Hybrid Density Functional Theory Comparison of Oxygen Release and Solvent Decomposition Kinetics on LixNiO2 Surfaces

Leung, Kevin; Zhang, Minghao

doi:10.1021/acs.jpclett.4c00424

Hybrid Density Functional Theory Comparison of Oxygen Release and Solvent Decomposition Kinetics on Li_xNiO₂ Surfaces

Journal Article · Wed Apr 24 00:00:00 EDT 2024 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.4c00424· OSTI ID:2369211

^[1]; Zhang, Minghao ^[2]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Univ. of California, San Diego, La Jolla, CA (United States)

High-nickel-content layered oxides are among the most promising electric vehicle battery cathode materials. However, their interfacial reactivity with electrolytes and tendency toward oxygen release (possibly yielding reactive ¹O₂) remain degradation concerns. Elucidating the most relevant (i.e., fastest) interfacial degradation mechanism will facilitate future mitigation strategies. We apply screened hybrid density functional (HSE06) calculations to compare the reaction kinetics of Li_xNiO₂ surfaces with ethylene carbonate (EC) with those of O₂ release. Further, on both the (001) and (104) facets, EC oxidative decomposition exhibits lower activation energies than O₂ release. Our calculations, coupled with previously computed liquid-phase reaction rates of ¹O₂ with EC, strongly question the role of “reactive ¹O₂” species in electrolyte oxidative degradation. The possible role of other oxygen species is discussed. To deal with the challenges of modeling Li_xNiO₂ surface reactivity, we emphasize a “local structure” approach instead of pursuing the global energy minimum.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2369211

Report Number(s):: SAND--2024-06752J

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 17 Vol. 15; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Hybrid Density Functional Theory Comparison of Oxygen Release and Solvent Decomposition Kinetics on Li_xNiO₂ Surfaces