Hittorf's violet phosphorus is the most stable phosphorus allotrope with a layered structure. The corresponding Hittorf's violet phosphorene, a more stable two-dimensional semiconducting structure than black phosphorene, is a promising two-dimensional material for electronic and optoelectronic devices. In this work, the adsorption and anisotropic diffusion process of Li and Na atoms have been studied using first-principles calculations. The adsorption energies of Li and Na atoms are calculated to be 1.65 and 1.32 eV, respectively. Based on the structural nature of Hittorf's violet phosphorene, two possible diffusion paths (in-trench diffusion and inter-trench diffusion) are proposed and investigated. The results of transition state calculation indicate that in-trench diffusion of metal atom has lower barrier that inter-trench diffusion, indicating the significant anisotropic diffusion of Li and Na atom on Hittorf's violet phosphorene. Our work suggests the promising application of Hittorf's violet phosphorene in ion batteries research and development.

希托夫的紫磷是最稳定的磷同素异形体，具有分层结构。相应的希托夫的紫色磷光体（比黑色磷光体更稳定的二维半导体结构）是一种有前途的电子和光电设备二维材料。在这项工作中，使用第一性原理研究了Li和Na原子的吸附和各向异性扩散过程。Li和Na原子的吸附能经计算分别为1.65和1.32 eV。基于Hittorf紫磷烯的结构性质，提出并研究了两种可能的扩散路径（沟槽内扩散和沟槽间扩散）。过渡态计算结果表明，金属原子的沟槽内扩散具有比沟槽间扩散低的势垒，表明锂和钠原子在希托夫的紫色磷光体上显着各向异性扩散。我们的工作表明，希托夫的紫色磷光体在离子电池研究和开发中具有广阔的应用前景。