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Materials Letters 78 (2012) 106109

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis of graphene oxide/polypyrrole nanowire composites for supercapacitors


Jing Li, Huaqing Xie
School of Urban Development and Environmental Engineering, Shanghai Second Polytechnic University, Shanghai 201209, PR China

a r t i c l e

i n f o

a b s t r a c t
Polypyrrole (PPy) nanowires have been successfully grown on the surface of graphene oxide (GO) nanosheets by using a facile chemical method. The GO/PPy composites exhibit a predominant specic capacitance of 633 F/g at a current density of 1 A/g by charge/discharge analysis, in comparison with 227 F/g for pure PPy. The composites also show superior electrochemical rate capability and cycle stability. The attenuation of the specic capacitance is less than 6% after 1000 charge/discharge processes. The high specic capacitance and good stability of the GO/PPy composites are very promising for applications in electrochemical supercapacitor devices. 2012 Elsevier B.V. All rights reserved.

Article history: Received 18 December 2011 Accepted 5 March 2012 Available online 9 March 2012 Keywords: Graphene oxide Polymers Nanocomposites Supercapacitors

1. Introduction Supercapacitors combining the advantages of the high power and energy density, are considered as promising candidates for energy storage [1]. Various advanced materials [2,3] have been studied extensively for supercapacitors due to their better rate capability than traditional materials. For conductive polymers, polypyrrole (PPy) is considered as a most potential electrode material due to its intrinsic electrical conductivity, high energy storage capacity, and ease of low cost synthesis [3]. However, the cycle lifetime of PPy is poor, because the repeated ion exchange in electrochemical cycles would change structural conformation of PPy and thus diminish the electrical properties. Graphene, a new carbonous material with two-dimensional nanostructure, has attracted great attention both in fundamental science and applied research. Due to extraordinarily high electronic and mechanical properties, graphene has been proposed as an outstanding electrode material for energy storage devices [4]. Graphene oxide (GO), a single layer of graphite oxide, has a large amount of oxygen functional groups bearing on its basal planes and edges, which could couple with various active nanomaterials. The increase in oxygen content would induce a superior hydrophilicity toward aqueous electrolyte. Recent reports on supercapacitors based on graphenebased materials have attracted great interest [57]. However, there are a few reports that have been carried out on the application of GO-based materials in supercapacitors [810]. In this paper, composites of PPy nanowires and GO nanosheets are synthesized by in situ polymerization of pyrrole monomer in the presence of GO suspension. The high specic capacitance of 633 F/g is

obtained at a constant charge/discharge current density of 1 A/g, which is much larger than that of each pristine component. 2. Experimental Graphite oxide was prepared from natural graphite powder by the modied Hummers method [11]. Pyrrole was distilled under the protection of high purity N2 and then kept in a refrigerator before use. At rst, 1.82 g of cetyltrimethylammonium bromide (CTAB) and 30 mg of graphite oxide were added into deionized water under ultrasonication for 2 h. Then, 550 L of pyrrole was added into the GO suspension, followed by stirring for more than 3 h. Pyrrole monomer can be adsorbed to the surface of GO nanosheets. Afterwards, ammonium persulfate (APS, 0.008 mol) was dissolved in 20 mL of 0.35 M oxalic acid, and added dropwise to the above reaction system. Polymerization of pyrrole started in a few minutes, and the reaction was allowed to stir at 04 C for 5 h. The rapid chemical reaction can promote homogeneous nucleation of growing PPy chains and thus form uniform nanowires. The black precipitate was ltered and washed with a large amount of water to remove any excess surfactant, and dried at 60 C for 12 h under vacuum. For comparison, the pure PPy was also prepared by using the similar procedure. The morphologies of as-prepared samples were analyzed by scanning electron microscopy (SEM, HITACHI S-4800) and transmission electron microscopy (TEM, JEOL 2100F), respectively. Atomic force microscopic (AFM) image was taken on Scanning Probe Microscope (SPM, SHIMADZU 9600). XRD measurements were recorded on X-ray diffraction system (D8-Advance, Germany). The electrochemical tests were carried out in 1 M KCl aqueous electrolyte solution. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were performed on CHI 660C electrochemical workstation (ChenHua Instruments Co., Shanghai, China). A threeelectrode system was used, consisting of the working electrode,

Corresponding author. Tel./fax: + 86 21 50217331. E-mail address: hqxie@eed.sspu.cn (H. Xie). 0167-577X/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2012.03.013

J. Li, H. Xie / Materials Letters 78 (2012) 106109

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platinum as the counter electrode, and a saturated calomel electrode (SCE) as the reference electrode. Galvanostatic charge/discharge curves were measured using computer controlled cycling equipment (LAND, Wuhan, China). The working electrode was prepared by casting Naon-impregnated sample onto glassy carbon electrode (GCE). The mixture contained 15 mg of samples and 10 L of Naon (5 wt.% in ethanol), and then 3 mL of ethanol was added to the above mixture for ultrasonication of 1 h. Then, 5 L of the suspension was dropped onto GCE surface and dried at room temperature. 3. Results and discussion The GO nanosheets are investigated by AFM analysis. As shown in Fig. 1a, the GO sheets have a height prole of the thickness 0.9 nm, indicating the formation of a single layer. Fig. 1b shows the XRD patterns of pristine graphite and GO, respectively. The pristine graphite (002) diffraction peak appears at 2 = 26.4. The GO reveals a diffraction peak at 2 = 12.1, due to the chemical oxidation which disrupts

the ordering of layers and introduces functional groups to the graphite sheets. The morphologies of the as-prepared samples are characterized by TEM. The PPy shows nanowire morphology (Fig. 2a). As Fig. 2b shown, the PPy nanowires with diameter of 60 nm are attached to the surface of GO nanosheets. The GO sheets as a functional support material could supply a large number of active sites for nucleation of PPy. Superior interaction between PPy and GO facilitates the dispersion of PPy throughout GO nanosheets. The electrochemical performances of GO, PPy and GO/PPy composites are investigated by using CV techniques. The specic capacitance of the electrode can be calculated according to the following equation from CV curves:   C I dV =vmV where C is the specic capacitance based on the mass of electroactive materials (F/g), I is the response current (A), V is the potential (V), v is the potential scan rate (V/s), and m is the mass of the active electrode materials (g). The representative CV curves measured with these electrodes are presented in Fig. 3a, which show nearly rectangular and symmetric currentpotential characteristics. The maximum specic capacitance of 612 F/g is obtained for the GO/PPy composites, in comparison with 210 and 17 F/g for PPy nanowires and GO, respectively. The rectangular CV shape of the GO/PPy composites can remain even at a high scan rate of 400 mV/s, indicative of high capacitive nature with good ion response. The variation in the specic capacitance as a function of scan rates is shown in Fig. 3b. Evidently, the capacitance degrades slightly with increasing the scan rate. The specic capacitance of the GO/PPy composites is markedly higher than that of GO and PPy electrodes at the same scan rate, owing to the synergistic effect between GO and

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Fig. 1. (a) AFM image of exfoliated GO sheets on mica surface with height proles, (b) XRD patterns of pristine graphite and GO, respectively.

Fig. 2. TEM images of (a) PPy nanowires and (b) GO/PPy composites.

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J. Li, H. Xie / Materials Letters 78 (2012) 106109

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Fig. 3. (a) CVs of GO, PPy and GO/PPy composites at a scan rate of 5 mV/s in 1 M KCl aqueous solution. (b) The specic capacitances of GO, PPy and GO/PPy composites at different scan rates. (c) Galvanostatic charge/discharge curves of PPy and GO/PPy composites at a current density of 1 A/g. (d) Nyquist plots for three electrodes recorded at an open circuit potential.

PPy nanowires. Fig. 3c displays the galvanostatic charge/discharge curves of the PPy and GO/PPy electrodes at a constant current density of 1 A/g. The curves present a triangular shape, indicating a good capacitance behavior. The specic capacitance can be evaluated as 633 and 227 F/g for the GO/PPy and PPy electrodes. The GO nanosheets provide enhanced electrode/electrolyte interface areas, which can enable the electrochemical accessibility of electrolyte through the loosely packed PPy nanowire structure. Therefore, the composites can greatly reduce the diffusion length, resulting in the improvement of electrochemical properties of GO/PPy composite materials. The EIS analysis is also conducted to examine the fundamental behavior of electrode, as shown in Fig. 3d. It is notable that PPy and GO electrodes present well-dened semicircles over the high-frequency range, followed by a straight sloped line in the low-frequency region. The diagrams of the GO/PPy composites do not present a semicircle at high-frequency, probably due to the low faradaic charge-transfer resistances. The GO/PPy electrode also exhibits a more vertical line than PPy and GO electrodes at low-frequency, illustrating a better capacitor behavior and lower diffusion resistance of ions. Long cycle life is a crucial parameter for electrode materials. The electrochemical stability of the PPy and GO/PPy composite electrodes was evaluated by repeating the CV test between 0.3 and 0.6 V at a scan rate of 50 mV/s. The specic capacitance keeps 94% for the GO/PPy composite electrode after 1000 charge/discharge cycles, while just only 68% for PPy. The obviously enhanced cycle stability for the composites is resulted from GO nanosheets which can stabilize the nanostructured PPy during the repeated charge/discharge processes. GO can undertake some mechanical deformation in the redox process

of PPy nanowires, which avoid destroying the electrode material and is beneted to a better stability. 4. Conclusions A facile approach to grown PPy nanowires onto the GO nanosheets was reported. With introducing a small content of GO into the composites, the GO/PPy composite electrodes exhibit large specic capacitance, good rate capability and cycle stability. The composites present a specific capacitance of 588 F/g even after 1000 charge/discharge cycles at a current density of 1 A/g. The high ionic and electronic transport is probably attributed to the interactions of PPy nanowire network and GO nanosheets. Acknowledgments This work was supported by the Shanghai Municipal Education Commission, the Shanghai Educational Development Foundation (11CG64), the Innovation Program of Shanghai Municipal Education Commission (12YZ179), the Program for New Century Excellent Talents in University (NCET-10-883) and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. References
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