A 3.90 V iron-based fluorosulphate material for lithium-ion batteries crystallizing in the triplite structure

Article metrics

Abstract

Li-ion batteries have empowered consumer electronics and are now seen as the best choice to propel forward the development of eco-friendly (hybrid) electric vehicles. To enhance the energy density, an intensive search has been made for new polyanionic compounds that have a higher potential for the Fe2+/Fe3+ redox couple. Herein we push this potential to 3.90 V in a new polyanionic material that crystallizes in the triplite structure by substituting as little as 5 atomic per cent of Mn for Fe in Li(Fe1−δMnδ)SO4F. Not only is this the highest voltage reported so far for the Fe2+/Fe3+ redox couple, exceeding that of LiFePO4 by 450 mV, but this new triplite phase is capable of reversibly releasing and reinserting 0.7–0.8 Li ions with a volume change of 0.6% (compared with 7 and 10% for LiFePO4 and LiFeSO4F respectively), to give a capacity of ~125 mA h g−1.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: Crystal structure and diffraction patterns of the tavorite and triplite phases.
Figure 2: Structural changes on Mn substitution.
Figure 3: Voltage–composition curves for the tavorite and triplite phases.
Figure 4: Changes in electrochemistry with Mn substitution.
Figure 5: Synchrotron XRD Rietveld refinement of the chemically oxidized Li0.25(Fe0.8Mn0.2)SO4F sample.
Figure 6: Structural relationship between the tavorite and triplite phases.

References

  1. 1

    Armand, M. & Tarascon, J-M. Building better batteries. Nature 451, 652–657 (2008).

  2. 2

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

  3. 3

    Yamada, A. et al. Lithium iron borates as high capacity battery electrodes. Adv. Mater. 22, 3583–3587 (2010).

  4. 4

    Nyten, A., Abouimrane, A., Armand, M., Gustafsson, T. & Thomas, J.O. Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material. Electrochem. Commun. 7, 156–160 (2005).

  5. 5

    Nishimura, S. et al. Structure of Li2FeSiO4 . J. Am. Chem. Soc. 130, 13212–13213 (2008).

  6. 6

    Nishimura, S., Makamura, M., Natsui, R. & Yamada, A. New lithium iron pyrophosphate as 3.5 V class cathode material for lithium ion battery. J. Am. Chem. Soc. 132, 13596–13597 (2010).

  7. 7

    Barker, J., Saidi, M. Y. & Swoyer, J. L. A comparative investigation of the Li insertion properties of the novel fluorophosphate phases, NaVPO4F and LiVPO4F. J. Electrochem. Soc. 151, 1670–1677 (2004).

  8. 8

    Padhi, A. K., Nanjundaswamy, K. S. & Goodenough, J. B. Tuning the position of the redox couples in materials with NASICON structure by anionic substitution. J. Electrochem. Soc. 145, 1518–1520 (1998).

  9. 9

    Recham, N. et al. A 3.6 V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries. Nature Mater. 9, 68–74 (2010).

  10. 10

    Barpanda, P. et al. Structure and electrochemical properties of novel mixed Li(Fe1−xMx)SO4F (M=Co, Ni) phases fabricated by low temperature ionothermal synthesis. J. Mater. Chem. 20, 1659–1668 (2010).

  11. 11

    Rea, J. R. & Kostiner, E. The crystal structure of manganese fluorophosphate, Mn2(PO4)F. Acta Crystallogr. B 28, 2525–2529 (1972).

  12. 12

    Recham, N. et al. Ionothermal synthesis of tailor-made LiFePO4 powders for Li-ion battery applications. Chem. Mater. 21, 1096–1107 (2009).

  13. 13

    Ati, M. et al. Fluorosulphate positive electrodes for Li-ion batteries made via a solid-state dry process. J. Electrochem. Soc. 157, 1007–1015 (2010).

  14. 14

    Barpanda, P. et al. Structural and electrochemical investigation of novel AMSO4F(A=Na,Li;M=Fe,Co,Ni,Mn) metal fluorosulphates prepared using low temperature synthesis routes. Inorg. Chem. 49, 7401–7413 (2010).

  15. 15

    Barpanda, P. et al. LiZnSO4F made in an ionic liquid: A new ceramic electrolyte composite for solid-state Li-batteries. Angew. Chem. Int. Ed. 50, 2526–2531 (2010).

  16. 16

    Ati, M. et al. Fluorosulfate positive electrode materials made with polymers as reacting media. Electrochem. Solid-State. Lett. 13, 150–153 (2010).

  17. 17

    Rodrı´guez-Carvajal, J. Recent advances in magnetic structure determination by neutron powder diffraction. Physica B 192, 55–69 (1993).

  18. 18

    Shannon, R. D. & Prewitt, C. T. Effective ionic radii in oxides and fluorides. Acta. Cryst B25, 925 (1969).

  19. 19

    Tarantino, S. C., Ghigna, P., McCammon, C., Amantea, R. & Carpenter, M. A. Local structure properties of (Mn,Fe)Nb2O6 from Mössbauer and X-ray absorption spectroscopy. Acta Cryst. B 61, 250–257 (2005).

  20. 20

    Hanaor, D. & Sorrell, C. Review of the anatase to rutile phase transformation. J. Mater. Sci. 46, 1–20 (2011).

  21. 21

    Frayret, C. et al. LiMSO4F (M=Fe, Co, and Ni): Promising new positive electrode materials through the DFT microscope. Phys. Chem. Chem. Phys. 12, 15512–15522 (2010).

  22. 22

    Cai, Y. et al. First-principles calculations on the LiMSO4F/MSO4F (M=Fe, Co, and Ni) systems. J. Phys. Chem. C 115, 7032–7037 (2011).

  23. 23

    Ramzan, M., Lebegue, S., Kang, T. W. & Ahuja, R. Hybrid density functional calculations and molecular dynamics study of lithium fluorosulphate, a cathode material for lithium-ion batteries. J. Phys. Chem. C 115, 2600–2603.

  24. 24

    Tripathi, R., Gardiner, G. R., Islam, M. S. & Nazar, L. F. Alkali-ion conduction paths in LiFeSO4F and NaFeSO4F tavorite-type cathode materials. Chem. Mater. 23, 2278–2284 (2011).

  25. 25

    Liu, Z. & Huang, X. Structural, electronic, and Li diffusion properties of LiFeSO4F. Solid State Ion. 181, 57–61 (2010).

  26. 26

    Sirisopanaporn, C., Masquelier, C., Bruce, P., Armstrong, A. & Dominko, R. Dependence of Li2FeSiO4 electrochemistry on structure. J. Am. Chem. Soc. 133, 1263–1265 (2011).

  27. 27

    Favre-Nicolin, V. & Cerny, R. Fox, ‘free objects for crystallography’: A modular approach to ab initio structure determination from powder diffraction. J. Appl. Cryst. 35, 734–743 (2002).

  28. 28

    Varret, F. & Teillet, J. Unpublished Mosfit Program (Universite du Maine, 1976).

  29. 29

    Dent, A. J. B18: A core XAS spectroscopy beamline for diamond. J. Phys. Conf. Ser. 190, 012039 (2009).

  30. 30

    Webb, S. M. SIXPack: A graphical user interface for XAS analysis using IFEFFIT. Phys. Scr. T115, 1011–1014 (2005).

  31. 31

    Leriche, J. B. et al. An electrochemical cell for operando study of lithium batteries using synchrotron radiation. J. Electrochem. Soc. 157, A606–A610 (2010).

Download references

Acknowledgements

Many discussions with M. Armand, N. Recham, C. Delacourt, C. Masquelier, D. Larcher, G. Férey, Y. Chabre, C. Frayret and D.W. Murphy are gratefully acknowledged. We thank C. Davoisne for the TEM images and ALISTORE-ERI for sponsoring this research. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The EXAFS measurements were carried out with the support of the Diamond Light Source and we gratefully acknowledge G. Cibin for help with running the X-ray absorption spectroscopy experiments as well as E. J. Schofield and A. V. Chadwick for discussions in analysing the XANES data.

Author information

P.B., M.A. and J-M.T. carried out the synthesis, the electrochemical work and designed the research approach; B.C.M., G.R. and J-N.C. analysed the crystal structure and diffraction patterns; M.T.S. and J-C.J. collected the Mössbauer measurements; B.C.M. and S.A.C. collected and analysed the EXAFS measurements; M-L.D. conducted the DFT calculations and developed the theoretical framework; B.C.M., G.R. and J-M.T. wrote the manuscript and all authors discussed the experiments and final manuscript.

Correspondence to J-M. Tarascon.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 5139 kb)

Rights and permissions

Reprints and Permissions

About this article

Further reading