Elsevier

Electrochimica Acta

Volume 240, 20 June 2017, Pages 7-15
Electrochimica Acta

Carbon nanotube-graphene nanosheet conductive framework supported SnO2 aerogel as a high performance anode for lithium ion battery

https://doi.org/10.1016/j.electacta.2017.04.031Get rights and content

Highlights

  • 3D conductive frameworks supported SnO2 aerogel composite is fabricated.

  • Carbon nanotube(CNT) is assist to interconnect independent porous graphene(GN).

  • Interplay between CNT and GN enhance the stability of SnO2/CNT-GN composite.

  • Stable specific capacity and excellent rate capability are achieved.

Abstract

Tin oxide (SnO2) based materials are considered promising anodes for high-energy lithium ion batteries (LIBs). However, significant challenges including low initial coulombic efficiency, poor cycling stability and low rate capability are still hindering their practical applications. Effectively constructing a conductive material structure plays a vital role in improving the electrochemical performance of tin based composite anodes for LIBs. In this work, we utilize carbon nanotube-graphene nanosheet with 3D conductive framework to fabricate a SnO2/carbon nanotube-graphene nanosheet (SnO2/CNT-GN) aerogel composite, in which a small amount of carbon nanotube is introduced to increase the electronic transportation by interconnecting the independent porous graphene structure. In addition, the synergistic interplay between high mechanical property of CNT and flexibility of graphene significantly enhance the stability of SnO2/CNT-GN composite. As a result, the SnO2/CNT-GN composite exhibit a very decent cycling stability, retaining a stable specific capacity of 809 mAh g−1 (87% capacity retention) after 100 cycles at 0.2 A g−1, as well as an excellent rate capability, delivering 787 mAh g−1 even at a high current density of 5A g−1.

Introduction

During the past decades, a large amount of effort has been devoted to developing rechargeable lithium-ion batteries (LIBs) with high energy density, high safety and long cycling performance for various applications such as smart electronics, electric vehicles, and large scale energy storage system [1], [2]. However, rapid development of market, especially the increasing demand for high-energy-density LIBs to be deployed in hybrid electric vehicles has prompted the consideration of electrode material candidates for LIBs [3], [4]. Among those anode materials under being explored, tin oxide (SnO2) based material is regarded as a promising anode candidate due to its high theoretical reversible Li+ storage capacity (782 mAh g−1), low cost, and facile synthesis technology [5], [6]. However, the practical use of tin based materials is greatly hampered by its huge volume change (∼300%) during the lithiation of Sn, leading to pulverization of particles as well as exfoliation of electrode materials. It is recently reported that designing the tin based materials of nanostructures, such as 1D tin dioxide nanowires [7], nanotubes [8], [9], 2D tin nanosheets [10], 3D hollow sphere [11], hollow submicroboxes [12], or porous nanosphere [13], is proved to be an effective strategy to enhance the capacity of tin based anode. However, some technical challenges still exist in pure tin based anode for LIBs. For example, the volume expansion of electrode materials cannot be effectively suppressed by some nanostructure design. In addition, the large surface area of nanoparticles gives rise to serious parasitic side reactions, and aggravates the formation and fracture of unstable solid electrolyte interphase (SEI) film, resulting in continuing capacity degradation.

To address those issues, some positive methods have been made to introduce carbon buffer matrix for tin based anodes to improve their electrochemical properties in LIBs [14], [15], [16], [17], [18]. Among those carbonaceous materials, graphene exhibiting several inherent advantages, such as excellent conductivity, superior flexibility and chemical stability, has been investigated as a carbon matrix to fabricate of SnO2/graphene hybrid anode materials [19], [20], [21], [22], [23]. Firstly, graphene play an important role in promoting the electron transfer during the lithiation and delithiation process. Moreover, the flexibility of graphene can help release the residual stress arising from the volume change of SnO2 particles. Owing to these merits, various preparation methods have been conducted to construct SnO2/graphene composite, including solution-based synthesis [24], [25], [26], hydrothermal synthesis [27], [28], self-assembly synthesis [29], [30] and so on. A representative example can be found in anchoring SnO2 nanocrystals into 3D macroscopic frameworks built up by graphene, which can provide abundant interconnected porous structure with large surface area [27], [31]. These 3D frameworks avoid the π−π restacking of graphene nanosheets, significantly enhancing the accessible surface area and strengthening the electrochemical reaction kinetics. Therefore, improved capacity of SnO2/graphene composites has been achieved. However, the low electrical conductivity in the graphene-based aerogel structures may result in low rate capability (below 500 mAh g−1 at 2 A g−1) [32], [33], [34], which is primarily due to the inadequate conductive frameworks established in these porous structures. Therefore, it is greatly important to effectively construct a conductive structure as a bridge to connect the relatively independent porous graphene aerogel. To realize these aims, different kinds of tin based/graphene composites for LIBs have been focused on adopting a second carbon precursor, such as glucose, dopamine, polyvinyl alcohol to form a supporting layer on the surface of tin oxide [35], [36], [37]. The double conductive layer can offer fast electron transportation and enough Li+ ion diffusion pathway, which enables improved rate performance for LIBs [38]. However, it is still a big challenge to control the uniformity of coating layer on the tin matrix and the optimal thickness of coating layer for those tin dioxide/carbon-graphene composites.

In this study, we have fabricated carbon nanotube-graphene nanosheet (CNT-GN) conductive framework supported SnO2 aerogel composites by one-pot hydrothermal process. CNT is chosen as a conductive additive agent to build interconnected conductive framework. A systematic electrochemical analysis discloses that the 3D CNT-GN framework could suppress the volume expansion/shrinkage due to the synergistic effect of high mechanical property of CNT and flexibility of graphene, which increase the reversibility and kinetic behaviors of the composite. Thus, the as-prepared tin oxide/carbon nanotube-graphene nanosheet (SnO2/CNT-GN) composite exhibits a higher reversible capacity, better cycling stability and significantly enhanced rate capability as compared to its SnO2/GN counterpart.

Section snippets

Materials

Graphene oxide (GO) (GO, 99 wt%; Thinkness, 0.55–3.58 nm; layer number <10) and carbon nanotube (CNT, >95 wt%; OD, >50 nm; Length, 10–20 um; −OH content, 0.71 wt%) were purchased from Daying Juneng Technology and Development Co., Ltd without further purification. Stannic chloride pentahydrate (SnCl4∙5H2O >99.0%) and polyvinylpyrrolidone K30 (PVP) were purchased from Chengdu Kelong Chemical Reagent Factory (China).

Synthesis of SnO2/CNT-GN composite

The SnO2/CNT-GN composite was prepared by a facile hydrothermal process followed by the

Results and discussion

Fig. 1 illustrates the synthesis procedure of the SnO2/CNT-GN composites. The SnO2/CNT-GN composites were fabricated by one pot hydrothermal route. CNT was homogeneously distributed in a solution of graphene oxide (GO) by the assistance of PVP as surfactant. During the hydrothermal process, Sn4+ ions can be anchored onto the surface of GO as the function of electrostatic attraction by the abundant functional groups such as hydroxyl, carboxyl, and epoxy groups. Meanwhile, the GN anchored with SnO

Conclusions

CNT-GN 3D conductive framework supported SnO2 aerogel composites have been successfully synthesized by one-pot hydrothermal treatment followed by freeze drying and pyrolysis process. The design sufficiently takes advantages of porous structure by reconstructing graphene nanosheet, where a large amount of SnO2 nanocrystals are anchored. The introduction of CNT increases the connection of relatively independent graphene sheets, which provide much faster charge transfer pathways at the SnO2

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant No. 51502250, 51604250, 51474196, 51302232), the Science & Technology Department of Sichuan Province (grant no. 2015JY0089, 2016RZ0071), and Education Department of Sichuan Province (No. 16ZB0085).

References (48)

  • P. Lian et al.

    Porous SnO2@C/graphene nanocomposite with 3D carbon conductive network as a superior anode material for lithium-ion batteries

    Electrochim. Acta

    (2014)
  • J. Zhu et al.

    Carbon and graphene double protection strategy to improve the SnO(x) electrode performance anodes for lithium-ion batteries

    Nanoscale

    (2014)
  • M.S. Wang et al.

    Scalable preparation of porous micron-SnO2/C composites as high performance anode material for lithium ion battery

    J. Power Sources

    (2016)
  • Y. Wan et al.

    Facile synthesis of tin dioxide-based high performance anodes for lithium ion batteries assisted by graphene gel

    J. Power Sources

    (2015)
  • M. Armand et al.

    Building better batteries

    Nature

    (2008)
  • N. Recham et al.

    A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries

    Nature Mater.

    (2010)
  • A.S. Arico et al.

    Nanostructured materials for advanced energy conversion and storage devices

    Nat. Mater.

    (2005)
  • Y. Idota et al.

    Tin-based amorphous oxide: a high-capacity lithium-ion-storage material

    Science

    (1997)
  • M.S. Park et al.

    Preparation and electrochemical properties of SnO2 nanowires for application in lithium on batteries

    Angew. Chem Int. Ed.

    (2007)
  • Z. Liu et al.

    Ultrafast and scalable laser liquid synthesis of tin oxide nanotubes and its application in lithium ion batteries

    Nanoscale

    (2014)
  • X. Zhou et al.

    Nanowire-templated formation of SnO2/carbon nanotubes with enhanced lithium storage properties

    Nanoscale

    (2016)
  • C. Wang et al.

    Ultrathin SnO2 nanosheets: oriented attachment mechanism, nonstoichiometric defects, and enhanced lithium-ion battery performances

    J. Phys. Chem. C

    (2012)
  • X. Zhou et al.

    Formation of uniform N-doped carbon-coated SnO2 submicroboxes with enhanced lithium storage properties

    Adv. Energy. Mater.

    (2016)
  • X. Zhou et al.

    A robust composite of SnO2 hollow nanospheres enwrapped by graphene as a high-capacity anode material for lithium-ion batteries

    J. Mater. Chem.

    (2012)
  • Cited by (40)

    • Tubular carbon nanofibers loaded with different MnO<inf>2</inf>: Preparation and electrochemical performance

      2023, Fabrication and Functionalization of Advanced Tubular Nanofibers and their Applications
    • Recent progress in the three-dimensional structure of graphene-carbon nanotubes hybrid and their supercapacitor and high-performance battery applications

      2022, Composites Part A: Applied Science and Manufacturing
      Citation Excerpt :

      They also compared the G-CNTs hybrid produced by hydrothermal and conventional melt-heating, where the former had a perfect crystal and a highly integrated structure because water served as a pressure transfer medium during the hydrothermal process. Since the hydrothermal and solvothermal methods are superficial, researchers proposed numerous combination of G-CNT hybrid with other materials to form other unique hybrid structures, such as G-CNT/VO2 [100], G-CNT/Au [101], G-CNT/MoS2 [102], G-CNT/Pd [103], G-CNT/Co3S4 [104], G-CNT/ZnMn2O4 [105], G-CNT/Fe [106], G-CNT/V2O5 [107], G-CNT/TiO2 [108], G-CNT/Ni [109], G-CNT/Si [110], G-CNT/Fe2O3 [111], G-CNT/S [99], G-CNT/NiCo2O4 [112], G-CNT/Ni(OH)2 [113], G-CNT/V3O7 [114], G-CNT/SnO2 [115], G-CNT/MnO2 [116], G-CNT/Pt [117], G-CNT/CuO [118], G-CNT/TiO2 [119], and G-CNT/CdS [120]. The processing parameters of both hydrothermal and solvothermal methods reported in the literature are detailed in Table 4.

    • Carbon aerogel based materials for secondary batteries

      2021, Sustainable Materials and Technologies
    View all citing articles on Scopus
    View full text