Stable 4.6 V Anode‐Free Li Metal Batteries Enabled by Orchestrating Direct and Indirect Pre‐Lithiation

ABSTRACT Anode‐free lithium metal batteries (AFLMBs) have attracted significant interest due to their low manufacturing cost and enhanced energy density. However, practical application faces challenges including active Li deficiency and unstable electrode‐electrolyte interfaces. This work designs a synergistic direct‐indirect pre‐lithiation approach to form a stable, dendrite‐free interface. Li 2 C 2 O 4 serves as the direct pre‐lithiation agent, decomposing at low applied voltage via recrystallization‐ball milling to replenish active Li. Li 2 O acts as the indirect pre‐lithiation agent, leveraging its electrolyte solubility, diffusion effects, and interaction with Li ions to significantly enhance the Li 2 O content in the solid electrolyte interphase (SEI), thereby promoting SEI stability. The robust SEI further suppresses side reactions and inhibits Li dendrite growth, enabling seamless Li deposition. Simultaneously, this design establishes cathode‐anode coupling that reinforces the cathode electrolyte interphase (CEI), substantially improving high‐voltage performance. Specifically, the AFLMBs with LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode using this strategy demonstrates 86.35% capacity retention after 100 cycles at 4.3 V and 79% retention after 50 cycles at 4.6 V. This strategy facilitates AFLMBs toward high‐voltage and provide new insights into cathode‐anode interface relationships for advanced AFLMBs.