Covalently‐Bonded Interfaces Stabilizing Radially‐Oriented P/Ti ₃ C ₂ Microspheres for High‐Performance Lithium‐Ion Batteries

Red phosphorus (P), with high theoretical specific capacity and environmental benignity, represents a promising anode material for lithium-ion batteries (LIBs). However, its practical application is hindered by intrinsic limitations, such as poor electronic conductivity and substantial volume fluctuation, resulting in sluggish redox reaction kinetics and compromised reaction reversibility. Herein, we design a 3D P-bonded radially-oriented Ti₃C₂ microsphere composite electrode (P80/MS-Ti₃C₂) via an innovative electrostatic spraying technique. The unique, highly conductive, radially-oriented Ti₃C₂ matrix uniformly and tightly encapsulates P nanoparticles within the channels, which establish continuous ion/electron pathways and prevent the aggregation of 2D Ti₃C₂ sheets. Simultaneously, the formation of robust Ti-O-P covalent bonds at the interface significantly enhances the intrinsic electronic conductivity and alleviates the volume expansion and exfoliation of red P during cycling. The synergistic integration of stabilized covalent interfaces and meticulously-engineered architecture endow the optimized P80/MS-Ti₃C₂ electrode with high reversible specific capacities and outstanding cycling stability, achieving 1269.5 mAh g^- ¹ at 500 mA g^- ¹ after 700 cycles and 1064.3 mAh g^- ¹ at 1 A g^- ¹ after 1000 cycles even under a high P loading of 36.7%, with P approaching its theoretical capacity. This work provides an effective structural and interfacial engineering strategy to overcome the fundamental challenges of P-based electrodes, demonstrating great potential for high-performance LIBs.