Origins of possible synergistic effects in the interactions between metal atoms and MoS₂/graphene heterostructures for battery applications

Abstract

The interactions between metals and two-dimensional materials, in particular, the adsorption energies, strongly determine the performances of rechargeable batteries. Previously, it has been demonstrated that heterostructures of two dimensional (2D) materials can lead to enhanced metal adsorptions, which were ascribed to the existence of 'synergistic' effects amongst metal atoms and two different 2D materials. However, further investigations are still required to reveal the physical mechanisms behind the contribution of these possible 'synergistic' effects for metal intercalations in 2D heterostructures. Here, we selected MoS2/graphene as a prototypical system, and we examined the adsorption and intercalation thermochemistry of monovalent atoms (Li, Na and K) and multivalent atoms (Mg, Ca and Al) using density-functional theory (DFT) calculations. The synergistic effects arising from charge polarizations in these systems were quantified using the three-body interaction energy terms. Our results show strong system dependencies whereby the interactions between the Mg or Ca atom with the MoS2/graphene heterostructures might exhibit cooperative bindings. Nevertheless, metal adsorptions on top of the graphene surface were all found to be anti-cooperative in this case. Our results suggest that enhancement of metal adsorptions using 2D heterostructures is predominantly driven by increasing dispersion interactions due to increases in the interaction surface areas.

Nanoscale fracture of defective popgraphene monolayers

“…The remarkable properties 1-3 and promising applications [4][5][6] offered by two-dimensional (2D) graphene have triggered great scientific interest to discover other 2D carbon allotropes. For example, following the success of graphene, penta-graphene, 7,8 phagraphene, 9,10 phographene, 11 ψ-graphene, 12 and θ -graphene 13 have been intensively studied for exciting applications such as in nanoelectronics and energy storage.…”

Coal-Derived Graphene/MoS2 Heterostructure Electrodes for Li-Ion Batteries: Experiment and Simulation Study

“…Unfortunately, the hypothesis of the synergistic effects on the electrochemical performance of heterostructures has not been systematically studied and confirmed. Fan et al proposed the possible synergistic effects of the MoS 2 -G heterostructure by examining the adsorption and intercalation chemistry of monovalent and multivalent atoms; however, this article does not substantially describe how the synergistic effects contribute to the real system . A deep understanding of the physical and chemical properties of the MoS 2 -G heterostructure is necessary to reveal the mechanisms that govern synergistic property enhancement in these 2D heterostructures.…”

“…Fan et al proposed the possible synergistic effects of the MoS 2 -G heterostructure by examining the adsorption and intercalation chemistry of monovalent and multivalent atoms; however, this article does not substantially describe how the synergistic effects contribute to the real system. 39 A deep understanding of the physical and chemical properties of the MoS 2 -G heterostructure is necessary to reveal the mechanisms that govern synergistic property enhancement in these 2D heterostructures. Various carbons, polydopamine, dimethylacetamide 4,4-bipyridine, and mesoporous carbon, have been used to expand the 2D materials interlayer, and subsequent interfacial studies have been carried out to explore ion storage at the heterostructures.…”

Prediction of Co and Ru Nanocluster Morphology on 2D MoS2 from Interaction Energies

“…Typically, theoretical studies focus on the adsorption of either single atoms of a series of metals [23,27,24,25,21] or large nanoparticle-like structures [19,20]. In our previous study we identified that while these studies do deliver useful insights, there is a knowledge gap in the understanding of metal thin film nucleation on 2D materials.…”