Regulating the Lithium Ions’ Local Coordination Environment through Designing a COF with Single Atomic Co Site to Achieve Dendrite‐Free Lithium‐Metal Batteries

Abstract The detrimental growth of lithium dendrites and unstable solid electrolyte interphase (SEI) inhibit the practical application of lithium‐metal batteries. Herein, atomically dispersed cobalt coordinate conjugated bipyridine‐rich covalent organic framework (sp²c‐COF) is explored as an artificial SEI on the surface of the Li‐metal anode to resolve these issues. The single Co atoms confined in the structure of COF enhance the number of active sites and promote electron transfer to the COF. The synergistic effects of the Co─N coordination and strong electron‐withdrawing cyano‐group can adsorb the electron from the donor (Co) at a maximum and create an electron‐rich environment, hence further regulating the Li⁺ local coordination environment and achieving uniform Li‐nucleation behavior. Furthermore, in situ technology and density functional theory calculations reveal the mechanism of the sp²c‐COF‐Co inducing Li uniform deposition and promoting Li⁺ rapid migration. Based on these advantages, the sp²c‐COF‐Co modified Li anode exhibits a low Li‐nucleation barrier of 8 mV, and excellent cycling stability of 6000 h.