Delocalized Electronic Engineering of Ni₅P₄ Nanoroses for Durable Li–O₂ Batteries

Abstract The sluggish kinetics and issues associated with the parasitic reactions of cathodes are major obstacles to the large‐scale application of Li–O₂ batteries (LOBs), despite their large theoretical energy density. Therefore, efficient electrocatalyst design is critical for optimizing their performance. Ni₅P₄ is analyzed theoretically as a cathode material, and the downshift of the d‐band center is found to enhance electron occupation in antibonding orbits, providing a valuable descriptor for understanding and enhancing the intrinsic electrocatalytic activity. In this study, it is demonstrated that incorporating additional nitrogen atoms into Ni₅P₄ nanoroses regulates the electronic structure, resulting in superior electrocatalytic performance in LOBs. Further spectroscopic analysis and density functional theory calculations reveal that the incorporated nitrogen sites can effectively induce localized structure polarization, lowering the energy barrier for the production of desirable intermediates and thus enhancing battery capacity and preventing cell degradation. This approach provides a sound basis for developing advanced electrode materials with optimized electronic structures for high‐performance LOBs.