Constructing Three-Dimensional Flexible Lithiophilic Scaffolds with Bi₂O₃ Nanosheets toward Stable Li Metal Anodes

The practical application of lithium metal batteries (LMBs) is obstructed by the uncontrollable dendrite growth and large volume change. Herein, we construct a flexible carbon cloth modified with Bi2O3 nanosheets (Bi2O3/CC) as a three-dimensional (3D) lithiophilic skeleton to regulate uniform Li nucleation and deposition. Benefiting from the initial lithiation, dense lithiophilic Li3Bi layers with lithium conductor Li2O (Li3Bi/Li2O) are in-situ-formed through conversion and alloying reactions, which can promote adsorption ability of lithium and improve the speed of Li+ transport according to DFT calculations, thus boosting homogeneous Li plating/stripping behavior. Meanwhile, the conductive 3D structure effectively suppresses Li dendrite formation by reducing the local current density and eliminates volume change. Consequently, the Bi2O3/CC facilitates a high Coulombic efficiency and dendrite-free morphology, near-zero volume change, and superior cyclic stability over 2400 h at 1 mA cm–2 with an ultralow overpotential of 11 mV. Notably, there is no obvious dendritic morphology in Bi2O3/CC even under an ultrahigh areal capacity of 20 mAh cm–2. Moreover, the Li@Bi2O3/CC-LiFePO4 full cell also achieves outstanding cycling performance and rate capability, shedding light on the facile design of the 3D lithiophilic host for advanced lithium-metal anodes.