High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance

Journal name:
Nature Materials
Volume:
12,
Pages:
518–522
Year published:
DOI:
doi:10.1038/nmat3601
Received
Accepted
Published online

Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2·xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1, 2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 μm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

At a glance

Figures

  1. Kinetic analysis of the electrochemical behaviour of
T-Nb2O5.
    Figure 1: Kinetic analysis of the electrochemical behaviour of T-Nb2O5.

    a, Cyclic voltammograms from 100 to 500 mV s−1 demonstrate the high-rate capability of the material. bb-value determination of the peak anodic and cathodic currents shows that this value is approximately 1 up to 50 mV s−1. This indicates that even at the peak currents, charge storage is capacitive. c, Capacity versus v−1/2 allows for the separation of diffusion-controlled capacity from capacitive-controlled capacity; two distinct kinetic regions emerge when the sweep rate is varied from 1 to 500 mV s−1. The dashed diagonal line corresponds to the extrapolation of the infinite sweep rate capacitance using the capacity between 2 and 20 mV s−1. d, The variation of the cathodic peak voltage with the sweep rate exhibits a region of small peak separation followed by increased separation at 20 mV s−1, and represents another method of identifying systems with facile intercalation kinetics.

  2. Electrochemical cycling of a 40-μm-thick
T-Nb2O5 electrode.
    Figure 2: Electrochemical cycling of a 40-μm-thick T-Nb2O5 electrode.

    a, Galvanostatic cycling of a thick Nb2O5 electrode at a 10C rate. b, Comparison of the rate capability of T-Nb2O5 with a high-rate lithium-ion anode, Li4Ti5O12, at various C-rates (Li4Ti5O12 data reproduced from ref. 16).

  3. Structural features of lithium intercalation in
T-Nb2O5.
    Figure 3: Structural features of lithium intercalation in T-Nb2O5.

    a, The structure of T-Nb2O5 stacked along the c axis demonstrates the layered arrangement of oxygen (red) and niobium (inside polyhedra) atoms along the ab plane. b, Derivative of Nb K-edge X-ray absorption near-edge spectra at selected cell voltages, showing a systematic shift to lower energies as Nb5+ is reduced to Nb4+. ck2-weighted Fourier-transformed Nb K-edge EXAFS at selected cell voltages.

References

  1. Brezesinski, K. et al. Pseudocapacitive contributions to charge storage in highly ordered mesoporous Group V transition metal oxides with iso-oriented layered nanocrystalline domains. J. Am. Chem. Soc. 132, 69826990 (2010).
  2. Kim, J. W., Augustyn, V. & Dunn, B. The effect of crystallinity on the rapid pseudocapacitive response of Nb2O5. Adv. Energy Mater. 2, 141148 (2012).
  3. Conway, B. E. Electrochemical Supercapacitors: Scientific Fundamentals and Technological Applications (Kluwer-Academic, 1999).
  4. Herrero, E., Buller, L. J. & Abruña, H. D. Underpotential deposition at single crystal surfaces of Au, Pt, Ag and other materials. Chem. Rev. 101, 18971930 (2001).
  5. Huggins, R. A. Supercapacitors and electrochemical pulse sources. Solid State Ion. 134, 179195 (2000).
  6. Angerstein-Kozlowska, H., Klinger, J. & Conway, B. E. Computer simulations of the kinetic behavior of surface reactions driven by a linear potential sweep. Part I: Model 1-electron reaction with a single adsorbed species. J. Electroanal. Chem. 75, 4560 (1977).
  7. Brezesinski, T., Wang, J., Polleux, J., Dunn, B. & Tolbert, S. H. Templated nanocrystal-based porous TiO2 films for next-generation electrochemical capacitors. J. Am. Chem. Soc. 131, 18021809 (2009).
  8. Lindström, H. et al. Li+ insertion in TiO2 (anatase). 2. Voltammetry on nanoporous films. J. Phys. Chem. B 101, 77177722 (1997).
  9. Come, J., Taberna, P-L., Hamelet, S., Masquelier, C. & Simon, P. Electrochemical kinetic study of LiFePO4 using cavity microelectrode. J. Electrochem. Soc. 158, A1090A1093 (2011).
  10. Ohzuku, T., Sawai, K. & Hirai, T. Electrochemistry of L-niobium pentoxide in a lithium/non-aqueous cell. J. Power Sources 19, 287299 (1987).
  11. Park, M., Zhang, X., Chung, M., Less, G. B. & Sastry, A. M. A review of conduction phenomena in Li-ion batteries. J. Power Sources 195, 79047929 (2010).
  12. Ardizzone, S., Fregonara, G. & Trasatti, S. ‘Inner’ and ‘outer’ active surface of RuO2 electrodes. Electrochim. Acta 35, 263267 (1990).
  13. Baronetto, D., Krstajić, N. & Trasatti, S. Reply to Note on a method to interrelate inner and outer electrode areas by H. Vogt. Electrochim. Acta 39, 23592362 (1994).
  14. Conway, B. E. Transition from ‘supercapacitor’ to ‘battery’ behavior in electrochemical energy storage. J. Electrochem. Soc. 138, 15391548 (1991).
  15. Xia, H., Lu, L. & Ceder, G. Substrate effect on the microstructure and electrochemical properties of LiCoO2 thin films grown by PLD. J. Alloys Compd. 417, 304310 (2006).
  16. Zhang, N. Q. et al. Facile preparation of nanocrystalline Li4Ti5O12 and its high electrochemical performance as anode material for lithium-ion batteries. Electrochem. Commun. 13, 654656 (2011).
  17. Kato, K. & Tamura, S. The crystal structure of T-Nb2O5. Acta Cryst. B31, 673677 (1975).
  18. Liu, C-P., Zhou, F. & Ozolins, V. First principles study for lithium intercalation and diffusion behavior in orthorhombic Nb2O5 electrochemical supercapacitor American Physical Society March Meeting 2012 abstr. B26.00003. Accessed March 20, 2013. http://meetings.aps.org/link/BAPS.2012.MAR.B26.3.
  19. Kodama, R., Terada, Y., Nakai, I., Komaba, S. & Kumagai, N. Electrochemical and in situ XAFS-XRD investigation of Nb2O5 for rechargeable lithium batteries. J. Electrochem. Soc. 153, A583A588 (2006).
  20. Kumagai, N., Koishikawa, Y., Komada, S. & Koshiba, N. Thermodynamics and kinetics of lithium intercalation into Nb2O5 electrodes for a 2 V rechargeable lithium battery. J. Electrochem. Soc. 146, 32033210 (1999).
  21. Long, J. W., Swider, K. E., Merzbacher, C. I. & Rolison, D. R. Voltammetric characterization of ruthenium oxide-based aerogels and other RuO2 solids: The nature of capacitance in nanostructured materials. Langmuir 15, 780785 (1999).
  22. Zheng, J. P., Cygan, P. J. & Jow, T. R. Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. J. Electrochem. Soc. 142, 26992703 (1995).
  23. Dmowski, W., Egami, T., Swider-Lyons, K. E., Love, C. T. & Rolison, D. R. Local atomic structure and conduction mechanism of nanocrystalline hydrous RuO2 from X-ray scattering. J. Phys. Chem. B 106, 1267712683 (2002).
  24. Liu, Y., Zhou, F. & Ozolins, V. Ab initio study of the charge-storage mechanisms in RuO2-based electrochemical ultracapacitors. J. Phys. Chem. C 116, 14501457 (2012).

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Affiliations

  1. Department of Materials Science and Engineering, University of California, Los Angeles, California 90095, USA

    • Veronica Augustyn,
    • Jong Woung Kim &
    • Bruce Dunn
  2. Department of Materials Science, Université Paul Sabatier, CIRIMAT UMR CNRS 5085, Toulouse 31062, France

    • Jérémy Come,
    • Pierre-Louis Taberna &
    • Patrice Simon
  3. Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, France

    • Jérémy Come,
    • Pierre-Louis Taberna &
    • Patrice Simon
  4. Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, USA

    • Michael A. Lowe &
    • Héctor D. Abruña
  5. Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA

    • Sarah H. Tolbert

Contributions

V.A., J.C., M.A.L. and J.W.K.: experimental work, data analysis. P-L.T., S.H.T., H.D.A., P.S., B.D.: project planning, data analysis.

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The authors declare no competing financial interests.

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