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

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

doi:10.1038/s41563-024-02032-6

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

Journal Article · Thu Oct 17 00:00:00 EDT 2024 · Nature Materials

DOI:https://doi.org/10.1038/s41563-024-02032-6· OSTI ID:2585851

^[1]; ^[2]; Busse, Grace M. ^[1]; Lim, Kipil ^[1]; ^[1]; ^[3]; ^[4]; ^[5]

Stanford University, CA (United States)
University of Bath (United Kingdom)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
University of Oxford (United Kingdom)
Stanford University, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

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. Furthermore, 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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: National Science Foundation Graduate Research Fellowship; US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 2585851

Alternate ID(s):: OSTI ID: 2572683

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 1 Vol. 24; ISSN 1476-4660; ISSN 1476-1122

Publisher:: Springer Science and Business Media LLCCopyright Statement

Country of Publication:: United States

Language:: English

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Experimental Data for "Substantial Oxygen Loss and Chemical Expansion in Lithium-Rich Layered Oxides at Moderate Delithiation" Csernica, Peter Zenodo https://doi.org/10.5281/zenodo.13823472	dataset	January 2024

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