Single- and Multilayers of Alkali Metal Atoms Inside Graphene/MoS₂ Heterostructures: a Systematic First-Principles Study

Stacking various two-dimensional (2D) materials in van der Waals (vdW) het- erostructures is a novel approach to design new systems, which can host alkali metal (AM) atoms to tune their electronic properties or store energy. Using state-of-the-art first-principles calculations, we systematically study the intercalation of the most wide- spread AMs (Li, Na, K) into a graphene/MoS2 heterostructure. Contrary to previous work on the intercalation of AMs into various heterostructures based on 2D materials, we consider not only single-, but also multi-layer configurations of AM atoms. We assess the intercalation energetics for various concentrations of AM atoms, calculate charge transfer from AM atoms to the host system, and show that although interca- lation of AMs as single layer is energetically preferable, multi-layer configurations can exist at high concentrations of AM atoms. We further demonstrate that the transition of the MoS2 layer from the H to T ′ phase is possible upon Li intercalation, but not Na or K. Our findings should help to better understand the behavior of heterostructures upon AM atom intercalation and may stimulate further experiments aimed at the tai- loring of heterostructure properties and increasing the capacity of anode materials in AM ion batteries.