The serious safety issues caused by uncontrollable lithium (Li) dendrite growth, especially at high current densities, seriously hamper the rapid charging of Li metal‐based batteries. Here, the construction of Al–Li alloy/LiCl‐based Li anode (ALA/Li anode) is reported by displacement and alloying reaction between an AlCl3‐ionic liquid and a Li foil. This layer not only has high ion‐conductivity and good electron resistivity but also much improved mechanical strength (776 MPa) as well as good flexibility compared to a common solid electrolyte interphase layer (585 MPa). The high mechanical strength of the Al–Li alloy interlayer effectively eliminates volume expansion and dendrite growth in Li metal batteries, so that the ALA/Li anode achieves superior cycling for 1600 h (2.0 mA cm−2) and 1000 cycles at an ultrahigh current density (20 mA cm−2) without dendrite formation in symmetric batteries. In lithium–sulfur batteries, the dense alloy layer prevents direct contact between polysulfides and Li metal, inhibiting the shuttle effect and electrolyte decomposition. Long cycling performance is achieved even at a high current density (4 C) and a low electrolyte/sulfur (6.0 µL mg−1). This easy fabrication process provides a strategy to realize reliable safety during the rapid charging of Li‐metal batteries.

The shuttle effect of lithium polysulfides (LiPSs) from sulfur cathode to lithium (Li) anode is one of the main obstacles for lithium‐sulfur (Li−S) batteries. The severe corrosion of Li metal anode by the dissolved LiPSs bottlenecks the efficient operation of Li−S batteries, however, the anode part has not been received much attention compared to those extensive efforts related to the cathode designs. Herein, we show that the interface between Ti3C2Tx (T=−OH, −F)‐based MXene and reduced graphene oxide (rGO) is able to guide uniform Li nucleation, promoting highly reversible and dendrite‐free Li plating/stripping. Such the Li anode demonstrates excellent cycling stability for more than 1000 hours even under ultra‐high rate (10 mA cm−2) and high areal capacity (3 mAh cm−2). More importantly, the well‐designed 2D layered structure by coupling the Ti3C2Tx with a graphene scaffold, is highly efficient to block the shuttled polysulfides and inhibit the corrosion of the lithium metal anode. As a result, the Li−S full battery exhibits a stable cycling stability with a high Coulombic efficiency of 99.8 % over 300 cycles. This work suggests the design strategy of Li metal anode especially targeting at the sulfur cathode, and we hope it can provide valuable inspirations for the future design of Li metal anodes for more practical Li−S batteries.