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The use of elemental sulfur as an alternative feedstock for polymeric materials

Nature Chemistry volume 5, pages 518–524 (2013)Cite this article

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Abstract

An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li–S batteries, exhibiting high specific capacity (823 mA h g−1 at 100 cycles) and enhanced capacity retention.

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Figure 1: Elemental sulfur as a feedstock.
Figure 2: The copolymerization of S8 with DIB.
Figure 3: Transparent glass films of poly(S-r-DIB).
Figure 4: Thermal and rheological properties of poly(S-r-DIB).
Figure 5: Imprint lithography of poly(S-r-DIB) copolymers to form micropatterned films.
Figure 6: Electrochemical performance of 10-wt% DIB sulfur copolymer.

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Acknowledgements

We acknowledge the University of Arizona (UA), Arizona Research Institute for Solar Energy, the World Class University Program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (R31-10013), the Laboratory for Electrochemical Energy at the UA and the American Chemical Society Petroleum Research Fund (51026-ND10) for support of this work. K.C. acknowledges financial support from the National Research Foundation for the National Creative Research Initiative Center for Intelligent Hybrids (2010-0018290). Y-E.S. acknowledges financial support from the Korean Ministry of Education, Science and Technology through the Institute of Basic Science Program.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of Arizona, 1306 East University Boulevard, Tucson, 85721, Arizona, USA

    Woo Jin Chung, Jared J. Griebel, Adam G. Simmonds, Hyun Jun Ji, Philip T. Dirlam, Richard S. Glass, Árpád Somogyi & Jeffrey Pyun

  2. School of Chemical and Biological Engineering, World Class University Program for Chemical Convergence for Energy and Environment, The National Creative Research Initiative Center for Intelligent Hybrids, Center for Nanoparticle Research, Institute for Basic Science, Seoul, 151-744, Korea

    Eui Tae Kim, Hyunsik Yoon, Jungjin Park, Patrick Theato, Yung-Eun Sung, Kookheon Char & Jeffrey Pyun

  3. Department of Chemical and Biomolecular Engineering, University of Delaware, 150 Academy Street, Newark, 19716, Delaware, USA

    Jeong Jae Wie, Brett W. Guralnick & Michael E. Mackay

  4. Department of Materials Science and Engineering, University of Delaware, 201 DuPont Hall, Newark, 19716, Delaware, USA

    Ngoc A. Nguyen & Michael E. Mackay

  5. Universität Hamburg, Institut für Technische und Makromolekular, Chemie, Bundesstraße 45, Hamburg, 20146, Germany

    Patrick Theato

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Contributions

W.J.C., J.J.G., E.T.K., H.S.Y., R.S.G., P.T., Y-E.S., K.C. and J.P. developed the concept and conceived the experiments. J.J.G., E.T.K., W.J.C., A.G.S., P.T.D., H.J.J., J.J.P., A.S. and H.S.Y. performed the laboratory experiments and analysed the results. J.J.W., N.A.N., B.W.G. and M.E.M. provided support for polymer characterization. W.J.C., K.C. and J.P. co-wrote the manuscript.

Corresponding authors

Correspondence to Yung-Eun Sung, Kookheon Char or Jeffrey Pyun.

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Chung, W., Griebel, J., Kim, E. et al. The use of elemental sulfur as an alternative feedstock for polymeric materials. Nature Chem 5, 518–524 (2013). https://doi.org/10.1038/nchem.1624

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