Letter | Published:

Battery materials for ultrafast charging and discharging

Nature volume 458, pages 190193 (12 March 2009) | Download Citation

Subjects

Abstract

The storage of electrical energy at high charge and discharge rate is an important technology in today’s society, and can enable hybrid and plug-in hybrid electric vehicles and provide back-up for wind and solar energy. It is typically believed that in electrochemical systems very high power rates can only be achieved with supercapacitors, which trade high power for low energy density as they only store energy by surface adsorption reactions of charged species on an electrode material1,2,3. Here we show that batteries4,5 which obtain high energy density by storing charge in the bulk of a material can also achieve ultrahigh discharge rates, comparable to those of supercapacitors. We realize this in LiFePO4 (ref. 6), a material with high lithium bulk mobility7,8, by creating a fast ion-conducting surface phase through controlled off-stoichiometry. A rate capability equivalent to full battery discharge in 10–20 s can be achieved.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    Transition from supercapacitor to battery behavior in electrochemical energy-storage. J. Electrochem. Soc. 138, 1539–1548 (1991)

  2. 2.

    , , , & Nanostructured materials for advanced energy conversion and storage devices. Nature Mater. 4, 366–377 (2005)

  3. 3.

    , , & An asymmetric hybrid nonaqueous energy storage cell. J. Electrochem. Soc. 148, A930–A939 (2001)

  4. 4.

    & Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001)

  5. 5.

    & Role of electronic structure in the susceptibility of metastable transition-metal oxide structures to transformation. Chem. Rev. 104, 4513–4533 (2004)

  6. 6.

    , & Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997)

  7. 7.

    , , & Atomic-scale investigation of defects, dopants, and lithium transport in the LiFePO4 olivine-type battery material. Chem. Mater. 17, 5085–5092 (2005)

  8. 8.

    , & Li conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) olivine materials. Electrochem. Solid State Lett. 7, A30–A32 (2004)

  9. 9.

    , & Electronically conductive phospho-olivines as lithium storage electrodes. Nature Mater. 1, 123–128 (2002)

  10. 10.

    , , , & Electroactivity of natural and synthetic triphylite. J. Power Sources 97–8, 503–507 (2001)

  11. 11.

    , , & Nano-network electronic conduction in iron and nickel olivine phosphates. Nature Mater. 3, 147–152 (2004)

  12. 12.

    , , & Size effects on carbon-free LiFePO4 powders. Electrochem. Solid State Lett. 9, A352–A355 (2006)

  13. 13.

    & Synthesis of LiFePO4 nanoparticles in polyol medium and their electrochemical properties. Electrochem. Solid State Lett. 9, A439–A442 (2006)

  14. 14.

    , & Electron microscopy study of the LiFePO4 to FePO4 phase transition. Electrochem. Solid State Lett. 9, A295–A298 (2006)

  15. 15.

    , , & Ionic conductivities and structure of lithium phosphorus oxynitride glasses. J. Non-Cryst. Solids 183, 297–306 (1995)

  16. 16.

    & Transport properties of semiconducting phosphate glasses. Phys. Rev. B 6, 4629–4643 (1972)

  17. 17.

    , , & Study of electrical properties of MoO3-Fe2O3-P2O5 and SrO-Fe2O3-P2O5 glasses by impedance spectroscopy. II. J. Non-Cryst. Solids 330, 128–141 (2003)

  18. 18.

    , , & A self-ordered, crystalline-glass, mesoporous nanocomposite for use as a lithium-based storage device with both high power and high energy densities. Angew. Chem. Int. Edn Engl. 44, 797–802 (2005)

  19. 19.

    , , & Li-Fe-P-O2 phase diagram from first principles calculations. Chem. Mater. 20, 1798–1807 (2008)

  20. 20.

    Ionic-conduction in phosphate-glasses. J. Am. Ceram. Soc. 74, 1767–1784 (1991)

  21. 21.

    & Investigation of phosphate glasses with the general formula AxByP3O12 where A = Li, Na or K and B = Fe, Ga, Ti, Ge, V or Nb. J. Non-Cryst. Solids 201, 52–65 (1996)

  22. 22.

    et al. Effect of synthesis conditions on the properties of LiFePO4 for secondary lithium batteries. J. Power Sources 159, 237–240 (2006)

  23. 23.

    et al. Nanostructured materials for lithium-ion batteries: Surface conductivity vs. bulk ion/electron transport. Faraday Discuss. 134, 119–141 (2007)

  24. 24.

    , , & Surface chemistry of LiFePO4 studied by Mossbauer and X-ray photoelectron spectroscopy and its effect on electrochemical properties. J. Electrochem. Soc. 154, A283–A289 (2007)

  25. 25.

    , , , & Effect of structure on the Fe3+/Fe2+ redox couple in iron phosphates. J. Electrochem. Soc. 144, 1609–1613 (1997)

  26. 26.

    , & Inner-orbital photoelectron spectroscopy of alkali-metal halides, perchlorates, phosphates, and pyrophosphates. J. Am. Chem. Soc. 95, 751–755 (1973)

  27. 27.

    et al. Nanosize effect on high-rate Li-ion intercalation in LiCoO2 electrode. J. Am. Chem. Soc. 129, 7444–7452 (2007)

  28. 28.

    , , & First-principles study of surface properties of LiFePO4: Surface energy, structure, Wulff shape, and surface redox potential. Phys. Rev. B 76, 165435 (2007)

  29. 29.

    , , , & Carbon nanocoatings on active materials for Li-ion batteries. J. Eur. Ceram. Soc. 27, 909–913 (2007)

  30. 30.

    , , , & Mass and charge transport in hierarchically organized storage materials. Example: Porous active materials with nanocoated walls of pores. Solid State Ionics 177, 3015–3022 (2006)

Download references

Acknowledgements

B.K. thanks D. S. Yun and Y. Zhang for the help with transmission electron microscope measurements and K. Kang and Y. S. Meng for experimental help and discussions. Support from the US National Science Foundation through the Materials Research Science and Engineering Centers programme and the Batteries for Advanced Transportation Program of the US Department of Energy is gratefully acknowledged.

Author Contributions B.K. performed the experiments and G.C. supervised and analysed the work.

Author information

Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA

    • Byoungwoo Kang
    •  & Gerbrand Ceder

Authors

  1. Search for Byoungwoo Kang in:

  2. Search for Gerbrand Ceder in:

Corresponding author

Correspondence to Gerbrand Ceder.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains Supplementary Notes, Supplementary Figures S1-S6 with Legends, Supplementary Table 1, Supplementary Methods and Supplementary References.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature07853

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.