One-pot synthesis and electrochemical properties of graphene/SnO2/poly (p-phenylenediamine) ternary nanocomposites
Introduction
Nowadays, with the rapid development of economy and deterioration of environment, seeking for one kind of environmentally–friendly and sustainable energy storage devices has become a huge challenge [1]. Supercapacitors, also called electrochemical capacitors, have been a research hotspot in recent years because of the advantages of high power density, fast charge–discharge process and long cycle life [2], [3], [4]. Now, the emphasis on supercapacitors is preparing resulting products with high energy density and low production costs [5]. The selection and optimization of electrode materials are the keys to improve the electrochemical performance of supercapacitors [6], [7].
At present, carbon materials, conducting polymers and transition metal oxides are widely used as electrode materials for supercapacitors. Carbon materials represent a very attractive candidate for electrochemical applications because of their accessibility, relatively low cost and high stability. Meanwhile, conducting polymers and transition metal oxides possess higher specific capacitance than carbon materials on account of fast redox reaction, but high resistance, low conductivity and poor cycle stability limit their application conversely [8], [9], [10], [11], [12]. A variety of researches have demonstrated that the combination of two or more electrode materials together can produce a synergistic effect, which compensates for shortcomings of single material, and obtain superb composite materials with high specific capacity, excellent cycle stability and rate capability [13], [14], [15].
So far, the research on the binary composites has been mature. A variety of elements, such as experimental approach, test conditions, the types of material, unique structure of products and so on, have been studied and binary electrode materials have been fabricated widely, such as graphene/NiCo2O4 [16], graphene/MnO2 [17], polyaniline/SnO2 [18], graphene/polyaniline [10], nickel–manganese oxide [19], carbon nanotube (CNT)/MnO2 [20] and so on. Recently, some superior ternary composites begin to emerge. Graphene/CoFe2O4/polyaniline composite [21] has been explored by Wang et al. The result demonstrates obviously that ternary composites possess huge improvement in the electrochemical performance (The capacities of CoFe2O4, PANI, reduced graphene oxide, binary CoFe2O4/G, binary PANI/CoFe2O4, binary CoFe2O4/G and ternary CGP were calculated to be 39.4 F g−1, 24.6 F g−1, 171.5 F g−1, 183.2 F g−1, 30.0 F g−1, 578.8 F g−1 and 716.4 F g−1, respectively). Tang et al. also have done a comparison between graphene/MnO2/polyaniline ternary composites and binary composites [22]. It shows that the ternary composite electrode delivers a highest specific capacitance, which is 45% higher than the MnO2/graphene binary composite. In addition, a ternary composite of CNT/MnO2/polypyrrole [23] has been prepared and the specific capacitance of the ternary composite, CNT/MnO2 and polypyrrole/MnO2 binary composites are 281, 150 and 35 F g−1, respectively. According to these influential studies, which demonstrate the fact that reasonable combination of these three electrode materials would produce novel materials with better electrochemical performance than binary composites, more and more researchers shift their attention to the ternary composites [24], [25], [26].
SnO2, known as an extraordinary transition metal oxide, has attracted lots of attention because of its high capacitance and low cost [27], [28]. Meanwhile, poly (p-phenylenediamine) (PpPD), which is synthesized via in-situ polymerization of p-phenylenediamine (pPD), is one kind of derivatives of polyaniline possessing several advantages, such as low cost, simple synthesis and special doping mechanism [29], [30], [31]. Taking into account that the binary hybrids based on PpPD and SnO2 can afford higher specific capacitance, the combination of PpPD and SnO2 may also result in an enhanced electrochemical performance. Nevertheless, the main shortcoming of this binary composite as a supercapacitor electrode is the poor cycling stability aroused by volume change [32], [33]. To overcome this problem, it is necessary to disperse them on a high surface area support. Graphene is one of the most typical supports owing to its high theoretical specific surface area, good mechanical stability and excellent cycle stability [20], [34], [35], [36]. In addition, a lot of nitrogen atoms coming from PpPD and active sites are able to change the chemical properties of graphene surfaces conversely, which is beneficial for improving the comprehensive properties of composites [37].
In this study, a new ternary composite, graphene/SnO2/PpPD (GSP) composite, has been prepared via one-pot method for the first time. First of all, the reduction of GO and the generation of SnO2 nanoparticles occur simultaneously using Sn2+ as a reducing agent directly and then the by-product, hydrochloric acid, is used as a doping agent to facilitate in-situ polymerization of pPD. In GSP composites, SnO2 and PpPD can not only play their special roles in providing faradic capacitance, but also can hold back the agglomeration and stacking of the graphene sheets. Moreover, graphene can also prevent the volume change of SnO2 and PpPD conversely because of the strong interaction force. Therefore, the resulting GSP composites used as electrode materials for supercapacitors, which possess the synergistic effect aroused from three active components, exhibit high specific capacitance 777.5 F g−1 at 5 mV s−1 in 1 M H2SO4 and retain 97.8% of the initial capacitance after 2000 cycles.
Section snippets
Synthesis of GSP ternary composite
GO was fabricated on the basis of the modified Hummers method [38], and dispersed in distilled water to obtain homogeneous GO solution, in which concentration was about 1 mg mL−1. The GSP composite was prepared via one-pot method. The specific procedure (Fig. 1) was as follows: firstly, 100 mL distilled water containing 200 mg SnCl2•2H2O was added into 100 mL as-prepared GO solution followed by ultrasonication for 2 h. Then, the mixture was moved to an oil bath and continually stirred at 60 °C
Characterization of GSP ternary composite
A new graphene/SnO2/PpPD ternary composite is prepared. GO due to the oxygen-containing groups on the surfaces, such as hydroxyl, carbonyl and epoxide, can attract and further fix Sn2+ and pPD nanocrystals to complete the following generation of SnO2 and PpPD. During the fabrication process, the reduction of GO and the formation of SnO2 occur synchronously using Sn2+ as reducing regent and the by-product, the hydrochloric acid, is used as a doping agent for the following in-situ polymerization
Conclusion
To sum up, a novel graphene/SnO2/PpPD (GSP) ternary composite is prepared successfully via one-pot method. During the fabrication process, the reduction of GO and the formation of SnO2 occur synchronously using Sn2+ as reducing regent and the by-product, the hydrochloric acid, is used as a doping agent for the following in-situ polymerization of pPD. The massive characterizations can indicate that SnO2 and PpPD nanoparticles, which benefit for preventing agglomeration and stacking of graphene,
Acknowledgment
The authors gratefully appreciate the financial supports from the Major Research Training Program of Chongqing University of Arts and Sciences, Natural Science Foundation of Jiangsu Province (BK20130617, BK20130619) and National Natural Science Foundation of China (21304018, 21374016).
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