Scivetti, Ivan and Teobaldi, Gilberto ORCID: 0000-0001-6068-6786
(2015)
(Sub)surface-Promoted Disproportionation and Absolute Band Alignment in High-Power LiMn<sub>2</sub>O<sub>4</sub> Cathodes.
JOURNAL OF PHYSICAL CHEMISTRY C, 119 (37).
pp. 21358-21368.
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Abstract
We present an isotropic (Ueff) and anisotropic (U-J) Hubbard and van der Waals (vdW)-corrected density functional theory study of bulk and low-index surfaces of lithium manganese oxide LiMn2O4 (LMO), a promising cathode material for high-power Li-ion batteries. Use of anisotropic (U-J) corrections in the simulation of bulk LMO leads to improved agreement with available experimental data, whereas vdW corrections do not affect the results. Carefully converged relaxation of slab geometries indicates that when vdW corrections are included the spinel-reconstructed Li-terminated (111) surface is always energetically favored for both Ueff and (U-J) methods regardless of the LMO phase. In contrast, neglect of vdW corrections leads to the (001) surface in orthorhombic phase being favored when applying (U-J) corrections. Independent of the simulation protocol and crystalline phase, (111) truncation, reconstructed or not, promotes LMO disproportionation and appearance of Mn2+ cations without the need of any chemical or electrochemical surface treatment. Absolute band alignment of the considered surfaces reveals increased reductive propensity for the (111) terminations. Finally, our computational findings are discussed with respect to available data on the observed surface dependence of Mn disproportionation and electrochemical passivation of LMO substrates.
Item Type: | Article |
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Subjects: | ?? QC ?? ?? QD ?? |
Depositing User: | Symplectic Admin |
Date Deposited: | 22 Sep 2015 10:03 |
Last Modified: | 05 Oct 2023 09:26 |
DOI: | 10.1021/acs.jpcc.5b06522 |
Open Access URL: | http://pubs.acs.org/doi/10.1021/acs.jpcc.5b06522 |
Related URLs: | |
URI: | https://livrepository.liverpool.ac.uk/id/eprint/2027279 |
Available Versions of this Item
- (Sub)surface-Promoted Disproportionation and Absolute Band Alignment in High-Power LiMn<sub>2</sub>O<sub>4</sub> Cathodes. (deposited 22 Sep 2015 10:03) [Currently Displayed]