Lithiophilic Carbon Nanofiber/Graphene Nanosheet Composite Scaffold Prepared by a Scalable and Controllable Biofabrication Method for Ultrastable Dendrite‐Free Lithium‐Metal Anodes

Li metal is regarded as a promising anode for high‐energy‐density Li batteries, while the limited cycle life and fast capacity decay caused by notorious Li dendrite growth seriously impedes its application. Herein, a robust and highly lithiophilic bacterial cellulose‐derived carbon nanofiber@reduced graphene oxide nanosheet (BC‐CNF@rGO) composite scaffold is fabricated as a host for dendrite‐free Li metal anode through an in situ biofabrication method. The abundant lithiophilic functional groups, conductive 3D network, and excellent mechanical property can effectively regulate uniform Li nucleation and deposition, enable fast reaction kinetics, and alleviate volume change. As a result, the BC‐CNF@rGO skeleton achieves exceptional Li plating/stripping performance with a high average Coulombic efficiency of 98.3% over 800 cycles, and a long cycle life span of 5000 h at 2 mA cm−2@1 mAh cm−2 with a low overpotential of ≈15 mV for lithium plating. Furthermore, full cells coupling BC‐CNF@rGO‐Li anode with LiFePO4 cathode achieves an unprecedented cycling stability with a long cycle life of 3000 cycles at 1 C. This work sheds light on a promising material design and fabrication strategy for realizing high performance Li metal batteries. Lithiophilic carbon nanofiber@reduced graphene oxide nanosheet composite scaffolds are fabricated through an in situ biofabrication method. The abundant lithiophilic functional groups and conductive 3D network can effectively regulate uniform Li nucleation and deposition, realizing exceptional Li plating/stripping, and full cell cycling performance. The findings provide a promising material fabrication strategy for realizing high performance Li metal batteries.