Epitaxial Electrodeposition of Lithium Metal in Cubic Wulff Structures

Electrodeposition of lithium (Li) metal is a crucial process for high‐energy‐density rechargeable Li batteries. The morphology of Li deposits during electrodeposition governs the reversibility of the deposition/dissolution reaction, thereby significantly affecting the performance and safety of Li metal batteries. Various morphologies, including hemispherical, granular, columnar and whisker‐like structures have been realized by modulating the thermodynamics and kinetics of the deposition process. However, the intrinsic Li deposition structure matching the body‐centered cubic (BCC) structure remains unexplored. In this work, we first successfully achieved precise control over cubic Li deposits with (100) planes as the primary exposed surfaces via modulating the anodic interface and optimizing the deposition pressure, while demonstrated kinetic‐driven morphology evolution and substrate‐engineered epitaxial growth of cubic Li. These findings integrate the thermodynamic theory of crystal growth with interface engineering, not only completing the missing piece in the cubic Wulff construction of Li metal but also providing a new paradigm for controlling the morphology of metal electrodes.