Elsevier

Chemical Engineering Journal

Volume 373, 1 October 2019, Pages 660-667
Chemical Engineering Journal

Robust C–S bond integrated graphdiyne-MoS2 nanohybrids for enhanced lithium storage capability

https://doi.org/10.1016/j.cej.2019.05.086Get rights and content

Highlights

  • Conductive GDY contacts through C–S bond with MoS2 to form GDY-MoS2 hybrids.

  • Robust C–S bond provides effective electron transport paths between MoS2 and GDY.

  • Large contact surface area of MoS2 and GDY shorten li-ion diffusion distance.

  • Li storage capacity of GDY-MoS2 at 0.05 A g−1 reached as high as 1450 mAh g−1.

Abstract

A novel Graphdiyne-Molybdenum disulfide (GDY-MoS2) hybrid nanostructure is successfully synthesized through in-situ method. The compactly contact through carbon–sulfur (C–S) bond between graphdiyne (GDY) and molybdenum disulfide (MoS2) effectively prevents the detachment problem and also provides effective electron transport paths between them. Highly conductive GDY layer not only acts as an electron collector, but also provides the volume expansion space for MoS2. And the large contact surface area of GDY and MoS2 can exceedingly shorten the diffusion distance of lithium-ion. As the synergistic results of the distinct hybrid structure, highly conductive GDY layer, as well as the robust interconnection, GDY-MoS2 (with 77.9 wt% MoS2) exhibits excellent lithium-ion storage performance (1463 mAh g−1 at 0.05 A g−1) and super cycling stability when serving as lithium-ion batteries (LIBs) anode.

Introduction

Rechargeable Li-ion batteries (LIBs) have been identified as the greatest potential energy storage technologies [1], [2], [3] to meet the ever-increasing energy requirements in modern society. Despite considerable advances have been made, there is still room to further improve their performance through the development of new materials [4], [5]. 2D material-Molybdenum disulfide (MoS2) has attracted tremendous interests as potential Li-ion batteries electrode material because of its distinct 2D layered structure that provides the ability to hold vast lithium ions and promote diffusion path for Li ion [6], [7], [8], [9]. As a result of the four-electron transfer reaction during charge/discharge processes, MoS2 has a specific capacity of 667 mAh g−1 theoretically [10]. Nevertheless, the volume swelling problem caused by the physical degradation of MoS2 in the charge/discharge process, the side reaction between Li2S and electrolyte, particularly its low conductivity, result in a poor rate performance and fast capacity decay, hindering its further development [11], [12].

Many efforts have been made to solve these undesired issues. One strategy is reducing particles to nanostructures, such as nanoflowers [13], nanosheets [14], and et al, to bridge the length of li-ions diffusion and enlarge the effective surface area between electrode materials and electrolyte. Nevertheless, these nanostructures are easy to restack to bulk structure and larger specific surface areas are likely to form a larger area of solid electrolyte interphase (SEI) film. More critically, the problem of conductivity is still not solved [15]. Another strategy is the incorporation of conductive carbon material with MoS2. Many kinds of carbon materials, for instance, porous carbon [16], carbon fibers/nanotubes [17], [18], graphene [19], [20], and et al. [21], [22], [23], [24], [25], [26], [27] have been studied. However, in most of the composites, the combination between carbon material and MoS2 usually through a weak physical contact, which may lead to the detachment of active material and generation of large charge–transfer resistance.

Graphdiyne (GDY), 2D π-conjugated carbon network composed by sp2 and sp hybridized carbon bonds, has been successfully synthesized by Li [28], [29], [30], [31]. On account of the abundant π bond in triplet bond, GDY have an electronic conductivity of 2.56 × 10−4 S m−1 [32]. And a charge carrier mobility higher than graphene of 2 × 105 cm2 V−1 s−1 can be possessed [33]. The density of Li intercalation in GDY revealed by theoretical studies could be LiC3. More prominent, Li ions could diffuse both in parallel and vertical to the plane of GDY [34], [35], [36], [37], [38], [39], [40], [41], [42], [43], [44], [45]. What is more, large area GDY films have been controllably fabricated using hexaethynylbenzene on copper via cross-coupling reaction. The unparalleled electrochemical properties and facile synthetic method make GDY a potential conductive material to combine with MoS2. Firstly, the monomer-hexaethynylbenzene could diffuse to the surface or even to the interlayer of MoS2, promising for the formation of hybrid structures on a large scale. Meanwhile, the highly active atom of C at the terminal acetylene and the edged S in MoS2 may form chemical bond which offers a high effective electron transport channel during the charge-discharge progress. More importantly, as the hybridization of two 2D planar materials, the 2D/2D stacking provides large contact area due to the face-to-face contact facilitating more rapidly charge and mass transfer by shorten the diffusion distance. Moreover, the intrinsic 3D porous structure of GDY offers more space for the volume expansion of the MoS2.

Herein, we demonstrate a novel hybrid nanostructure of GDY and MoS2 via a facile solution synthesis strategy, designating as GDY-MoS2. GDY and MoS2 contact compactly through strong C–S bond, which effectively prevents the detachment problem and also provides a resultful electron transport path between GDY and MoS2. The large contact area of GDY and MoS2 can greatly abridge diffusion distance. As the synergistic result, capacity decay issue of MoS2 has been effectively settled. The reversible Li storage capacity of GDY-MoS2 at 0.05 A/g for 100 cycles attained up to 1450 mAh g−1, 5.8-fold greater than that of nanoflower-like MoS2 (250 mAh g−1).

Section snippets

Synthesis of MoS2 nanoflower

0.16 g thiourea was dispersed in deionized water (60 mL) and stirred (10 min), then 0.16 g molybdenum trioxide was added and stirred for another 20 min. The mixture was put into a 100 mL PTFE lined stainless steel reaction still, and reacted at 180 °C for 48 h. After the reaction, it was cooled to the ambient temperature naturally, deionized water and anhydrous ethanol were used to wash away the redundant impurities. The MoS2 powder was collected through centrifugation. Then vacuum drying for

Synthesis and materials characterization

Synthetic procedure of GDY-MoS2 hybrid materials is shown in Scheme 1 and described detailed in the experimental section. As shown in Scheme 1, it comprises mainly two steps: the fabrication of flower-like MoS2 by hydrothermal method and cross-coupling reaction of hexaethynylbenzene on the surface or the interlayer of MoS2 to obtain GDY-MoS2 hybrid structure under the catalysis of Cu. Small molecule-hexaethynylbenzene could diffuse to the surface or may even to the interlayer of MoS2, promising

Conclusion

In summary, novel GDY-MoS2 hybrid nanostructure had been successfully obtained by a facile in-situ method. The distinct structure endows GDY-MoS2 with good mechanical stability and excellent energy storage behavior. The distribution of MoS2 nanosheets on the GDY film through C–S band not only inhibits the aggregation during cycling but also effectively increases electron transport. GDY layer of high electrical conductivity also performs as current collector during charge/discharge progress.

Acknowledgments

This study was supported by the National Natural Science Foundation of China (21790050, 21790051, 51822208, 21771187, 21875274, 21805299), the Frontier Science Research Project (QYZDB-SSW-JSC052) of the Chinese Academy of Sciences, the Natural Science Foundation of Shandong Province (China) for Distinguished Young Scholars (JQ201610), and Postdoctoral Research Foundation of China (2017M622299).

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