Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation

Peter M. Csernica; Kit McColl; Grace M. Busse; Kipil Lim; Diego F. Rivera; David A. Shapiro; M. Saiful Islam; William C. Chueh

doi:10.1038/s41563-024-02032-6

Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation

Peter M. Csernica, Kit McColl, Grace M. Busse, Kipil Lim, Diego F. Rivera, David A. Shapiro, M. Saiful Islam, William C. Chueh

Department of Chemistry

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Abstract

Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li_1.18–xNi_0.21Mn_0.53Co_0.08O_2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O₂ per gram of Li_1.18–xNi_0.21Mn_0.53Co_0.08O_2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g⁻¹ for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li⁺. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.

Original language	English
Article number	2091
Pages (from-to)	92-100
Number of pages	9
Journal	Nature Materials
Volume	24
Issue number	1
Early online date	17 Oct 2024
DOIs	https://doi.org/10.1038/s41563-024-02032-6
Publication status	Published - 31 Jan 2025

Data Availability Statement

Experimental data for this work are available via Zenodo at https://doi.org/10.5281/zenodo.13823472 (ref. 63). This repository hosts the data for Figs. 1–3 and 5, Supplementary Figs. 2–5, 7–9, 13–15, 17 and 18 and Supplementary Table 3. Computational data for all computational figures (Fig. 4 and Supplementary Figs. 10–13) are available via Zenodo at https://doi.org/10.5281/zenodo.13786035 (ref. 64).

Acknowledgements

We thank Samsung Advanced Institute of Technology (S.-J. Ahn) for providing the material used in this work.

Funding

This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, Battery Materials Research Program, US Department of Energy (DOE). M.S.I. and K.M. are grateful to the Faraday Institution CATMAT project (EP/S003053/1, FIRG016) for financial support, and to the HEC Materials Chemistry Consortium (EP/R029431/1) for Archer-2 supercomputer facilities. P.M.C. acknowledges support through the Stanford Graduate Fellowship as a Winston and Fu-Mei Chen fellow and through the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. D.F.R. acknowledges support through the National Science Foundation Graduate Research Fellowship under grant no. DGE-1656518. Use of the SSRL, SLAC National Accelerator Laboratory, is supported by DOE, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-76SF00515. This research used resources of the ALS, which is a DOE Office of Science User Facility, under contract no. DE-AC02-05CH11231

Funders	Funder number
Office of Energy Efficiency and Renewable Energy
SSRL
SLAC National Accelerator Laboratory
Samsung Advanced Institute of Technology
Vehicle Technologies Office
U.S. Department of Energy
Office of Science	DE-AC02-05CH11231
Basic Energy Sciences	DE-AC02-76SF00515
Faraday Institution	EP/S003053/1, FIRG016
Higher Education Commission, Pakistan	EP/R029431/1
National Science Foundation	DGE-1656518

ASJC Scopus subject areas

General Chemistry
General Materials Science
Condensed Matter Physics
Mechanics of Materials
Mechanical Engineering

UN SDGs

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

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10.1038/s41563-024-02032-6

Substantial_O_Loss_Accepted
This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: https://doi.org/10.1038/s41563-024-02032-6
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Cite this

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abstract = "Delithiation of layered oxide electrodes triggers irreversible oxygen loss, one of the primary degradation modes in lithium-ion batteries. However, the delithiation-dependent mechanisms of oxygen loss remain poorly understood. Here we investigate the oxygen non-stoichiometry in Li1.18–xNi0.21Mn0.53Co0.08O2–δ electrodes as a function of Li content by using cycling protocols with long open-circuit voltage steps at varying states of charge. Surprisingly, we observe substantial oxygen loss even at moderate delithiation, corresponding to 2.5, 4.0 and 7.6 ml O2 per gram of Li1.18–xNi0.21Mn0.53Co0.08O2–δ after resting at upper capacity cut-offs of 135, 200 and 265 mAh g−1 for 100 h. Our observations suggest an intrinsic oxygen instability consistent with predictions of high oxygen activity at intermediate potentials versus Li/Li+. In addition, we observe a large chemical expansion coefficient with respect to oxygen non-stoichiometry, which is about three times greater than those of classical oxygen-deficient materials such as fluorite and perovskite oxides. Our work challenges the conventional wisdom that deep delithiation is a necessary condition for oxygen loss in layered oxide electrodes and highlights the importance of calendar ageing for investigating oxygen stability.",

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Substantial oxygen loss and chemical expansion in lithium-rich layered oxides at moderate delithiation

Abstract

Data Availability Statement

Acknowledgements

Funding

ASJC Scopus subject areas

UN SDGs

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