Lithiophilic Mo₂C Clusters‐Embedded Carbon Nanofibers for High Energy Density Lithium Metal Batteries

Abstract Lithium metal anodes are widely regarded as the ideal candidate for the next generation of high‐energy‐density lithium batteries. Here, a 3D host made of lithiophilic Mo₂C clusters‐embedded carbon nanofibers (Mo₂C@CNF) is developed. The uniformly dispersed clusters and large specific surface areas of Mo₂C@CNF provide numerous nucleation sites for lithium deposition. Mo₂C clusters exhibit ultralow nucleation overpotential compared to MoO₂, which is also supported by density functional theory calculations. Furthermore, the transition metal element serves as a catalyst for the formation of a stable and robust solid electrolyte interphase layer containing LiF on Mo₂C@CNF, effectively mitigating the occurrence of dead lithium and enhancing the Coulombic efficiency during prolonged operation. As a result, the Mo₂C@CNF composite delivers superior electrochemical performance (>1600 h) at 1 mA cm⁻² and lower nucleation overpotential (13 mV) for lithium plating. The Li/Mo₂C@CNF anode coupled with the commercial LiFePO₄ cathode exhibits excellent cycling stability (300 cycles at 1 C) and high rate capability at low N/P ratios.