Constructing Fast Ion/Electron Conducting Pathway within 3D Stable Scaffold for Dendrite‐Free Lithium Metal Anode

Abstract Utilizing limited Li‐metal (<10 mAh cm⁻²) is desirable to achieve high‐specific‐energy Li‐metal batteries (LMBs). However, the rapid Li‐metal depletion and anode pulverization severely restrict the cycle life of LMBs. Herein, 3D carbon‐based scaffold is proposed as a host to construct a composite Li‐metal anode (ZOS‐CF@Li) with a limited Li amount of 8 mAh cm⁻² via molten Li infusion assisted by the lithiophilic ZnO/ZnS. In situ TEM reveals that the ZnO/ZnS can spontaneously convert into ionically conductive Li₂O/Li₂S and electronically conductive LiZn‐alloy, contributing to faster ion/electron transport and favorable dendrite‐free deposition. The experiment results combined with theoretical calculations confirm that the inorganic Li‐salts with high elastic modulus and super lithiophilicity enable homogenous electric field distribution and reduced Li‐diffusion energy barriers. Therefore, the ZOS‐CF@Li anode exhibits stable cycling over 1100 h with low overpotential under 5 mAh cm⁻² in the symmetric cell. Furthermore, stable cycle performances coupled with high mass loading of LiFePO₄ (20 mg cm⁻²) and LiNi_0.8Co_0.1Mn_0.1O₂ (18 mg cm⁻²) at low N/P ratios of 2.38 and 2.25 are achieved in the full‐cells, respectively. The Li||LFP pouch‐cell can maintain a high‐capacity retention of 97.7% after 90 cycles. This work will shed light on the design of a carbon‐based host for building stable Li‐anode in high‐energy‐density LMBs.