Unraveling the Interactions between Lithium and Twisted Graphene

Graphene is undoubtedly the carbon allotrope that has attracted the attention of a myriad of researchers in the last decades more than any other. The interaction of external or intercalated Li and Li⁺ with graphene layers has been the subject of particular attention for its importance in the applications of graphene layers in Lithium Batteries (LiBs). It is well known that lithium atoms and Li⁺ can be found inside and/or outside the double layer of graphene, and the graphene layers are often twisted around its parallel plane to obtain twisted graphene with tuneable properties. Thus, in this research, the interactions between Li and Li⁺ with bilayer graphene and twisted bilayer graphene were investigated by a first-principles density functional theory method, considering the lithium atom and the cation at different symmetry positions and with two different adsorption configurations. Binding energies and equilibrium interlayer distances of filled graphene layers were obtained from the computed potential energy profiles. This work shows that the twisting can regulate the interaction of bilayer graphene with Li and Li⁺. The binding energies of Li⁺ systematically increase from bilayer graphene to twisted graphene regardless of twisted angles, while for lithium atoms, the binding energies decrease or remain substantially unchanged depending on the twist angles. This suggests a higher adsorption capacity of twisted graphene towards Li⁺, which is important for designing twisted graphene-based material for LiB anode coating. Furthermore, when the Li or Li⁺ is intercalated between two graphene layers, the equilibrium interlayer distances in the twisted layers increase compared to the unrotated bilayer, and the relaxation is more significant for Li⁺ with respect to Li. This suggests that the twisted graphene can better accommodate the cation in agreement with the above result. The outcomes of this research pave the way for the study of the selective properties of twisted graphene.