Spin‐Orbit Coupling Enabled Spin‐Selective Oxygen Redox in Ce Single‐Atom Catalysts for High‐Performance Li‐O ₂ Batteries

ABSTRACT

Lithium–oxygen (Li–O ₂ ) batteries hold great promise for next‐generation energy storage owing to their ultrahigh theoretical energy density, yet their practical application is severely hindered by sluggish reaction kinetics and large overpotentials arising from the spin‑multiplicity mismatch between triplet O ₂ and singlet Li ₂ O ₂ . Here, we report a cerium single‑atom catalyst with atomically dispersed Ce‐N ₄ sites (Ce _SA ‐NC), which inherently resolves this spin‑forbidden barrier via strong spin‐orbit coupling (SOC). The heavy‑atom effect and abundant 4f electrons of Ce endow the active sites with pronounced SOC, which breaks the symmetry of Ce f orbitals and enables selective hybridization between spin‑up Ce f states and the p orbitals of oxygen species. This creates distinct spin‑selective charge‑transfer pathways for both oxygen reduction/evolution reactions, substantially reducing the Li ₂ O ₂ decomposition energy barrier. Consequently, Ce _SA ‐NC delivers a remarkably low overpotential of 0.64 V, impressive rate performance, and long‐term cycling stability of over 1600 h. This work not only demonstrates a high‑performance cathode catalyst for Li–O ₂ batteries but also establishes spin‐orbit coupling as a powerful and general principle for overcoming spin‑related kinetic bottlenecks in oxygen electrocatalysis, offering new design avenues for advanced energy devices.