Electron‐Rich Fluorine‐Mediated Phosphorus Activation Enables Durable Phosphorus Anode for Lithium‐Ion Batteries

Achieving high charging rate typically compromises cycling stability. Rather than fabricating chemically bonded black phosphorus (BP)/carbon composites, essentially activating topologically stable BP‐based anode redox kinetics is a more meaningful alternative, but unfortunately it has been rarely studied so far. Herein, we demonstrate that electron‐rich F‐mediated activation of BP anode enhances the chemisorption of polyphosphide intermediates via the formation of F‐doped BP at the interface between BP particle and fluorinated graphite (F‐graphite). Moreover, self‐expanding Li + transport channels are created through the in situ electrochemical formation of LiF nanoparticles between the F‐graphite layers. This process reduces the energy barrier of Li + transport, activates the kinetics of multiphase BP redox reactions and promotes the formation of a robust solid electrolyte interphase layer. By leveraging these synergistic advantages, a durable fast‐charging BP anode is achieved, delivering an ultra‐long cycle life of nearly 10 000 cycles at 1.6 A g −1 . When coupled with NCM 811 cathode, the full cell maintains high cycling stability for more than 1000 cycles. This work establishes a paradigm for enhancing polyphosphides adsorption‐conversion kinetics and establishing self‐expanding ion transport channels in multiphase energy storage, advancing the design of next‐generation batteries with both high stability and long cycle life.