In‐Situ Laser Synthesis of Molecularly Dispersed and Covalently Bound Phosphorus‐Graphene Adducts as Self‐Standing 3D Anodes for High‐Performance Fast‐Charging Lithium‐Ion Batteries

Abstract Phosphorus shows promise as a next‐generation anode material due to its high theoretical capacity of 2596 mAh g −1 . However, challenges such as low conductivity, severe volume expansion, and the dissolution and migration of electrolyte‐soluble lithium polyphosphides hamper high‐performance capabilities. While carbon composites are widely researched as a solution through the physical encapsulation of micro‐nano‐phosphorus domains, anodes still exhibit low cycling stability and rate performance. In response, this work proposes a new approach, focusing on chemical anchoring and molecular dispersion of phosphorus within the carbon host. Through laser irradiation of a red phosphorus/phenolic resin blend, in‐situ covalent binding of molecular phosphorus adducts to the as‐forming laser‐induced graphene is observed; directly synthesizing an additive‐free, flexible and 3‐dimensional mesoporous composite anode with high phosphorus content (33 wt.%), specific surface area (163.4 m 2 g −1 ) and intrinsic conductivity (12 S cm −1 ). These anodes demonstrate remarkable cycling stability, with capacity retention of 98% after 3000 cycles at a high current density of 2 A g −1 and capacity of 673 mAh g −1 . The high cycling stability is further confirmed through the complete inhibition of lithium polyphosphide “shuttle effect” by chemical anchoring of the molecularly dispersed active material. Furthermore, scale‐up prospects utilizing laser‐assisted additive manufacturing are investigated.