LiPF6 under pressure: a symmetry-mode-based structural analysis

C. J. Ridley; C. L. Bull; N. P. Funnell

doi:10.1080/08957959.2025.2524384

LiPF₆ under pressure: a symmetry-mode-based structural analysis

C. J. Ridley
, C. L. Bull
, N. P. Funnell

Materials Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

The lithium salt LiPF (Formula presented.) is a key component in commercial lithium-ion battery (LIB) electrolytes. However, its structural properties under pressure remain unexplored, despite increasing interest in the effect of pressure on electrolyte behaviour, and a growing interest in high pressure synthesis of new Li-hexafluoride cathode materials. Here, we present the first high pressure neutron diffraction study of solid LiPF (Formula presented.) up to 7.4 GPa. Refinements reveal that the ambient rhombohedral structure (space group R (Formula presented.)) remains stable throughout, with pressure accommodated primarily by tilting of the corner-shared LiF (Formula presented.) and PF (Formula presented.) octahedra and contraction of the LiF (Formula presented.) units. This study establishes a foundation for understanding the phase behaviour of Li-based hexafluorides under extreme conditions.

Original language	English
Pages (from-to)	210-214
Number of pages	5
Journal	High Pressure Research
Volume	45
Issue number	3
DOIs	https://doi.org/10.1080/08957959.2025.2524384
State	Published - 2025

Funding

The authors acknowledge the Neutron Scattering Division, Department of Energy (DOE) Office of Science User Facilities operated by the Oak Ridge National Laboratory and the Science and Technology Facilities Council for funding and facilitating this research. Raw data collected from the PEARL measurements are available at 10.5286/ISIS.E.RB2310007-3. Crystallographic Information Files (cifs), of the refined structures, have been deposited on CCDC.

Keywords

LiPF
lithium-ion electrolytes
neutron diffraction
symmetry-mode analysis

Access to Document

10.1080/08957959.2025.2524384

Cite this

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title = "LiPF6 under pressure: a symmetry-mode-based structural analysis",

abstract = "The lithium salt LiPF (Formula presented.) is a key component in commercial lithium-ion battery (LIB) electrolytes. However, its structural properties under pressure remain unexplored, despite increasing interest in the effect of pressure on electrolyte behaviour, and a growing interest in high pressure synthesis of new Li-hexafluoride cathode materials. Here, we present the first high pressure neutron diffraction study of solid LiPF (Formula presented.) up to 7.4 GPa. Refinements reveal that the ambient rhombohedral structure (space group R (Formula presented.)) remains stable throughout, with pressure accommodated primarily by tilting of the corner-shared LiF (Formula presented.) and PF (Formula presented.) octahedra and contraction of the LiF (Formula presented.) units. This study establishes a foundation for understanding the phase behaviour of Li-based hexafluorides under extreme conditions.",

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T2 - a symmetry-mode-based structural analysis

AU - Ridley, C. J.

AU - Bull, C. L.

AU - Funnell, N. P.

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Y1 - 2025

N2 - The lithium salt LiPF (Formula presented.) is a key component in commercial lithium-ion battery (LIB) electrolytes. However, its structural properties under pressure remain unexplored, despite increasing interest in the effect of pressure on electrolyte behaviour, and a growing interest in high pressure synthesis of new Li-hexafluoride cathode materials. Here, we present the first high pressure neutron diffraction study of solid LiPF (Formula presented.) up to 7.4 GPa. Refinements reveal that the ambient rhombohedral structure (space group R (Formula presented.)) remains stable throughout, with pressure accommodated primarily by tilting of the corner-shared LiF (Formula presented.) and PF (Formula presented.) octahedra and contraction of the LiF (Formula presented.) units. This study establishes a foundation for understanding the phase behaviour of Li-based hexafluorides under extreme conditions.

AB - The lithium salt LiPF (Formula presented.) is a key component in commercial lithium-ion battery (LIB) electrolytes. However, its structural properties under pressure remain unexplored, despite increasing interest in the effect of pressure on electrolyte behaviour, and a growing interest in high pressure synthesis of new Li-hexafluoride cathode materials. Here, we present the first high pressure neutron diffraction study of solid LiPF (Formula presented.) up to 7.4 GPa. Refinements reveal that the ambient rhombohedral structure (space group R (Formula presented.)) remains stable throughout, with pressure accommodated primarily by tilting of the corner-shared LiF (Formula presented.) and PF (Formula presented.) octahedra and contraction of the LiF (Formula presented.) units. This study establishes a foundation for understanding the phase behaviour of Li-based hexafluorides under extreme conditions.

KW - LiPF

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KW - neutron diffraction

KW - symmetry-mode analysis

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