies

Mechanism of Li nucleation at graphite anodes and mitigation strategies
Mechanism of Li nucleation at graphite anodes and mitigation strategies
Lithium metal plating is a critical safety issue in Li-ion cells with graphite anodes, and contributes significantly to ageing, drastically limiting the lifetime and inducing capacity loss. Nonetheless, the nucleation mechanism of metallic Li on graphite anodes is still poorly understood. But in-depth understanding is needed to rationally design mitigation measures. In this work, we conducted First-Principles studies to elucidate the Li nucleation mechanism on graphite surfaces. These large-scale density-functional-theory (DFT) calculations indicate that nano-particulate Li forms much more readily than classical nucleation theory predicts. Further, our calculations indicate a crucial role of topological surface states near the zigzag edge, lowering the nucleation barrier by a further 1.32 eV relative to nucleation on the basal plane. Li nucleation, therefore, is likely to initiate at or near the zigzag edges of graphitic particles. Finally, we suggest that chemical doping with a view to reducing the effect of the topological surface states might be a potential mitigation strategy to increase nucleation barriers and reduce the propensity to plate Li near the zigzag edge.
2050-7488
16798-16804
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d
Skylaris, Chris-Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4

Peng, Chao, Bhandari, Arihant, Dziedzic, Jacek, Owen, John R., Skylaris, Chris-Kriton and Kramer, Denis (2021) Mechanism of Li nucleation at graphite anodes and mitigation strategies. Journal of Materials Chemistry A, 9 (31), 16798-16804. (doi:10.1039/D1TA03447B).

Record type: Article

Abstract

Lithium metal plating is a critical safety issue in Li-ion cells with graphite anodes, and contributes significantly to ageing, drastically limiting the lifetime and inducing capacity loss. Nonetheless, the nucleation mechanism of metallic Li on graphite anodes is still poorly understood. But in-depth understanding is needed to rationally design mitigation measures. In this work, we conducted First-Principles studies to elucidate the Li nucleation mechanism on graphite surfaces. These large-scale density-functional-theory (DFT) calculations indicate that nano-particulate Li forms much more readily than classical nucleation theory predicts. Further, our calculations indicate a crucial role of topological surface states near the zigzag edge, lowering the nucleation barrier by a further 1.32 eV relative to nucleation on the basal plane. Li nucleation, therefore, is likely to initiate at or near the zigzag edges of graphitic particles. Finally, we suggest that chemical doping with a view to reducing the effect of the topological surface states might be a potential mitigation strategy to increase nucleation barriers and reduce the propensity to plate Li near the zigzag edge.

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More information

Accepted/In Press date: 19 July 2021
e-pub ahead of print date: 20 July 2021
Published date: 21 August 2021
Additional Information: Funding Information: The authors acknowledge the nancial support from the Faraday Institution and EPSRC (https://www.faraday.ac.uk; EP/ S003053/1) with grant number of FIRG003. We are grateful for access to the Iridis5 Supercomputer of the University of Southampton, the Michael Supercomputer of the Faraday Institution, the Tryton Supercomputer at the TASK Academic Computer Centre (Gdańsk, Poland) and the UK Materials and Molecular Modelling Hub for computational resources, partially funded by the EPSRC (Grant No. EP/P020194/1 and EP/ T022213/1). Funding Information: The authors acknowledge the financial support from the Faraday Institution and EPSRC (/S003053/1) with grant number of FIRG003. We are grateful for access to the Iridis5 Supercomputer of the University of Southampton, the Michael Supercomputer of the Faraday Institution, the Tryton Supercomputer at the TASK Academic Computer Centre (Gda?sk, Poland) and the UK Materials and Molecular Modelling Hub for computational resources, partially funded by the EPSRC (Grant No. EP/P020194/1 and EP/T022213/1). Publisher Copyright: © The Royal Society of Chemistry 2021.

Identifiers

Local EPrints ID: 450872
URI: http://eprints.soton.ac.uk/id/eprint/450872
ISSN: 2050-7488
PURE UUID: 806ea95b-17a2-44cd-a8de-847a6e4d961c
ORCID for Arihant Bhandari: ORCID iD orcid.org/0000-0002-2914-9402
ORCID for Jacek Dziedzic: ORCID iD orcid.org/0000-0003-4786-372X
ORCID for John R. Owen: ORCID iD orcid.org/0000-0002-4938-3693
ORCID for Chris-Kriton Skylaris: ORCID iD orcid.org/0000-0003-0258-3433

Catalogue record

Date deposited: 17 Aug 2021 16:32
Last modified: 06 Jun 2024 02:06

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Contributors

Author: Chao Peng
Author: Arihant Bhandari ORCID iD
Author: Jacek Dziedzic ORCID iD
Author: John R. Owen ORCID iD
Author: Denis Kramer

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