DFT analysis of spin configurations and its impact on manganese oxide cathodes

¹ Materials Modelling Centre, University of Limpopo, Private Bag x1106 Sovenga, 0727, South Africa
² Data Intensive Research Initiative of South Africa, Council for Scientific and Industrial Research, P.O. Box 395, Pretoria, 0001, South Africa

¹ Corresponding author: This email address is being protected from spambots. You need JavaScript enabled to view it.

Abstract

The electronic structure of lithium manganese oxide cathode materials is dependent on the choice of functional and spin configuration, necessitating a thorough analysis to accurately describe their structural and electronic properties. While these materials are appealing for lithium-ion batteries due to their high capacity, abundance, and low cost, accurately modelling their electronic properties remains challenging due to strong correlations in the manganese d orbitals. In this study, we employ first-principles calculations using the GGA+U functional to investigate the influence of spin configurations on the structural and electronic properties of these cathode materials. Our results shows that the antiferromagnetic (AFM) configuration gives a band gap consistent with experimental observations, whereas the ferromagnetic (FM) configuration produces a larger band gap. This shows the critical role of spin configuration in determining the electronic properties of these materials, indicating the importance of precise spin state modelling for accurate materials. These findings shows the importance of benchmarking beyond default ferromagnetic settings, including AFM configurations, to improve the accuracy of calculated properties in Mn-based cathode materials.