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.

  • Article
  • Published:

Electronically conductive phospho-olivines as lithium storage electrodes

Nature Materials volume 1, pages 123–128 (2002)Cite this article

Abstract

Lithium transition metal phosphates have become of great interest as storage cathodes for rechargeable lithium batteries because of their high energy density, low raw materials cost, environmental friendliness and safety. Their key limitation has been extremely low electronic conductivity, until now believed to be intrinsic to this family of compounds. Here we show that controlled cation non-stoichiometry combined with solid-solution doping by metals supervalent to Li+ increases the electronic conductivity of LiFePO4 by a factor of ∼108. The resulting materials show near-theoretical energy density at low charge/discharge rates, and retain significant capacity with little polarization at rates as high as 6,000 mA g−1. In a conventional cell design, they may allow development of lithium batteries with the highest power density yet.

Access through your institution
Buy or subscribe

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

Access options

Access through your institution

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

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

Figure 1: Doped olivines of stoichiometry Li 1− x M x FePO 4 show electrical conductivity at room temperature that is a factor of ∼10 8 greater than in undoped LiFePO 4 , and absolute values >10 −3 S cm −1 over the temperature range −20 °C to +150 °C of interest for battery applications.
Figure 2: Ordered-olivine structure of LiFePO4: Pmnb space group, with Li in M1 site and Fe in M2 site.
Figure 3: Morphologies of undoped (insulating) and doped (conductive) powders.
Figure 4: Elemental mapping by scanning TEM (STEM).
Figure 5: X-ray diffraction of various powders showing the effect of cation stoichiometry on dopant solid-solubility.
Figure 6: Electrochemical test data for electronically conductive olivine.

Similar content being viewed by others

References

  1. Padhi, A.K., Najundaswamy, K.S. & Goodenough, J.B. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J. Electrochem. Soc. 144, 1188–1194 (1997).

    Article  CAS  Google Scholar 

  2. Padhi, A.K., Najundaswamy, K.S., Masquelier, C., Okada, S. & Goodenough, J.B. Effect of structure on the Fe3+/Fe2+ redox couple in iron phosphates. J. Electrochem. Soc. 144, 1609–1613 (1997).

    Article  CAS  Google Scholar 

  3. Najundaswamy, K.S. et al. Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds. Solid State Ionics 92, 1–10 (1996).

    Article  Google Scholar 

  4. Tarascon, J.-M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Article  CAS  Google Scholar 

  5. Gaubicher, J., Le Mercier, T., Chabre, Y., Angenault, J. & Quarton, M. Li/β-VOPO4: a new 4V system for lithium batteries. J. Electrochem. Soc. 146, 4375–4379 (1999).

    Article  CAS  Google Scholar 

  6. Amine, K., Yasuda, H. & Yamachi, M. Olivine LiCoPO4 as 4.8V electrode material for lithium batteries. Electrochem. Solid State Lett. 3, 178–179 (2000).

    Article  CAS  Google Scholar 

  7. Yamada, A., Chung, S.C. & Hinokuma, K. Optimized LiFePO4 for lithium battery cathodes. J. Electrochem. Soc. 148, A224–A229 (2001).

    Article  CAS  Google Scholar 

  8. Andersson, A.S., Thomas, J.O., Kalska, B. & Häggström, L. Thermal stability of LiFePO4-based cathodes. Electrochem. Solid State Lett. 3, 66–68 (2000).

    Article  CAS  Google Scholar 

  9. Ravet, N. et al. Improved iron based cathode material. Abstract No. 127, Electrochemical Society Fall meeting, Honolulu, Hawaii, (1999).

  10. Huang, H., Yin, S.-C. & Nazar, L.F. Approaching theoretical capacity of LiFePO4 at room temperature at high rates. Electrochem. Solid State Lett. 4, A170–A172 (2001).

    Article  CAS  Google Scholar 

  11. Prosini, P.P., Zane, D. & Pasquali, M. Improved electrochemical performance of a LiFePO4-based composite cathode. Electrochim. Acta 46, 3517–3523 (2001).

    Article  CAS  Google Scholar 

  12. Yang, S., Song, Y., Zavalij, P.Y. & Whittingham, M.S. Reactivity, Stability and electrochemical behavior of lithium iron phosphates. Electrochem. Comm. 4, 239–244 (2002).

    Article  CAS  Google Scholar 

  13. Molenda, J., Stoklosa, A. & Bak, T. Modifications in the electronic structure of cobalt bronze LixCoO2 and the resulting electrochemical properties. Solid State Ionics 36, 53–58 (1989).

    Article  CAS  Google Scholar 

  14. Shimakawas, Y., Numata, T. & Tabuchi, J. Verwey-type transition and magnetic properties of the LiMn2O4 spinels. J. Solid State Chem. 131, 138–143 (1997).

    Article  Google Scholar 

  15. Kawaia, H., Nagatab, M., Kageyamac, H., Tukamoto, H. & West, A. R.5V lithium cathodes based on spinel solid solutions Li2Co1+XMn3−XO8: −1≤ X≤1. Electrochim. Acta 45, 315–327 (1999).

    Article  Google Scholar 

  16. Papike, J.J. & Cameron, M. Crystal chemistry of silicate minerals of geophysical interest. Rev. Geophys. Space Phys. 14, 37–80 (1976).

    Article  CAS  Google Scholar 

  17. Streltsov, V., Belokoneva, E.L., Tsirelson, V.G. & Hansen, N.K. Multipole analysis of the electron density in tryphylite, LiFePO4, using X-ray diffraction data. Acta Crystallogr. B 49, 147–153 (1993).

    Article  Google Scholar 

  18. Schock, R.N., Duba, A.G. & Shankland, T.J. Electrical conductivity in olivine. J. Geophys. Res. 94, 5829–5839 (1989).

    Article  CAS  Google Scholar 

  19. Alonso, J.A., Rasines, I., Rodriguez-Carvajal, J. & Torrance, J.B. Hole and electron doping of R2BaNiO5 (R = rare earths). J. Solid State Chem. 109, 231–240 (1994).

    Article  CAS  Google Scholar 

  20. Moriga, T. et al. Characterization of oxygen-deficient phases appearing in reduction of the perovskite-type LaNiO3 to La2Ni2O5 . Solid State Ionics 79, 252–255 (1995).

    Article  CAS  Google Scholar 

  21. Andersson, A.S., Kalska, B., Häggström, L. & Thomas, J.O. Lithium extraction/insertion in LiFePO4: an X-ray diffraction and Mössbauer spectroscopy study. Solid State Ionics 130, 41–52 (2000).

    Article  CAS  Google Scholar 

  22. Atkinson, A. in Advances in Ceramics Vol. 23 (eds Catlow, C.R.A. & Macrodt, W.C.) 3–26 (American Ceramic Society, Westerville, 1987).

    Google Scholar 

  23. Peterson, N.L. Point defects and diffusion mechanisms in the monoxide of the iron-group metals. Mater. Sci. Forum 1, 85–108 (1984).

    Article  CAS  Google Scholar 

  24. Kofstad, P. Nonstoichiometry, Diffusion, and Electrical Conductivity in Binary Metal Oxides 213–264 (Wiley, New York, 1972).

    Google Scholar 

  25. Shannon, R.D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. A 32, 751–767 (1976).

    Article  Google Scholar 

  26. Goñi, A. et al. Magnetic properties of the LiMPO4 (M = Co, Ni) compounds. J. Magn. Magn. Mater. 164, 251–255 (1996).

    Article  Google Scholar 

  27. Kornev, I. et al. Magnetoelectric properties of LiCoPO4: microscopic theory. Physica B 271, 304–308 (1999).

    Article  CAS  Google Scholar 

  28. Xu, Y.-N., Ching, W.Y., Chung, S.-Y., Bloking, J.T. & Chiang, Y.-M. Electronic structure and electronic conductivity of undoped LiFePO4 . Appl. Phys. Lett. (submitted).

  29. Kröger, F.A. The Chemistry of Imperfect Crystals (North-Holland, Amsterdam, 1964).

    Book  Google Scholar 

Download references

Acknowledgements

We thank W. D. Moorehead, P. Limthongkul and B. P. Nunes for assistance. This research was supported by the US Department of Energy, Basic Energy Sciences, Grant No. DE-FG02-87-ER45307, and used Shared Experimental Facilities at MIT supported by NSF Grant No. 94004-DMR.

Author information

Authors and Affiliations

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

    Sung-Yoon Chung, Jason T. Bloking & Yet-Ming Chiang

Authors
  1. Sung-Yoon Chung
    View author publications

    You can also search for this author inPubMed Google Scholar

  2. Jason T. Bloking
    View author publications

    You can also search for this author inPubMed Google Scholar

  3. Yet-Ming Chiang
    View author publications

    You can also search for this author inPubMed Google Scholar

Corresponding author

Correspondence to Yet-Ming Chiang.

Ethics declarations

Competing interests

The authors declare personal financial interests in a commercial entity to which patent filings based on certain of the subject matter in this publication have been licensed by Massachusetts Institute of Technology.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Chung, SY., Bloking, J. & Chiang, YM. Electronically conductive phospho-olivines as lithium storage electrodes. Nature Mater 1, 123–128 (2002). https://doi.org/10.1038/nmat732

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat732

Search

Advanced 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