Unusual double ligand holes as catalytic active sites in LiNiO₂

Designing efficient catalyst for the oxygen evolution reaction (OER) is of importance for energy conversion devices. The anionic redox allows formation of O-O bonds and offers higher OER activity than the conventional metal sites. Here, we successfully prepare LiNiO₂ with a dominant 3d⁸L configuration (L is a hole at O 2p) under high oxygen pressure, and achieve a double ligand holes 3d⁸L² under OER since one electron removal occurs at O 2p orbitals for Ni^III oxides. LiNiO₂ exhibits super-efficient OER activity among LiMO₂, RMO₃ (M = transition metal, R = rare earth) and other unary 3d catalysts. Multiple in situ/operando spectroscopies reveal Ni^III→Ni^IV transition together with Li-removal during OER. Our theory indicates that Ni^IV (3d⁸L²) leads to direct O-O coupling between lattice oxygen and *O intermediates accelerating the OER activity. These findings highlight a new way to design the lattice oxygen redox with enough ligand holes created in OER process.