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Assessing cathode property prediction: Via exchange-correlation functionals with and without long-range dispersion corrections

Long, OY and Sai Gautam, G and Carter, EA (2021) Assessing cathode property prediction: Via exchange-correlation functionals with and without long-range dispersion corrections. In: Physical Chemistry Chemical Physics, 23 (43). pp. 24726-24737.

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Official URL: https://doi.org/10.1039/d1cp03163e


We benchmark calculated interlayer spacings, average topotactic voltages, thermodynamic stabilities, and band gaps in layered lithium transition-metal oxides (TMOs) and their de-lithiated counterparts, which are used in lithium-ion batteries as positive electrode materials, against available experimental data. Specifically, we examine the accuracy of properties calculated within density functional theory (DFT) using eight different treatments of electron exchange-correlation: the strongly constrained and appropriately normed (SCAN) and Perdew-Burke-Ernzerhof (PBE) density functionals, Hubbard-U-corrected SCAN and PBE (i.e., SCAN+U and PBE+U), and SCAN(+U) and PBE(+U) with added long-range dispersion (D) interactions (i.e., DFT(+U)+D). van der Waals interactions are included respectively via the revised Vydrov-Van Voorhis (rVV10) for SCAN(+U) and the DFT-D3 for PBE(+U). We find that SCAN-based functionals predict larger voltages due to an underestimation of stability of the MO2 systems, while also predicting smaller interlayer spacings compared to their PBE-based counterparts. Furthermore, adding dispersion corrections to PBE has a greater effect on voltage predictions and interlayer spacings than with SCAN, indicating that DFT-SCAN-despite being a ground-state theory-fortuitously captures some short and medium-range dispersion interactions better than PBE. While SCAN-based and PBE-based functionals yield qualitatively similar band gap predictions, there is no significant quantitative improvement of SCAN-based functionals over the corresponding PBE-based versions. Finally, we expect SCAN-based functionals to yield more accurate property predictions than the respective PBE-based functionals for most TMOs, given SCAN's stronger theoretical underpinning and better predictions of systematic trends in interlayer spacings, intercalation voltages, and band gaps obtained in this work. © the Owner Societies.

Item Type: Journal Article
Publication: Physical Chemistry Chemical Physics
Publisher: Royal Society of Chemistry
Additional Information: The copyright for this article belongs to Royal Society of Chemistry
Keywords: Cathodes; Dispersions; Energy gap; Forecasting; Ground state; Lithium compounds; Lithium-ion batteries; Transition metal oxides; Transition metals; Van der Waals forces, Density-functional-theory; Dispersion correction; Exchange-correlation functionals; Functionals; Interlayer spacings; Perdew-burke-ernzerhof; Positive-electrode materials; Property predictions; Range dispersion; Transition-metal oxides, Density functional theory
Department/Centre: Division of Mechanical Sciences > Materials Engineering (formerly Metallurgy)
Date Deposited: 21 Dec 2021 05:52
Last Modified: 21 Dec 2021 05:52
URI: http://eprints.iisc.ac.in/id/eprint/70695

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