Dual‐Site Geometry Mediates Dynamic LiO ₂ Binding for Efficient Lithium–Oxygen Batteries

Abstract

ABSTRACT Lithium–oxygen batteries (LOBs) offer high energy density through multi‐electron transfer, but their 2e − pathway generates unstable intermediates such as lithium superoxide (LiO 2 ), leading to complex reaction kinetics and poor reversibility. Herein, we propose an electronegativity‐mediated strategy to dynamically regulate LiO 2 binding on catalyst surfaces. By tuning the geometry and spacing of dual‐active sites (DAS), we reshape orbital interactions and coordination environments, enabling precise control over electron density and adsorption‐desorption microenvironments. This atomic‐scale regulation establishes a “bridged adsorption” mode that stabilizes key intermediates, optimizes Li‐O bond activation, and enhances the “adsorption‐activation‐dissociation” sequence of reactive species. Consequently, lithium–oxygen batteries exhibit high capacity and prolonged cycling stability. More broadly, we identify a universal DAS spacing descriptor that integrates symmetry breaking with electronic configuration, providing a general design principle to overcome linear scaling relationships (LSRs) and unlock intrinsic catalytic activity for oxygen electrocatalysis.