First-Principles Study of Na Intercalation and Diffusion Mechanisms at 2D MoS₂/Graphene Interfaces

Na-ion batteries (NIBs) are emerging as promising energy storage devices for large-scale applications. Great research efforts are devoted to design new effective NIB electrode materials, especially for the anode side. A hybrid 2D heterojunction with graphene and MoS₂ has been recently proposed for this purpose: while MoS₂ has shown good reversible capacity as a NIB anode, graphene is expected to improve conductivity and resistance to mechanical stress upon cycling. The most relevant processes for the anode are the intercalation and diffusion of the large Na ion, whose complex mechanisms are determined by the structural and electronic features of the MoS₂/graphene interface. Understanding these processes and mechanisms is crucial for developing new nanoscale anodes for NIBs with high performances. To this end, here we report a state-of-the-art DFT study to address (a) the structural and electronic properties of heterointerfaces between the MoS₂ monolayers and graphene, (b) the most convenient insertion sites for Na, and (c) the possible diffusion paths along the interface and the corresponding energy barrier heights. We considered two MoS₂ polymorphs: 1T and 3R. Our results show that 1T-MoS₂ interacts more strongly with graphene than 3R-MoS₂. In both cases, the best Na host site is found at the MoS₂ side of the interface, and the band structure reveals a proper n-type character of the graphene moiety, which is responsible for electronic conduction. Minimum-energy paths for Na diffusion show very low barrier heights for the 3R-MoS₂/graphene interface (<0.25 eV) and much higher values for its 1T counterpart (∼0.7 eV). Analysis of structural features along the diffusion transition states allows us to identify the strong coordination of Na with the exposed S atoms as the main feature hindering an effective diffusion in the 1T case. These results provide new hints on the physicochemical details of Na intercalation and diffusion mechanisms at complex 2D heterointerfaces and will help further development of advanced electrode materials for efficient NIBs.