Skip to main content
SpringerLink
Log in

One-step strategy to graphene/Ni(OH)2 composite hydrogels as advanced three-dimensional supercapacitor electrode materials

  • Research Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Graphene-based three-dimensional (3D) macroscopic materials have recently attracted increasing interest by virtue of their exciting potential in electrochemical energy conversion and storage. Here we report a facile one-step strategy to prepare mechanically strong and electrically conductive graphene/Ni(OH)2 composite hydrogels with an interconnected porous network. The composite hydrogels were directly used as 3D supercapacitor electrode materials without adding any other binder or conductive additives. An optimized composite hydrogel containing ∼82 wt.% Ni(OH)2 exhibited a specific capacitance of ∼1,247 F/g at a scan rate of 5 mV/s and ∼785 F/g at 40 mV/s (∼63% capacitance retention) with excellent cycling stability. The capacity of the 3D hydrogels greatly surpasses that of a physical mixture of graphene sheets and Ni(OH)2 nanoplates (∼309 F/g at 40 mV/s). The same strategy was also applied to fabricate graphene-carbon nanotube/Ni(OH)2 ternary composite hydrogels with further improved specific capacitances (∼1,352 F/g at 5 mV/s) and rate capability (∼66% capacitance retention at 40 mV/s). Both composite hydrogels obtained here can deliver high energy densities (∼43 and ∼47 Wh/kg, respectively) and power densities (∼8 and ∼9 kW/kg, respectively), making them attractive electrode materials for supercapacitor applications. This study opens a new pathway to the design and fabrication of functional 3D graphene composite materials, and can significantly impact broad areas including energy storage and beyond.

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

Similar content being viewed by others

References

  1. Whittingham, M. S. History, evolution, and future status of energy storage. Proc. IEEE. 2012, 100, 1518–1534.

    Article  CAS  Google Scholar 

  2. Armaroli, N.; Balzani, V. Towards an electricity-powered world. Energy Environ. Sci. 2011, 4, 3193–3222.

    Article  Google Scholar 

  3. Arico, A. S.; Bruce, P.; Scrosati, B.; Tarascon, J. M.; Van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nat. Mater. 2005, 4, 366–377.

    Article  CAS  Google Scholar 

  4. Simon, P.; Gogotsi, Y. Materials for electrochemical capacitors. Nat. Mater. 2008, 7, 845–854.

    Article  CAS  Google Scholar 

  5. Hall, P. J.; Mirzaeian, M.; Fletcher, S. I.; Sillars, F. B.; Rennie, A. J. R.; Shitta-Bey, G. O.; Wilson, G.; Cruden, A.; Carter, R. Energy storage in electrochemical capacitors: Designing functional materials to improve performance. Energy Environ. Sci. 2010, 3, 1238–1251.

    Article  CAS  Google Scholar 

  6. Wang, G. P.; Zhang, L.; Zhang, J. J. A review of electrode materials for electrochemical supercapacitors. Chem. Soc. Rev. 2012, 41, 797–828.

    Article  CAS  Google Scholar 

  7. Zhu, Y. W.; Murali, S.; Stoller, M. D.; Ganesh, K. J.; Cai, W. W.; Ferreira, P. J.; Pirkle, A.; Wallace, R. M.; Cychosz, K. A.; Thommes, M., et al. Carbon-based supercapacitors produced by activation of graphene. Science 2011, 332, 1537–1541.

    Article  CAS  Google Scholar 

  8. Sun, Y. Q.; Wu, Q.; Shi, G. Q. Graphene based new energy materials. Energy Environ. Sci. 2011, 4, 1113–1132.

    Article  CAS  Google Scholar 

  9. Huang, Y.; Liang, J. J.; Chen, Y. S. An overview of the applications of graphene-based materials in supercapacitors. Small 2012, 8, 1805–1834.

    Article  CAS  Google Scholar 

  10. Zhai, Y. P.; Dou, Y. Q.; Zhao, D. Y.; Fulvio, P. F.; Mayes, R. T.; Dai, S. Carbon materials for chemical capacitive energy storage. Adv. Mater. 2011, 23, 4828–4850.

    Article  CAS  Google Scholar 

  11. Stoller, M. D.; Park, S. J.; Zhu, Y. W.; An, J. H.; Ruoff, R. S. Graphene-based ultracapacitors. Nano Lett. 2008, 8, 3498–3502.

    Article  CAS  Google Scholar 

  12. Yu, D. S.; Dai, L. M. Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J. Phys. Chem. Lett. 2010, 1, 467–470.

    Article  CAS  Google Scholar 

  13. Wang, Y.; Shi, Z. Q.; Huang, Y.; Ma, Y. F.; Wang, C. Y.; Chen, M. M.; Chen, Y. S. Supercapacitor devices based on graphene materials. J. Phys. Chem. C 2009, 113, 13103–13107.

    Article  CAS  Google Scholar 

  14. Xu, Y. X.; Shi, G. Q. Assembly of chemically modified graphene: Methods and applications. J. Mater. Chem. 2011, 21, 3311–3323.

    Article  CAS  Google Scholar 

  15. Li, C.; Shi, G. Q. Three-dimensional graphene architectures. Nanoscale 2012, 4, 5549–5563.

    Article  CAS  Google Scholar 

  16. Xu, Y. X.; Wu, Q.; Sun, Y. Q.; Bai, H.; Shi, G. Q. Threedimensional self-assembly of graphene oxide and DNA into multifunctional hydrogels. ACS Nano 2010, 4, 7358–7362.

    Article  CAS  Google Scholar 

  17. Worsley, M. A.; Pauzauskie, P. J.; Olson, T. Y.; Biener, J.; Satcher, J. H.; Baumann, T. F. Synthesis of graphene aerogel with high electrical conductivity. J. Am. Soc. Chem. 2010, 132, 14067–14069.

    Article  CAS  Google Scholar 

  18. Bai, H.; Sheng, K. X.; Zhang, P. F.; Li, C.; Shi, G. Q. Graphene oxide/conducting polymer composite hydrogels. J. Mater. Chem. 2011, 21, 18653–18658.

    Article  CAS  Google Scholar 

  19. Chen, W. F.; Li, S. R.; Chen, C. H.; Yan, L. F. Self-assembly and embedding of nanoparticles by in situ reduced graphene for preparation of a 3D graphene/nanoparticle aerogel. Adv. Mater. 2011, 23, 5679–5683.

    Article  CAS  Google Scholar 

  20. Wu, Z. S.; Yang, S. B.; Sun, Y.; Parvez, K.; Feng, X. L.; Mullen, K. 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient eletrocatalysts for the oxygen reduction reaction. J. Am. Chem. Soc. 2012, 134, 9082–9085.

    Article  CAS  Google Scholar 

  21. Xu, Y. X.; Sheng, K. X.; Li, C.; Shi, G. Q. Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano 2010, 4, 4324–4330.

    Article  CAS  Google Scholar 

  22. Zhang, L.; Shi, G. Q. Preparation of highly conductive graphene hydrogels for fabricating supercapacitors with high rate capability. J. Phys. Chem. C 2011, 115, 17206–17212.

    Article  CAS  Google Scholar 

  23. Sheng, K. X.; Sun, Y. Q.; Li, C.; Yuan, W. J.; Shi, G. Q. Ultrahigh-rate supercapacitors based on eletrochemically reduced graphene oxide for ac line-filtering. Sci. Rep. 2012, 2, 247.

    Article  Google Scholar 

  24. Chen, J.; Sheng, K. X.; Luo, P. H.; Li, C.; Shi, G. Q. Graphene hydrogels deposited in nickel foams for high-rate electrochemical capacitors. Adv. Mater. 2012, 24, 4569–4573.

    Article  CAS  Google Scholar 

  25. Chen, W. F.; Yan, L. F. In situ self-assembly of mild chemical reduction graphene for three-dimensional architectures. Nanoscale 2011, 3, 3132–3137.

    Article  CAS  Google Scholar 

  26. Zhang, X. T.; Sui, Z. Y.; Xu, B.; Yue, S. F.; Luo, Y. J.; Zhan, W. C.; Liu, B. Mechanically strong and highly conductive graphene aerogel and its use as electrodes for electrochemical power sources. J. Mater. Chem. 2011, 21, 6494–6497.

    Article  CAS  Google Scholar 

  27. Wu, Z. S.; Winter, A.; Chen, L.; Sun, Y.; Turchanin, A.; Feng, X. L.; Mullen, K. Three-dimensional nitrogen and boron co-doped graphene for high-performance all-solid-state supercapacitors. Adv. Mater. 2012, 24, 5130–5135.

    Article  CAS  Google Scholar 

  28. Dong, X. C.; Xu, H.; Wang, X. W.; Huang, Y. X.; Chan-Park, M. B.; Zhang, H.; Wang, L. H.; Huang, W.; Chen, P. 3D graphene-cobalt oxide electrode for high-performance supercapacitor and enzymeless glucose detection. ACS Nano 2012, 6, 3206–3213.

    Article  CAS  Google Scholar 

  29. Choi, B. G.; Yang, M.; Hong, W. H.; Choi, J. W.; Huh, Y. S. 3D macroporous graphene frameworks for supercapacitors with high energy and power densities. ACS Nano 2012, 6, 4020–4028.

    Article  CAS  Google Scholar 

  30. Cao, X. H.; Shi, Y. M.; Shi, W. H.; Lu, G.; Huang, X.; Yan, Q. Y.; Zhang, Q. C.; Zhang, H. Preparation of novel 3D graphene networks for supercapacitor applications. Small 2011, 7, 3163–3168.

    Article  CAS  Google Scholar 

  31. Du, F.; Yu, D. S.; Dai, L. M.; Ganguli, S.; Varshney, V.; Roy, A. K. Preparation of tunable 3D pillared carbon nanotube-graphene networks for high-performance capacitance. Chem. Mater. 2011, 23, 4810–4816.

    Article  CAS  Google Scholar 

  32. Wang, H. L.; Robinson, J. T.; Diankov, G.; Dai, H. J. Nanocrystal growth on graphene with various degrees of oxidation. J. Am. Chem. Soc. 2010, 132, 3270–3271.

    Article  CAS  Google Scholar 

  33. Wang, H. L.; Casalongue, H. S.; Liang, Y. Y.; Dai, H. J. Ni(OH)2 Nanoplates grown on graphene as advanced electrochemical pseudocapacitor materials. J. Am. Chem. Soc. 2010, 132, 7472–7477.

    Article  CAS  Google Scholar 

  34. Xu, Y. X.; Sheng, K. X.; Li, C.; Shi, G. Q. Highly conductive chemically converted graphene prepared from mildly oxidized graphene oxide. J. Mater. Chem. 2011, 21, 7376–7380.

    Article  CAS  Google Scholar 

  35. Kim, J.; Cote, L. J.; Kim, F.; Yuan, W.; Shull, K. R.; Huang, J. X. Graphene oxide sheets at interfaces. J. Am. Chem. Soc. 2010, 132, 8180–8186.

    Article  CAS  Google Scholar 

  36. Qiu, J.; Yang, X. W.; Gou, X. L.; Yang, W. R.; Ma, Z. F.; Wallace, G. G.; Li, D. Dispersing carbon nanotubes with graphene oxide in water and synergistic effects between graphene derivatives. Chem. Eur. J. 2010, 16, 10653–10658.

    Article  CAS  Google Scholar 

  37. Yan, J.; Fang, Z. J.; Sun, W.; Ning, G. Q.; Wei, T.; Zhang, Q.; Zhang, R. F.; Zhi, L. J.; Wei, F. Advanced asymmetric supercapacitors based on Ni(OH)2/graphene and porous graphene electrodes with high energy density. Adv. Funct. Mater. 2012, 22, 2632–2641.

    Article  CAS  Google Scholar 

  38. Yan, J.; Sun, W.; Wei, T.; Zhang, Q.; Fang, Z. J.; Wei, F. Fabrication and electrochemical performances of hierarchical porous Ni(OH)2 nanoflakes anchored on graphene sheets. J. Mater. Chem. 2012, 22, 11494–11502.

    Article  CAS  Google Scholar 

  39. Lee, J. W.; Ahn, T.; Soundararajan, D.; Ko, J. M.; Kim, J. D. Non-aqueous approach to the preparation of reduced graphene oxide/α-Ni(OH)2 hybrid composites and their high capacitance behavior. Chem. Commun. 2011, 47, 6305–6307.

    Article  CAS  Google Scholar 

  40. Yang, S. B.; Wu, X. L.; Chen, C. L.; Dong, H. L.; Hu, W. P.; Wang, X. K. Spherical α-Ni(OH)2 nanoarchitecture grown on graphene as advanced electrochemical pseudocapacitor materials. Chem. Commun. 2012, 48, 2773–2775.

    Article  CAS  Google Scholar 

  41. Chang, J.; Xu, H.; Sun, J.; Gao, L. High pseudocapacitance material prepared via in situ growth of Ni(OH)2 nanoflakes on reduced graphene oxide. J. Mater. Chem. 2012, 22, 11146–11150.

    Article  CAS  Google Scholar 

  42. Hummers, W. S.; Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 1958, 80, 1339–1339.

    Article  CAS  Google Scholar 

  43. Xu, Y. X.; Zhao, L.; Bai, H.; Hong, W. J.; Li, C.; Shi, G. Q. Chemically converted graphene induced molecular flattening of 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin and its application for optical detection of cadmium(II) ions. J. Am. Chem. Soc. 2009, 131, 13490–13497.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, California, 90095, USA

    Yuxi Xu, Zhaoyang Lin, Xing Zhong & Xiangfeng Duan

  2. Department of Materials Science and Engineering, University of California, Los Angeles, California, 90095, USA

    Xiaoqing Huang & Yu Huang

  3. California Nanosystems Institute, University of California, Los Angeles, California, 90095, USA

    Yu Huang & Xiangfeng Duan

Authors
  1. Yuxi Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaoqing Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhaoyang Lin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xing Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yu Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Xiangfeng Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiangfeng Duan.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Cite this article

Xu, Y., Huang, X., Lin, Z. et al. One-step strategy to graphene/Ni(OH)2 composite hydrogels as advanced three-dimensional supercapacitor electrode materials. Nano Res. 6, 65–76 (2013). https://doi.org/10.1007/s12274-012-0284-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-012-0284-4

Keywords

Search

Navigation