Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Alex Squires; David O. Scanlon

doi:10.1039/d3ta02088f

Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Alex Squires^*, David O. Scanlon^*

^*Corresponding author for this work

Chemistry

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Abstract

Suppressing unfavourable short-range ordering in disordered rock salt lithium-ion cathode materials is seen as a key research goal on their route to commercialisation. In this study we use cluster-expansion-driven Monte Carlo simulations of a model 3d-transition metal disordered rock salt oxyfluoride system to investigate the effect of many component cation substitution on the suppression of short-range ordering in disordered rock salt cathode materials. We confirm that many-cation substitution is effective in suppressing short-range ordering, but has diminishing returns on increasing the number of component transition metals, or alternatively, increasing the size of the long-range lithium diffusion network as the number of transition metals increases. We particularly emphasize the critical role of lithium excess and fluorine content in the success of the “high-entropy” cation substitution strategy: short-range ordering is strongly influenced by cation-anion bonding preferences, underscoring the need to consider the full composition of the target system when designing high entropy lithium-ion cathode materials.

Original language	English
Pages (from-to)	13765-13773
Number of pages	9
Journal	Journal of Materials Chemistry A
Volume	11
Issue number	25
Early online date	2 Jun 2023
DOIs	https://doi.org/10.1039/d3ta02088f
Publication status	Published - 7 Jul 2023

Bibliographical note

Funding Information:
This work was supported by the Faraday Institution grant number FIRG017 and used the Michael Supercomputer (FIRG030). Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by the UK Engineering and Physical Sciences Research Council (EPSRC; EP/L000202, EP/R029431, EP/T022213), this work used ARCHER2 UK National Supercomputing Services. This work also used the the Myriad (Myriad@UCL) and Kathleen (Kathleen@UCL) supercomputers. We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1)

Publisher Copyright:
© 2023 The Royal Society of Chemistry.

ASJC Scopus subject areas

General Chemistry
Renewable Energy, Sustainability and the Environment
General Materials Science

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Cite this

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abstract = "Suppressing unfavourable short-range ordering in disordered rock salt lithium-ion cathode materials is seen as a key research goal on their route to commercialisation. In this study we use cluster-expansion-driven Monte Carlo simulations of a model 3d-transition metal disordered rock salt oxyfluoride system to investigate the effect of many component cation substitution on the suppression of short-range ordering in disordered rock salt cathode materials. We confirm that many-cation substitution is effective in suppressing short-range ordering, but has diminishing returns on increasing the number of component transition metals, or alternatively, increasing the size of the long-range lithium diffusion network as the number of transition metals increases. We particularly emphasize the critical role of lithium excess and fluorine content in the success of the “high-entropy” cation substitution strategy: short-range ordering is strongly influenced by cation-anion bonding preferences, underscoring the need to consider the full composition of the target system when designing high entropy lithium-ion cathode materials.",

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note = "Funding Information: This work was supported by the Faraday Institution grant number FIRG017 and used the Michael Supercomputer (FIRG030). Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by the UK Engineering and Physical Sciences Research Council (EPSRC; EP/L000202, EP/R029431, EP/T022213), this work used ARCHER2 UK National Supercomputing Services. This work also used the the Myriad (Myriad@UCL) and Kathleen (Kathleen@UCL) supercomputers. We are also grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1) Publisher Copyright: {\textcopyright} 2023 The Royal Society of Chemistry.",

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Understanding the limits to short-range order suppression in many-component disordered rock salt lithium-ion cathode materials

Abstract

Bibliographical note

ASJC Scopus subject areas

UN SDGs

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