Design and tailoring of carbon-Al₂O₃ double coated nickel-based cation-disordered cathodes towards high-performance Li-ion batteries

Li-excess cation-disordered oxide cathodes have attracted increasing interests owing to their high energy density originated from cumulative cationic & anionic redox activity. In particular, Ni-based cation-disordered oxides exhibit high theoretical capacity for 2 e⁻ reactions of Ni²⁺/Ni⁴⁺, while the severe overlapping between Ni 3d and O 2p orbitals restricts Ni redox capacity and unstable O redox deteriorates the cycling performance. Benefiting from advanced data mining and high-throughput theoretical calculations technology, we demonstrated that the capacity and cycling performance of Ni-based cation-disordered oxide can be synergically enhanced by carbon/Al₂O₃ double coating and partial Al³⁺ substitution. The synergistic mechanism is unveiled via X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS) characterization together with first-principles calculations. It is confirmed that carbon coating increases the capacity by promoting the formation of peroxo-like species, which boosts O redox activity. Partial intercalating Al³⁺ enhances the Ni redox reaction by shortening the band overlap between Ni and O. Furthermore, Al₂O₃ coating and Al³⁺ doping improved the cycling stability of the cathode material owing to the shielding effect on side reaction and more stable O lattice. This synergistic strategy with nano-coating layer provides a promising pathway to accelerate the discovery of high-energy cation-disordered oxides based cathode materials. © 2022 Elsevier Ltd