Kinetically Engineered Lithiophilic Dual‐Metal Layers for Dendrite‐Free, High‐Energy Anode‐Less All‐Solid‐State Batteries

ABSTRACT Anode‐less all‐solid‐state batteries (ASSBs) are emerging as promising candidates for next‐generation energy storage, offering exceptional energy density, inherent safety, and streamlined manufacturability. However, their widespread adoption is hindered by the risk of internal short‐circuiting stemming from the uncontrolled propagation of lithium (Li) dendrites, especially during high‐current operation. This study introduces a nanoscale dual‐layer lithiophilic architecture for the anode‐less electrode—a gold (Au) film as the outer layer with a magnesium (Mg) layer underneath—to address this challenge. By exploiting the divergent electrochemical kinetics of these metals, Li nucleation is selectively confined to the underlying Mg layer, while the Au overlayer serves as a conformal barrier to mitigate dendrite penetration. The engineered interface enabled stable cycling with 81.4% capacity retention after 100 cycles at a high current density of 3.5 mA cm −2 and room temperature (25°C), alongside robust operation in a pouch‐cell configuration under a modest stack pressure of 4 MPa. These findings highlight the strategic importance of dual‐metal lithiophilic designs with the ability to synergistically tailor the nucleation dynamics, as a scalable pathway for practical anode‐less ASSBs.