Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance

Abstract

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.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Kinetic analysis of the electrochemical behaviour of T-Nb2O5.
Figure 2: Electrochemical cycling of a 40-μm-thick T-Nb2O5 electrode.
Figure 3: Structural features of lithium intercalation in T-Nb2O5.

Similar content being viewed by others

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, 6982–6990 (2010).

    Article  CAS  Google Scholar 

  2. Kim, J. W., Augustyn, V. & Dunn, B. The effect of crystallinity on the rapid pseudocapacitive response of Nb2O5 . Adv. Energy Mater. 2, 141–148 (2012).

    Article  CAS  Google Scholar 

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

    Book  Google Scholar 

  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, 1897–1930 (2001).

    Article  CAS  Google Scholar 

  5. Huggins, R. A. Supercapacitors and electrochemical pulse sources. Solid State Ion. 134, 179–195 (2000).

    Article  CAS  Google Scholar 

  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, 45–60 (1977).

    Article  CAS  Google Scholar 

  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, 1802–1809 (2009).

    Article  CAS  Google Scholar 

  8. Lindström, H. et al. Li+ insertion in TiO2 (anatase). 2. Voltammetry on nanoporous films. J. Phys. Chem. B 101, 7717–7722 (1997).

    Article  Google Scholar 

  9. Come, J., Taberna, P-L., Hamelet, S., Masquelier, C. & Simon, P. Electrochemical kinetic study of LiFePO4 using cavity microelectrode. J. Electrochem. Soc. 158, A1090–A1093 (2011).

    Article  CAS  Google Scholar 

  10. Ohzuku, T., Sawai, K. & Hirai, T. Electrochemistry of L-niobium pentoxide in a lithium/non-aqueous cell. J. Power Sources 19, 287–299 (1987).

    Article  CAS  Google Scholar 

  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, 7904–7929 (2010).

    Article  CAS  Google Scholar 

  12. Ardizzone, S., Fregonara, G. & Trasatti, S. ‘Inner’ and ‘outer’ active surface of RuO2 electrodes. Electrochim. Acta 35, 263–267 (1990).

    Article  CAS  Google Scholar 

  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, 2359–2362 (1994).

    Article  CAS  Google Scholar 

  14. Conway, B. E. Transition from ‘supercapacitor’ to ‘battery’ behavior in electrochemical energy storage. J. Electrochem. Soc. 138, 1539–1548 (1991).

    Article  CAS  Google Scholar 

  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, 304–310 (2006).

    Article  CAS  Google Scholar 

  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, 654–656 (2011).

    Article  CAS  Google Scholar 

  17. Kato, K. & Tamura, S. The crystal structure of T-Nb2O5 . Acta Cryst. B31, 673–677 (1975).

    Article  CAS  Google Scholar 

  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, A583–A588 (2006).

    Article  CAS  Google Scholar 

  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, 3203–3210 (1999).

    Article  CAS  Google Scholar 

  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, 780–785 (1999).

    Article  CAS  Google Scholar 

  22. Zheng, J. P., Cygan, P. J. & Jow, T. R. Hydrous ruthenium oxide as an electrode material for electrochemical capacitors. J. Electrochem. Soc. 142, 2699–2703 (1995).

    Article  CAS  Google Scholar 

  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, 12677–12683 (2002).

    Article  CAS  Google Scholar 

  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, 1450–1457 (2012).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Molecularly Engineered Energy Materials and the Energy Materials Center at Cornell, Energy Frontiers Research Centers funded by the US DOE Office of Basic Energy Sciences (DE-SC001342 and DE-SC0001086, respectively). XAS was performed at the Cornell High Energy Synchrotron Source, supported by the NSF and NIH/NIGMS (DMR-0936384). M.A.L. acknowledges support from the US DOD National Defense Science and Engineering Fellowship. J.C. was supported by Delegation Generale pour l’Armement (DGA). P.S. and P-L.T. acknowledge the support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543—IONACES) and the Chair of Excellence ‘Embedded multi-functional nanomaterials’ from the EADS Foundation.

Author information

Authors and Affiliations

Authors

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.

Corresponding author

Correspondence to Bruce Dunn.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 1190 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Augustyn, V., Come, J., Lowe, M. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nature Mater 12, 518–522 (2013). https://doi.org/10.1038/nmat3601

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat3601

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing