In Situ‐Constructed Multifunctional Composite Anode with Ultralong‐Life Toward Advanced Lithium‐Metal Batteries

Abstract Metallic lithium is the most competitive anode material for next‐generation high‐energy batteries. Nevertheless, the extensive volume expansion and uncontrolled Li dendrite growth of lithium metal not only cause potential safety hazards but also lead to low Coulombic efficiency and inferior cycling lifespan for Li metal batteries. Herein, a multifunctional dendrite‐free composite anode (Li/SnS₂) is proposed through an in situ melt‐infusion strategy. In this configuration, the 3D cross‐linked porous Li₂S/Li₂₂Sn₅ framework facilitates the rapid penetration of electrolytes and accommodates the volume expansion during the repeated Li⁻plating process. Meanwhile, the lithiophilic Li₂S phases with a low Li⁺ transport barrier ensure preferential Li deposition, effectively avoiding uneven electron distribution. Moreover, the Li₂₂Sn₅ electron conductors with appropriate Li⁺ bonding ability guarantee rapid charge transport and mass transfer. Most importantly, the steady multifunctional skeleton with sufficient inner interfaces (Li₂S/Li₂₂Sn₅) in the whole electrode, not only realizes the redistribution of the localized free electron, contributing to the decomposition of Li clusters, but also induces a planar deposition model, thus restraining the generation of Li dendrites. Consequently, an unprecedented cyclability of over 6 500 h under an ultrahigh areal capacity of 10 mAh cm⁻² and a current rate of 20 mA cm⁻² is achieved for the prepared Li₂S/Li₂₂Sn₅ composite anode. Moreover, the assembled Li/SnS₂||LiFePO₄ (LFP) pouch full‐cells also demonstrate remarkable rate capability and a convincing cycling lifespan of more than 2 000 cycles at 2 C.