Understanding Lithium Local Environments in LiMn0.5Ni0.5O2 Cathodes: A DFT-Supported 6Li Solid-State NMR Study

Shin, Woochul; Garcia, Juan C.; Vu, Anh; Ji, Xiulei; Iddir, Hakim; Dogan, Fulya

doi:10.1021/acs.jpcc.1c10470

Title: Understanding Lithium Local Environments in LiMn_0.5Ni_0.5O₂ Cathodes: A DFT-Supported ⁶Li Solid-State NMR Study

Journal Article · 22 February 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.1c10470 · OSTI ID:1905077

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Oregon State Univ., Corvallis, OR (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Oregon State Univ., Corvallis, OR (United States)

LiMn_0.5Ni_0.5O₂ has been plagued by the structural failure driven by the irreversible phase change upon subsequent cycling and the structural degradation caused by the seemingly unavoidable Li/Ni exchange. This begs for a better understanding of the correlation between lithium local structures, synthesis conditions, and overall electrochemical properties of materials. In this study, we use density functional theory (DFT) to assist experimental ⁶Li solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy to understand the nature and change in lithium local structures with extended annealing times (168 vs 15 h) synthesized at 900 °C. To correlate the NMR peak changes after different synthesis conditions, we calculated the NMR spectra of representative low-energy model configurations of LiMn_0.5Ni_0.5O₂ composition–zigzag, row, and flower structures–as well as the influence of Ni/Mn ordering and Li/Ni exchange on each spectrum using a supercell that is large enough to allow us to consider the effect of different relative configurations of adjacent transition metal (TM) layers. The analysis based on a combination of the calculated NMR and the experimental spectra suggests that most configurations contributing to the experimental spectra are in fact composed of a blend of configurations higher in energy than the classical well-ordered ground-state structures. Further, the extended annealing of LiMn_0.5Ni_0.5O₂ slightly enhances Ni/Mn and Li/Mn orderings while reducing the Li/Ni mixing ratio. This study shows how DFT calculations are crucial in providing a better understanding of the experimental characterization data and therefore local environments and domain structures in oxide materials, such as Li-ion battery cathodes.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Laboratory Computing Resource Center (LCRC)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1905077

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 9 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemical structure
Energy
Layers
Lithium
Transition metals

Title: Understanding Lithium Local Environments in LiMn0.5Ni0.5O2 Cathodes: A DFT-Supported 6Li Solid-State NMR Study

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References (44)

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Title: Understanding Lithium Local Environments in LiMn_0.5Ni_0.5O₂ Cathodes: A DFT-Supported ⁶Li Solid-State NMR Study