Polyaniline/fullerene derivative nanocomposite for highly efficient supercapacitor electrode

https://doi.org/10.1016/j.ijhydene.2020.04.093Get rights and content

Highlights

  • Fabrication of polyaniline/fullerene derivative (PCBM) nanocomposites electrodes.

  • PANI/PCBM composites cast onto nickel foam substrate as supercapacitor electrodes.

  • PANI/PCBM5 supercapacitor electrode showed high specific capacitance of 2201 F/g.

  • Supercapacitor electrode has cyclic stability of 96% after 1000 cycles at 50 mV/s.

Abstract

The effect of intercalation of fullerene derivative Phenyl-C60-butyric acid methyl ester (PCBM) into polyaniline (PANI) matrix with different ratio is reported. The PANI/PCBMx (where x = 0, 2.5, 5 and 10) nanocomposites are characterized by UV-VIS spectroscopy, Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and X-ray diffraction spectroscopy (XRD). The results confirm that the PANI/PCBM nanocomposites are synthesized successfully. The prepared nanocomposites are cast onto Nickel foam as a current collector and tested as a supercapacitor electrode in 2 M KOH electrolyte using cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). The effect of different current collector substrates including stainless steel, nickel metal and graphite sheet on the supercapacitor performance is compared. The electrochemical measurements show an improvement by more than two times in the specific capacitance of PANI/PCBM5 electrode compared to pure PANI electrode. It is found that, the specific capacitance is 2201 F/g at a current density of 2 A/g with a good rate capability of about 73% at 10 A/g. The energy and power densities of PANI/PCBM5 electrode are 61.9 W h/Kg and 2250 W/Kg, respectively. Furthermore, the PANI/PCBM5 electrode shows an excellent cycling stability with 96% of the capacity retention after 1000 cycles.

Introduction

The era of renewable energy resources began due to the harmful effects of the green-house gasses emission which caused by traditional fossil fuel-based resources. These renewable sources need an energy storage device to store these forms of energy. Supercapacitors, also known ultracapacitors are considered as the most candidate for energy storage device that have a relatively high energy density compared to conventional capacitor and higher power density than batteries. Supercapacitors have numerous advantages when compared with lithium ion batteries such as long life cycle (> 100,000 cycles) due to the absence of chemical reactions, fast charging-discharging capability, widespread operating temperature and great power density (often> 10 kW/kg) [1,2]. Based on the chemical composition, there are three types of supercapacitor electrode materials; carbon-based, conducting polymers and metal oxides.

Conducting polymers are broadly studied for supercapacitor in recent years. Although their low mechanical stability and short cycle life due to imperfect reversibility of redox reaction that influences on the shape of electrode, there are great efforts to overcome these problems. Polyaniline (PANI) is the most studied conducting polymers as battery material or electrode in supercapacitors device [[3], [4], [5]]. PANI has many attractive properties for energy storage application such as low cost, facile synthesis, different oxidation states and high doping level that enhance the electrical conductivity of PANI. Moreover, the reported specific capacitance of PANI in range of 30–3000 F/g is attributed to the variation of polyaniline structure, morphology and level of doping [6].

The key factor to get large specific capacitance with good cyclability and high rate capability can be achieved by combining PANI and carbon materials which have good stability and large surface area due to its pores [7]. Phenyl-C60-butyric acid methyl ester (PCBM) was widely applied in solar cells due to great conductivity, high surface areas and excessive carrier mobility [8]. It is expected that PCBM plays an important role in energy storage application when mixing with conducting polymer. Poly (3-hexylthiophene) (P3HT:PCBM) blends used in organic solar cells [9,10] and recently applied in supercapacitors application [11,12].

An expected high-performance hybrid supercapacitor can be obtained by the matrix of polyaniline as a donor with an electron acceptor of PCBM. This work aims to improve the electrochemical performance of PANI supercapacitor electrode by PCBM addition with different ratios through in situ polymerization. This will be achieved by the measurement of the cyclic voltammetry, the morphology properties, surface area, electrochemical impedance and capacitive behavior of nanocomposite electrodes. The insertion of PCBM not only increases the specific capacitance of PANI, but also improves the cyclic stability. To the best of our knowledge, it is the first successful demonstration of nanocomposite between PANI and PCBM for supercapacitor application. The specific capacitance, energy density and charge transfer resistance are determined and compared for the fabricated supercapacitors.

Section snippets

Materials

Aniline monomer and N-methyl-2-pyrrolidone (NMP, 98%) were purchased from Loba Chemie, PCBM and ammonium peroxodisulfate (APS) were purchased from Ossila and Chem-Lab, respectively. Sulfuric acid (H2SO4, 95–97%), hydrochloric acid (HCl, 30–34%) and polyvinylidene difluoride powder (PVDF) were obtained from J.T.Baker, SDFCL and Alfa Aesar, respectively. Ethanol (99.8%) and dimethylformamide (DMF, 99%) were procured from Fisher chemical. All chemicals were used without further purification.

Preparation of PANI/PCBM nanocomposite

Absorption property

The optical absorption spectra of the doped and dedoped PANI, PCBM and PANI/PCBM nanocomposites samples are shown in Fig. 1. The spectrum of dedoped PANI (after treating with 1 M ammonium hydroxide) have two peaks. The peaks at 325 nm and 613 nm are attributed to π-π∗ transition of benzenoid ring and exciton formation in the quinonoid, respectively. PANI doped with H2SO4 shows a peak at 355 nm corresponds to π-π∗ transition of benzenoid ring and a peak at 440 nm attributed to the localized

Conclusions

PANI/PCBM nanocomposites with different ratios were successfully synthesized via chemical oxidation polymerization. The morphological results revealed the formation of aggregated and a spongy irregular shaped with porous structure. BET data confirmed the existence of meso/macroporos and few microporos in the composite and reduced ions diffusion resistance. The electrochemical measurements showed the highest specific capacitance of 2201 F/g for PANI/PCBM5 nanocomposite at current density of

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