Electron Donor‐Acceptor Systems With Black Phosphorus and Tellurium for High‐Performance Interfacial Lithium Diffusion and Storage

ABSTRACT Black phosphorus (BP), with high theoretical capacity and electrical conductivity, has emerged as a promising candidate for an advanced energy storage system. However, its huge volume expansion caused by the solubility of intermediate discharge products, i.e., Li x P, leads to significant capacity fading. Herein, a specially designed BP/Te@C anode with a 3D network structure is constructed via interfacial electron transfer between BP and Te, forming a typical electron donor‐acceptor system. Besides, Tellurium, with metalloid properties and high ductility, not only strengthens the interfacial interaction within BP but also significantly enhances the overall electrical conductivity. 3D tomography reconstruction and ToF‐SIMS confirm the structural integrity and stability of this unique architecture during long‐term cycling. Additionally, theoretical calculations reveal a special interfacial lithium diffusion and storage mechanism in BP/Te@C composites, which contributes to the grain size refinement and the improved utilization of BP and Te during cycling. BP/Te@C anodes deliver a capacity of 734.4 mAh g −1 at 3 A g −1 with well cycling performance, along with the low‐temperature adaptability (−20°C). LiFePO 4 ||BP/Te@C full cells achieve an outstanding power density of 4051.6 W kg −1 while maintaining a high‐capacity retention of 90.7%. This work builds an ingenious protocol for designing robust phosphorus‐based anodes with superior electrochemical performance.