Skip to main content
Log in

Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

A novel approach was developed to prepare hollow polypyrrole (PPy) nanospheres and nitrogen-doped graphene/hollow PPy nanospheres (NG/H-PPy) composites. In this process, uniform poly (methyl methacrylate-butyl methacrylate-methacrylic acid) (PMMA-PBMA-PMAA) latex microspheres as sacrificial templates were synthesized by using an emulsion polymerization method. Then, hollow PPy nanospheres were obtained on the surface of PMMA-PBMA-PMAA microspheres by in situ chemical oxidative polymerization. Finally, H-PPy was embedded in NG layers successfully through a simple approach. The nanobeads have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectra, and Fourier transform infrared spectra (FTIR). Different electrochemical methods including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) have been applied to study the electrochemical properties. The specific capacitance of NG/H-PPy composites based on the three-electrode system is as high as 575 F g−1 at a current density of 1 A g−1 and enhanced stability about 90.1 % after 500 cycles, indicating that the composite has an impressive capacitance and excellent cycling performance.

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

Access this article

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

Instant access to the full article PDF.

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

Similar content being viewed by others

References

  1. Zhang YY, Zhen Z, Zhang ZL, Lao JC, Wei JQ, Wang KL, Kang FY, Zhu HW (2015) In-site synthesis of carbon nanotube/graphene composite sponge and its application as compressible supercapacitor electrode. Electrochim Acta 157:134

    Article  CAS  Google Scholar 

  2. Meng YN, Wang K, Zhang YJ, Wei ZX (2013) Hierarchical porous graphene/polyaniline composite film with superior rate performance for flexible supercapacitors. Adv Mater 25:6985

    Article  CAS  Google Scholar 

  3. Staaf LGH, Lundgren P, Enoksson P (2014) Present and future supercapacitor carbon electrode materials for improved energy storage used in intelligent wireless sensor systems. Nano Energy 9:128

    Article  CAS  Google Scholar 

  4. Wei WF, Cui XW, Chen WX (2013) Manganese oxide-based materials as electrochemical supercapacitor electrodes. Nanoscale 5:72

    Article  Google Scholar 

  5. Wang GP, Zhang L, Zhang JJ (2012) A review of electrode materials for electrochemical supercapacitors. Chem Soc Rev 41:797

    Article  CAS  Google Scholar 

  6. Ehsani A, Jaleh B, Nasrollahzadeh M (2014) Electrochemical properties and electrocatalytic activity of conducting polymer/copper nanoparticles supported on reduced graphene oxide composite. J Power Sources 257:300

    Article  CAS  Google Scholar 

  7. Song HK, Palmore GRT (2006) Redox-active polypyrrole: toward polymer-based batteries. Adv Mater 18:1764

    Article  CAS  Google Scholar 

  8. Zhang DC, Zhang X, Chen Y, Peng Y, Wang CH, Ma YW (2011) Enhanced capacitance and rate capability of graphene/polypyrrole composite as electrode material for supercapacitors. J Power Sources 196:5990

    Article  CAS  Google Scholar 

  9. Wang X, Yang C, Liu P (2012) Facile decoration of polypyrrole nanoparticles onto graphene nanosheets for supercapacitors. Synth Met 162:2349

    Article  CAS  Google Scholar 

  10. Zhang LL, Li HH, Fan CY, Wang K, Wu XL, Sun HZ, Xie HM, Zhang JP (2015) Polypyrrole nanosphere embedded in wrinkled graphene layers to obtain cross-linking network for high performance supercapacitors. Electrochim Acta 184:179

    Article  CAS  Google Scholar 

  11. Yang C, Zhang LL, Hu NT, Yang Z, Wei H, Zhang YF (2016) Reduced graphene oxide/polypyrrole nanotube papers for flexible all-solid-state supercapacitors with excellent rate capability and high energy density. J Power Sources 302:39

    Article  CAS  Google Scholar 

  12. Mahmoudian MR, Alias Y, Basirun WJ (2012) The electrical properties of a sandwich of electrodeposited polypyrrole nanofibers between two layers of reduced graphene oxide nanosheets. Electrochim Acta 72:53

    Article  CAS  Google Scholar 

  13. Xu CH, Sun J, Gao L (2011) Synthesis of novel hierarchical graphene/polypyrrole nanosheet composites and their superior electrochemical performance. J Mater Chem 21:11253

    Article  CAS  Google Scholar 

  14. Ehsani A, Mohammad Shiri H, Kowsari E, Safari R, Torabian J, Kazemi S (2016) Nanocomposite of p-type conductive polymer/functionalized grapheme oxide nanosheets as novel and hybrid electrodes for highly capacitive pseudocapacitors. J Colloid Interf Sci 478:181

    Article  CAS  Google Scholar 

  15. Xie KW, Yin JW, Shi HM, Zhu QY, Ping W, Tang TW, Zhou YM, Lu TH (2015) Designed synthesis of NiO@polypyrrole hollow spheres for long-life lithium storage. Ionics 21:359

    Article  CAS  Google Scholar 

  16. Liu RQ, Li DY, Wang C, Li N, Li Q, Lv XJ, Spendelow JS, Wu G (2014) Core–shell structured hollow SnO2–polypyrrole nanocomposite anodes with enhanced cyclic performance for lithium-ion batteries. Nano Energy 6:73

    Article  CAS  Google Scholar 

  17. Lu XF, Mao H, Zhang WJ (2009) Fabrication of core-shell Fe3O4/polypyrrole and hollow polypyrrole microspheres. Polym Compos 30:847

    Article  CAS  Google Scholar 

  18. Bai ZY, Zhang Q, Lv J, Chao SJ, Yang L, Qiao JL (2015) A facile preparation of palladium catalysts supported on hollow polypyrrole nanospheres for ethanol oxidation. Electrochim Acta 177:107

    Article  CAS  Google Scholar 

  19. Su DW, Zhang JQ, Dou SX, Wang GX (2015) Polypyrrole hollow nanospheres: stable cathode materials for sodium-ion batteries. Chem Commun 51:16092

    Article  CAS  Google Scholar 

  20. Lin ZY, Waller GH, Liu Y, Liu ML, Wong CP (2013) 3D Nitrogen-doped graphene prepared by pyrolysis of graphene oxide with polypyrrole for electrocatalysis of oxygen reduction reaction. Nano Energy 2:241

    Article  CAS  Google Scholar 

  21. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339

    Article  CAS  Google Scholar 

  22. Zhang J, Yu Y, Liu LWY (2013) Graphene–hollow PPy sphere 3D-nanoarchitecture with enhanced electrochemical performance. Nanoscale 5:3052

    Article  CAS  Google Scholar 

  23. Luo J, Ma Q, Gu HH, Zheng Y, Liu XY (2015) Three-dimensional graphene-polyaniline hybrid hollow spheres by layer-by-layer assembly for application in supercapacitor. Electrochim Acta 173:184

    Article  CAS  Google Scholar 

  24. Feng XM, Li RM, Ma YW, Chen RF, Shi NE, Fan QL, Huang W (2011) One-step electrochemical synthesis of graphene/polyaniline composite film and its applications. Adv Funct Mater 21:2989

    Article  CAS  Google Scholar 

  25. Lv H, Lin Q, Zhang K, Yu K, Yao TJ, Zhang XH, Zhang JH, Yang B (2008) Facile fabrication of monodisperse polymer hollow spheres. Langmuir 24:13736

    Article  CAS  Google Scholar 

  26. Canche-Escamilla G, Pacheco-Catalan DE, Andrade-Canto SB (2006) Modification of properties of rayon fibre by graft copolymerization with acrylic monomers. J Mater Sci 41:7296

    Article  CAS  Google Scholar 

  27. Zhong J, Gao S, Xue GB, Wang B (2015) Study on enhancement mechanism of conductivity induced by graphene oxide for polypyrrole nanocomposites. Macromolecules 48:1592

    Article  CAS  Google Scholar 

  28. Wang DW, Min YG, Yu YH, Peng B (2014) A general approach for fabrication of nitrogen-doped graphene sheets and its application in supercapacitors. J Colloid Interface Sci 417:270

    Article  CAS  Google Scholar 

  29. Du FH, Li B, Fu W, Xiong YJ, Wang KX, Chen JS (2014) Surface binding of polypyrrole on porous silicon hollow nanospheres for li-ion battery anodes with high structure stability. Adv Mater 26:6145

    Article  CAS  Google Scholar 

  30. Chen P, Yang JJ, Li SS, Wang Z, Xiao YT, Qian YH, Yu SH (2013) Hydrothermal synthesis of macroscopic nitrogen-doped graphene hydrogels for ultrafast supercapacitor. Nano Energy 2:249

    Article  CAS  Google Scholar 

  31. Sheng ZH, Shao L, Chen JJ, Bao WJ, Wang FB, Xia XH (2011) Catalyst-free synthesis of nitrogen- doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano 6:4350

    Article  Google Scholar 

  32. Chen CN, Fan W, Zhang Q, Wang ZB (2015) High performance of supercapacitor based on nitrogen-doped graphene/p-aminophenol electrodes. Ionics 21:2639

    Article  CAS  Google Scholar 

  33. Hu R, Dai SY, Shao DD, Alsaedi A, Ahmad B, Wang XK (2015) Efficient removal of phenol and aniline from aqueous solutions using graphene oxide/polypyrrole composites. J Molecular Liquids 203:80

    Article  CAS  Google Scholar 

  34. Biswas S, Drzal LT (2010) Multilayered nanoarchitecture of graphene nanosheets and polypyrrole nanowires for high performance supercapacitor electrodes. Chem Mater 22:5667

    Article  CAS  Google Scholar 

  35. Zhang JR, Wang X, Qi GC, Li BH, Jiang HB, Zhang XH, Qiao JL (2016) A novel N-doped porous carbon microsphere composed of hollow carbon nanospheres. Carbon 96:864

    Article  CAS  Google Scholar 

  36. Shabani Shayeh J, Ehsani A, Ganjali MR, Norouzi P, Jaleh B (2015) Conductive polymer/reduced graphene oxide/Au nano particles as efficient composite materials in electrochemical supercapacitors. Appl Surf Sci 353:594

    Article  CAS  Google Scholar 

  37. Qu GX, Cheng JL, Li XD, Yuan DM, Chen PN, Chen XL, Wang B, Peng HS (2016) A fiber supercapacitor with high energy density based on hollow graphene/conducting polymer fiber electrode. Adv Mater 28:3646

    Article  CAS  Google Scholar 

  38. Chang HH, Chang CK, Tsai YC, Liao CS (2012) Electrochemically synthesized graphene/polypyrrole composites and their use in supercapacitor. Carbon 50:2331

    Article  CAS  Google Scholar 

  39. Shiri HM, Ehsani A, Shayeh JS (2015) Synthesis and highly efficient supercapacitor behavior of a novel polypyrrole/ceramic oxide nanocomposite film. RSC Adv 5:91062

    Article  Google Scholar 

  40. Zhang K, Zhang LL, Zhao XS, Wu JS (2010) Graphene/polyaniline nanofiber composites as supercapacitor electrodes. Chem Mater 22:1392

    Article  CAS  Google Scholar 

  41. Mohammad Shiri H, Ehsani A (2016) A simple and innovative route to electrosynthesis of Eu2O3 nanoparticles and its nanocomposite with p-type conductive polymer: characterisation and electrochemical properties. J Colloid Interface Sci 473:126

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This study was supported by the Opening Project of CAS Key Laboratory of Materials for Energy Conversion.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Zhongbing Wang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Z., Zhang, C., Xu, C. et al. Hollow polypyrrole nanosphere embedded in nitrogen-doped graphene layers to obtain a three-dimensional nanostructure as electrode material for electrochemical supercapacitor. Ionics 23, 147–156 (2017). https://doi.org/10.1007/s11581-016-1803-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-016-1803-1

Keywords

Navigation