Driving inward growth of lithium metal in hollow microcapsule hosts by heteroatom‐controlled nucleation

Abstract The application of Li metal anodes in rechargeable batteries is impeded by safety issues arising from the severe volume changes and formation of dendritic Li deposits. Three‐dimensional hollow carbon is receiving increasing attention as a host material capable of accommodating Li metal inside its cavity; however, uncontrollable and nonuniform deposition of Li remains a challenge. In this study, we synthesize metal–organic framework‐derived carbon microcapsules with heteroatom clusters (Zn and Ag) on the capsule walls and it is demonstrated that Ag‐assisted nucleation of Li metal alters the outward‐to‐inward growth in the microcapsule host. Zn‐incorporated microcapsules are prepared via chemical etching of zeolitic imidazole framework‐8 polyhedra and are subsequently decorated with Ag by a galvanic displacement reaction between Ag⁺ and metallic Zn. Galvanically introduced Ag significantly reduces the energy barrier and increases the reaction rate for Li nucleation in the microcapsule host upon Li plating. Through combined electrochemical, microstructural, and computational studies, we verify the beneficial role of Ag‐assisted Li nucleation in facilitating inward growth inside the cavity of the microcapsule host and, in turn, enhancing electrochemical performance. This study provides new insights into the design of reversible host materials for practical Li metal batteries.