Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni₁/₃Mn₁/₃Co₁/₃)O₂: Insights from First-Principles
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Hudson, Blake G., et al. “Understanding the Mechanism of Secondary Cation Release from the (001) Surface of Li(Ni₁/₃Mn₁/₃Co₁/₃)O₂: Insights from First-Principles.” The Journal of Physical Chemistry C 127, no. 43 (2023): 21022–32. https://doi.org/10.1021/acs.jpcc.3c02764.
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.3c02764.
Abstract
The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(NiₓMnᵧCo₁₋ₓ₋ᵧ)O₂ (NMC), the mechanisms of chemical processes at the solid–water interface are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. The study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn.