High-power lithium batteries from functionalized carbon-nanotube electrodes

Journal name:
Nature Nanotechnology
Volume:
5,
Pages:
531–537
Year published:
DOI:
doi:10.1038/nnano.2010.116
Received
Accepted
Published online

Abstract

Energy storage devices that can deliver high powers have many applications, including hybrid vehicles and renewable energy. Much research has focused on increasing the power output of lithium batteries by reducing lithium-ion diffusion distances, but outputs remain far below those of electrochemical capacitors and below the levels required for many applications. Here, we report an alternative approach based on the redox reactions of functional groups on the surfaces of carbon nanotubes. Layer-by-layer techniques are used to assemble an electrode that consists of additive-free, densely packed and functionalized multiwalled carbon nanotubes. The electrode, which is several micrometres thick, can store lithium up to a reversible gravimetric capacity of ~200 mA h g−1electrode while also delivering 100 kW kgelectrode−1 of power and providing lifetimes in excess of thousands of cycles, both of which are comparable to electrochemical capacitor electrodes. A device using the nanotube electrode as the positive electrode and lithium titanium oxide as a negative electrode had a gravimetric energy ~5 times higher than conventional electrochemical capacitors and power delivery ~10 times higher than conventional lithium-ion batteries.

At a glance

Figures

  1. Physical characteristics of LBL-MWNT electrodes.
    Figure 1: Physical characteristics of LBL-MWNT electrodes.

    a, Digital image of representative MWNT electrodes on ITO-coated glass slides. The number on each image indicates the number of bilayers (n) in (MWNT–NH2/MWNT–COOH)n. b, Thickness of the LBL-MWNT electrodes as a function of the number of bilayers. A linear relationship is apparent for LBL-MWNT electrodes with thicknesses from 20 nm to 3 µm. Error bars show the standard deviation of the thickness, computed from three samples for each thickness. Transmittance measured at 550 nm as a function of the number of bilayers is shown in the inset. Error bars show the standard deviation of transmittance computed from three measurements. c, SEM cross-sectional image of an LBL-MWNT electrode on an ITO-coated glass slide after heat treatments. A higher-magnification image is shown in the inset, revealing that MWNTs are entangled in the direction perpendicular to the electrode surface. d, TEM image of an LBL-MWNT electrode slice, showing pore sizes of the order of ~20 nm.

  2. Potential-dependent electrochemical behaviour of LBL-MWNT and functionalized MWNT composite electrodes measured in two-electrode lithium cells.
    Figure 2: Potential-dependent electrochemical behaviour of LBL-MWNT and functionalized MWNT composite electrodes measured in two-electrode lithium cells.

    a, Cyclic voltammogram data for an LBL-MWNT electrode obtained with different upper- and lower-potential limits. Reducing the lower-potential limit from 3 to 1.5 V versus Li resulted in increased current and gravimetric capacitance. b, Cyclic voltammogram data for an LBL-MWNT electrode before and after 500 °C H2-treatment in 4% H2 and 96% Ar by volume for 10 h. c, XPS C 1s spectra of an LBL-MWNT electrode before and after this additional heat treatment, which is seen to remove a considerable amount of surface oxygen and nitrogen functional groups from the MWNT surface. d, Cyclic voltammogram data for an LBL-MWNT electrode and composite electrodes of pristine MWNT, MWNT–COOH and MWNT–NH2, with the LBL-MWNT electrode having higher current and capacitance normalized to the MWNT weight than the composite electrodes. The composite electrodes consisted of 20 wt% PVdF and 80 wt% MWNT. Composite MWNT electrodes were prepared from slurry casting and dried at 100 °C for 12 h under vacuum. The thickness of the LBL-MWNT electrode was 0.3 µm, and the thicknesses of the pristine MWNT, MWNT–COOH and MWNT–NH2 composite electrodes were 40, 50 and 30 µm, respectively. The density of the composite electrodes was ~0.45 g cm−3.

  3. Electrochemical characteristics of LBL-MWNT electrodes in two-electrode lithium cells with 1 M LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (volume ratio 3:7).
    Figure 3: Electrochemical characteristics of LBL-MWNT electrodes in two-electrode lithium cells with 1 M LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (volume ratio 3:7).

    a, Cyclic voltammogram data for a 0.3-μm LBL-MWNT electrode over a range of scan rates. The current at ~3 V versus scan rate is shown in the inset. b, Charge and discharge profiles of an electrode of 0.3 µm obtained over a wide range of gravimetric current densities between 1.5 and 4.5 V versus Li. Before each charge and discharge measurement for the data in Fig. 3b, cells were held at 1.5 and 4.5 V for 30 min, respectively. c, Cyclic voltammogram data for electrodes with different thicknesses collected at a scanning rate of 1 mV s−1 in the voltage range 1.5–4.5 V versus Li. The integrated charge increases linearly with electrode thickness, as shown in the inset.

  4. Gravimetric energy and power densities, and cycle life of LBL-MWNT electrodes obtained from measurements of two-electrode cells.
    Figure 4: Gravimetric energy and power densities, and cycle life of LBL-MWNT electrodes obtained from measurements of two-electrode cells.

    a, Ragone plot for Li/LBL-MWNT cells with different thicknesses (~0.3–3.0 µm). The corresponding loading density of LBL-MWNT electrodes ranges from ~0.025–0.25 mg cm−2. Only the LBL-MWNT weight was considered in the gravimetric energy and power density calculations. b, Gravimetric capacities of Li/LBL-MWNT cells as a function of cycle number, measured at a current density of ~0.25 A g−1 once every 100 cycles, after voltage holds at the end of charging and discharging for 30 min. Within each 100 cycles, these cells were cycled at an accelerated rate of ~2.5 A g−1. c, Voltage profiles of a 1.5-μm electrode in the first and 1,000th cycles, for which negligible changes were noted. d, Ragone plot for Li/LBL-MWNT (black squares), LTO/LBL-MWNT (green circles), LTO/LiNi0.5Mn1.5O4 (grey circles) and LBL-MWNT/LBL-MWNT (orange triangles) cells with 4.5 V versus Li as the upper-potential limit. The thickness of the LBL-MWNT electrode was 0.3 µm for asymmetric Li/LBL-MWNT and LTO/LBL-MWNT, and 0.4 µm for symmetric LBL-MWNT/LBL-MWNT. Gravimetric energy and maximum power densities were reduced for the LTO/LBL-MWNT cells subjected to the same testing conditions due to a lower cell voltage.

  5. Schematic of the energy storage mechanism of LBL-MWNT electrodes.
    Figure 5: Schematic of the energy storage mechanism of LBL-MWNT electrodes.

    Faradaic reactions between surface oxygen functional species (orange arrows) and Li schematically illustrated on an HRTEM image of the LBL-MWNT electrodes. Intact graphite layers inside the MWNTs (white arrows) are indicated as electron conduction channels.

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Author information

  1. These authors contributed equally to this work

    • Seung Woo Lee &
    • Naoaki Yabuuchi

Affiliations

  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    • Seung Woo Lee,
    • Byeong-Su Kim &
    • Paula T. Hammond
  2. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    • Naoaki Yabuuchi,
    • Betar M. Gallant,
    • Shuo Chen &
    • Yang Shao-Horn
  3. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    • Yang Shao-Horn

Contributions

Y.S.H., S.W.L., N.Y. and B.M.G. conceived and designed the experiments. S.W.L., B.S.K. and P.T.H. were involved with the methods of film assembly. S.C. carried out microscopy analysis. Y.S.H., S.W.L., N.Y. and B.M.G. co-wrote the manuscript, and P.T.H. edited the manuscript.

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The authors declare no competing financial interests.

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