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Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon

Abstract

Electrochemical capacitors, also called supercapacitors, store energy in two closely spaced layers with opposing charges, and are used to power hybrid electric vehicles, portable electronic equipment and other devices1. By offering fast charging and discharging rates, and the ability to sustain millions of cycles2,3,4,5, electrochemical capacitors bridge the gap between batteries, which offer high energy densities but are slow, and conventional electrolytic capacitors, which are fast but have low energy densities. Here, we demonstrate microsupercapacitors with powers per volume that are comparable to electrolytic capacitors, capacitances that are four orders of magnitude higher, and energies per volume that are an order of magnitude higher. We also measured discharge rates of up to 200 V s−1, which is three orders of magnitude higher than conventional supercapacitors. The microsupercapacitors are produced by the electrophoretic deposition of a several-micrometre-thick layer of nanostructured carbon onions6,7 with diameters of 6–7 nm. Integration of these nanoparticles in a microdevice with a high surface-to-volume ratio, without the use of organic binders and polymer separators, improves performance because of the ease with which ions can access the active material. Increasing the energy density and discharge rates of supercapacitors will enable them to compete with batteries and conventional electrolytic capacitors in a number of applications.

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Figure 1: Design of the interdigital microsupercapacitor with OLC electrodes.
Figure 2: Electrochemical characterizations of the microdevices.
Figure 3: Comparison of microsupercapacitors and other energy storage devices.
Figure 4: Comparison, in a Ragone plot, of the specific energy and power density (per cm3 of stack) of typical electrolytic capacitors, supercapacitors and batteries with the microdevices.

References

  1. Miller, J. R. & Simon, P. Electrochemical capacitors for energy management. Science 321, 651–652 (2008).

    CAS  Article  Google Scholar 

  2. Conway, B. E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (Kluwer, 1999).

  3. Kötz, R. & Carlen, M. Principles and applications of electrochemical capacitors. Electrochim. Acta 45, 2483–2498 (2000).

    Article  Google Scholar 

  4. Burke, A. R&D considerations for the performance and application of electrochemical capacitors. Electrochim. Acta 53, 1083–1091 (2007).

    CAS  Article  Google Scholar 

  5. Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nature Mater. 7, 845–854 (2008).

    CAS  Article  Google Scholar 

  6. Sano, N., Wang, H., Chhowalla, M., Alexandrou, I. & Amaratunga, G. A. J. Nanotechnology: synthesis of carbon ‘onions’ in water. Nature 414, 506–507 (2001).

    CAS  Article  Google Scholar 

  7. Gogotsi, Y. (ed.) Carbon Nanomaterials (CRC, 2006).

  8. 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  Article  Google Scholar 

  9. Tarascon, J.-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    CAS  Article  Google Scholar 

  10. Aricò, A. S., Bruce, P., Scrosati, B., Tarason, J.-M. & Van Schalkwijk, W. Nanostructured materials for advanced energy conversion and storage devices. Nature Mater. 4, 366–377 (2005).

    Article  Google Scholar 

  11. Woo Lee, S. et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nature Nanotech. 5, 531–537 (2010).

    Article  Google Scholar 

  12. Long, J. W., Dunn, B., Rolison, D. R. & White, H. S. Three-dimensional battery architectures. Chem. Rev. 104, 4463–4492 (2004).

    CAS  Article  Google Scholar 

  13. In, H. J., Kumar, S., Shao-Horn, Y. & Barbastathis, G. Origami fabrication of nanostructured, three-dimensional devices: electrochemical capacitors with carbon electrodes. Appl. Phys. Lett. 88, 0831041 (2006).

    Article  Google Scholar 

  14. Pech, D. et al. Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor. J. Power Sources 195, 1266–1269 (2010).

    CAS  Article  Google Scholar 

  15. Kajdos, A., Kvit, A., Jones, F., Jagiello, J. & Yushin, G. Tailoring the pore alignment for rapid ion transport in microporous carbons. J. Am. Chem. Soc. 132, 3252–3253 (2010).

    CAS  Article  Google Scholar 

  16. Dash, R. et al. Titanium carbide derived nanoporous carbon for energy-related applications. Carbon 44, 2489–2497 (2006).

    CAS  Article  Google Scholar 

  17. Futaba, D. N. et al. Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes. Nature Mater. 5, 987–994 (2006).

    CAS  Article  Google Scholar 

  18. Li, X. et al. Transfer of large-area graphene films for high-performance transparent conductive electrodes. Nano Lett. 9, 4359–4363 (2009).

    CAS  Article  Google Scholar 

  19. Bushueva, E. G. et al. Double layer supercapacitor properties of onion-like carbon materials. Phys. Status Solidi B 245, 2296–2299 (2008).

    CAS  Article  Google Scholar 

  20. Park, S., Lian, K. & Gogotsi, Y. Pseudocapacitive behaviour of carbon nanoparticles modified by phosphomolybdic acid. J. Electrochem. Soc. 156, 921–926 (2009).

    Article  Google Scholar 

  21. Plonska-Brzezinska, M. E., Palkar, A., Winkler, K. & Echegoyen, L. Electrochemical properties of small carbon nano-onions films. Electrochem. Solid State Lett. 13, 35–38 (2010).

    Article  Google Scholar 

  22. Ugarte, D. Curling and closure of graphitic networks under electron-beam irradiation. Nature 359, 707–709 (1992).

    CAS  Article  Google Scholar 

  23. Kuznetsov, V. L. et al. Effect of explosion conditions on the structure of detonation soots: ultradisperse diamond and onion carbon. Carbon 32, 873–882 (1994).

    Article  Google Scholar 

  24. Portet, C., Yushin, G. & Gogotsi, Y. Electrochemical performance of carbon onions, nanodiamonds, carbon black and multiwalled nanotubes in electrical double layer capacitors. Carbon 45, 2511–2518 (2007).

    CAS  Article  Google Scholar 

  25. Du, C. & Pan, N. High power density supercapacitor electrodes of carbon nanotube films by electrophoretic deposition. Nanotechnology 17, 5314–5318 (2006).

    CAS  Article  Google Scholar 

  26. Portet, C., Chmiola, J., Gogotsi, Y., Park, S. & Lian, K. Electrochemical characterizations of carbon nanomaterials by the cavity microelectrode technique. Electrochim. Acta 53, 7675–7680 (2008).

    CAS  Article  Google Scholar 

  27. Lin, R. et al. Microelectrode study of pore size, ion size and solvent effects on the charge/discharge behaviour of microporous carbons for electrical double-layer capacitors. J. Electrochem. Soc. 156, 7–12 (2009).

    Article  Google Scholar 

  28. Lin, R. et al. Solvent effect on the ion adsorption from ionic liquid electrolyte into sub-nanometer carbon pores. Electrochim. Acta 54, 7025–7032 (2009).

    CAS  Article  Google Scholar 

  29. Kaempgen, M., Chan, C. K., Ma, J., Cui, Y. & Gruner, G. Printable thin film supercapacitors using single-walled carbon nanotubes. Nano. Lett. 9, 1872–1876 (2009).

    CAS  Article  Google Scholar 

  30. Taberna, P.-L., Simon, P. & Fauvarque, J. F. Electrochemical characteristics and impedance spectroscopy studies of carbon–carbon supercapacitors. J. Electrochem. Soc. 150, 292–300 (2003).

    Article  Google Scholar 

  31. Huang, J. et al. Curvature effects in carbon nano-materials: exohedral versus endohedral supercapacitors. J. Mater. Res. doi: 10.1557/JMR.2010.195 (2010).

    CAS  Article  Google Scholar 

  32. Banerjee, P., Perez, I., Henn-Lecordier, L., Lee, S. B. & Rubloff, G. W. Nanotubular metal–insulator–metal capacitor arrays for energy storage. Nature Nanotech. 4, 292–296 (2009).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

The authors would like to thank M. Heon, J.-J. Niu and J. McDonough (Drexel University) for experimental help. Raman spectroscopy and TEM analyses were conducted using instruments in the Centralized Research Facility of the College of Engineering, Drexel University. The effort at Drexel University is based upon work supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under award no. ERKCC61. Microdevice fabrication including EPD, and electron microscopy of the deposited material were performed in the technological facilities of LAAS-CNRS. Electrochemical characterization was conducted at CIRIMAT laboratory. Work at LAAS-CNRS was supported by the FRAE (Fondation de Recherche pour l'Aéronautique et l'Espace). P. Huang was supported by a PhD grant from the PRES of the Université de Toulouse. H. Durou was supported by a PhD grant from CNRS (BDI: Bourse Docteur Ingénieur). Collaboration between the participating universities was supported by a Partnership University Fund (PUF) grant.

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M.B. and D.P. conceived and designed the experiments for the elaboration of the electrochemical microcapacitors. H.D. was involved in the conception of the microdevice patterns. D.P. established the EPD process. Y.G. was involved in material synthesis and characterization. V.M. carried out the simulation of OLC formation. D.P., P.H., P.L.T. and P.S. performed the electrochemical characterizations. D.P., M.B., P.S. and Y.G. co-wrote the paper, and all authors discussed the results and commented on the manuscript.

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Correspondence to Magali Brunet.

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Pech, D., Brunet, M., Durou, H. et al. Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. Nature Nanotech 5, 651–654 (2010). https://doi.org/10.1038/nnano.2010.162

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