P-N-P Bridge Bond Engineering in Black Phosphorus Overcomes Phosphorus Redox Reaction Kinetic Barriers for Fast-charging Lithium Batteries

It is known that there existing the "energy versus power dilemma" in electrochemical energy storage devices. Most conventional electrode materials, whether based on ion insertion-extraction or pseudo-capacitance, inevitably require a trade-off, enhancing one performance metric at the cost of another. For the high-theoretical-capacity (2596 mA h g ^-1 ) black phosphorus (BP) electrode materials, the sluggish kinetics of multiphase phosphorus redox reactions (PRR) fundamentally constrain the fast-charging and high-power performance of BP-based batteries. Although catalytic strategies can accelerate redox kinetics, their application to BP’s complex solid-state transformations remains challenging. Here we report a catalytic approach through engineered P–N–P bridge bonds within the BP/carbon composite materials, which is first designed within the backbone of BP lattice, distinguishing it from previous studies on heteroatom-doped carbon materials. The formation of P-N-P bridge bonds within BP lattice can transform semi-conductive BP into a metallic state and reduce the energy barriers for Li-ions diffusion, improving PRR dynamics, structural stability and environmental stability. The resulting nitrogen-doped BP/carbon (N-BP/C) anode achieves ultrafast PRR kinetics and higher capacity, the N-BP/C anode shows the specific capacity of 1482 mA h g ^-1 with a coulombic efficiency (CE) exceeding 99.6% after 200 cycles, more than twice the 687 mA h g ^-1 of BP/C sample. Furthermore, an assembled LiFePO₄ ‖ N-BP/C pouch cell delivers 282 Wh kg⁻¹ energy density with 80% capacity retention within 10 minutes at a high current density of 10 A g⁻¹—meeting the U.S. Department of Energy’s Extreme Fast Charging (XFC) targets. This pouch cell also exhibits exceptional cyclability (> 3,400 cycles), more than 10 times longer than existing phosphorus-based LIBs. This work establishes a paradigm for catalytic enhancement in multiphase energy storage, advancing the design of new batteries with both high energy density and high power density.