Structures, electronic properties, and delithiation thermodynamics of the heteroepitaxial α-Al₂O₃//LiMn₂O₄ (001) and (111) interfaces

Surface coatings play a pivotal role in enhancing the performance of secondary lithium-ion batteries by mitigating undesirable electrolyte activity towards the cathode materials. Metal oxide candidates have been investigated extensively, with α-Al2O3 emerging as a particularly promising coating material owing to its exceptional mechanical and thermal stability alongside low electrical conductivity. Despite the extensive exploration of this application of α-Al2O3, insight into the interplay between the coating layer and the cathode substrate remains incomplete. To address this lack of knowledge, this study employs density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+U-D3) to comprehensively investigate the interfacial geometries, stabilities, and electronic properties of α-Al2O3-coated LiMn2O4 (001) and (111) interfaces of varying thicknesses. The individual surfaces were modelled first before constructing the interfaces. We found that the α-Al2O3 (11 0) and (0001) surfaces match the LiMn2O4 (001) and (111) facets well, exhibiting {1132} and {3121} configurations, respectively, with corresponding misfits of 2.40% and 2.75%. We calculated the largest adhesion energies of 0.16 and 0.10 eV/A2 for monolayers with the {1132} and {3121} configurations, respectively, with the stability decreasing as the thickness of the α-Al2O3 layer increases. Further analysis reveals a minor charge accumulation on the substrate, attributed to charge accumulation on the oxygen atoms that participate in the Al-O bond. In contrast, we observed a depletion of charge on the manganese atoms that form the MnO6 units. The vacancy formation energies increase following partial delithiation, prompting minor charge depletion on neighbouring Mn atoms in the form of charge redistribution. The calculated work function increases with respect to the pristine surfaces, indicating that the coated interfaces are less reactive.