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Burning lithium in CS2 for high-performing compact Li2S–graphene nanocapsules for Li–S batteries

Abstract

Tremendous efforts have been made to design the cathode of Li–S batteries to improve their energy density and cycling life. However, challenges remain in achieving fast electronic and ionic transport while accommodating the significant cathode volumetric change, especially for the cathode with a high practical mass loading. Here we report a cathode architecture, which is constructed by burning lithium foils in a CS2 vapour. The obtained structure features crystalline Li2S nanoparticles wrapped by few-layer graphene (Li2S@graphene nanocapsules). Because of the improvement on the volumetric efficiency for accommodating sulfur active species and electrical properties, the cathode design enables promising electrochemical performance. More notably, at a loading of 10 mgLi2S cm−2, the electrode exhibits a high reversible capacity of 1,160 mAh g−1s, namely, an area capacity of 8.1 mAh cm−2. Li2S@graphene cathode demonstrates a great potential for Li-ion batteries, where the Li2S@graphene-cathode//graphite-anode cell displays a high capacity of 730 mAh g−1s as well as stable cycle performance.

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Figure 1: Morphology and structure of Li2S@graphene nanocapsules.
Figure 2: Electrochemical characterization of Li2S@graphene cathodes in Li//Li2S@graphene cells and graphite//Li2S@graphene cells.
Figure 3: Electrochemical impedance spectra characterization of the Li2S@graphene cathode in comparison with the bare Li2S cathode in three-electrode cells.
Figure 4: Material characterizations of Li2S@graphene cathodes cycled in Li//Li2S@graphene cells during electrochemical reactions.
Figure 5: Chemical structure and electrochemical mechanism study.

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References

  1. Ji, X., Lee, K. T. & Nazar, L. F. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries. Nat. Mater. 8, 500–506 (2009).

    Google Scholar 

  2. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li-O2 and Li-S batteries with high energy storage. Nat. Mater. 11, 19–29 (2012).

    Google Scholar 

  3. 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).

    Google Scholar 

  4. Zhang, Q. et al. Understanding the anchoring effect of two-dimensional layered materials for lithium–sulfur batteries. Nano Lett. 15, 3780–3786 (2015).

    Google Scholar 

  5. Liang, Z. et al. Sulfur cathodes with hydrogen reduced titanium dioxide inverse opal structure. ACS Nano 8, 5249–5256 (2014).

    Google Scholar 

  6. Yang, Y., Zheng, G. & Cui, Y. Nanostructured sulfur cathodes. Chem. Soc. Rev. 42, 3018–3032 (2013).

    Google Scholar 

  7. Manthiram, A., Fu, Y., Chung, S.-H., Zu, C. & Su, Y.-S. Rechargeable lithium–sulfur batteries. Chem. Rev. 114, 11751–11787 (2014).

    Google Scholar 

  8. Xu, R., Lu, J. & Amine, K. Progress in mechanistic understanding and characterization techniques of Li-S batteries. Adv. Energy Mater. 5, 1500408 (2015).

    Google Scholar 

  9. Zheng, G., Yang, Y., Cha, J. J., Hong, S. S. & Cui, Y. Hollow carbon nanofiber-encapsulated sulfur cathodes for high specific capacity rechargeable lithium batteries. Nano Lett. 11, 4462–4467 (2011).

    Google Scholar 

  10. Zheng, G. et al. Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. Nano Lett. 13, 1265–1270 (2013).

    Google Scholar 

  11. Li, W. et al. High-performance hollow sulfur nanostructured battery cathode through a scalable, room temperature, one-step, bottom-up approach. Proc. Natl Acad. Sci. USA 110, 7148–7153 (2013).

    Google Scholar 

  12. Seh, Z. W. et al. Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries. Nat. Commun. 4, 1331 (2013).

    Google Scholar 

  13. Chen, R. et al. Graphene-based three-dimensional hierarchical sandwich-type architecture for high-performance Li/S batteries. Nano Lett. 13, 4642–4649 (2013).

    Google Scholar 

  14. Manthiram, A., Fu, Y. & Su, Y.-S. Challenges and prospects of lithium–sulfur batteries. Acc. Chem. Res. 46, 1125–1134 (2012).

    Google Scholar 

  15. Yin, Y. X., Xin, S., Guo, Y. G. & Wan, L. J. Lithium–sulfur batteries: electrochemistry, materials, and prospects. Angew. Chem. Int. Ed. 52, 13186–13200 (2013).

    Google Scholar 

  16. Ji, X., Evers, S., Black, R. & Nazar, L. F. Stabilizing lithium–sulphur cathodes using polysulphide reservoirs. Nat. Commun. 2, 325 (2011).

    Google Scholar 

  17. Qie, L. & Manthiram, A. A facile layer-by-layer approach for high-areal-capacity sulfur cathodes. Adv. Mater. 27, 1694–1700 (2015).

    Google Scholar 

  18. Yang, Y. et al. High-capacity micrometer-sized Li2S particles as cathode materials for advanced rechargeable lithium-ion batteries. J. Am. Chem. Soc. 134, 15387–15394 (2012).

    Google Scholar 

  19. Seh, Z. W. et al. Facile synthesis of Li2S–polypyrrole composite structures for high-performance Li2S cathodes. Energy Environ. Sci. 7, 672–676 (2014).

    Google Scholar 

  20. Hwa, Y., Zhao, J. & Cairns, E. J. Lithium sulfide (Li2S)/graphene oxide nanospheres with conformal carbon coating as a high-rate, long-life cathode for Li/S cells. Nano Lett. 15, 3479–3486 (2015).

    Google Scholar 

  21. Yang, Y. et al. New nanostructured Li2S/silicon rechargeable battery with high specific energy. Nano Lett. 10, 1486–1491 (2010).

    Google Scholar 

  22. Fu, Y., Zu, C. & Manthiram, A. In situ-formed Li2S in lithiated graphite electrodes for lithium–sulfur batteries. J. Am. Chem. Soc. 135, 18044–18047 (2013).

    Google Scholar 

  23. Fu, Y., Su, Y. S. & Manthiram, A. Li2S-carbon sandwiched electrodes with superior performance for lithium–sulfur batteries. Adv. Energy Mater. 4, 1300655 (2014).

    Google Scholar 

  24. Chakrabarti, A. et al. Conversion of carbon dioxide to few-layer graphene. J. Mater. Chem. 21, 9491–9493 (2011).

    Google Scholar 

  25. Xing, Z. et al. Reducing CO2 to dense nanoporous graphene by Mg/Zn for high power electrochemical capacitors. Nano Energy 11, 600–610 (2015).

    Google Scholar 

  26. Cai, K., Song, M.-K., Cairns, E. J. & Zhang, Y. Nanostructured Li2S–C composites as cathode material for high-energy lithium/sulfur batteries. Nano Lett. 12, 6474–6479 (2012).

    Google Scholar 

  27. Ferrari, A. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006).

    Google Scholar 

  28. Tan, G. et al. Freestanding three-dimensional core-shell nanoarrays for lithium-ion battery anodes. Nat. Commun. 7, 11774 (2016).

    Google Scholar 

  29. Wall, M. The Raman Spectroscopy of graphene and the determination of layer thickness. Thermo Scientific Application Note AN52252 (2011).

  30. Seh, Z. W. et al. High-capacity Li2S–graphene oxide composite cathodes with stable cycling performance. Chem. Sci. 5, 1396–1400 (2014).

    Google Scholar 

  31. Seh, Z. W. et al. Two-dimensional layered transition metal disulphides for effective encapsulation of high-capacity lithium sulphide cathodes. Nat. Commun. 5, 5017 (2014).

    Google Scholar 

  32. Wang, L., Wang, Y. & Xia, Y. A high performance lithium-ion sulfur battery based on a Li2S cathode using a dual-phase electrolyte. Energy Environ. Sci. 8, 1551–1558 (2015).

    Google Scholar 

  33. Wu, F. et al. Harnessing steric separation of freshly nucleated Li2S nanoparticles for bottom-up assembly of high-performance cathodes for lithium–sulfur and lithium-ion batteries. Adv. Energy Mater. 4, 1400196 (2014).

    Google Scholar 

  34. Wu, F., Lee, J. T., Magasinski, A., Kim, H. & Yushin, G. Solution-based processing of graphene–Li2S composite cathodes for lithium-ion and lithium–sulfur batteries. Part. Part. Syst. Charact. 31, 639–644 (2014).

    Google Scholar 

  35. Nan, C. et al. Durable carbon-coated Li2S core–shell spheres for high performance lithium/sulfur cells. J. Am. Chem. Soc. 136, 4659–4663 (2014).

    Google Scholar 

  36. Yang, Z. et al. In situ synthesis of lithium sulfide–carbon composites as cathode materials for rechargeable lithium batteries. J. Mater. Chem. A 1, 1433–1440 (2013).

    Google Scholar 

  37. Liu, J., Nara, H., Yokoshima, T., Momma, T. & Osaka, T. Micro-scale Li2S–C composite preparation from Li2SO4 for cathode of lithium ion battery. Electrochim. Acta 183, 70–77 (2015).

    Google Scholar 

  38. Zhang, K., Wang, L., Hu, Z., Cheng, F. & Chen, J. Ultrasmall Li2S nanoparticles anchored in graphene nanosheets for high-energy lithium-ion batteries. Sci. Rep. 4, 6467 (2014).

    Google Scholar 

  39. Fu, Y. & Manthiram, A. Orthorhombic bipyramidal sulfur coated with polypyrrole nanolayers as a cathode material for lithium–sulfur batteries. J. Phys. Chem. C 116, 8910–8915 (2012).

    Google Scholar 

  40. Su, Q., Dong, Z., Zhang, J., Du, G. & Xu, B. Visualizing the electrochemical reaction of ZnO nanoparticles with lithium by in situ TEM: two reaction modes are revealed. Nanotechnology 24, 255705 (2013).

    Google Scholar 

  41. Assary, R. S., Curtiss, L. A. & Moore, J. S. Toward a molecular understanding of energetics in Li–S batteries using nonaqueous electrolytes: a high-level quantum chemical study. J. Phys. Chem. C 118, 11545–11558 (2014).

    Google Scholar 

  42. Gyulassy, A. et al. Interstitial and interlayer ion diffusion geometry extraction in graphitic nanosphere battery materials. IEEE Trans. Vis. Comput. Graphics 22, 916–925 (2016).

    Google Scholar 

Download references

Acknowledgements

This work was financially supported by the US Department of Energy under Contract DE-AC0206CH11357 with the main support provided by the Vehicle Technologies Office, Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy (EERE). X.J. is grateful for the financial support from National Science Foundation Award No. 1551693. The ex situ TEM was conducted at the Electron Microscopy Center in the Center for Nanoscale Materials at Argonne National Laboratory, a DOE-BES Facility, supported under Contract No. DE-AC0206CH11357 by UChicago Argonne, LLC. Use of the Advanced Photon Source (9-BM and 11-ID) was supported by the US Department of Energy, Office of Basic Energy Sciences, under contract No. DE-AC0206CH11357. DFT calculations were supported by the US DOE, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under Contract DE-AC0206CH11357.

Author information

Authors and Affiliations

Authors

Contributions

J.L. conceived the concept and design the experiments. Z.X. and Z.J. synthesized the Li2S@graphene capsule materials; G.T. and R.X. performed materials characterization and electrochemical measurements; J.W. and D.J.M. carried out the TEM observation; L.M. and T.W. carried out the XANES experiments; C.Z. and G.T carried out the in situ EIS measurements; Y.Y. and R.S.-Y. performed the in situTEM observation; Q.L. and Y.R. performed the in situ XRD experiments; C.L. and L.A.C. performed the DFT theoretical calculations; J.L., X.J. and K.A. supervised the project; G.T., X.J. and J.L. wrote the paper. All authors discussed the results and reviewed the manuscript.

Corresponding authors

Correspondence to Jun Lu, Xiulei Ji or Khalil Amine.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–14, Supplementary Tables 1–2, Supplementary References. (PDF 1958 kb)

Supplementary Video 1

In-situ TEM time-lapse video of a Li2S@graphene nanocapsule during the prime three (de)-lithiation cycles within the operating bias of 3.0 V. The Li2S@graphene nanocapsule exhibits a good structural integrity during the (de)-lithiation cycling, with a very small volume variation 10%. (WMV 8818 kb)

Supplementary Video 2

In-situ TEM time-lapse video of a Li2S nanoparticle during the prime three (de)-lithiation cycles within the operating bias of 3.0 V. The bare Li2S nanoparticle shows a severe structural vulnerability during the (de)-lithiation cycling, where the particle can hardly survive after three cycles. This leads to the drastic decomposition and severe mass loss of Li2S electrode and subsequently the fast capacity fading of the cell. (WMV 2464 kb)

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Tan, G., Xu, R., Xing, Z. et al. Burning lithium in CS2 for high-performing compact Li2S–graphene nanocapsules for Li–S batteries. Nat Energy 2, 17090 (2017). https://doi.org/10.1038/nenergy.2017.90

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