Realized Stable BP-N at Ambient Pressure by Phosphorus Doping

Matter Radiat. at Extremes, 10, 015801 (2024) Black phosphorus nitrogen (BP-N) is an attractive high-energy-density material. However, high-pressure synthesized BP-N will decompose at low-pressure and cannot be quenched to ambient conditions. Finding a method to stabilize it at 0 GPa is of great significance for its practical applications. However, unlike cg-N, LP-N, and HLP-N, it is always a metastable phase at high-pressure up to 260 GPa, and decomposes into chains at 23 GPa. Here, based on the first-principles simulations, we find that P atom doping can effectively reduce the synthesis pressure of BP-N and maintain its stability at 0 GPa. Uniform distribution of P atom dopants within the layer helps maintain the structural stability of BP-N layer at 0 GPa, while interlayer electrostatic interaction induced by N-P dipoles enhances its dynamic stability by eliminating interlayer slipping. Furthermore, pressure is conducive to enhancing the stability of BP-N and its doped forms by suppressing N-chain dissociation. For the configuration with 12.5% doping concentration, a gravimetric energy density of 8.07 kJ/g can be realized, which is nearly two times higher than TNT.