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

Journal name:
Nature Nanotechnology
Volume:
5,
Pages:
651–654
Year published:
DOI:
doi:10.1038/nnano.2010.162
Received
Accepted
Published online

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.

At a glance

Figures

  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.

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Author information

Affiliations

  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

Contributions

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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The authors declare no competing financial interests.

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