Origin of Double Ligand Holes and Abnormal Inductive Effect of np6 Elements in Ni‐rich Cathodes

Ni‐rich cathodes stand out for their ability to achieve high energy density in Li‐ion batteries. However, their long‐term cycling stability is challenged by excessive oxygen redox activity, the fundamental atomic‐scale behavior of which remains poorly understood—particularly the nature of oxygen double ligand hole states and their suppression. This study demonstrates that Jahn–Teller distortion promotes unexpected intralayer O─O pairing, coupled with Ni─O hybridization, leading to the formation of double ligand holes in LiNiO2 and oxygen evolution at high state‐of‐charge (SoC). These intralayer O─O pairs are visualized by 4D scanning transmission electron microscopy and identified as peroxo‐like species with an average O─O distance of 2.428 Å at 60% SoC. Meanwhile, substitution with elements such as Al3+ and Sc3+, which possess low electronegativity and an np6 electron configuration, induces an abnormal inductive effect that deviates from conventional electronegativity‐based frameworks. This phenomenon is attributed to electron localization on lattice oxygen, which effectively prevents local lattice distortion and the accumulation of TM─O and O─O ligand holes. These findings establish a fundamental correlation between structural deformation and ligand hole states, advancing the conceptual framework for Ni‐rich cathode design beyond conventional molecular orbital theory and electronegativity‐guided substitution strategies.