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

Journal name:
Nature Nanotechnology
Year published:
Published online


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.

At a glance


  1. Design of the interdigital microsupercapacitor with OLC electrodes.
    Figure 1: Design of the interdigital microsupercapacitor with OLC electrodes.

    a, Cross-section of a charged zero-dimensional OLC (grey) capacitor, consisting of two layers of charges (blue and pink) forming the inner and outer spheres, respectively. b, Transmission electron microscopy image of a carbon onion produced at 1,800 °C. Lattice spacing between the bent graphitic layers in the onions is close to 0.35 nm. c, Schematic of the microdevice (25 mm2). Two gold current collectors made of 16 interdigital fingers were deposited by evaporation on an oxidized silicon substrate and patterned using a conventional photolithography/etching process. Carbon onions (active material) were then deposited by electrophoretic deposition onto the gold current collectors. d, Optical image of the interdigital fingers with 100-μm spacing. e, Scanning electron microscope image of the cross-section of the carbon onion electrode. A volumetric power density of 1 kW cm−3 was obtained with a deposited layer thickness in the micrometre range, not the nanometre range.

  2. Electrochemical characterizations of the microdevices.
    Figure 2: Electrochemical characterizations of the microdevices.

    a, CVs obtained at different scan rates in a 1 M Et4NBF4/anhydrous propylene carbonate on a 16-interdigital electrochemical microcapacitor with a 7-μm-thick OLC deposit. A typical rectangular shape, as expected for double-layer capacitive materials, is observed at an ultrahigh scan rate over a 3 V potential window. b, Evolution of the discharge current versus scan rate. A linear dependence is obtained up to at least 100 V s−1 in the capacitive region, indicating an ultrahigh power ability for the microdevices.

  3. Comparison of microsupercapacitors and other energy storage devices.
    Figure 3: Comparison of microsupercapacitors and other energy storage devices.

    a, Evolution of the stack capacitance versus scan rate. Carbon onion microsupercapacitors can sustain very high scan rates, like electrolytic capacitors. The stack capacitance is, however, four orders of magnitude higher than that of the electrolytic capacitors. b, Evolution of the volumetric energy of different energy-storage devices. c,d, Evolution of the real and imaginary part (C′ and C′′) of the stack capacitance of a 16-interdigital electrochemical microcapacitor based on OLC (c) and AC (d). An extremely low relaxation time constant τ0 (26 ms) was obtained for the OLC, revealing fast accessibility of the ions for electrosorption.

  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.
    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.

    All the devices (macro and micro) were tested under the same dynamic conditions. A very high energy density was obtained with the AC-based microsupercapacitor, whereas ultrahigh power density was obtained with the OLC-based microsupercapacitor.


  1. Miller, J. R. & Simon, P. Electrochemical capacitors for energy management. Science 321, 651652 (2008).
  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, 24832498 (2000).
  4. Burke, A. R&D considerations for the performance and application of electrochemical capacitors. Electrochim. Acta 53, 10831091 (2007).
  5. Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nature Mater. 7, 845854 (2008).
  6. Sano, N., Wang, H., Chhowalla, M., Alexandrou, I. & Amaratunga, G. A. J. Nanotechnology: synthesis of carbon ‘onions’ in water. Nature 414, 506507 (2001).
  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, 480483 (2010).
  9. Tarascon, J.-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359367 (2001).
  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, 366377 (2005).
  11. Woo Lee, S. et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nature Nanotech. 5, 531537 (2010).
  12. Long, J. W., Dunn, B., Rolison, D. R. & White, H. S. Three-dimensional battery architectures. Chem. Rev. 104, 44634492 (2004).
  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).
  14. Pech, D. et al. Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor. J. Power Sources 195, 12661269 (2010).
  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, 32523253 (2010).
  16. Dash, R. et al. Titanium carbide derived nanoporous carbon for energy-related applications. Carbon 44, 24892497 (2006).
  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, 987994 (2006).
  18. Li, X. et al. Transfer of large-area graphene films for high-performance transparent conductive electrodes. Nano Lett. 9, 43594363 (2009).
  19. Bushueva, E. G. et al. Double layer supercapacitor properties of onion-like carbon materials. Phys. Status Solidi B 245, 22962299 (2008).
  20. Park, S., Lian, K. & Gogotsi, Y. Pseudocapacitive behaviour of carbon nanoparticles modified by phosphomolybdic acid. J. Electrochem. Soc. 156, 921926 (2009).
  21. Plonska-Brzezinska, M. E., Palkar, A., Winkler, K. & Echegoyen, L. Electrochemical properties of small carbon nano-onions films. Electrochem. Solid State Lett. 13, 3538 (2010).
  22. Ugarte, D. Curling and closure of graphitic networks under electron-beam irradiation. Nature 359, 707709 (1992).
  23. Kuznetsov, V. L. et al. Effect of explosion conditions on the structure of detonation soots: ultradisperse diamond and onion carbon. Carbon 32, 873882 (1994).
  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, 25112518 (2007).
  25. Du, C. & Pan, N. High power density supercapacitor electrodes of carbon nanotube films by electrophoretic deposition. Nanotechnology 17, 53145318 (2006).
  26. Portet, C., Chmiola, J., Gogotsi, Y., Park, S. & Lian, K. Electrochemical characterizations of carbon nanomaterials by the cavity microelectrode technique. Electrochim. Acta 53, 76757680 (2008).
  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, 712 (2009).
  28. Lin, R. et al. Solvent effect on the ion adsorption from ionic liquid electrolyte into sub-nanometer carbon pores. Electrochim. Acta 54, 70257032 (2009).
  29. Kaempgen, M., Chan, C. K., Ma, J., Cui, Y. & Gruner, G. Printable thin film supercapacitors using single-walled carbon nanotubes. Nano. Lett. 9, 18721876 (2009).
  30. Taberna, P.-L., Simon, P. & Fauvarque, J. F. Electrochemical characteristics and impedance spectroscopy studies of carbon–carbon supercapacitors. J. Electrochem. Soc. 150, 292300 (2003).
  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).
  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, 292296 (2009).

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Author information


  1. CNRS, LAAS, 7 avenue du Colonel Roche, F-31077 Toulouse, France

    • David Pech,
    • Magali Brunet,
    • Hugo Durou &
    • Peihua Huang
  2. Université de Toulouse, UPS, INSA, INP, ISAE, LAAS, F-31077 Toulouse, France

    • David Pech,
    • Magali Brunet,
    • Hugo Durou &
    • Peihua Huang
  3. Department of Materials Science Engineering and A.J. Drexel Nanotechnology Institute, Drexel University, Philadelphia, Pennsylvania 19104, USA

    • Vadym Mochalin &
    • Yury Gogotsi
  4. Université Paul Sabatier de Toulouse, CIRIMAT, UMR CNRS 5085, 118 route de Narbonne, F-31062 Toulouse, France

    • Peihua Huang,
    • Pierre-Louis Taberna &
    • Patrice Simon


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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