Electrochemical characterization of in situ polypyrrole coated graphene nanocomposites

doi:10.1016/j.synthmet.2011.06.011

Synthetic Metals

Volume 161, Issues 15–16, August 2011, Pages 1713-1719

https://doi.org/10.1016/j.synthmet.2011.06.011 Get rights and content

Abstract

Graphene/polypyrrole nanocomposites were prepared by in situ oxidative polymerization method by varying the weight percentage of graphene. FTIR study confirmed the formation of polypyrrole in presence of graphene. Field Emission Scanning Electron Microscopy (FESEM) and High Resolution Transmission Electron Microscopy (HRTEM) were used to characterize the morphology of the nanocomposites which showed a uniform coating of graphene with the polypyrrole. From the cyclic voltammetry (CV) measurement it was found that the capacitances of the nanocomposites were increased up to a certain percentage of graphene and after which it showed a downward trend. The maximum capacitance value and energy density, among the composites studied, were found to be 409 F/g and 227.2 Wh/Kg at 10 mV/s scan rate. However, maximum power density achieved was 4617 W/kg at a scan rate of 200 mV/s.

Highlights

► In this study we have prepared the in situ graphene/polypyrrole nanocomposite with varying percentage of graphene. ► The morphological, electrochemical and thermal analyses of the different nanocomposites are carried out. ► The specific capacitance, energy density and power density of the nanocomposites are found to be increasing with the increase in graphene percentage up to certain extent and then decreases.

Introduction

A great deal of researches has been devoted towards the development of various types of energy storage devices, for the last two decades. Lithium ion battery and other secondary batteries are the results of these researches [1]. But for today's energy demands these are not sufficient, as a result of which the present research has been diverted towards development of supercapacitors. There are two types of supercapacitor, which are under development, namely electronic double layer capacitor (EDLC) and redox capacitor [2].Among these two, EDLC have longer cycle life than batteries and also possess higher energy density with respect to conventional capacitor. Further they have higher power capability, wide thermal operating range, and low maintenance cost [3]. The electrode for the fabrication of supercapacitors is mainly consists of carbon, metal oxide and conducting polymer [4]. Many carbon containing material like activated carbon, masoporous carbon, carbon nanotubes (CNTs), etc. are used as the carbon source for electrode material. Conducting polymers such as polypyrrole (PPy), polyaniline, polythiophene are also used as another part of the electrode material. Composites based on conducting polymer and CNTs have been studied as supercapacitor electrode and a good thermal stability have been achieved [5], [6], [7]. But the major drawbacks of these EDLCs are their low energy density and low specific capacitance, due to the presence of pristine CNTs (generally less than 100F/g) [8].

Presently graphene based supercapacitor electrodes are studied hugely by the researchers around the world. Graphene is a transparent single layer of carbon atoms, arranged in a “honeycomb” fashion. It has attracted rapidly growing research interest since it was discovered in 2004 by Geim [9], [10], [11], due to its unique electrical, thermal and mechanical properties. Graphene and chemically modified graphene sheets possess high conductivity, high surface area, and good mechanical properties [12], comparable with or even better than CNTs. Further it possesses higher capacitance (10–135 F/g) value than CNTs [13]. Among the conducting polymers, PPy was widely investigated as a part of electrode material due to its good chemical and thermal stability, easy synthesis, high specific capacitance and high electrical conductivity [14], [15], [16], [17]. Presently many researches are going on to develop graphene based supercapacitor. Biswas et al. studied the electrochemical properties of PPy/graphene nanocomposites and reported a specific capacitance of 165 F/g [18]. But the effect of graphene percentage on the electrochemical properties of graphene/PPy has not been studied by any research group.

In this paper we focused on graphene/PPy composites, prepared by in situ oxidative polymerization method using ammonium persulfate as oxidant. The objective of this work is to study the effect of graphene percentage on the electrochemical properties of the graphene/PPy composites. We have prepared four composites at different weight percentage of graphene. Further electrochemical characterizations of these composites were done using the cyclic voltammetry.

Section snippets

Materials

Graphene was obtained from Sinocarbon Materials Technology Co. Ltd. China. Ammonium persulphate (APS) and Cetyltrimethylammonium bromide (CTAB) were supplied by Loba Chemie Pvt. Ltd. Mumbai (India). Pyrrole was obtained from E. Merck Ltd. (India). All the chemicals were used as received, without any further purification.

FTIR study

The FTIR plots of the composites are depicted in Fig. 1.The peaks at 1562, 1469 and 3410, for pure PPy, are corresponds to the C–C, C–N and N–H stretching vibration in the pyrrole ring. Whereas, the peaks at 2855 and 2962 cm⁻¹ are associated with the symmetric and asymmetric vibrations of CH₂ [21]. The characteristic peaks of polypyrrole at 1469 cm⁻¹ and 1562 cm⁻¹ are also observed for the composites, indicating towards the formation of PPy in presence of graphene. It is important to note that the

TGA analysis

The effect of graphene percentage on thermal stability of the composites was analyzed by TGA, in nitrogen atmosphere, and the plots are depicted in Fig. 8. As can be seen from Fig. 8, pure PPy follows a two-step weight loss process, where the first weight loss corresponds to the evaporation of water or volatile impurities [25]. The TGA results of the composites are summarized in Table 6. Pure PPy shows around 10% weight loss at 100 °C which decreased to 7.5 and 4.8% for GP1 and GP3,

Conclusion

Graphene/PPy composites were prepared by in situ oxidative polymerization method. The morphology and chemical structure of the composites and pure PPy are characterized by different characterization techniques such as FTIR, FESEM, HR-TEM. From the morphological study it is clear that PPy and Graphene forms a uniform thin coating at nanometer scale in GP3. From the electrochemical studies it has been found that the electrochemical performances of composites are remarkably enhanced compared with

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Electrochemical characterization of in situ polypyrrole coated graphene nanocomposites

Abstract

Highlights

Introduction

Section snippets

Materials

FTIR study

TGA analysis

Conclusion

J. Power Sources

J. Power Sources

Electrochem. Commun.

Electrochim. Acta

Compos. Sci. Technol.

Prog. Poly. Sci.

Syn. Met.

Comps. Sci. Technol.

Polymer

Mater. Lett.

Nanostructured materials for advanced energy conversion and storage devices

Nat. Mater.

Materials for electrochemical capacitors

Nat. Mater.

Graphene/polyaniline nanofiber composites as supercapacitor electrodes

Chem. Mater.