Hierarchical porous structure construction for highly stable self-supporting lithium metal anode

Lithium (Li) metal, with extremely high specific capacity and low reduction potential, is considered one of the most promising anode candidates for next-generation batteries. However, uncontrolled growth of dendritic Li and extreme volume fluctuation during cycles hinder the broad application of Li metal anodes. Herein, Li dendrite growth can be effectively suppressed by constructing a unique hierarchical porous structure. ~300 nm rigid carbon nano-box contains abundant ~20 nm Cu3P/CoP heterostructural nanobubbles. Densely growth villiform carbon tubes tangled with ~50 µm carbon nanotubes cover the surface of the carbon nano-box. This flexible interlaced matrix (Cu3P/[email protected]/CNT) possessing 3D hierarchical porous interspace and structure can effectively confine metallic Li. More than physical confinement, strong chemical bonding between Cu3P/CoP heterostructures and Li atoms is also proved by DFT calculation to regulate Li plating behavior. The LiǀCu3P/[email protected]/CNT composite anode exhibits a high average efficiency of 94.6% over 220 cycles and a long-running lifespan for 400 h with an exceptionally low voltage hysteresis of 24 mV. LiFePO4|[email protected]3P/[email protected]/CNT full cells can be cycled 300 times at a negligible capacity decay of 0.01% per cycle at 1 C. This work inspires a self-supporting and hollow heterostructured Li container design, promoting the development of Li metal host anodes.