Synergizing Conformal Lithiophilic Granule and Dealloyed Porous Skeleton toward Pragmatic Li Metal Anodes

Li metal is regarded as one of the most promising anodes for next‐generation rechargeable batteries. Nonetheless, infinite volume change and severe dendrite growth impede its practicability. To date, unremitting efforts have been devoted to stabilizing Li metal anode via the rational design of 3D current collectors. In this sense, optimizing Li nucleation behavior plays a pivotal role in alleviating the dendrite formation. Herein, a practically viable route is devised by in situ crafting lithiophilic CuSe granules on the dealloyed Cu skeleton (D‐Cu@CuSe). Persuasive electrochemical analysis and systematic theoretical calculation disclose the underlying Li nucleation mechanism on the CuSe overlayer. Impressively, the D‐Cu@CuSe‐Li symmetric cell can sustain a stable plating/stripping operation over 1000 h at a high depth of discharge at 62.5%. More crucially, when paired with high‐loading sulfur cathodes, D‐Cu@CuSe‐Li||S batteries harvest advanced areal capacity and stable cycling performance even under stringent working conditions of low negative‐to‐positive (N/P) (≈2) and electrolyte‐to‐sulfur (8 μL mg s −1 ) ratios. Overall, a fresh perspective into rationalizing current collector design is afforded, which extends Li utilization and cycling durability in the pursuit of pragmatic Li metal anodes.