Vacancy-induced Modification of Electronic Band Structure of LiBO$_{2}$ Material as Cathode Surface Coating of Lithium-ion Batteries (2503.11941v1)

Abstract: LiBO${2}$ is an electronic insulator and a promising surface coating for stabilizing high-voltage cathodes in lithium-ion batteries. Despite its potential, the functional mechanisms of this coating remain unclear, particularly the transport of lithium ions and electrons through LiBO${2}$ in the presence of lattice vacancies. This understanding is critical for the design and development of LiBO${2}$-based materials. In our previous work [Ziemke $\textit{et al.}$, J. Mater. Chem. A, 2025, $\textbf{13}$, 3146-3162], we used density functional theory (DFT) calculations to investigate the impact of lattice vacancies on Li-ion transport in both tetragonal (t-LBO) and monoclinic (m-LBO) polymorphs of LiBO${2}$, revealing that B vacancies in either polymorph enhanced lithium-ion transport. In this study, we expand on these findings by using DFT calculations to examine the effects of lattice vacancies on the electronic properties of both t-LBO and m-LBO polymorphs,focusing on the electronic band structure. Our analysis shows that B vacancies can enhance the electronic insulation of t-LBO while improving the ionic conduction of m-LBO. The combined results of our previous and current works indicate that B vacancy generation in LiBO${2}$ may enable t-LBO to function as a promising solid electrolyte and enhance the performance of m-LBO as a conformal cathode coating in lithium-ion batteries. Overall, generating B vacancies, such as through neutron irradiation, would offer a viable strategy to improve the functionality of LiBO${2}$ as a promising material for energy storage applications.