Synthetic design of crystalline inorganic chalcogenides exhibiting fast-ion conductivity

Abstract

Natural porous solids such as zeolites are invariably formed with inorganic cations such as Na+ and K+ (refs 1, 2). However, current research on new porous materials is mainly focused on the use of organic species as either structure-directing or structure-building units; purely inorganic systems have received relatively little attention in exploratory synthetic work3,4,5,6,7,8,9. Here we report the synthesis of a series of three-dimensional sulphides and selenides containing highly mobile alkali metal cations as charge-balancing extra-framework cations. Such crystalline inorganic chalcogenides integrate zeolite-like architecture with high anionic framework polarizability and high concentrations of mobile cations. Such structural features are particularly desirable for the development of fast-ion conductors10. These materials demonstrate high ionic conductivity (up to 1.8 × 10-2 ohm-1 cm-1) at room temperature and moderate to high humidity. This synthetic methodology, together with novel structural, physical and chemical properties, may lead to the development of new microporous and open-framework materials with potential applications in areas such as batteries, fuel cells, electrochemical sensors and photocatalysis.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Figure 1: The structural diagrams of the inorganic chalcogenide frameworks.
Figure 2
Figure 3: The dependence of the ionic conductivity on the relative humidity for ICF-5 CuInS-Na.
Figure 4: The dependence of the ionic conductivity on the relative humidity for ICF-21 InSe-Na.
Figure 5: The a.c. impedance plot of ICF-22 InS-Li at 24.0 °C under 31.7% relative humidity.

References

  1. 1

    Flanigen, E. M. in Introduction to Zeolite Science and Practice (eds van Bekkum, H., Flanigen, E. M. & Jansen, J. C.) 13–34 (Elsevier, New York, 1991)

    Google Scholar 

  2. 2

    Breck, D. W. Zeolite Molecular Sieves, Structure, Chemistry, and Use (John Wiley & Sons, New York, 1974)

    Google Scholar 

  3. 3

    Davis, M. E. Ordered porous materials for emerging applications. Nature 417, 813 (2002)

    ADS  CAS  Article  Google Scholar 

  4. 4

    Feng, P., Bu, X. & Stucky, G. D. Hydrothermal syntheses and structural characterization of zeolite analogue compounds based on cobalt phosphate. Nature 388, 735–741 (1997)

    ADS  CAS  Article  Google Scholar 

  5. 5

    Scott, R. W. J., MacLachlan, M. J. & Ozin, G. A. Synthesis of metal sulfide materials with controlled architecture. Curr. Opin. Solid State Mater. Sci. 4, 113–121 (1999)

    ADS  CAS  Article  Google Scholar 

  6. 6

    Huo, Q., Leon, R., Petroff, P. M. & Stucky, G. D. Mesostructure design with gemini surfactants: supercage formation in a three-dimensional hexagonal array. Science 68, 1324–1327 (1995)

    ADS  Article  Google Scholar 

  7. 7

    Zhao, D. et al. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores. Science 279, 548–552 (1998)

    ADS  CAS  Article  Google Scholar 

  8. 8

    Johnson, S. A., Ollivier, P. J. & Mallouk, T. E. Ordered mesoporous polymers of tunable pore size from colloidal silica templates. Science 283, 963–965 (1999)

    ADS  CAS  Article  Google Scholar 

  9. 9

    Cheetham, A. K., Ferey, G. & Loiseau, T. Open-framework inorganic materials. Angew. Chem. Int. Edn 38, 3268–3292 (1999)

    CAS  Article  Google Scholar 

  10. 10

    West, A. R. Solid State Chemistry and its Applications (Wiley, New York, 1992)

    Google Scholar 

  11. 11

    Zheng, N., Bu, X. & Feng, P. Microporous and photoluminescent chalcogenide zeolite analogs. Science 298, 2366–2369 (2002)

    ADS  CAS  Article  Google Scholar 

  12. 12

    Bedard, R. L., Wilson, S. T., Vail, L. D., Bennett, J. M. & Flanigen, E. M. in Zeolites: Facts, Figures, Future. Proc. 8th Int. Zeolite Conf. (eds Jacobs, P. A. & van Santen, R. A.) 375 (Elsevier, Amsterdam, 1989)

    Google Scholar 

  13. 13

    Cahill, C. L. & Parise, J. B. On the formation of framework indium sulfides. J. Chem. Soc. Dalton Trans. 1475–1482 (2000)

  14. 14

    Dhingra, S. & Kanatzidis, M. G. Open framework structures based on Sex2- fragments: synthesis of (Ph4P)[M(Se6)2] (M = Ga, In, Tl) in molten (Ph4P)2Sex . Science 258, 1769–1772 (1992)

    ADS  CAS  Article  Google Scholar 

  15. 15

    Li, H., Laine, A., O'Keeffe, M. & Yaghi, O. M. Supertetrahedral sulfide crystals with giant cavities and channels. Science 283, 1145–1147 (1999)

    ADS  CAS  Article  Google Scholar 

  16. 16

    Wehmschulte, R. J. & Power, P. P. Low-temperature synthesis of aluminum sulfide as the solvate Al4S6(NMe3)4 in hydrocarbon solution. J. Am. Chem. Soc. 119, 9566–9567 (1997)

    CAS  Article  Google Scholar 

  17. 17

    Bu, X., Zheng, N., Li, Y. & Feng, P. Pushing up the size limit of chalcogenide supertetrahedral clusters: two- and three-dimensional photoluminescent open frameworks from (Cu5In30S54)13- clusters. J. Am. Chem. Soc. 124, 12646–12647 (2002)

    CAS  Article  Google Scholar 

  18. 18

    Hoppe, R., Lidecke, W. & Frotath, F. C. Sodium thioindate and sodium selenoindate. Z. Anorg. Allgem. Chem. 309, 49–54 (1961)

    CAS  Article  Google Scholar 

Download references

Acknowledgements

We acknowledge the support of this work by the NSF. We also thank Y. Yan and his group for assistance with impedance measurements.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Pingyun Feng.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Zheng, N., Bu, X. & Feng, P. Synthetic design of crystalline inorganic chalcogenides exhibiting fast-ion conductivity. Nature 426, 428–432 (2003). https://doi.org/10.1038/nature02159

Download citation

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.

Search

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