First-principles calculations to investigate the impact of fluorine doping on electrochemical properties of Li-rich LiMnO layered cathode materials.

Li-rich layered oxides are promising candidates for high-capacity Li-ion battery cathode materials. In this study, we employ first-principles calculations to investigate the effect of F doping on Li-rich LiMnO layered cathode materials. Our findings reveal that both LiMnO and LiMnOF exhibit significant volume changes (greater than 10%) during deep delithiation, which could hinder the cycling of more Li ions from these two materials. For LiMnO, it is observed that oxygen ions lose electrons to compensate for charge during the delithiation process, leading to a relatively high voltage plateau. After F doping, oxidation occurs in both the cationic (Mn) and anionic (O) components, resulting in a lower voltage plateau at the beginning of the charge, which can be attributed to the oxidation of Mn to Mn. Additionally, F doping can somewhat suppress the release of oxygen in LiMnO, improving the stability of anionic oxidation. However, the increase of the activation barriers for Li diffusion can be observed after F doping, due to stronger electrostatic interactions between F and Li, which adversely affects the cycling kinetics of LiMnOF. This study enhances our understanding of the impact of F doping in LiMnO based on theoretical calculations.