文献类型：期刊文献

英文题名：Modulating the band gaps, binding energetics, and diffusion kinetics of black and blue phosphorene via K+ adsorption: a DFT Study

作者：Mu, Liuhua[1];Sheng, Shiqi[2];Kong, Weijie[1];Li, Xiao-Yan[3]

机构：[1]Ningbo Univ, Sch Phys Sci & Technol, Ningbo 315211, Peoples R China;[2]East China Univ Sci & Technol, Sch Phys, Shanghai 200237, Peoples R China;[3]Natl Univ Singapore, Dept Chem, 3 Sci Dr 3, Singapore 117543, Singapore

年份：2026

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20262320844866);WOS:【SCI-EXPANDED(收录号:WOS:001783583000001)】；

基金：This research was funded by the National Natural Science Foundation of China (12405036 and 12005062).

语种：英文

外文关键词：Adsorption - Anode materials - Anodes - Charge transfer - Density functional theory - Design for testability - Diffusion barriers - High pressure engineering - Ion exchange - Ions - Molecular orbitals - Polarization

摘要：Two-dimensional (2D) phosphorene allotropes, particularly 2D black phosphorene (2D-BlackP) and 2D blue phosphorene (2D-BlueP), are emerging as promising anode materials for next-generation potassium ion batteries (PIBs) due to their high theoretical capacities and favorable electrochemical properties. However, the microscopic interaction mechanisms by which K+ ions and phosphorene allotropes alter their electronic structures remain insufficiently understood. In this work, we employ density functional theory (DFT) calculations to systematically investigate the effects of K+ adsorption on the valence electronic structures of 2D-BlackP and 2D-BlueP. Molecular orbital analysis reveals that K+ adsorption significantly reduces the bandgap of 2D-BlueP, enhancing charge-transfer capability, while exerting only minimal influence on the bandgap of 2D-BlackP. Energetic and charge analyses demonstrate that the extent of ion-induced charge transfer predominantly governs the modulation of the electronic structure, especially under high-pressure conditions where ions approach the basal plane. Furthermore, charge polarization calculations indicate that K+ cations induce a stronger polarization in BlueP than in BlackP, disrupting the intrinsic symmetry of pristine 2D-BlueP and further modulating its electronic characteristics. Diffusion barrier calculations additionally suggest that 2D-BlueP offers favorable ionic transport pathways, underscoring its promise as a high-performance anode material for PIBs. These findings provide molecular-level insights into ion-phosphorene interactions and highlight design principles for exploiting phosphorene allotropes in efficient, fast-charging energy storage systems.