Inside‐Outside Lithium Deposition Achieved by the Unusual Strategy of Constructing the Hierarchical Lithiophilicity for Dendrite‐Free and Durable Lithium Metal Anode

Abstract Uncontrollable dendritic lithium (Li) growth and huge volume fluctuation are critical issues for the commercialization of Li metal anode. This work reports a three‐dimensional conductive host with hierarchical lithiophilicity to promote the uniform Li plating/stripping. Except for the common merits of the large surface area and excellent conductivity, the unique structural and compositional design, Ag nanoparticles encapsulated inside nitrogen‐doped carbon hollow spheres (Ag@NCHSs), allows a model of inside‐outside Li deposition due to the promising lithiophilicity of Ag component. This type of Li deposition strategy is evidenced by in‐situ optical microscope, in‐situ X‐ray diffraction (XRD) patterns and endows a promising ability to overcome the fatal issues of Li metal anode even at high areal capacities and current densities. As a result, the developed host with the hierarchical lithiophilicity enables a remarkable enhancement of cycling performances. The strategy of constructing hierarchical lithiophilicity brings new insights to stabilize the Li metal anode.