Enhancing surface oxygen retention through theory-guided doping selection in Li_{1-: x} NiO₂for next-generation lithium-ion batteries

Layered lithium metal oxides have become the cathode of choice for state-of-the-art Li-ion batteries (LIBs), particularly those with high Ni content. However, the Ni-rich cathode materials suffer from extensive oxygen evolution, which contributes to the formation of surface rocksalt phases as well as thermal instability. Using first-principles calculations, we systematically evaluate the effectiveness of doping elements to enhance surface oxygen retention of Li1-xNiO2. The evaluation process includes (i) choosing the most stable surface facet from the perspective of equilibrium surface stability analysis of as-synthesized LiNiO2, (ii) determining the preferable atomic site and segregation behavior for each dopant, and (iii) evaluating the surface oxygen retention ability of doped-Li1-xNiO2 (0.25 ≤ x ≤ 1) compared to the pristine material. We also discuss and rationalize the ability of these elements to enhance surface oxygen retention based on local environment descriptors such as dopant-oxygen bond strength. Overall, W, Sb, Ta and Ti are predicted as the most promising surface dopants due to their strong oxygen bonds and robust surface segregation behavior. Finally, Sb-doped LiNiO2 is synthesized and shown to present a surface enrichment of Sb and a significantly improved electrochemical performance, comparing with pristine LiNiO2. This work provides a generic approach that can lead to the greatly enhanced stabilization of all high-energy cathode materials, particularly the high Ni and low Co oxides.