Elsevier

Journal of Power Sources

Volume 293, 20 October 2015, Pages 784-789
Journal of Power Sources

Improved sodium-storage performance of stannous sulfide@reduced graphene oxide composite as high capacity anodes for sodium-ion batteries

https://doi.org/10.1016/j.jpowsour.2015.06.015Get rights and content

Highlights

  • The SnS@RGO as Na storage anode is synthesized by a simple precipitation method.

  • The SnS@RGO can deliver large reversible capacity (457 mAh g−1 at 20 mA g−1).

  • The SnS@RGO also shows excellent cycling stability over 100 cycles.

Abstract

Stannous sulfide@reduced graphene oxide (SnS@RGO) composite is successfully synthesized via a facile precipitation route. The structural and morphological characterizations reveal SnS@RGO composites are composed of SnS nanoparticles of the size 5–10 nm, which are uniformly anchored on the surface of RGO. The electrochemical measurements demonstrate the reversible capacity of the SnS@RGO composite – that includes contributions from the conversion reaction of SnS to Sn and NaxS and the alloying reaction of Sn to NaxSn. The SnS@RGO electrode exhibits a reversible capacity of 457 mAh g−1 at 20 mA g−1, superior cycling stability (94% capacity retention over 100 cycles at 100 mA g−1) and adequate rate performance. Compared to the neat SnS nanoparticles, the enhanced electrochemical performance of the SnS@RGO composite is primarily due to the incorporation of RGO as a highly conductive, flexible component as well as possessing a large available surface area, which provides desirable properties such as improved electronic contact between active materials, aggregation suppression of intermediate products, and alleviation of the volume change during sodiation and desodiation. Encouraging experimental results suggest that the SnS@RGO composite is a promising material to achieve a high-capacity and stable anode for NIBs.

Introduction

Sodium-ion batteries (NIBs) have attracted an increasing amount of attention in recent years to meet application demands of low-cost energy storage, primarily due to the wide availability of Na resources compared to Li [1], [2], [3], [4], [5], [6]. However, in contrast to Li ion intercalation chemistry, seldom cathodic materials have been found that enable fast and reversible insertion/deinsertion of the large-sized Na ions yielding and adequate capacity, examples of cathodic materials include, layer and tunnel structured metal oxides [7], [8], [9], [10], [11], open-framework ferrocyanides [12], and amorphous FePO4 [13]. In regard to the anodic component of the NIB, hard carbon [14], [15], [16], [17], alloys [18], [19], [20], [21], [22] and metal sulfides [23], [24] are commonly studied. Hard carbon materials display Na storage capacity in the range of 200–300 mAh g−1 [14], [15], [16], [17] with limited cyclability, whereas alloy materials (primarily alloys of Sn and Sb) show much higher reversible capacity [18], [19], [25], [26], [27], [28], [29], [30], [31], [32], such as higher than 600 mAh g−1 for a Sb–C composite [19] and 550 mAh g−1 for a Sn-based materials after 80 cycles [30].

Additionally, Sn(or Sb, W, Mo) oxides [33] and sulfides [23], [24], [29], [30] have also been investigated for their potential as anode materials due to their potentially high capacity offered by both alloying and conversion reactions, such as 667 mAh g−1 for SnO2, 1227 mAh g−1 for Sb2O4, 1136 mAh g−1 for SnS2, and 1022 mAh g−1 for SnS [30], [33], [34], [35]. Sun et al. reported a Sb2O4 thin film electrode demonstrating a reversible capacity of 896 mAh g−1 [34]. The Sn–SnS–C and SnS–C nanocomposites, revealed in our previous publications, show reversible capacities of 664 mAh g−1 and 568 mAh g−1 at 20 mA g−1, respectively [29], [30]. However, due to their diminished electron conductivity and large volumetric change during sodiation and desodiation, these Sn/Sb oxides or sulfides suffer from low utilization and poor cycling performance. In order to address said challenges, various methods have been developed, such as designing peculiar nanostructures [19], [25], [27], [36], [37] and combining oxides/sulfides with conductive supporters [19], [29]. Due to graphene's advantages of high surface area, adequate electronic conductivity, and flexible framework, it is an ideal scaffold for electrochemical reactions [38]. Graphene hybrid nanocomposites have demonstrated a dramatically improved electrochemical performance of electrodes for Na ion storage [26], [39], [40]. Yu et al. reported a SbS2/graphene anode possessing a superior Na storage capacity of 730 mAh g−1 at 50 mA g−1 [26]. SnO2/graphene nanocomposite demonstrates a reversible Na storage capacity of above 700 mAh g−1 [39], [41], [42].

Generally, the sulfides exhibit better electrochemical performance than the oxides for sodium ion storage [29], [39]. It is possibly because that M−S bonds in metal sulfides are weaker than the corresponding M−O bonds in metal oxides, which would be kinetically favorable for the conversion reactions. In this publication, the synthesis of SnS@RGO (reduced graphene oxide) hybrid structure with SnS nanocrystals uniformly anchored onto RGO nanosheets via a simple precipitation method (Fig. 1). The as-prepared SnS@RGO nanocomposite demonstrated a high reversible capacity of 457 mAh g−1 at 20 mA g−1 and an excellent cycling stability in a Na-ion battery. To the best of our knowledge, said material is the first demonstration of Na ion storage performance using a SnS@RGO-based material.

Section snippets

Experimental

The SnS@RGO composite was prepared by a simple precipitation method described as follows. 40 mL of GO (Graphene Oxide, 98.5% purity, Sinocarbon Graphene Marketing Center, Shanxi, China) dispersion (2 mg mL−1) was dispersed in 40 mL of 0.05 mol L−1 thioacetamide (C2H5NS, 99% purity, National Medicine Co., Ltd, Shanghai, China) solution under sonication for 0.5 h, and then 80 mL of 0.05 mol L−1 SnCl2 (SnCl2•2H2O, 98% purity, National Medicine Co., Ltd, Shanghai, China) solution was added into the

Results and discussion

The SnS@RGO composite was prepared by a simple precipitation method. The scheme of the synthetic reactions is shown in Fig. 1. Morphological and structural features of the SnS@RGO composite were characterized using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). In Fig. 2a, the SnS@RGO composite displays a flexible structure containing thin sheets, which is similar to that of the neat RGO, suggesting that the SnS nanoparticles uniformly

Conclusions

In summary, a facile precipitation synthesis is reported to yield nanocrystalline SnS@RGO composite with ultrafine yet crystallized SnS nanoparticles uniformly dispersed on the surface of RGO. The SnS@RGO electrodes exhibit a high Na storage capacity of 457 mAh g−1 at 20 mA g−1 and demonstrating excellent cyclability (94% of capacity retention over 100 cycles at 100 mA g−1) as well as remarkable rate capability. The enhanced electrochemical performance of the SnS@RGO composite originates from

Acknowledgments

We thank financial support by the National Key Basic Research Program of China (No. 2015CB251100), National Science Foundation of China (No. 21173160, 21333007) and, Program for New Century Excellent Talents in University (NCET-12-0419) and Hubei National Funds for Distinguished Young Scientists (2014CFA038).

References (48)

  • B.L. Ellis et al.

    Curr. Opin. Solid State Mater. Sci.

    (2012)
  • E. Lee et al.

    Electrochim. Acta

    (2014)
  • D. Su et al.

    Nano Energy

    (2015)
  • L. Wu et al.

    Electrochim. Acta

    (2013)
  • Y. Wang et al.

    Electrochem. Commun.

    (2013)
  • Q. Sun et al.

    Electrochem. Commun.

    (2011)
  • M.K. Datta et al.

    J. Power Sources

    (2013)
  • J. Guo et al.

    J. Power Sources

    (2014)
  • S. Stankovich et al.

    Carbon

    (2007)
  • P. Guo et al.

    Electrochem. Commun.

    (2009)
  • H. Pan et al.

    Energy Environ. Sci.

    (2013)
  • V. Palomares et al.

    Energy Environ. Sci.

    (2013)
  • S.Y. Hong et al.

    Energy Environ. Sci.

    (2013)
  • M.D. Slater et al.

    Adv. Funct. Mater.

    (2013)
  • S.-W. Kim et al.

    Adv. Energy Mater.

    (2012)
  • D. Yuan et al.

    J. Mater. Chem. A

    (2013)
  • Y. Cao et al.

    Adv. Mater.

    (2011)
  • D. Yuan et al.

    Adv. Mater.

    (2014)
  • N. Yabuuchi et al.

    Adv. Energy Mater.

    (2014)
  • J. Qian et al.

    Adv. Energy Mater.

    (2012)
  • Y. Fang et al.

    Nano Lett.

    (2014)
  • S. Komaba et al.

    Adv. Funct. Mater.

    (2011)
  • Y. Cao et al.

    Nano Lett.

    (2012)
  • S. Wenzel et al.

    Energy Environ. Sci.

    (2011)
  • Cited by (82)

    View all citing articles on Scopus
    View full text