Skip to main content
SpringerLink
Log in

One-pot synthesis of covalently functionalized reduced graphene oxide–polyaniline nanocomposite for supercapacitor applications

  • Original Paper
  • Published:
Clean Technologies and Environmental Policy Aims and scope Submit manuscript

Abstract

A high-performance reduced graphene oxide–polyaniline (RGO-PANI) electrode material was prepared through commercially viable, facile one-pot synthesis, applying famed diazotization chemistry and grafting strategy. In this work, 4-nitroaniline was utilized as a grafting substrate to bind reduced graphene oxide and polyaniline covalently to a highly stable and efficient supercapacitor electrode material. The chemical composition and structural analysis of covalently functionalized RGO-PANI nanocomposites were characterized by X-ray diffraction, field-emission scanning electron microscopy, Raman spectroscopy, UV–visible spectroscopy, and Fourier-transform infrared spectroscopy. The electrochemical behavior of the nanocomposites was analyzed through cyclic voltammetry, galvanostatic charge and discharge, and electrochemical impedance spectroscopy. The prepared nanocomposite shows a high specific capacitance of 490 F g−1 in 1 M Na2SO4 with outstanding cyclic stability (10,000 cycles). The applied covalent functionalization through grafting strategy was the principal factor for both high specific capacitance and excellent cyclic stability.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  • Aricò AS, Bruce P, Scrosati B, Tarascon J-M, Van Schalkwijk W (2005) Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 4:366–377

    Article  Google Scholar 

  • Arjun N, Pan G-T, Yang TC (2017) The exploration of Lanthanum based perovskites and their complementary electrolytes for the supercapacitor applications. Results Phys 7:920–926

    Article  Google Scholar 

  • Baker CO, Huang X, Nelson W, Kaner RB (2017) Polyaniline nanofibers: broadening applications for conducting polymers. Chem Soc Rev 46:1510–1525

    Article  CAS  Google Scholar 

  • Basnayaka PA, Ram MK (2017) A review of supercapacitor energy storage using nanohybrid conducting polymers and carbon electrode materials. In: Kalia S (ed) Conducting polymer hybrids. Springer, Berlin, pp 165–192

    Chapter  Google Scholar 

  • Behera SR, Dash DP (2017) The effect of urbanization, energy consumption, and foreign direct investment on the carbon dioxide emission in the SSEA (South and Southeast Asian) region. Renew Sustain Energy Rev 70:96–106

    Article  CAS  Google Scholar 

  • Bertinelli F, Palmieri P, Brillante A, Taliani C (1977) Electronic-excited states of nitroanilines. II. A configuration interaction study and UV spectrum of the paranitroaniline single crystal. Chem Phys 25:333–341

    Article  CAS  Google Scholar 

  • Borenstein A, Hanna O, Attias R, Luski S, Brousse T, Aurbach D (2017) Carbon-based composite materials for supercapacitor electrodes: a review. J Mater Chem A 5(25):12653–12672

    Article  CAS  Google Scholar 

  • Chen J, Yao B, Li C, Shi G (2013) An improved Hummers method for eco-friendly synthesis of graphene oxide. Carbon 64:225–229

    Article  CAS  Google Scholar 

  • Chen J et al (2016) The origin of improved electrical double-layer capacitance by inclusion of topological defects and dopants in graphene for supercapacitors. Angew Chem Int Ed 55:13822–13827

    Article  CAS  Google Scholar 

  • Chen F, Wan P, Xu H, Sun X (2017a) Flexible transparent supercapacitors based on hierarchical nanocomposite films. ACS Appl Mater Interfaces 9(21):17865–17871

    Article  CAS  Google Scholar 

  • Chen L-F, Lu Y, Yu L, Lou XWD (2017b) Designed formation of hollow particle-based nitrogen-doped carbon nanofibers for high-performance supercapacitors. Energy Environ Sci 10(8):1777–1783

    Article  CAS  Google Scholar 

  • Dai W et al (2016) Fabrication of sandwich nanostructure graphene/polyaniline hollow spheres composite and its applications as electrode materials for supercapacitor. Mater Res Bull 76:344–352

    Article  CAS  Google Scholar 

  • Dong L, Xu C, Li Y, Huang Z-H, Kang F, Yang Q-H, Zhao X (2016) Flexible electrodes and supercapacitors for wearable energy storage: a review by category. J Mater Chem A 4:4659–4685

    Article  CAS  Google Scholar 

  • Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240

    Article  CAS  Google Scholar 

  • Eng AYS, Chua CK, Pumera M (2016) Facile labeling of graphene oxide for superior capacitive energy storage and fluorescence applications. Phys Chem Chem Phys 18:9673–9681

    Article  CAS  Google Scholar 

  • Feng H, Cheng R, Zhao X, Duan X, Li J (2013) A low-temperature method to produce highly reduced graphene oxide. Nat Commun 4:1539. https://doi.org/10.1038/ncomms2555

    Article  CAS  Google Scholar 

  • Gao Z et al (2014) Chemically grafted graphene-polyaniline composite for application in supercapacitor. Electrochim Acta 133:325–334. https://doi.org/10.1016/j.electacta.2014.04.033

    Article  CAS  Google Scholar 

  • González A, Goikolea E, Barrena JA, Mysyk R (2016) Review on supercapacitors: technologies and materials. Renew Sustain Energy Rev 58:1189–1206

    Article  Google Scholar 

  • Guo B et al (2017) Redox-active organic molecules functionalized nitrogen-doped porous carbon derived from metal-organic framework as electrode materials for supercapacitor. Electrochim Acta 223:74–84

    Article  CAS  Google Scholar 

  • Hong X, Zhang B, Murphy E, Zou J, Kim F (2017) Three-dimensional reduced graphene oxide/polyaniline nanocomposite film prepared by diffusion-driven layer-by-layer assembly for high-performance supercapacitors. J Power Sources 343:60–66

    Article  CAS  Google Scholar 

  • Hwang M, Oh J, Kang J, Seong K-D, Piao Y (2016) Enhanced active sites possessing three-dimensional ternary nanocomposites of reduced graphene oxide/polyaniline/Vulcan carbon for high-performance supercapacitors. Electrochim Acta 221:23–30

    Article  CAS  Google Scholar 

  • Konios D, Stylianakis MM, Stratakis E, Kymakis E (2014) Dispersion behavior of graphene oxide and reduced graphene oxide. J Colloid Interface Sci 430:108–112

    Article  CAS  Google Scholar 

  • Krukiewicz K, Katunin A (2016) The effect of reaction medium on the conductivity and morphology of polyaniline doped with camphor sulfonic acid. Synth Met 214:45–49

    Article  CAS  Google Scholar 

  • Kudin KN, Ozbas B, Schniepp HC, Prudomme RK, Aksay IA, Car R (2008) Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett 8:36–41

    Article  CAS  Google Scholar 

  • Kumar NA (2012) Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors. ACS Nano 6:1715–1723. https://doi.org/10.1021/nn204688c

    Article  CAS  Google Scholar 

  • Kumar M et al (2013) Synthesis and characterization of covalently-grafted graphene–polyaniline nanocomposites and its use in a supercapacitor. Chem Eng J 231:397–405. https://doi.org/10.1016/j.cej.2013.07.043

    Article  CAS  Google Scholar 

  • Li W, Yao H, Zhang G, Yang Y (2017) A Ni/Zn bi-metallic coordination supramolecular network applied for high-performance energy storage material. Electrochim Acta 228:233–240

    Article  CAS  Google Scholar 

  • Ma H, He J, Xiong D-B, Wu J, Li Q, Dravid V, Zhao Y (2016) Nickel cobalt hydroxide@ reduced graphene oxide hybrid nanolayers for high-performance asymmetric supercapacitors with remarkable cycling stability. ACS Appl Mater Interfaces 8:1992–2000

    Article  CAS  Google Scholar 

  • Marcano DC et al (2010) Improved synthesis of graphene oxide. ACS Nano 4(8):4806–4814

    Article  CAS  Google Scholar 

  • Matthews M, Pimenta M, Dresselhaus G, Dresselhaus M, Endo M (1999) Origin of dispersive effects of the Raman D band in carbon materials. Phys Rev B 59:R6585

    Article  CAS  Google Scholar 

  • Mokhtar N, Chye DAT, Phang SW (2017) Morphology, conductivity and microwave absorption behavior of polyaniline nanocomposites after chemical treatment. Polym Polym Compos 25:545

    Article  CAS  Google Scholar 

  • Mondal S, Rana U, Malik S (2017) Reduced graphene oxide/Fe3O4/polyaniline nanostructures as electrode materials for an all-solid-state hybrid supercapacitor. J Phys Chem C 121:7573–7583

    Article  Google Scholar 

  • Mousavi MF, Hashemi M, Rahmanifar MS, Noori A (2017) Synergistic effect between redox additive electrolyte and PANI-rGO nanocomposite electrode for high energy and high power supercapacitor. Electrochim Acta 228:290–298

    Article  CAS  Google Scholar 

  • Palanisamy S, Chen S-M, Sarawathi R (2012) A novel nonenzymatic hydrogen peroxide sensor based on reduced graphene oxide/ZnO composite modified electrode. Sens Actuators B Chem 166:372–377

    Article  Google Scholar 

  • Palanisamy S, Ku S, Chen S-M (2013) Dopamine sensor based on a glassy carbon electrode modified with a reduced graphene oxide and palladium nanoparticles composite. Microchim Acta 180:1037–1042

    Article  CAS  Google Scholar 

  • Palanisamy S et al (2017a) A novel laccase biosensor based on laccase immobilized graphene-cellulose microfiber composite modified screen-printed carbon electrode for sensitive determination of catechol. Sci Rep 7:41214

    Article  CAS  Google Scholar 

  • Palanisamy S et al (2017b) Synthesis and characterization of polypyrrole decorated graphene/β-cyclodextrin composite for low level electrochemical detection of mercury (II) in water. Sens Actuators B Chem 243:888–894

    Article  CAS  Google Scholar 

  • Salunkhe RR et al (2014) Fabrication of symmetric supercapacitors based on MOF-derived nanoporous carbons. J Mater Chem A 2:19848–19854

    Article  CAS  Google Scholar 

  • Salunkhe RR, Young C, Tang J, Takei T, Ide Y, Kobayashi N, Yamauchi Y (2016) A high-performance supercapacitor cell based on ZIF-8-derived nanoporous carbon using an organic electrolyte. Chem Commun 52:4764–4767

    Article  CAS  Google Scholar 

  • Sumboja A, Foo CY, Wang X, Lee PS (2013) Large areal mass, flexible and free-standing reduced graphene oxide/manganese dioxide paper for asymmetric supercapacitor device. Adv Mater 25:2809–2815

    Article  CAS  Google Scholar 

  • Sun G et al (2014) Fabrication of ultralong hybrid microfibers from nanosheets of reduced graphene oxide and transition-metal dichalcogenides and their application as supercapacitors. Angew Chem 126:12784–12788

    Article  Google Scholar 

  • Sun H, She P, Xu K, Shang Y, Yin S, Liu Z (2015) A self-standing nanocomposite foam of polyaniline@ reduced graphene oxide for flexible super-capacitors. Synth Met 209:68–73

    Article  CAS  Google Scholar 

  • Takahashi A et al (2017) Effect of evacuation on liver function after the Fukushima Daiichi Nuclear Power Plant accident: the Fukushima Health Management Survey. J Epidemiol 27:180–185

    Article  Google Scholar 

  • Tayel MB, Soliman MM, Ebrahim S, Harb ME (2016) Sprayed polyaniline layer onto chemically reduced graphene oxide as electrode for high performance supercapacitor. Synth Met 217:237–243

    Article  CAS  Google Scholar 

  • Unnikrishnan B, Wu C-W, Chen I-WP, Chang H-T, Lin C-H, Huang C-C (2016) Carbon dot-mediated synthesis of manganese oxide decorated graphene nanosheets for supercapacitor application. ACS Sustain Chem Eng 4:3008–3016

    Article  CAS  Google Scholar 

  • Velusamy V, Palanisamy S, Chen S-M, Chen T-W, Selvam S, Ramaraj SK, Lou B-S (2017) Graphene dispersed cellulose microfibers composite for efficient immobilization of hemoglobin and selective biosensor for detection of hydrogen peroxide. Sens Actuators B Chem 252:175–182

    Article  CAS  Google Scholar 

  • Wang G, Zhang L, Zhang J (2012a) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41:797–828

    Article  CAS  Google Scholar 

  • Wang H, Maiyalagan T, Wang X (2012b) Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catal 2:781–794

    Article  CAS  Google Scholar 

  • Wu W, Li Y, Yang L, Ma Y, Pan D, Li Y (2014) A facile one-pot preparation of dialdehyde starch reduced graphene oxide/polyaniline composite for supercapacitors. Electrochim Acta 139:117–126

    Article  CAS  Google Scholar 

  • Xia X et al (2014) Synthesis of free-standing metal sulfide nanoarrays via anion exchange reaction and their electrochemical energy storage application. Small 10:766–773

    Article  CAS  Google Scholar 

  • Xia C, Jiang Q, Zhao C, Beaujuge PM, Alshareef HN (2016) Asymmetric supercapacitors with metal-like ternary selenides and porous graphene electrodes. Nano Energy 24:78–86

    Article  CAS  Google Scholar 

  • Xiong C et al (2017) Two-step approach of fabrication of interconnected nanoporous 3D reduced graphene oxide-carbon nanotube-polyaniline hybrid as a binder-free supercapacitor electrode. J Alloys Compd 695:1248–1259

    Article  CAS  Google Scholar 

  • Yadav B, Ali I, Kumar P, Yadav P (2007) FTIR and laser Raman spectra of 2-hydroxy-5-methyl-3-nitropyridine. Indian J Pure Appl Phys 45:979–983

    CAS  Google Scholar 

  • Yamamura H, Yaguchi S, Itoh K (2017) The new radiation emergency medical system in Japan: lessons from the Fukushima Nuclear Plant Accident. Prehospital Disaster Med 32:S4–S4

    Article  Google Scholar 

  • Yu P, Zhao X, Huang Z, Li Y, Zhang Q (2014) Free-standing three-dimensional graphene and polyaniline nanowire arrays hybrid foams for high-performance flexible and lightweight supercapacitors. J Mater Chem A 2:14413–14420

    Article  CAS  Google Scholar 

  • Yu N, Yin H, Zhang W, Liu Y, Tang Z, Zhu MQ (2016) High-performance fiber-shaped all-solid-state asymmetric supercapacitors based on ultrathin MnO2 nanosheet/carbon fiber cathodes for wearable electronics. Adv Energy Mater 6:1501458

    Article  Google Scholar 

  • Yuan C, Wu HB, Xie Y, Lou XWD (2014) Mixed transition-metal oxides: design, synthesis, and energy-related applications. Angew Chem Int Ed 53:1488–1504

    Article  CAS  Google Scholar 

  • Zhang J, Jiang J, Li H, Zhao XS (2011) A high-performance asymmetric supercapacitor fabricated with graphene-based electrodes. Energy Environ Sci 4:4009. https://doi.org/10.1039/c1ee01354h

    Article  CAS  Google Scholar 

  • Zhong C, Deng Y, Hu W, Qiao J, Zhang L, Zhang J (2015) A review of electrolyte materials and compositions for electrochemical supercapacitors. Chem Soc Rev 44:7484–7539

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors thank the Centre for Precision Analysis and Research, National Taipei University of Technology, Taipei, for financial support for this research. Also, the authors want to thank Professor Chaochin Su, Department of molecular science and engineering, National Taipei University of Technology, Taipei, for assistance in the electrochemical stability tests.

Author information

Authors and Affiliations

  1. Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei, 106, Taiwan

    Nadarajan Arjun, Guan-Ting Pan & Thomas C-K. Yang

  2. Centre for Precision Analysis and Research Center, National Taipei University of Technology, Taipei, 106, Taiwan

    Kasimayan Uma & Thomas C-K. Yang

  3. School of Chemistry, Bharathidasan University, Trichy, India

    Ganapathi Sharmila

Authors
  1. Nadarajan Arjun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kasimayan Uma
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Guan-Ting Pan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Thomas C-K. Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ganapathi Sharmila
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Thomas C-K. Yang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Arjun, N., Uma, K., Pan, GT. et al. One-pot synthesis of covalently functionalized reduced graphene oxide–polyaniline nanocomposite for supercapacitor applications. Clean Techn Environ Policy 20, 2025–2035 (2018). https://doi.org/10.1007/s10098-018-1573-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10098-018-1573-8

Keywords

Search

Navigation