Hybrid Interfacial Modulation for Stabilizing Anode‐Less Lithium‐Sulfur Batteries: Guided Lithium Nucleation and Polysulfide Regulation

Anode-less lithium-sulfur (Li-S) batteries offer a promising route to high energy density and cost-effective energy storage, yet suffer from unstable Li deposition and polysulfide crossover at the current collector interface. Here, we introduce a hybrid interfacial modulation layer (HIML) designed to simultaneously regulate dendrite-free Li deposition behavior and block polysulfide migration. The HIML consists of lithiophilic Au nano seeds coated with a porous ionic-selective overlayer, enabling guided, uniform Li nucleation and selective Li⁺ transport. When applied to an anode-less Li-S full cell with a Li₂S cathode, the HIML-enabled current collector achieves an initial charge capacity of 1272 mAh g^-1, a Coulombic efficiency of 95.7%, and a low polarization of 0.14 V. The HIML-introduced full cell exposes a high energy density of 389 Wh kg^-1, indicating a notably higher value among the reported Li₂S-based Li metal batteries. These findings demonstrate that HIML offers a robust and scalable strategy for stabilizing Li plating interfaces, paving the way toward practical, high-performance anode-less Li-S batteries.