Unveiling the Li/Electrolyte Interface Behavior for Dendrite‐Free All‐Solid‐State Lithium Metal Batteries by Operando Nano‐Focus WAXS

N, are found to initially deposit on the electrolyte side, progressively extending toward the lithium metal anode. This growth process effectively protected the metallic lithium, inhibited electron transfer, and facilitated Li⁺ transport. The study not only demonstrates a high-performance interfacial-stable lithium metal battery with composite electrolyte but also introduces a novel strategy for real-time visualizing dendrite formation and SEI growth directing at the interface area of electrolyte and metallic lithium.