The electronic structure of the van der Waals heterostructures (HSs) of the phosphorene (P) nanoflakes (NFs) with graphene (G) and its allotropy (H1 and H2) NFs, and their complexes with Li have been studied using dispersion-corrected TPSS functional. According to the calculations, the attractive interactions in HSs come from dispersion. It has a relatively small contribution to the binding energy in Li complexes, especially for these forming complexes with G, H1, or H2 NF side. The binding energies between the individual NFs and Li atoms increase in the order G < H1 = H2 = P. The formation of HSs results in a synergetic effect for Li binding energies. This effect is the most notable for phosphorene binding sites; however, it also holds for G, H1, and H2 NFs. The formation of complexes with Li always leads to the almost complete charge transfer from Li to the NFs or HSs. In the case of HSs, the unpaired electron of Li is always located at the carbon NF side independently on the Li binding location. The activation energies of Li hopping for individual NFs are notably higher for P comparing with G, H1, or H2 NFs. The formation of HSs rises slightly the activation energies of Li hopping due to the increase of binding energies in Li-HS complexes.

Graphical abstract

中文翻译：

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黑色磷光体的纳米薄片与石墨烯和方铁矿的纳米薄片形成的范德华异质结构的电子结构：它们与Li的配合物。

用色散校正的TPSS研究了磷（P）纳米薄片（NFs）与石墨烯（G）的范德华杂结构（HSs）的电子结构及其同素异形体（H1和H2）NFs及其与Li的配合物。功能。根据计算，HS中有吸引力的相互作用来自分散。它对Li络合物中的结合能的贡献相对较小，尤其是对于这些具有G，H1或H2 NF侧的形成络合物。各个NFs与Li原子之间的结合能以G  <  H1  =  H2  = P。HS的形成导致Li结合能的协同作用。对于磷结合位点，这种作用最为明显。但是，它对于G，H1和H2 NF也成立。与Li形成配合物通常会导致从Li到NF或HS的电荷几乎完全转移。在HS s的情况下，Li的未成对电子始终独立于Li结合位置位于碳NF侧。与G，H1或H2相比，P的各个NF的Li跳跃的活化能明显更高。NFs。由于Li-HS络合物中结合能的增加，HS的形成使Li跳跃的活化能略微增加。

图形概要