Tuning 4f‐Center Electron Structure by Schottky Defects for Catalyzing Li Diffusion to Achieve Long‐Term Dendrite‐Free Lithium Metal Battery

Lithium metal is considered as the most prospective electrode for next‐generation energy storage systems due to high capacity and the lowest potential. However, uncontrollable spatial growth of lithium dendrites and the crack of solid electrolyte interphase still hinder its application. Herein, Schottky defects are motivated to tune the 4f‐center electronic structures of catalysts to provide active sites to accelerate Li transport kinetics. As experimentally and theoretically confirmed, the electronic density is redistributed and affected by the Schottky defects, offering numerous active catalytic centers with stronger ion diffusion capability to guide the horizontal lithium deposition against dendrite growth. Consequently, the Li electrode with artificial electronic‐modulation layer remarkably decreases the barriers of desolvation, nucleation, and diffusion, extends the dendrite‐free plating lifespan up to 1200 h, and improves reversible Coulombic efficiency. With a simultaneous catalytic effect on the conversions of sulfur species at the cathodic side, the integrated Li–S full battery exhibits superior rate performance of 653 mA h g−1 at 5 C, high long‐life capacity retention of 81.4% at 3 C, and a high energy density of 2264 W h kg−1 based on sulfur in a pouch cell, showing the promising potential toward high‐safety and long‐cycling lithium metal batteries. The electronic structure of CeO2 is initially modulated by introducing Schottky defects, providing more active sites for interacting with lithium ion/atom. Higher Schottky defect concentration is more beneficial to motivate charge transfer effect on manipulating horizontal deposition, achieving uniform and smooth plating Li surface with long‐term cycling of 1200h and ultra‐low overpotentials.