One‐Step Constructed F‐Doped Porous Carbon‐Gradient CuZn Alloy Current Collector for Durable Anode‐Less Lithium Metal Batteries

ABSTRACT Practical high‐energy‐density lithium metal batteries (LMBs) require strictly limited lithium inventory (N/p < 2), yet suffer from rapid capacity fade due to unstable solid electrolyte interphase (SEI) formation and erratic lithium deposition. Herein, a gradient lithiophilic metal–porous carbon (GLMC) composite current collector is developed via a one‐step in situ pyrolysis‐doping strategy to address these interconnected challenges. The top fluorinated carbon layer suppresses excessive solvent decomposition and fosters a uniform, robust SEI, while the underlying CuZn alloy provides lithiophilic sites for preferential nucleation and guides bottom‐up lithium plating. This orchestrated design reduces irreversible active Li loss by approximately 60% and enables highly reversible cycling, achieving an average Coulombic efficiency of 99.57% over 1500 cycles. Calculations reveal that the fluorinated carbon elevates the reduction energy barrier of solvent molecules, thereby inhibiting their decomposition. Symmetric cells based on GLMC maintain stable cycling for over 4300 h even at 50% Li utilization. When paired with a high‐loading NCM811 cathode, the anode‐free full cell exhibits significantly extended cycle life, delivering an energy density of 475 Wh kg −1 and retaining 81% capacity after 300 cycles. This work demonstrates rational design of current collectors is a potent strategy to achieve durable, high‐energy‐density LMBs under limited lithium conditions.