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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References
Kutney, G. Sulfur. History, Technology, Applications and Industry (ChemTec Publising, 2007).
Rauchfuss, T. B. Under sulfur's spell. Nature Chem. 3, 648 (2011).
Angelici, R. J. Heterogeneous catalysis of the hydrodesulfurization of thiophenes in petroleum: an organometallic perspective of the mechanism. Acc. Chem. Res. 21, 387–394 (1988).
Meyer, C. & Kharasch, N. Elemental Sulfur: Chemistry and Physics (Interscience Publishers, 1965).
Wang, J. L. et al. Sulfur composite cathode materials for rechargeable lithium batteries. Adv. Func. Mater. 13, 487–492 (2003).
Song, M-S. et al. Effects of nanosized adsorbing material on electrochemical properties of sulfur cathodes for Li/S secondary batteries. J. Electrochem. Soc. 151, A791–A795 (2004).
Kiya, Y., Iwata, A., Sarukuwa, T., Henderson, J. C. & Abruna, H. D. Poly[dithio-2,5-(1,3,4-thiadiazole)] (PDMcT)–poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for high energy lithium/lithium ion rechargable batteries. J. Power Sources 173, 522–530 (2007).
Armand, M. & Tarascon, J-M. Building better batteries. Nature 451, 652–657 (2008).
Choi, Y-J. et al. Effects of carbon coating on the electrochemical properties of sulfur cathode for lithium/sulfur cell. J. Power Sources 184, 548–552 (2008).
Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries. Nature Mater. 8, 500–506 (2009).
Ellis, B. L., Lee, K. T. & Nazar, L. F. Positive electrode materials for Li-ion and Li-batteries. Chem. Mater. 22, 691–714 (2010).
Wu, F., Wu, S., Chen, R., Chen, J. & Chen, S. Sulfur–polythiophene composite cathode materials for rechargeable lithium batteries. Electrochem. Solid-State Lett. 13, A29–A31 (2010).
Jayaprakash, N., Shen, J., Moganty, S. S., Corona, A. & Archer, L. A. Porous hollow carbon@sulfur composites for high-power lithium–sulfur batteries. Angew. Chem. Int. Ed. 50, 5904–5908 (2011).
Wang, H. et al. Graphene-wrapped sulfur particles as a rechargeable lithium–sulfur battery cathode material with high capacity and cycling stability. Nano Lett. 11, 2644–2647 (2011).
Wu, F. et al. Sulfur/polythiophene with a core/shell structure: synthesis and electrochemical properties of the cathode for rechargeable lithium batteries. J. Phys. Chem. C 115, 6057–6063 (2011).
Yu, G. et al. Enhancing the supercapacitor performance of graphene/MnO2 nanostructured electrodes by conductive wrapping. Nano Lett. 11, 4438–4442 (2011).
Okutsu, R., Ando, S. & Ueda, M. Sulfur-containing poly(meth)acrylates with high refractive indices and high Abbe's numbers. Chem. Mater. 20, 4017–4023 (2008).
Liu, J-G. & Ueda, M. High refractive index polymers: fundamental research and practical applications. J. Mater. Chem. 19, 8907–8919 (2009).
Boros, E. et al. On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium, and phosphorous) in ionic liquids. Chem. Commun. 46, 716–718 (2010).
Penczek, S., Slazak, R. & Duda, A. Anionic copolymerization of elemental sulfur. Nature 273, 738–739 (1978).
Duda, A. & Penczek, S. Anionic copolymerization of elemental sulfur with 2,2-dimethylthiirane. Makromol. Chem. Macromol. Chem. Phys. 181, 995–1001 (1980).
Blight, L. B., Currell, B. R., Nash, B. J., Scott, T. M. & Stillo, C. Chemistry of the modification of sulphur by the use of dicyclopentadiene and of styrene. Br. Polym. J. 5–11 (1980).
Tsuda, T. & Takeda, A. Palladium-catalysed cycloaddition copolymerisation of diynes with elemental sulfur to poly(thiophene)s. Chem. Commun. 1317–1318 (1996).
Ding, Y. & Hay, A. S. Copolymerization of elemental sulfur with cyclic (arylene disulfide) oligomers. J. Polym. Sci. A 35, 2961–2968 (1997).
Chung, W-J. et al. Elemental sulfur as a reactive medium for gold nanoparticles and nanocomposite materials. Angew. Chem. Int. Ed. 50, 11409–11412 (2011).
Calatldo, F. A study on the structure and properties of polymeric sulfur. Die Angew. Makromol. Chem. 249, 137–149 (1997).
Hong, Y. et al. A novel processing aid for polymer extrusion: rheology and processing of polyethylene and hyperbranched polymer blends. J. Rheol. 43, 781–793 (1999).
Leibfarth, F. A. et al. A facile route to ketene-functionalized polymers for general materials applications. Nature Chem. 2, 207–212 (2010).
Gupta, N. et al. A versatile approach to high-throughput microarrays using thiol-ene chemistry. Nature Chem. 2, 138–145 (2010).
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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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.
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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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DOI: https://doi.org/10.1038/nchem.1624
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