Synthesis of hierarchical reduced graphene oxide/SnO2/polypyrrole ternary composites with high electrochemical performance

doi:10.1016/j.materresbull.2016.04.015

Materials Research Bulletin

Volume 80, August 2016, Pages 303-308

https://doi.org/10.1016/j.materresbull.2016.04.015 Get rights and content

Highlights

•
Reduced graphene oxide/SnO₂/polypyrrole composites are prepared by one-pot method.
•
PPy nanofibers and SnO₂ nanoparticles distribute in the graphene nanosheets.
•
The composites with hierarchical nanostructures show higher specific capacitance.
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The composites exhibit good rate capability and cycling stability.

Abstract

The hierarchical reduced graphene oxide/SnO₂/polypyrrole ternary composites are prepared in a one-pot method via in situ redox reaction between graphene oxide and Sn²⁺ ions, followed by the polymerization of pyrrole monomers in the presence of methyl orange. The ternary composites are composed of one-dimensional polyprrole nanofibers and SnO₂ nanoparticles distributed in the network of graphene nanosheets. Supercapacitors based on the hierarchical composite show larger specific capacitance compared with the ternary composite prepared without methyl orange and reduced graphene oxide/SnO₂ binary composite. They also exhibit superior electrochemical rate capability and cyclic stability. The capacitance retained about 95% after 800 galvanostatic cycles at 1 A/g. The high electrochemical performance results from the hierarchical nanostructure, the efficient combination of components and the synergistic interaction among the three components. The hierarchical ternary composites are promising electrode material for high-performance supercapacitors.

Graphical abstract

Introduction

During the decades, increasing demand for energy and growing concerns about environmental issues have accelerated the development of energy storage and conversion devices. Supercapacitors have attracted significant academic and industrial attention due to their high power capacity, long cycle life, high energy density and high charge/discharge rate [1], [2], [3]. They have been applied in hybrid electric vehicles, mobile electronic devices, and medical systems. Nowadays, great efforts are underway to develop new electrode materials with lower fabrication cost and improve power and energy density.

In general, metal oxides, conducting polymers and carbonaceous materials are three main kinds of potential electrode materials for high performance supercapacitors. Conducting polymers and transition metal oxides are two typical pseudocapacitive materials, but are also limited by their poor stability during cycling and poor electrical conductivity, respectively [4], [5], [6], [7], [8], [9]. Carbonaceous materials with high specific surface area, such as mesoporous carbon, carbon nanotubes and graphene, exhibit electrochemical double layer capacitance. However, its application in high performance supercapacitors is restricted due to easy agglomeration and stacking [10], [11], [12], [13]. Therefore, the combination of any two materials mentioned above can improve the electrochemical performance of supercapacitors compared with the single electrode material [14], [15], [16], [17], [18].

Recently, the ternary composites composed of conducting polymer, metal oxide and graphene with enhanced conductivity, specific capacitance and cycling stability have been reported. Mu et al. prepared the graphene/MnO₂/polyaniline ternary composites by in situ chemical polymerization of polyaniline on the graphene sheets decorated by MnO₂ nanoparticles, which were obtained via the hydrothermal process of graphene oxide and KMnO₄ in a water-glycol system [19]. Polypyrrole (PPy) film was covered on the surface of graphene/SnO₂ nanoparticles by Wang et al. [20]. SnO₂ nanoparticles were anchored into the polyaniline-reduced graphene oxide layers with mesoporous structures [21]. However, it is still a big challenge to design and synthesize the ternary materials with controlled hierarchical nanostructures for supercapacitor electrodes.

In our previous work, PPy nanofibers were successfully synthesized through the template of the complex of Fe³⁺ and methyl orange (MO) [22], [23]. Herein, a one-pot synthetic route is presented for the preparation of reduced graphene oxide/SnO₂/polypyrrole (rGO/SnO₂/PPy) ternary composites with hierarchical nanostructures. First, the redox reaction between graphene oxide and Sn²⁺ ions results in the simultaneous generation of reduced graphene oxide and SnO₂ (rGO/SnO₂). Then, PPy nanofibers are formed in the presence of methyl orange (MO). The two-dimensional graphene sheets, one-dimensional PPy nanofibers and SnO₂ nanoparticles co-exist in the as-prepared ternary composites. The introduction of one-dimensional PPy nanofibers restricts the aggregation of rGO sheet. Electrochemical tests demonstrate that rGO/SnO₂/PPy ternary composites with hierarchical nanostructures exhibit higher specific capacitance, rate ability and long-term stability compared with rGO/SnO₂/PPy ternary composite prepared without MO and rGO/SnO₂ binary composite.

Section snippets

Sample preparation

GO was prepared using the method in our previous report [24]. All of the other chemicals were purchased from Shanghai Chemical Co., Ltd., and used without further purification. 1 mmol of SnCl₂·2H₂O was added into 20 mL of GO suspension with the concentration of 1 mg/mL. After stirring at room temperature for 6 h, rGO/SnO₂ was obtained through the redox reaction between GO and Sn²⁺ ions. Subsequently, 20 mL of the solution containing 1 mmol of FeCl₃ and 0.1 mmol MO was added into the above rGO/SnO₂

Results and discussion

In order to assess the reduction of GO by SnCl₂, Raman spectra are performed to record the structural changes from GO to rGO, as shown in Fig. 1. In general, the Raman spectrum of graphene material is characterized by two obvious peaks. The G peak at about 1580 cm⁻¹ is attributed to the order scattering of the sp² carbon atoms and the D peak at about 1340 cm⁻¹ is associated to the disorder of carbon [25]. The relative intensity of the D and G peaks (D/G) is indicative of the density of defects in

Conclusion

Novel rGO/SnO₂/PPy ternary composites with the hierarchical structures of one-dimensional PPy nanofibers and SnO₂ nanoparticles distributed in the network of graphene nanosheets have been successfully prepared in a one-pot synthesis. The specific capacitance of rGO/SnO₂/PPy prepared with MO is 280.5 F/g at 0.5 A/g in Na₂SO₄ electrolyte solutions, much higher than those of rGO/SnO₂ and rGO/SnO₂/PPy prepared without MO. The specific capacitance of rGO/SnO₂/PPy prepared with MO still reaches 169 F/g

Acknowledgements

The work was supported by Outstanding Youth Scientific Innovation Team of Colleges and Universities in Hubei Province (T201406), National Natural Science Foundation of China (51403167, 51374155), Natural Science Foundation of Hubei Province (2014CFB796), and Science and Technology Support Program of Hubei Province (2014BCB034).

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Synthesis of hierarchical reduced graphene oxide/SnO2/polypyrrole ternary composites with high electrochemical performance

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Sample preparation

Results and discussion

Conclusion

Acknowledgements

Mater. Res. Bull.

Electrochim. Acta

J. Power Sour.

Carbon

Acta

Mater. Sci. Engin. B

Synth. Met.

Carbon

Mater. Res. Bull.

Water Res.

Electrochim. Acta

What are batteries fuel cells, and supercapacitors

Chem. Rev.

Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage

Nano Lett.

Fabrication and characterization of free-standing polypyrrole/graphene oxide nanocomposite paper

J. Nanopart. Res.

High rate performance of flexible pseudocapacitors fabricated using ionic-liquid-based proton conducting polymer electrolyte with poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) and its hydrous ruthenium oxide composite electrodes

ACS Appl. Mater. Interfaces

Synthesis of hierarchical reduced graphene oxide/SnO₂/polypyrrole ternary composites with high electrochemical performance