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Li nucleation on the graphite anode under potential control in Li-ion batteries

Li nucleation on the graphite anode under potential control in Li-ion batteries
Li nucleation on the graphite anode under potential control in Li-ion batteries

Application of Li-ion batteries in electric vehicles requires improved safety, increased lifetime and high charging rates. One of the most commonly used intercalation anode material for Li-ion batteries, graphite, is vulnerable to Li nucleation, a side reaction which competes with the intercalation process and leads to loss of reversible capacity of the battery, ageing and short-circuits. In this study, we deploy a combined grand canonical large-scale electronic density-functional theory (DFT) and Poisson-Boltzmann electrolyte theory to study the nucleation and growth of Li clusters on the graphite anode in the presence of its surrounding electrolyte environment at different applied voltages with respect to the Li metal reference electrode. We find the voltage below which the nucleation energy becomes negative (corresponding to Li nucleation becoming energetically favourable), the ‘potential of zero nucleation energy’ (UPZN). We observe a distinct minimum in the plots of UPZN as a function of the size of nucleated clusters. When the applied voltage on the graphite electrode is below the minimum value of UPZN, the nucleated clusters start growing unbounded on graphite electrode. This potential for cluster growth (UPCG) is found to be −0.12 V on the periodic basal plane of unlithiated graphite and −0.08 V on lithiated graphite. The corresponding potential for the zigzag edge termination is −0.06 V on unlithiated graphite and −0.04 V on lithiated graphite. Thus, the nucleation and cluster growth is favored on the zigzag edge termination of the graphite electrode as compared to the periodic basal plane and on the lithiated graphite as compared to the unlithiated graphite. We find that the surrounding environment plays a significant role and that nucleation is more likely to occur in electrolyte environment than that predicted from calculations in vacuum. We observe that the potentials obtained with grand canonical ensemble DFT method in electrolyte are close to experimentally available data. The study has profound implications for the nucleation, growth and control of metal dendrites in a battery cell.

2050-7488
11426-11436
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Skylaris, Chris Kriton
8f593d13-3ace-4558-ba08-04e48211af61
Bhandari, Arihant
f2f12a89-273f-4c5e-a52e-e21835aaacfc
Peng, Chao
20f4467b-1786-4e11-97f2-2ab5885bcd7a
Dziedzic, Jacek
8e2fdb55-dade-4ae4-bf1f-a148a89e4383
Owen, John R.
067986ea-f3f3-4a83-bc87-7387cc5ac85d
Kramer, Denis
1faae37a-fab7-4edd-99ee-ae4c30d3cde4
Skylaris, Chris Kriton
8f593d13-3ace-4558-ba08-04e48211af61

Bhandari, Arihant, Peng, Chao, Dziedzic, Jacek, Owen, John R., Kramer, Denis and Skylaris, Chris Kriton (2022) Li nucleation on the graphite anode under potential control in Li-ion batteries. Journal of Materials Chemistry A, 10 (21), 11426-11436. (doi:10.1039/d2ta02420a).

Record type: Article

Abstract

Application of Li-ion batteries in electric vehicles requires improved safety, increased lifetime and high charging rates. One of the most commonly used intercalation anode material for Li-ion batteries, graphite, is vulnerable to Li nucleation, a side reaction which competes with the intercalation process and leads to loss of reversible capacity of the battery, ageing and short-circuits. In this study, we deploy a combined grand canonical large-scale electronic density-functional theory (DFT) and Poisson-Boltzmann electrolyte theory to study the nucleation and growth of Li clusters on the graphite anode in the presence of its surrounding electrolyte environment at different applied voltages with respect to the Li metal reference electrode. We find the voltage below which the nucleation energy becomes negative (corresponding to Li nucleation becoming energetically favourable), the ‘potential of zero nucleation energy’ (UPZN). We observe a distinct minimum in the plots of UPZN as a function of the size of nucleated clusters. When the applied voltage on the graphite electrode is below the minimum value of UPZN, the nucleated clusters start growing unbounded on graphite electrode. This potential for cluster growth (UPCG) is found to be −0.12 V on the periodic basal plane of unlithiated graphite and −0.08 V on lithiated graphite. The corresponding potential for the zigzag edge termination is −0.06 V on unlithiated graphite and −0.04 V on lithiated graphite. Thus, the nucleation and cluster growth is favored on the zigzag edge termination of the graphite electrode as compared to the periodic basal plane and on the lithiated graphite as compared to the unlithiated graphite. We find that the surrounding environment plays a significant role and that nucleation is more likely to occur in electrolyte environment than that predicted from calculations in vacuum. We observe that the potentials obtained with grand canonical ensemble DFT method in electrolyte are close to experimentally available data. The study has profound implications for the nucleation, growth and control of metal dendrites in a battery cell.

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Accepted/In Press date: 8 May 2022
Published date: 10 May 2022
Additional Information: Funding Information: This work was carried out with the funding from the Faraday Institution ( https://www.Faraday.ac.uk ; EP/S003053/1), grant numbers FIRG003 and FIRG025. The calculations presented in this work were performed on the Iridis5 supercomputer of the University of Southampton, the Michael supercomputer of the Faraday Institution, the Young supercomputer at the UCL and the ARCHER2 UK National Supercomputing Service ( https://www.archer2.ac.uk ; via EPSRC grant: EP/P022030/1). We acknowledge the United Kingdom Materials and Molecular Modelling Hub for computational resources, partially funded by EPSRC (EP/P020194/1). Funding Information: This work was carried out with the funding from the Faraday Institution (https://www.Faraday.ac.uk; EP/S003053/1), grant numbers FIRG003 and FIRG025. The calculations presented in this work were performed on the Iridis5 supercomputer of the University of Southampton, the Michael supercomputer of the Faraday Institution, the Young supercomputer at the UCL and the ARCHER2 UK National Supercomputing Service (https://www.archer2.ac.uk; via EPSRC grant: EP/P022030/1). We acknowledge the United Kingdom Materials and Molecular Modelling Hub for computational resources, partially funded by EPSRC (EP/P020194/1). Publisher Copyright: © 2022 The Royal Society of Chemistry.

Identifiers

Local EPrints ID: 468474
URI: http://eprints.soton.ac.uk/id/eprint/468474
ISSN: 2050-7488
PURE UUID: ccd64727-9271-49b1-a04c-dfd4e5f380f8
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

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Date deposited: 16 Aug 2022 16:37
Last modified: 01 Feb 2023 02:55

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Contributors

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

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