First-principles study of MoSSe_graphene heterostructures as anode for Li-ion batteries

doi:10.1016/j.chemphys.2019.110583

Chemical Physics

Volume 529, 15 January 2020, 110583

https://doi.org/10.1016/j.chemphys.2019.110583 Get rights and content

Highlights

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We model two different structures come from MoS_2(1−x)Se_2x which are very popular these years.
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The adsorption sites are more stable after forming a heterojunction with graphene.
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Energy barriers are declined obviously after forming a heterojunction with graphene.
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MoSSe_graphene heterostructures show good theoretical storage and excellent stability.

Abstract

By using means of density functional theory calculations, we reported the heterostructure consisting of monolayer MoSSe and graphene, as a promising anode material for lithium ion batteries. We investigated the adsorption and diffusion of lithium atoms in the MoSSe and MoSSe_graphene heterostructures, and we found that the combination with graphene makes the lithium atoms’ adsorption more stable, meanwhile, the diffusion barriers on the surface are lower than that at the interface, which are comparable to the barriers on the corresponding monolayers. The maximum lithium storage capacity of the heterostructure is enhanced to 390 mAh/g. Our work made a comparison with all the typical structures of MoSSe and MoSSe_graphene, and suggests that the S side of MoSSe-2 combined with graphene and the Se side of MoSSe-2 combined with graphene are the promising materials for their higher lithium capacity and charge/discharge rates.

Introduction

Lithium ion batteries (LIBs) are preferred in these years’ investigations as the most up-and-coming energy storage systems (ESSs). They are widespreadly applied to the electronic equipment over the past decades on account of the high reversible specific capacity and the environmentally friendly performance. The anode materials is vital for the development of high-performance batteries [1], [2], [3]. Graphite as anode materials for lithium ion batteries has been well commercialized due to its good conductivity, high crystallinity and fine cycle performance [4], [5], [6]. However, the instability of the graphite structure and the low Lithium storage capacity hinders its further development [7]. With the increasing demand of the high-performance electronics, better electrochemical properties’ batteries are imperative to be designed [8], [9].

With the rapid development of graphene research and sustaining innovation of manufacturing materials technology, other materials with two-dimensional layered structural characteristics, such as transition-metal dichalcogenides (TMDCs) [10], [11], [12], [13], [14], [15], [16], have been gradually entered the scope of people's research due to their good mechanical flexibility and thermal stability, no surface dangling bonds, as well as compatibility with silicon CMOS processes [17], [18], [19], [20]. Compared with graphene, TMDCs have higher theoretical Lithium storage capacity and lower diffusion barrier.

As a promising TMDC, MoS_2(1−x)Se_2x has been demonstrated that it has a good performance on the hydrogen evolution reaction as well as exhibits excellent photocatalytic properties [21], [22], [23]. However, the exploration of applying MoS_2(1−x)Se_2x to be a kind of anode material is relatively rare. Recently, Ersan et al. [24] simulated the Li atom adsorption and diffusion on monolayer MoS_2(1−x)Se_2x with different ratios of sulfur and selenium and found that it was suitable to be a promising anode material. According to Wang et al. [22], a synthesized composite of rGO and MoS_2(1−x)Se_2x and the meso-GO/MoS_2(1−x)Se_2x was investigated as a high-capacity anode material, and it came to the highest capacity when the ratio of sulfur and selenium was almost 1:1. One typical structure of MoS_2(1−x)Se_2x, the Janus monolayer MoSSe has got a large number of researches in these two years [25], [26]. Janus monolayer MoSSe shows good photocatalytic performance and electronic properties. Therefore, the Janus monolayer MoSSe is a promising electrode material for us to investigate.

Nevertheless, TMDCs also have some deficiencies, such as low conductivity and structural instability [27], [28], [29], [30], [31]. Moreover, during the charge-discharge process, the volume expansion of the electrode is very serious, causing polarization of the electrode, resulting in serious degradation of the specific capacity. A frequently-used method is to construct complexes of TMDCs and carbon materials (graphene, amorphous carbon, etc. [32], [33]), and use the high conductivity and confinement of carbon materials to prevent the dissolution of polysulfide anions and increase their lithium storage capacity. In this way the VS₂/graphene heterostructure was studied both in experiment and theory and was proved to have higher lithium capacity and wider voltage range compared with VS₂ [34], [35]. In like manner, Samad et al. [36] investigated MoS₂/VS₂ composite and demonstrated its excellent electrochemical properties. Meanwhile, Yue et al. [37] synthesized MoS_2(1−x)Se_2x/graphene heterostructure and investigated its optical properties through experiments.

Despite many efforts have been made to experimentally and theoretically rationalize the excellent properties of heterostructures anode materials, there are still several important issues to be addressed. Thus, in this paper, we used the first-principles to simulate the lithium adsorption and diffusion in the different structure of MoSSe monolayer. To make a comparison with the Janus structure of MoSSe, we found another typical MoSSe structure, the MoSSe-1, with sulfur and selenium atoms are arranged alternately on the same surface, and the Janus monolayer MoSSe is defined as MoSSe-2. Then, we combined the two different structures with the graphene and got 3 MoSSe_graphene heterostructures which are defined as structure SeSC (MoSSe-1 combined with graphene), SC (the S side of MoSSe-2 combined with graphene), SeC (the Se side of MoSSe-2 combined with graphene), we explored the lithium adsorption energies, diffusion barriers, the maximal possible lithium content as well as made a comparison with the monolayer MoSSe. The results suggest that MoSSe_graphene have the potential to be universal anode materials.

Section snippets

Computational details

Spin-polarized calculations were performed using an all-electron method in the DMol³ code [38], [39] within the framework of density functional theory (DFT). We used the generalized gradient approximation (GGA) in the form of Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional [40]. The double numerical plus d functions (DND) basis set and the DFT + D2 method with the Grimme vdW [41] correction were adopted. We also use the dipole correction due to the different surface of the

The structures of MoSSe and MoSSe/graphene

First of beginning, we optimized the unit cell of MoSSe. And the lattice parameters are a = 3.286 Å, b = 3.298 Å, which are similar with the previous work (a = 3.198 Å, b = 3.328 Å) [24]. In the consideration of the isolated lithium atom, we constructed a 4 × 4 × 1 MoSSe monolayer, and the 30 Å vacuum region was chosen to avoid the interactions between the interlayers. Meanwhile, the bond lengths of Mo-Se and Mo-S in the MoSSe-1 are 2.563 Å and 2.444 Å, and in MoSSe-2 the values are 2.561 Å and

Conclusion

In this article, we investigated the adsorption and diffusion of lithium atoms in the MoSSe and MoSSe_graphene heterostructures by using the first principles method based on vdW corrected density functional theory, and we found that the combination with graphene makes the lithium atoms’ adsorption more stable, meanwhile, the diffusion barriers on the surface are lower than that at the interface, which are comparable to the barriers on the corresponding monolayers. The maximum lithium storage

Acknowledgement

This research was supported by the National Natural Science Foundation of China under No. 51574090.

Data availability

Te data sets generated and analysed during the current study are available from the corresponding author on reasonable request.

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First-principles study of MoSSe_graphene heterostructures as anode for Li-ion batteries

Highlights

Abstract

Introduction

Section snippets

Computational details

The structures of MoSSe and MoSSe/graphene

Conclusion

Acknowledgement

Data availability

Carbon

J. Power Sources

Appl. Mater. Today

Appl. Mater. Today

J. Power Sources

Electrochim. Acta

Chem. Phys. Lett.

Sustainability and in situ monitoring in battery development

Nat. Mater.

Magnetically aligned graphite electrodes for high-rate performance Li-ion batteries

Nat. Energy

Metal oxides and oxysalts as anode materials for Li ion batteries

Chem. Rev.

Effects of off-stoichiometry of LiC6 on the lithium diffusion mechanism and diffusivity by first principles calculations

J. Phys. Chem. C

First-principle calculation-assisted structural study on the nanoscale phase transition of Si for Li-ion secondary batteries

Inorg. Chem.

Feasibility of lithium storage on graphene and its derivatives

J. Phys. Chem. Lett.

Are MXenes promising anode materials for Li ion batteries? Computational studies on electronic properties and Li storage capability of Ti3C2 and Ti3C2X2 (X = F, OH) monolayer

J. Am. Chem. Soc.

TiC3 monolayer with high specific capacity for sodium-ion batteries

J. Am. Chem. Soc.

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Effects of off-stoichiometry of LiC₆ on the lithium diffusion mechanism and diffusivity by first principles calculations

Are MXenes promising anode materials for Li ion batteries? Computational studies on electronic properties and Li storage capability of Ti₃C₂ and Ti₃C₂X₂ (X = F, OH) monolayer

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An ab initio study of TiS₃: a promising electrode material for rechargeable Li and Na ion batteries

Highly efficient field emission properties of a novel layered VS₂/ZnO nanocomposite and flexible VS₂ nanosheet

Ultrathin MoS_2(1–x)Se_2x alloy nanoflakes for electrocatalytic hydrogen evolution reaction

The electronic and optical properties of MoS_2(1–x)Se_2x and MoS_2(1–x)Te_2x monolayers