Long‐Range Ordered Macroporous Graphene Carbon Monolith Enables Coble‐Creep‐Regulated Dendrite‐Free Lithium Metal Anodes Toward Industrial Dry‐Electrode Manufacturing

ABSTRACT Lithium metal anodes are pivotal for next‐generation high‐energy batteries, yet practical deployment is severely limited by rampant dendrite growth, fragile solid‐electrolyte interphase (SEI), and drastic volume expansion under high‐areal‐capacity and lean‐electrolyte industrial conditions. Conventional porous carbon hosts suffer from disordered pore geometry and tortuous ion transport, failing to balance deposition uniformity, interfacial stability, and manufacturing feasibility. Herein, an ordered macroporous graphene carbon monolith (OMGC‐O‐3 h) is fabricated via a dry‐pressing route, with long‐range pore ordering isolated as the sole structural regulatory variable. The low‐density bicontinuous ordered network homogenizes the interfacial electric field, eliminates current hotspots, and induces regulated Coble creep, achieving dendrite‐free Li deposition with volume expansion restricted below 33.9% at 30 mAh cm −2 . Combined with cryo‐FIB‐SEM tomography and multiphysics simulations, the inherent structure–activity correlation is clarified. Moderate oxygen functionalization in situ constructs a robust LiF/Li 2 O‐rich SEI to suppress parasitic side reactions. The optimized Li@OMGC‐O‐3 h anode achieves stable cycling over 1900 h at 1 mA cm −2 with negligible polarization. Paired with high‐loading LiFePO 4 cathodes under an N/P capacity ratio of 3.24, the full cell delivers superior cycling durability and a high energy density of 378.5 Wh kg −1 . This work provides a scalable, dry‐process‐compatible structural strategy toward industrially viable high‐stability lithium metal batteries.