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

Nature Energy volume 2, Article number: 17090 (2017) Cite this article

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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.

The lithium–sulfur (Li–S) battery represents one of the most promising solutions to the range anxiety of electric vehicles due to its extremely high theoretical energy density of 2,600 Wh kg−1, three- to fivefold higher than the state-of-the-art Li-ion batteries1,2,3,4,5,6,7,8. Commercialization of Li–S batteries, however, has been hindered by a series of obstacles9,10,11,12,13,14,15. The insulating nature of sulfur (S8) and lithium (di)sulfides (Li2S and Li2S2), the fully charged and discharged products of sulfur electrodes, respectively, requires heavy dosages of conductive additives. Meanwhile, lithium polysulfides (Li2Sx, 3 ≤ x ≤ 8) (LiPS), the cycling intermediates that are highly soluble in aprotic liquid electrolytes, act as internal redox shuttles that lead to the low Coulombic efficiency and rapid capacity fading of the cell. In addition, sulfur electrodes experience significant volumetric changes, with an expansion up to 180% when the denser S8 is reduced to Li2S during discharge.

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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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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.

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  1. Guoqiang Tan, Rui Xu, Zhenyu Xing and Yifei Yuan: These authors contributed equally to this work.

Authors and Affiliations

  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Guoqiang Tan, Rui Xu, Jun Lu, Cong Liu, Chun Zhan & Khalil Amine

  2. Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA

    Zhenyu Xing, Zelang Jian & Xiulei Ji

  3. Department of Mechanical and Industrial Engineering, The University of Illinois at Chicago, Chicago, Illinois 60607, USA

    Yifei Yuan & Reza Shahbazian-Yassar

  4. Center for Nanoscale Materials, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Jianguo Wen & Dean J. Miller

  5. X-ray Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Lu Ma, Qi Liu, Tianpin Wu & Yang Ren

  6. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA

    Larry A. Curtiss

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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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