Effect of non-magnetic doping on magnetic state and Li/Na adsorption and diffusion of black phosphorene

Black phosphorene (BP) have aroused great concern because of its great potential for the application in nanoelectronic devices and high-performance anode materials for alkali metal ion batteries (AIBs). However, the absence of magnetism for an ideal BP limits its wide application in spintronic devices which is one of the important nanoelectronic devices, and its application as a high-performance anode material for AIBs is still to be explored. In this paper, we adopt first-principles calculations to explore the effects of B, C, N, O, F, Al, Si and S atom doping on the magnetic state of monolayer BP and Li or Na atom adsorption and diffusion on the BP. Additionally, the thermal stability of the doped BP systems at room temperature is revealed by theab initiomolecular-dynamics calculations. Our calculated results indicate that O and S doping can make the doped BP become a magnetic semiconductor, C and Si doping makes the doped BP be metallic, and B, N, F and Al doping preserves semiconductor property. Moreover, little structural changes and significant decreases of diffusion barriers in armchair direction and slight increases of diffusion barriers in zigzag direction make B-doped BP beneficial as an anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). It reveals that S-doping is suitable for improving the performance of SIBs rather than LIBs. Interestingly, it is found that magnetic states of O- and S-doped BP disappear when Li or Na atoms adsorb on them, whereas Li or Na adsorption on B- and Al-doped BP induces magnetic states of these systems. The analyses indicate that the distinct electron transfer between the dopant atom, adatom and neighboring P atoms, and specific electron configuration of dopant atoms cause the magnetism of the systems. Our results suggest that selecting appropriate composition to dope can effectively manipulate magnetic state and improve Li/Na adsorption and diffusion on the BP. These results may inspire further theoretical and experimental exploration on doped two-dimensional (2D) materials in spintronics and doped 2D promising anode materials for high-performance metal ion batteries.