Epitaxial Electrodeposition of Lithium Metal in Cubic Wulff Structures

Abstract Electrodeposition of lithium (Li) metal is crucial for highenergydensity rechargeable Li batteries. The electrodeposition morphology governs the reversibility of the deposition/dissolution reaction, thereby impacting battery performance and safety. Various morphologies, including hemispherical, granular, columnar, and whisker‐like structures, have been realized by modulating the deposition thermodynamics and kinetics. However, the intrinsic Li deposition structure matching the body‐centered cubic (BCC) structure remains unexplored. Here, we first precisely controlled cubic Li deposits with (100) planes as the primary exposed surfaces via modulating anodic interface and optimizing deposition pressure, while demonstrating kinetically‐driven morphology evolution and substrate‐engineered epitaxial growth of cubic Li. These findings integrate the thermodynamic theory of crystal growth with interface engineering, completing the missing piece in the cubic Wulff construction of Li metal and providing a new paradigm for controlling the morphology of metal electrodes.