Cation Ordering in Substituted LiMn2O4 Spinels

MRS Online Proceedings Library volume 756, Article number: 54 (2002) Cite this article

Abstract

In order to overcome the capacity fading of LiMn2O4 in lithium batteries, various substitutions for Mn have been proposed. The structural implications of substitution in LiMn2-xMxO4 with x = 0.5, i.e. with exactly 1/4 octahedral (16d-site) cations replaced, are investigated here. For this stoichiometry, cationic ordering was known previously for M = Mg and Zn, resulting in a superstructure with primitive cubic symmetry. Given the poor chemical contrast of X-ray diffraction between Mn and Co, Ni or Cu, LiMn1.5M0.5O4 samples were studied by neutron diffraction and IR spectroscopy. Both techniques show the occurence of cationic ordering for M = Ni and Cu, but not for Co or Ga. In the case of M = Zn, further complication due Li/Zn ordering on the tetrahedral (8a) site is well resolved by FTIR. This investigation shows that the main driving force for octahedral cation ordering is the charge difference between Mn and M atoms.

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

Access options

Buy single article

Instant access to the full article PDF.

US$ 39.95

Tax calculation will be finalised during checkout.

References

  1. 1.

    M. M. Thackeray, J. Ceram. Soc. Amer. 82, 3347 (1999).

    CAS  Article  Google Scholar 

  2. 2.

    M. Broussely, P. Biensan, B. Simon, Electrochim. Acta 45, 3 (1999).

    CAS  Article  Google Scholar 

  3. 3.

    J. M. Tarascon, E. Wang, F.K. Shokoohi, W.R. McKinnon, S. Colson, J. Electrochem Soc. 138, 2859(1991).

    CAS  Article  Google Scholar 

  4. 4.

    H. Kawai, M. Nagata, H. Tukamoto, A.R. West, J. Power Sources 81–82 67 (1999).

    Article  Google Scholar 

  5. 5.

    G. Blasse, Philips Res. Rept. 1 (1964); JCPDS card 32–573.

    Google Scholar 

  6. 6.

    J.S. Braithwaite, C.R.A. Catlow, J.H. Harding and J.D. Gale, Phys. Chem. Chem. Phys. 2 38 (2000).

    Google Scholar 

  7. 7.

    F. Le Cras, D. Bloch, M. Anne and P. Strobel, Solid State Ionics 89 203 (1996).

    Article  Google Scholar 

  8. 8.

    P. Strobel, A. Ibarra Palos, F. Le Cras, M. Anne, J. Mater. Chem. 10 429 (2000).

    CAS  Article  Google Scholar 

  9. 9.

    J.C. Joubert and A. Durif, C.R. Acad. Sci. Paris 258 4482 (1964); JCPDS card 74–1260.

    CAS  Google Scholar 

  10. 10.

    V.F. Sears, AECL Report 8490 (1984).

  11. 11.

    P. Strobel, C. Poinsignon, A. Ibarra Palos and M. Anne, J. Solid State Chem. (submitted).

  12. 12.

    W.B. White and B.A. DeAngelis, Spectrochim. Acta 23A 985 (1967).

    Article  Google Scholar 

  13. 13.

    J. Preudhomme, Ann. Chim. (France) 9 31 (1974).

    CAS  Google Scholar 

  14. 14.

    T.J. Richardson, S.J. Wen, K.A. Striebel, P.N. Ross and E.J. Cairns, Mater. Res. Bull. 32 609 (1997).

    CAS  Article  Google Scholar 

  15. 15.

    C. Julien, M. Massot, E. Haro-Poniatowski, GA. Nazri, A. Rougier, MRS Proc. 496 415 (1998).

    CAS  Article  Google Scholar 

  16. 16.

    B. Ammundsen, G.R. Burns, M.S. Islam, H. Kanoh and J. RoziDre, J. Phys. Chem. B 103 5175(1999).

    CAS  Article  Google Scholar 

  17. 17.

    G.C. Allen and M. Paul, Appl. Spectrosc. 49 451 (1995).

    CAS  Article  Google Scholar 

  18. 18.

    V.AM. Brabers, Phys. Stat. Sol. A 12 629 (1972).

    CAS  Article  Google Scholar 

  19. 19.

    M. Laarj, S. Kacim and B. Gillot, J. Solid State Chem. 125 67 (1996).

    CAS  Article  Google Scholar 

Download references

Author information

Affiliations

  1. Laboratoire de Cristallographie CNRS BP 166, 38042, Grenoble Cedex 9, France

    P. Strobel & A. Ibarra-Palos

  2. LEPMI, ENSEEG, BP 75, 38402, Saint-Martin d’Hères Cedex, France

    C. Poinsignon

Authors
  1. P. Strobel
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. Ibarra-Palos
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Poinsignon
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to P. Strobel.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Strobel, P., Ibarra-Palos, A. & Poinsignon, C. Cation Ordering in Substituted LiMn2O4 Spinels. MRS Online Proceedings Library 756, 54 (2002). https://doi.org/10.1557/PROC-756-EE5.4

Download citation