Single‐Atom Iron‐Catalyzed Vapor‐Phase Polymerization of Phosphorus Enables Uniform Nanoconfinement in Carbon Frameworks for Durable Li‐Ion Batteries

ABSTRACT Red phosphorus (RP) anodes are promising candidates for fast‐charging, high‐energy lithium‐ion batteries due to their high Li‐ion conductivity, high specific capacity (2596 mAh g ⁻¹ ), and suitable lithiation potential (∼0.7 V vs. Li ⁺ /Li). However, its inherently low electrical conductivity and severe volume expansion limit its practical application. To solve these issues, the vaporization‐condensation strategy is widely considered an effective approach to incorporate phosphorus into a conductive carbon framework. Generally, this deposition process typically leads to the formation of RP particles with uneven size distributions. Consequently, the large bulk RP or particles exposed on the exterior surface of carriers are highly susceptible to fracture and deactivation during drastic volume changes. Herein, we demonstrate that nitrogen‐doped iron single‐atom catalytic sites provide strong adsorption for P ₄ molecules via the formation of Fe─P bonds. This interaction accelerates the adsorption of P ₄ gaseous molecules and their polymerization, thereby achieving exceptional uniformity and site‐selectivity in RP loading. Benefiting from the uniformly distributed small‐sized RP nanoparticles, the anode exhibits excellent electrochemical performance, with remaining capacity retention rates of 91.63%, 96.14%, and 83.75% after 300, 600, and 500 cycles at current densities of 0.26, 1.0, and 2.6 A g ⁻¹ , respectively.