Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Scalable synthesis of hierarchically structured carbon nanotube–graphene fibres for capacitive energy storage

An Author Correction to this article was published on 30 June 2020

This article has been updated

Abstract

Micro-supercapacitors are promising energy storage devices that can complement or even replace batteries in miniaturized portable electronics and microelectromechanical systems. Their main limitation, however, is the low volumetric energy density when compared with batteries. Here, we describe a hierarchically structured carbon microfibre made of an interconnected network of aligned single-walled carbon nanotubes with interposed nitrogen-doped reduced graphene oxide sheets. The nanomaterials form mesoporous structures of large specific surface area (396 m2 g−1) and high electrical conductivity (102 S cm−1). We develop a scalable method to continuously produce the fibres using a silica capillary column functioning as a hydrothermal microreactor. The resultant fibres show a specific volumetric capacity as high as 305 F cm−3 in sulphuric acid (measured at 73.5 mA cm−3 in a three-electrode cell) or 300 F cm−3 in polyvinyl alcohol (PVA)/H3PO4 electrolyte (measured at 26.7 mA cm−3 in a two-electrode cell). A full micro-supercapacitor with PVA/H3PO4 gel electrolyte, free from binder, current collector and separator, has a volumetric energy density of 6.3 mWh cm−3 (a value comparable to that of 4 V–500 µAh thin-film lithium batteries) while maintaining a power density more than two orders of magnitude higher than that of batteries, as well as a long cycle life. To demonstrate that our fibre-based, all-solid-state micro-supercapacitors can be easily integrated into miniaturized flexible devices, we use them to power an ultraviolet photodetector and a light-emitting diode.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Figure 1: Schematic of the synthesis of carbon hybrid microfibres.
Figure 2: Microstructures of the carbon hybrid microfibres.
Figure 3: Electrochemical performance of individual carbon hybrid microfibres in liquid electrolytes.
Figure 4: Electrochemical performances of all-solid-state micro-SCs.
Figure 5: Assembly of multiple microfibres in micro-SCs and their integration in a self-powered nanosystem.

Change history

  • 27 May 2014

    In the version of this Article originally published online, the author list in ref. 40 was incorrect. This error has now been corrected in all versions of the Article.

References

  1. Pech, D. et al. Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. Nature Nanotech. 5, 651–654 (2010).

    CAS  Google Scholar 

  2. Gao, W. et al. Direct laser writing of micro-supercapacitors on hydrated graphite oxide films. Nature Nanotech. 6, 496–500 (2011).

    CAS  Google Scholar 

  3. El-Kady, M. F. & Kaner, R. B. Scalable fabrication of high-power graphene micro- supercapacitors for flexible and on-chip energy storage. Nature Commun. 4, 1475 (2013).

  4. Bae, J. et al. Fibre supercapacitors made of nanowire–fibre hybrid structures for wearable/flexible energy storage. Angew. Chem. Int. Ed. 50, 1683–1687 (2011).

    CAS  Google Scholar 

  5. Chmiola, J., Largeot, C., Taberna, P. L., Simon, P. & Gogotsi, Y. Monolithic carbide-derived carbon films for micro-supercapacitors. Science 328, 480–483 (2010).

    CAS  Google Scholar 

  6. El-Kady, M. F., Strong, V., Dubin, S. & Kaner, R. B. Laser scribing of high performance and flexible graphene-based electrochemical capacitors. Science 335, 1326–1330 (2012).

    CAS  Google Scholar 

  7. Yang, X., Cheng, C., Wang, Y., Qiu, L. & Li, D. Liquid-mediated dense integration of graphene materials for compact capacitive energy storage. Science 341, 534–537 (2013).

    CAS  Google Scholar 

  8. Gogotsi, Y. & Simon, P. True performance metrics in electrochemical energy storage. Science 334, 917–918 (2011).

    CAS  Google Scholar 

  9. Nam, I. et al. Interdigitated supercapacitor chips are fabricated using pseudo-capacitive metal oxide electrodes. Nanoscale 4, 7350–7353 (2012).

    CAS  Google Scholar 

  10. Sun, W. & Chen, X. Y. Fabrication and tests of a novel three dimensional microsupercapacitor. Microelectron. Eng. 86, 1307–1310 (2009).

    CAS  Google Scholar 

  11. Wang, K. et al. An all-solid-state flexible micro-supercapacitor on a chip. Adv. Energy Mater. 1, 1068–1072 (2011).

    CAS  Google Scholar 

  12. Liu, W., Feng, Y., Chen, J. & Xue, Q. Superior micro-supercapacitors based on graphene quantum dots. Adv. Funct. Mater. 23, 4111–4122 (2013).

    CAS  Google Scholar 

  13. Beidaghi, M. & Wang, C. Micro-supercapacitors based on interdigital electrodes of reduced graphene oxide and carbon nanotube composites with ultrahigh power handling performance. Adv. Funct. Mater. 22, 4501–4510 (2012).

    CAS  Google Scholar 

  14. Yang, P. et al. Hydrogenated ZnO core–shell nanocables for flexible supercapacitors and self-powered systems. ACS Nano 7, 2617–2626 (2013).

    CAS  Google Scholar 

  15. Lee, V. T. et al. Coaxial fibre supercapacitor using all-carbon material electrodes. ACS Nano 7, 5940–5947 (2013).

    Google Scholar 

  16. Chen, X. et al. Novel electric double-layer capacitor with a coaxial fibre structure. Adv. Mater. 25, 6436–6441 (2013).

    CAS  Google Scholar 

  17. Ren, J., Bai, W., Guan, G., Zhang, Y. & Peng, H. Flexible and weaveable capacitor wire based on carbon nanocomposite fibre. Adv. Mater. 25, 5965–5970 (2013).

    CAS  Google Scholar 

  18. Meng, Y., Zhao, Y., Hu, C., Cheng, H. & Hu, Y. All-graphene core–sheath microfibres for all-solid-state, stretchable fibriform supercapacitors and wearable electronic textiles. Adv. Mater. 25, 2326–2331 (2013).

    CAS  Google Scholar 

  19. Ren, J. et al. Twisting carbon nanotube fibres for both wire-shaped micro-supercapacitor and micro-battery. Adv. Mater. 24, 1155–1159 (2012).

    Google Scholar 

  20. Xiao, X. et al. Fibre-based all-solid-state flexible supercapacitors for self-powered systems. ACS Nano 6, 9200–9206 (2012).

    CAS  Google Scholar 

  21. Tao, J. et al. Solid-state high performance flexible supercapacitors based on polypyrrole–MnO2–carbon fibre hybrid structure. Sci. Rep. 3, 2286 (2013).

  22. Lee, J. A. et al. Ultrafast charge and discharge biscrolled yarn supercapacitors for textiles and microdevices. Nature Commun. 4, 1970 (2013).

  23. Zhao, Y. et al. A versatile, ultralight, nitrogen-doped graphene framework. Angew. Chem. Int. Ed. 51, 11371–11375 (2012).

    CAS  Google Scholar 

  24. Yu, D. & Dai, L. Self-assembled graphene/carbon nanotube hybrid films for supercapacitors. J. Phys. Chem. Lett. 1, 467–470 (2010).

    CAS  Google Scholar 

  25. Jha, N., Ramesh, P., Bekyarova, E., Itkis, M. E. & Haddon, R. C. High energy density supercapacitor based on a hybrid carbon nanotube-reduced graphite oxide architecture. Adv. Energy Mater. 2, 438–444 (2012).

    CAS  Google Scholar 

  26. Zhu, Y. et al. A seamless three-dimensional carbon nanotube graphene hybrid material. Nature Commun. 3, 1225 (2012).

  27. Du, F. et al. Preparation of tunable 3D pillared carbon nanotube–graphene networks for high-performance capacitance. Chem. Mater. 23, 4810–4816 (2011).

    CAS  Google Scholar 

  28. Lin, J. et al. 3-dimensional graphene carbon nanotube carpet-based microsupercapacitors with high electrochemical performance. Nano Lett. 13, 72–78 (2013).

    Google Scholar 

  29. Chen, P. et al. Hydrothermal synthesis of macroscopic nitrogen-doped graphene hydrogels for ultrafast supercapacitor. Nano Energy 2, 249–256 (2013).

    CAS  Google Scholar 

  30. Cote, L. J. et al. Graphene oxide as surfactant sheets. Pure Appl. Chem. 83, 95–110 (2011).

    CAS  Google Scholar 

  31. Gong, K. P. et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323, 760–764 (2009).

    CAS  Google Scholar 

  32. Yu, D., Zhang, Q. & Dai, L. Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction. J. Am. Chem. Soc. 132, 15127–15129 (2010).

    CAS  Google Scholar 

  33. Song, S. et al. Reversible self-assembly of terpyridine functionalized graphene oxide for energy conversion. Angew. Chem. Int. Ed. 53, 1415–1419 (2013).

    Google Scholar 

  34. Li, Y., Li, Z. & Shen, P. Simultaneous formation of ultrahigh surface area and three-dimensional hierarchical porous graphene-like networks for fast and highly stable supercapacitors. Adv. Mater. 25, 2474–2480 (2013).

    CAS  Google Scholar 

  35. Dong, Z. L. et al. Facile fabrication of light, flexible and multifunctional graphene fibres. Adv. Mater. 24, 1856–1861 (2012).

    CAS  Google Scholar 

  36. Xu, Z. & Gao, C. Graphene chiral liquid crystals and macroscopic assembled fibres. Nature. Commun. 2, 571 (2011).

  37. Ericson, L. M. et al. Macroscopic, neat, single-walled carbon nanotube fibres. Science 305, 1447–1450 (2004).

    CAS  Google Scholar 

  38. Cheng, H. et al. Textile electrodes woven by carbon nanotube/graphene hybrid fibres for flexible electrochemical capacitors. Nanoscale 5, 3428–3434 (2013).

    CAS  Google Scholar 

  39. Zhao, X., Lu, X., Tze, W. T. Y. & Wang, P. A single carbon fibre microelectrode with branching carbon nanotubes for bioelectrochemical processes. Biosens. Bioelectron. 25, 2343–2350 (2010).

    CAS  Google Scholar 

  40. Neimark, A. V., Ruetsch, S., Kornev, K. G. & Ravikovitch, P. I. Hierarchical pore structure and wetting properties of single-wall carbon nanotube fibres. Nano Lett. 3, 419–423 (2003).

    CAS  Google Scholar 

  41. Xu, Z., Zhang, Y., Li, P. & Gao, C. Strong, conductive, lightweight, neat graphene aerogel fibres with aligned pores. ACS Nano 6, 7103–7113 (2011).

    Google Scholar 

  42. Pan, H. L. et al. Well-aligned carbon nanotubols from mechanochemical reaction. Nano Lett. 3, 29–32 (2003).

    CAS  Google Scholar 

  43. Byon, H. R., Lee, S. W., Chen, S., Hammond, P. T. & Shao-Horn, Y. Thin films of carbon nanotubes and chemically reduced graphenes for electrochemical micro-capacitors. Carbon 49, 457–467 (2011).

    CAS  Google Scholar 

  44. Cong, H. P., Ren, X-C. Wang, P. & Yu, S. H. Wet-spinning assembly of continuous, neat, and macroscopic graphene fibres. Sci. Rep. 2, 613 (2012).

  45. Lu, W., Zu, M., Byun, J. H., Kim, B. S. & Chou, T. W. State of the art of carbon nanotube fibres: opportunities and challenges. Adv. Mater. 24, 1805–1833 (2012).

    CAS  Google Scholar 

  46. Gao, F., Viry, L., Maugey, M., Poulin, P. & Mano, N. Engineering hybrid nanotube wires for high-power biofuel cells. Nature Commun. 1, 2 (2010).

  47. Lukatskaya, M. R. et al. Cation intercalation and high volumetric capacitance of two-dimensional titanium carbide. Science 341, 1502–1505 (2013).

    CAS  Google Scholar 

  48. Jeong, H. M. et al. Nitrogen-doped graphene for high-performance ultracapacitors and the importance of nitrogen-doped sites at basal planes. Nano Lett. 11, 2472–2477 (2011).

    CAS  Google Scholar 

  49. Tao, Y. et al. Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors. Sci. Rep. 3, 2975 (2013).

    Google Scholar 

  50. Kumar, A., Madaria, A. R. & Zhou, C. W. Growth of aligned single-crystalline rutile TiO2 nanowires on arbitrary substrates and their application in dye-sensitized solar cells. J. Phys. Chem. C 114, 7787–7792 (2010).

    CAS  Google Scholar 

  51. Liu, S. B. et al. Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: membrane and oxidative stress. ACS Nano 5, 6971–6980 (2011).

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Ministry of Education, Singapore (MOE2011-T2-2-062 and 2013-T1-002-132), the Asian Office of Aerospace Research and Development of the US Air Force (FA23861314110) and the US Air Force Office of Scientific Research (FA9550-12-1-0037 and FA9550-12-1-0069). The authors thank B. Zhang, D. S. Su and L. Hu for TEM analysis.

Author information

Authors and Affiliations

Authors

Contributions

D.Y., L.D. and Y.C. conceived and designed the experiments. D.Y. carried out fibre synthesis and supercapacitor fabrication and testing. D.Y., K.G., H.W., L.W., W.J. and Q.Z. performed material characterization. D.Y., L.D. and Y.C. analysed the data and co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Liming Dai or Yuan Chen.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary Information (PDF 3110 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Yu, D., Goh, K., Wang, H. et al. Scalable synthesis of hierarchically structured carbon nanotube–graphene fibres for capacitive energy storage. Nature Nanotech 9, 555–562 (2014). https://doi.org/10.1038/nnano.2014.93

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2014.93

This article is cited by

Search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research