17O NMR Spectroscopy in Lithium-Ion Battery Cathode Materials: Challenges and Interpretation

Euan N. Bassey; Philip J. Reeves; Ieuan D. Seymour; Clare P. Grey

doi:10.1021/jacs.2c02927

¹⁷O NMR Spectroscopy in Lithium-Ion Battery Cathode Materials: Challenges and Interpretation

Euan N. Bassey, Philip J. Reeves, Ieuan D. Seymour, Clare P. Grey^* (Corresponding Author)

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Review article › peer-review

7 Citations (Scopus)

Abstract

Modern studies of lithium-ion battery (LIB) cathode materials employ a large range of experimental and theoretical techniques to understand the changes in bulk and local chemical and electronic structures during electrochemical cycling (charge and discharge). Despite its being rich in useful chemical information, few studies to date have used ¹⁷O NMR spectroscopy. Many LIB cathode materials contain paramagnetic ions, and their NMR spectra are dominated by hyperfine and quadrupolar interactions, giving rise to broad resonances with extensive spinning sideband manifolds. In principle, careful analysis of these spectra can reveal information about local structural distortions, magnetic exchange interactions, structural inhomogeneities (Li⁺concentration gradients), and even the presence of redox-active O anions. In this Perspective, we examine the primary interactions governing ¹⁷O NMR spectroscopy of LIB cathodes and outline how ¹⁷O NMR may be used to elucidate the structure of pristine cathodes and their structural evolution on cycling, providing insight into the challenges in obtaining and interpreting the spectra. We also discuss the use of ¹⁷O NMR in the context of anionic redox and the role this technique may play in understanding the charge compensation mechanisms in high-capacity cathodes, and we provide suggestions for employing ¹⁷O NMR in future avenues of research.

Original language	English
Pages (from-to)	18714-18729
Number of pages	16
Journal	Journal of the American Chemical Society
Volume	144
Issue number	41
Early online date	6 Oct 2022
DOIs	https://doi.org/10.1021/jacs.2c02927
Publication status	Published - 19 Oct 2022

Bibliographical note

Funding Information:
E.N.B. acknowledges funding from the Engineering Physical Sciences Research Council (EPSRC) via the National Productivity Interest Fund (NPIF) 2018. C.P.G., I.D.S., and P.J.R. acknowledge the NorthEast Center for Chemical Energy Storage (NECCES), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0012583. E.N.B. would also like to dedicate this work to K.R. Bassey.

Data Availability Statement

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c02927.

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10.1021/jacs.2c02927Licence: CC BY

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Copyright © 2022 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/
Final published version, 6.1 MBLicence: CC BY

Cite this

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title = "17O NMR Spectroscopy in Lithium-Ion Battery Cathode Materials: Challenges and Interpretation",

abstract = "Modern studies of lithium-ion battery (LIB) cathode materials employ a large range of experimental and theoretical techniques to understand the changes in bulk and local chemical and electronic structures during electrochemical cycling (charge and discharge). Despite its being rich in useful chemical information, few studies to date have used 17O NMR spectroscopy. Many LIB cathode materials contain paramagnetic ions, and their NMR spectra are dominated by hyperfine and quadrupolar interactions, giving rise to broad resonances with extensive spinning sideband manifolds. In principle, careful analysis of these spectra can reveal information about local structural distortions, magnetic exchange interactions, structural inhomogeneities (Li+concentration gradients), and even the presence of redox-active O anions. In this Perspective, we examine the primary interactions governing 17O NMR spectroscopy of LIB cathodes and outline how 17O NMR may be used to elucidate the structure of pristine cathodes and their structural evolution on cycling, providing insight into the challenges in obtaining and interpreting the spectra. We also discuss the use of 17O NMR in the context of anionic redox and the role this technique may play in understanding the charge compensation mechanisms in high-capacity cathodes, and we provide suggestions for employing 17O NMR in future avenues of research.",

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N2 - Modern studies of lithium-ion battery (LIB) cathode materials employ a large range of experimental and theoretical techniques to understand the changes in bulk and local chemical and electronic structures during electrochemical cycling (charge and discharge). Despite its being rich in useful chemical information, few studies to date have used 17O NMR spectroscopy. Many LIB cathode materials contain paramagnetic ions, and their NMR spectra are dominated by hyperfine and quadrupolar interactions, giving rise to broad resonances with extensive spinning sideband manifolds. In principle, careful analysis of these spectra can reveal information about local structural distortions, magnetic exchange interactions, structural inhomogeneities (Li+concentration gradients), and even the presence of redox-active O anions. In this Perspective, we examine the primary interactions governing 17O NMR spectroscopy of LIB cathodes and outline how 17O NMR may be used to elucidate the structure of pristine cathodes and their structural evolution on cycling, providing insight into the challenges in obtaining and interpreting the spectra. We also discuss the use of 17O NMR in the context of anionic redox and the role this technique may play in understanding the charge compensation mechanisms in high-capacity cathodes, and we provide suggestions for employing 17O NMR in future avenues of research.

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