Fundamental Understanding of “Fresh” Lithium Nucleation and Growth in Sulfide‐Based Anode‐Free Solid‐State Batteries: Effects of Substrate, Current Density, and Li⁺ Supply

Understanding the electrochemical extraction and deposition of lithium (Li) from cathode is crucial for advancing anode‐free solid‐state batteries (AFSSBs). Herein, cryo‐transmission electron microscopy (cryo‐TEM) and electrochemical studies are employed to investigate how current collector surface properties, current densities, and cathode loadings influence the morphology of fresh electrochemically deposited Li and the electrochemical performance in sulfide‐based AFSSBs. Cryo‐TEM reveals that Cu current collectors induce irregular, dendritic Li deposits due to their lithiophobic nature and reactivity with Li 5.4 PS 4.4 Cl 1.6 (LPSC), while Ni and Au facilitate more uniform, planar‐like Li growth. The morphology of the deposited Li also depends on current density: higher rates produce smaller, porous particles versus larger, denser deposits at lower rates. Importantly, for the first time, we discovered that low cathode loadings lead to poor cycling stability due to insufficient Li + supply for complete anode coverage, contrary to conventional solid‐state batteries with preloaded Li metal anodes. This finding establishes a design principle where adequate cathode Li + reservoirs are essential for anode interface stability in AFSSBs. Overall, this work elucidates the interplayed effect of current collectors, current densities, and cathode loadings on Li morphology and cycle stability, offering fundamental insights into cathode‐derived Li behavior and practical guidelines for optimizing AFSSBs performance through nucleation control and interface engineering.