Tuning Lithiophilicity and Stability of 3D Conductive Scaffold via Covalent Ag‐S Bond for High‐Performance Lithium Metal Anode

Li metal anode holds great promise to realize high‐energy battery systems. However, the safety issue and limited lifetime caused by the uncontrollable growth of Li dendrites hinder its commercial application. Herein, an interlayer‐bridged 3D lithiophilic rGO‐Ag‐S‐CNT composite is proposed to guide uniform and stable Li plating/stripping. The 3D lithiophilic rGO‐Ag‐S‐CNT host is fabricated by incorporating Ag‐modified reduced graphene oxide (rGO) with S‐doped carbon nanotube (CNT), where the rGO and CNT are closely connected via robust Ag‐S covalent bond. This strong Ag‐S bond could enhance the structural stability and electrical connection between rGO and CNT, significantly improving the electrochemical kinetics and uniformity of current distribution. Moreover, density functional theory calculation indicates that the introduction of Ag‐S bond could further boost the binding energy between Ag and Li, which promotes homogeneous Li nucleation and growth. Consequently, the rGO‐Ag‐S‐CNT‐based anode achieves a lower overpotential (7.3 mV at 0.5 mA cm−2), higher Coulombic efficiency (98.1% at 0.5 mA cm−2), and superior long cycling performance (over 500 cycles at 2 mA cm−2) as compared with the rGO‐Ag‐CNT‐ and rGO‐CNT‐based anodes. This work provides a universal avenue and guidance to build a robust Li metal host via constructing a strong covalent bond, effectively suppressing the Li dendrites growth to prompt the development of Li metal battery. Unique interlayer‐bridged three‐dimensional lithiophilic rGO‐Ag‐S‐CNT composite is designed to guide uniform and stable Li plating/stripping. The Ag‐S bond enhanced the structural stability and electrical connection between rGO and CNT, significantly improving the lithiophilicity of the electrode and uniformity of the current distribution, which effectively suppressed the growth of Li dendrites.