文献类型：期刊文献

英文题名：A DFT Study of Band-Gap Tuning in 2D Black Phosphorus via Li+, Na+, Mg2+, and Ca2+ Ions

作者：Mu, Liuhua[1,2,3];Jiang, Jie[1];Gao, Shiyu[4];Li, Xiao-Yan[5];Sheng, Shiqi[4]

机构：[1]Ningbo Univ, Sch Phys Sci & Technol, Ningbo 315211, Peoples R China;[2]Univ Chinese Acad Sci, Wenzhou Inst, Wenzhou 325001, Peoples R China;[3]Univ Chinese Acad Sci, Sch Phys Sci, Beijing 100049, Peoples R China;[4]East China Univ Sci & Technol, Sch Phys, Shanghai 200237, Peoples R China;[5]Northwestern Univ, Dept Chem, Evanston, IL 60208 USA

年份：2024

卷号：25

期号：21

外文期刊名：INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001351338400001)】；

基金：This research was funded by the National Natural Science Foundation of China (12005062, and 12405036) and the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20232610.

语种：英文

外文关键词：2D black phosphorus; band gap; light metal ions; battery electrode; DFT calculations

摘要：Black phosphorus (BP) and its two-dimensional derivative (2D-BP) have garnered significant attention as promising anode materials for electrochemical energy storage devices, including next-generation fast-charging batteries. However, the interactions between BP and light metal ions, as well as how these interactions influence BP's electronic properties, remain poorly understood. Here, we employed density functional theory (DFT) to investigate the effects of monovalent (Li+ and Na+) and divalent (Mg2+ and Ca2+) ions on the valence electronic structure of 2D-BP. Molecular orbital analysis revealed that the adsorption of divalent cations can significantly reduce the band gap, suggesting an enhancement in charge transfer rates. In contrast, the adsorption of monovalent cations had minimal impact on the band gap, suggesting the preservation of 2D-BP's intrinsic electrical properties. Energetic and charge analyses indicated that the extent of charge transfer primarily governs the ability of ions to modulate 2D-BP's electronic structure, especially under high-pressure conditions where ions are in close proximity to the 2D-BP surface. Moreover, charge polarization calculations revealed that, compared with monovalent cations, divalent cations induced greater polarization, disrupting the symmetry of the pristine 2D-BP and further influencing its electronic characteristics. These findings provide a molecular-level understanding of how ion interactions influence 2D-BP's electronic properties during ion-intercalation processes, where ions are in close proximity to the 2D-BP surface. Moreover, the calculated diffusion barrier results revealed the potential of 2D-BP as an effective anode material for lithium-ion, sodium-ion, and magnesium-ion batteries, though its performance may be limited for calcium-ion batteries. By extending our understanding of interactions between ions and 2D-BP, this work contributes to the design of efficient and reliable energy storage technologies, particularly for the next-generation fast-charging batteries.