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

Nature Nanotechnology volume 9, pages 555–562 (2014)Cite this article

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

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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.

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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.

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  • 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.

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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.

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Authors and Affiliations

  1. School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore, 637459, Singapore

    Dingshan Yu, Kunli Goh, Hong Wang, Li Wei, Wenchao Jiang & Yuan Chen

  2. Department of Chemical Engineering, Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Tsinghua University, 1 Tsinghua Road, Beijing, 100084, China

    Qiang Zhang

  3. Department of Macromolecular Science and Engineering, Center of Advanced Science and Engineering for Carbon (Case4Carbon), Case Western Reserve University, Cleveland, 44106, Ohio, USA

    Liming Dai

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  1. Dingshan Yu
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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.

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Correspondence to Liming Dai or Yuan Chen.

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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

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