A 3D Lithiophilic Host for Dendrite‐Free Lithium Metal Anode via One‐Step Carbonization of an Energetic Metal‐Organic Framework

Abstract Low Coulombic efficiency (CE) and safety issues are huge problems that hinder the practical application of Li metal anodes. Constructing Li host structures decorated with functional species can restrain the growth of Li dendrites and alleviate the great volume change. Here, a 3D porous carbonaceous skeleton modified with rich lithiophilic groups (Zn, ZnO, and Zn(CN)2) is synthesized as a Li host via one‐step carbonization of a triazole‐containing metal‐organic framework. The nano lithiophilic groups serve as preferred sites for Li nucleation and growth, regulating a uniform Li+ flux and uniform current density distribution. In addition, the 3D porous network functions as a Li reservoir that provides rich internal space to store Li, thus alleviating the volumetric expansion during Li plating/stripping process. Thanks to these component and structural merits, an ultra‐low overpotential for Li deposition is achieved, together with high CE of over 99.5% for more than 500 cycles at 1 mA cm−2 and 1 mAh cm−2 in half cells. The symmetric cells exhibit a prolonged cycling of 900 h at 1 mA cm−2. The full cells by coupling Zn/ZnO/Zn(CN)2@C‐Li anode with LiFePO4 cathode deliver a high capacity retention of 94.3% after 200 cycles at 1 C.