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:

A new active Li–Mn–O compound for high energy density Li-ion batteries

Nature Materials volume 15, pages 173–177 (2016)Cite this article

Subjects

Abstract

The search for new materials that could improve the energy density of Li-ion batteries is one of today’s most challenging issues. Many families of transition metal oxides as well as transition metal polyanionic frameworks have been proposed during the past twenty years1,2. Among them, manganese oxides, such as the LiMn2O4 spinel or the overlithiated oxide Li[Li1/3Mn2/3]O2, have been intensively studied owing to the low toxicity of manganese-based materials and the high redox potential of the Mn3+/Mn4+ couple. In this work, we report on a new electrochemically active compound with the ‘Li4Mn2O5’ composition, prepared by direct mechanochemical synthesis at room temperature. This rock-salt-type nanostructured material shows a discharge capacity of 355 mAh g−1, which is the highest yet reported among the known lithium manganese oxide electrode materials. According to the magnetic measurements, this exceptional capacity results from the electrochemical activity of the Mn3+/Mn4+ and O2−/O− redox couples, and, importantly, of the Mn4+/Mn5+ couple also.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: XRPD analysis.
Figure 2: TEM analyses.
Figure 3: Electrochemical properties.
Figure 4: Magnetic measurements.

Similar content being viewed by others

References

  1. Ellis, B. L. et al. Positive electrode materials for Li-ion and Li-batteries. Chem. Mater. 22, 691–714 (2010).

    Article  CAS  Google Scholar 

  2. Song, H. K. et al. Recent progress in nanostructured cathode materials for lithium secondary batteries. Adv. Funct. Mater. 20, 3818–3834 (2010).

    Article  CAS  Google Scholar 

  3. Tarascon, J. M. Key challenges in future Li-battery research. Phil. Trans. R. Soc. A 368, 3227–3241 (2010).

    Article  Google Scholar 

  4. Amatucci, G. et al. Optimization of insertion compounds such as LiMn2O4 for Li-ion batteries. J. Electrochem. Soc. 149, K31–K46 (2002).

    Article  CAS  Google Scholar 

  5. Thackeray, M. M. et al. Structural fatigue in spinel electrodes in high voltage (4V) Li/LixMn2O4 cells. Electrochem. Solid State Lett. 1, 7–9 (1998).

    Article  CAS  Google Scholar 

  6. Jang, D. H. et al. Electrolyte effects on spinel dissolution and cathodic capacity losses in 4 V Li/LiMn2O4 cells. J. Electrochem. Soc. 143, 2204–2211 (1996).

    Article  CAS  Google Scholar 

  7. Huang, H. et al. Correlating capacity loss of stoichiometric and nonstoichiometric lithium manganese oxide spinel electrodes with their structural integrity. J. Electrochem. Soc. 146, 3649–3654 (1999).

    Article  CAS  Google Scholar 

  8. Shin, Y. et al. Factors influencing the capacity fade of spinel lithium manganese oxides. J. Electrochem. Soc. 151, A204–A208 (2004).

    Article  CAS  Google Scholar 

  9. Deng, B. H. et al. Capacity fading with oxygen loss for manganese spinels upon cycling at elevated temperatures. J. Power Sources 180, 864–868 (2008).

    Article  CAS  Google Scholar 

  10. Xia, Y. G. et al. Improved cycling performance of oxygen-stoichiometric spinel Li1+xAlyMn2−x−yO4+δ at elevated temperature. Electrochim. Acta 52, 4708–4714 (2007).

    Article  CAS  Google Scholar 

  11. Kim, J. S. et al. Layered xLiMO2 ⋅ (1 − x)Li2M′O3 electrodes for lithium batteries: A study of 0.95LiMn0.5Ni0.5O2 ⋅ 0.05Li2TiO3 . Electrochem. Commun. 4, 205–209 (2002).

    Article  CAS  Google Scholar 

  12. Kim, J. S. et al. Electrochemical and structural properties of xLi2M′O3 ⋅ (1 − x)LiMn0.5Ni0.5O2 electrodes for lithium batteries (M′ = Ti, Mn, Zr; 0 ≤ x ≤ 0.3). Chem. Mater. 16, 1996–2006 (2004).

    Article  CAS  Google Scholar 

  13. Martha, S. K. et al. Surface studies of high voltage lithium rich composition: Li1.2Mn0.525Ni0.175Co0.1O2 . J. Power Sources 216, 179–186 (2012).

    Article  CAS  Google Scholar 

  14. Tran, N. et al. Mechanisms associated with the ‘plateau’ observed at high voltage for the overlithiated Li1.12(Ni0.425Mn0.425Co0.15)0.88O2 system. Chem. Mater. 20, 4815–4825 (2008).

    Article  CAS  Google Scholar 

  15. Koga, H. et al. Reversible oxygen participation to the redox processes revealed for Li1.20Mn0.54Co0.13Ni0.13O2 . J. Electrochem. Soc. 160, A786–A792 (2013).

    Article  CAS  Google Scholar 

  16. Sathiya, M. et al. Reversible anionic redox chemistry in high-capacity layered-oxide electrodes. Nature Mater. 12, 827–835 (2013).

    Article  CAS  Google Scholar 

  17. Armstrong, A. R. et al. Demonstrating oxygen loss and associated structural reorganization in the lithium battery cathode Li[Ni0.2Li0.2Mn0.6]O2 . J. Am. Chem. Soc. 128, 8694–8698 (2006).

    Article  CAS  Google Scholar 

  18. Kosova, N. V. et al. Electronic state of cobalt and oxygen ions in stoichiometric and nonstoichiometric Li1+xCoO2 before and after delithiation according to XPS and DRS. J. Power Sources 119–121, 669–673 (2003).

    Article  Google Scholar 

  19. Whittingam, M. S. Inorganic nanomaterials for batteries. Dalton Trans. 40, 5424–5431 (2008).

    Article  Google Scholar 

  20. Kim, D. K. et al. Spinel LiMn2O4 nanorods as lithium ion battery cathodes. Nano Lett. 8, 3948–3952 (2008).

    Article  CAS  Google Scholar 

  21. Kosova, N. V. et al. Synthesis of nanosized materials for lithium-ion batteries by mechanical activation. Studies of their structure and properties. Russ. J. Electrochem. 48, 351–361 (2012).

    Article  Google Scholar 

  22. Jiao, F. et al. Synthesis of ordered mesoporous Li–Mn–O spinel as a positive electrode for rechargeable lithium batteries. Angew. Chem. Int. Ed. 47, 9711–9716 (2008).

    Article  CAS  Google Scholar 

  23. Popa, N. C. The (hkl) dependence of diffraction-line broadening caused by strain and size for all laue groups in Rietveld refinement. J. Appl. Crystallogr. 31, 176–180 (1998).

    Article  CAS  Google Scholar 

  24. Kittel, C. Introduction to Solid State Physics 8th Edition 308 (John Wiley, 2005).

    Google Scholar 

  25. Greedan, J. E. et al. Long range and short range magnetic order in orthorhombic LiMnO2 . J. Solid State Chem. 128, 209–214 (1997).

    Article  CAS  Google Scholar 

  26. Lu, J. et al. Magnetism in lithium–oxygen discharge product. ChemSusChem 6, 1196–1202 (2013).

    Article  CAS  Google Scholar 

  27. Gummow, R. J. et al. Improved capacity retention in rechargeable 4V lithium/lithium–manganese oxide (spinel) cells. Solid State Ion. 69, 59–67 (1994).

    Article  CAS  Google Scholar 

  28. Kim, D. et al. Comments on stabilizing layered manganese oxide electrodes for Li batteries. Electrochem. Commun. 36, 103–106 (2013).

    Article  CAS  Google Scholar 

  29. Davidson, I. J. et al. Lithium-ion cell based on orthorhombic LiMnO2 . J. Power Sources 54, 232–235 (1995).

    Article  CAS  Google Scholar 

  30. Johnson, C. S. Development and utility of manganese oxides as cathodes in lithium batteries. J. Power Sources 165, 559–565 (2007).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge S. Gascoin for her help in numerous XRPD collections. The authors gratefully acknowledge the CNRS.

Author information

Authors and Affiliations

  1. Laboratoire de Cristallographie et Sciences des Matériaux CRISMAT, ENSICAEN, Université de Caen, CNRS, 6 Boulevard Maréchal Juin, F-14050 Caen, France

    M. Freire, D. Chateigner, O. I. Lebedev, A. Maignan & V. Pralong

  2. Saft, Direction de la Recherche, 111/113 Boulevard Alfred Daney, 33074 Bordeaux, France

    M. Freire & C. Jordy

  3. Institute of Solid State Chemistry and Mechanochemistry SB RAS, 18 Kutateladze, Novosibirsk 630128, Russia

    N. V. Kosova

Authors
  1. M. Freire
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. N. V. Kosova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Jordy
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. D. Chateigner
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. O. I. Lebedev
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. Maignan
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. V. Pralong
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

M.F., N.V.K. and V.P. contributed to the synthesis of the materials and performed the electrochemical and chemical analysis. M.F. and A.M. performed the magnetic analysis of the samples. D.C. analysed the XRPD data and O.I.L. carried out the TEM analysis. C.J., N.V.K. and V.P. conceived and designed the project. All the authors contributed to writing the paper.

Corresponding author

Correspondence to V. Pralong.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 954 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Freire, M., Kosova, N., Jordy, C. et al. A new active Li–Mn–O compound for high energy density Li-ion batteries. Nature Mater 15, 173–177 (2016). https://doi.org/10.1038/nmat4479

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat4479

This article is cited by

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