3D Porous Sturdy Carbonaceous Framework Dispersion‐Strengthened Entire‐Lifecycle High‐Performance Lithium Metal Batteries

Inferior cycle stability and huge volume expansion are the two main obstacles for practical application of Li metal batteries. Composite Li metal anodes (LMAs) have been considered as the most effective solution to improve cycle stability and alleviate swelling of Li metal batteries, however, their frameworks lose the function as 3D host either in compositing process or during battery cycling. Here we demonstrate a scalable roll‐to‐roll calendaring method that achieves the dispersion‐strengthening of LMAs with a lithiophilic 3D porous sturdy carbonaceous skeleton (3DHC@Li). The 3DHC with 800 nm ordered pores features a highly cross‐linked network that effectively dissipates mechanical stress, imparting exceptional compressive resistance. This enables uniform 3DHC distribution within LMAs, which enhances the mechanical strength of 3DHC@Li by five times and keeps structural integrity throughout entire‐lifecycle. When assembled with ultrahigh‐loading LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811, 7.5 mAh cm −2 ), the pouch cell utilizing 3DHC@Li anode demonstrates a capacity retention of 84.65% after 300 cycles. Moreover, the volume expansion rate of NCM811||3DHC@Li pouch cell is only 1/3 of conventional NCM811||50 µm Li pouch cell. This work paves the way for the facile and scalable fabrication of composite LMAs toward practical applications.