Tailoring Li Deposition by Regulating Structural Connectivity of Electrochemical Li Reservoir in Li‐metal Batteries

Abstract Irregular Li deposition is the major reason for poor reversibility and cycle instability in Li metal batteries, even leading to safety hazards, the causes of which have been extensively explored. The structural disconnection induced by completely dissolving Li in the traditional testing protocol is a key factor accounting for irregular Li growth during the subsequent deposition process. Herein, the critical role played by the structural connectivity of electrochemical Li reservoir in subsequent Li deposition behaviors is elucidated and a morphology‐performance correlation is established. The structural connection and resultant well‐distributed morphology of the in situ electrochemical Li reservoir ensure efficient electron transfer and Li + diffusion pathway, finally leading to homogenized Li nucleation and growth. Tailoring the geometry of Li reservoir can improve the coulombic efficiency and cyclability of anode‐free Li metal batteries by optimizing Li deposition behavior.