Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li–S batteries

An Author Correction to this article was published on 04 April 2018

This article has been updated

Abstract

Among the candidates to replace Li-ion batteries, Li–S cells are an attractive option as their energy density is about five times higher (~2,600 Wh kg−1). The success of Li–S cells depends in large part on the utilization of metallic Li as anode material. Metallic lithium, however, is prone to grow parasitic dendrites and is highly reactive to several electrolytes; moreover, Li–S cells with metallic Li are also susceptible to polysulfides dissolution. Here, we show that ~10-nm-thick two-dimensional (2D) MoS2 can act as a protective layer for Li-metal anodes, greatly improving the performances of Li–S batteries. In particular, we observe stable Li electrodeposition and the suppression of dendrite nucleation sites. The deposition and dissolution process of a symmetric MoS2-coated Li-metal cell operates at a current density of 10 mA cm−2 with low voltage hysteresis and a threefold improvement in cycle life compared with using bare Li-metal. In a Li–S full-cell configuration, using the MoS2-coated Li as anode and a 3D carbon nanotube–sulfur cathode, we obtain a specific energy density of ~589 Wh kg−1 and a Coulombic efficiency of ~98% for over 1,200 cycles at 0.5 C. Our approach could lead to the realization of high energy density and safe Li-metal-based batteries.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Scheme and preparation of MoS2-coated Li metal.
Fig. 2: Morphological study and characterization of the MoS2-coated Li metal.
Fig. 3: Li deposition/dissolution cyclic behaviour between bare and MoS2-coated Li symmetric cells.
Fig. 4: Electrochemical performance of Li–MoS2/CNT–S full cells.
Fig. 5: DFT simulation of Li migration behaviour through MoS2 structure.

Similar content being viewed by others

Change history

  • 04 April 2018

    In the version of this Article originally published, a technical error in typesetting led to the traces in Fig. 3a being trimmed and made to overlap. The figure has now been corrected with the traces as supplied by the authors; the original and corrected Fig. 3a are shown below. Also, in the last paragraph of the section “Mechanistic study on Li diffusion in MoS2” the authors incorrectly included the term ‘high-concentration’ in the text “the Li diffusion will be dominated by high-concentration Li migration on the surface of T-MoS2 with a much smaller energy barrier (0.155 eV) to overcome”. This term has now been removed from all versions of the Article. Finally, the authors have added an extra figure in the Supplementary Information (Supplementary Fig. 19) to show galvanostatic tests at 1 and 3 mA cm–2 for the MoS2-coated Li symmetric cells. The caption to Fig. 3 of the Article has been amended to reflect this, with the added wording “Galvanostatic tests at 1 and 3 mA cm–2 can be found in Supplementary Fig. 19.”

References

  1. Grande, L. et al. The lithium/air battery: still an emerging system or a practical reality? Adv. Mater. 27, 784–800 (2015).

  2. Lu, Y. et al. Stable cycling of lithium metal batteries using high transference number electrolytes. Adv. Energy Mater. 5, 1402073 (2015).

    Article  Google Scholar 

  3. Xu, W. et al. Lithium metal anodes for rechargeable batteries. Energy Environ. Sci. 7, 513–537 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  5. Yamin, H., Gorenshtein, A., Penciner, J., Sternberg, Y. & Peled, E. Lithium sulfur battery. Oxidation/reduction mechanisms of polysulfides in THF solutions. J. Electrochem. Soc. 135, 1045–1048 (1988).

  6. Peled, E. The electrochemical behavior of alkali and alkaline earth metals in nonaqueous battery systems—the solid electrolyte interphase model. J. Electrochem. Soc. 126, 2047–2051 (1979).

    Article  Google Scholar 

  7. Li, G. et al. Three-dimensional porous carbon composites containing high sulfur nanoparticle content for high-performance lithium–sulfur batteries. Nat. Commun. 7, 10601 (2016).

    Article  Google Scholar 

  8. Ma, L. et al. Enhanced Li–S batteries using amine-functionalized carbon nanotubes in the cathode. ACS Nano 10, 1050–1059 (2016).

    Article  Google Scholar 

  9. Xiao, Z. et al Lightweight TiO2/graphene interlayer, applied as a highly effective polysulfide absorbent for fast, long-life lithium–sulfur batteries. Adv. Mater. 27, 2891–2898 (2015).

    Article  Google Scholar 

  10. Jin, S. et al. Covalently connected carbon nanostructure for current collectors in both the cathode and anode of Li–S batteries. Adv. Mater. 28, 9094–9102 (2016).

    Article  Google Scholar 

  11. Patel, M. D., Cha, E., Kang, C., Gwalani, B. & Choi, W. High performance rechargeable Li–S batteries using binder-free large sulfur loaded three-dimensional carbon nanotubes. Carbon 118, 120–126 (2017).

    Article  Google Scholar 

  12. Qian, J. et al. High rate and stable cycling of lithium metal anode. Nat. Commun. 6, 6362 (2015).

    Article  Google Scholar 

  13. Ding, F. et al. Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. J. Am. Chem. Soc. 135, 4450–4456 (2013).

  14. Zhang, J. et al. Superior conductive solid-like electrolytes: nano confining liquids within the hollow structures. Nano Lett. 15, 3398–3402 (2015).

  15. Dudney, N. J. Addition of a thin-film inorganic solid electrolyte (lipon) as a protective film in lithium batteries with a liquid electrolyte. J. Power Sources 89, 176–179 (2000).

    Article  Google Scholar 

  16. Zheng, G. Y. et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes. Nat. Nanotech. 9, 618–623 (2014).

    Article  Google Scholar 

  17. Lee, H., Lee, D. J., Kim, Y.-J., Park, J.-K. & Kim, H.-T. A simple composite protective layer coating that enhances the cycling stability of lithium metal batteries. J. Power Sources 284, 103–108 (2015).

    Article  Google Scholar 

  18. Kozen, A. C. et al. Next-generation lithium metal anode engineering via atomic layer deposition. ACS Nano 9, 5884–5892 (2015).

    Article  Google Scholar 

  19. Yan, K. et al. Ultrathin two-dimensional atomic crystals as stable interfacial layer for improvement of lithium metal anode. Nano Lett. 14, 6016–6022 (2014).

    Article  Google Scholar 

  20. Zhang, R. et al. Conductive nanostructured scaffolds render low local current density to inhibit lithium dendrite growth. Adv. Mater. 28, 2155–2162 (2016).

    Article  Google Scholar 

  21. Aurbach, D., Zinigrad, E., Cohen, Y. & Teller, H. A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405–416 (2002).

    Article  Google Scholar 

  22. Lu, Y., Tu, Z. & Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 13, 961–969 (2014).

    Article  Google Scholar 

  23. Wang, D. et al. Towards high-safe lithium metal anodes: suppressing lithium dendrites via tuning surface energy. Adv. Sci. 4, 1600168 (2017).

    Article  Google Scholar 

  24. Wang, Q. H., Kalantar-Zadeh, K., Kis, A., Coleman, J. N. & Strano, M. S. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotech. 7, 699–712 (2012).

    Article  Google Scholar 

  25. Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).

    Article  Google Scholar 

  26. Dickinson, R. G. & Pauling, L. The crystal structure of molybdenite. J. Am. Chem. Soc. 45, 1466–1471 (1923).

    Article  Google Scholar 

  27. Bieker, G., Winter, M. & Bieker, P. Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. Phys. Chem. Chem. Phys. 17, 8670–8679 (2015).

  28. Nayak, A. P. et al. Pressure-dependent optical and vibrational properties of monolayer molybdenum disulfide. Nano Lett. 15, 346–353 (2014).

    Article  Google Scholar 

  29. Py, M. & Haering, R. Structural destabilization induced by lithium intercalation in MoS2 and related compounds. Can. J. Phys. 61, 76–84 (1983).

    Article  Google Scholar 

  30. Santa Ana, M., Mirabal, N., Benayenta, E., Gomez-Romero, P. & Gonzalez, G. Electrochemical behavior of lithium intercalated in a molybdenum disulfide-crown ether nanocomposite. Electrochim. Acta 53, 1432–1438 (2007).

    Article  Google Scholar 

  31. Teng, Y. et al. MoS2 nanosheets vertically grown on graphene sheets for lithium-ion battery anodes. ACS Nano 10, 8526–8535 (2016).

    Article  Google Scholar 

  32. Nayak, A. P. et al. Pressure-induced semiconducting to metallic transition in multilayered molybdenum disulphide. Nat. Commun. 5, 3731 (2014).

    Article  Google Scholar 

  33. Yang, L. et al. Lattice strain effects on the optical properties of MoS2 nanosheets. Sci. Rep. 4, 5649 (2014).

    Article  Google Scholar 

  34. Kappera, R. et al. Phase-engineered low-resistance contacts for ultrathin MoS2 transistors. Nat. Mater. 13, 1128–1134 (2014).

    Article  Google Scholar 

  35. Fang, R. et al. 3D interconnected electrode materials with ultrahigh areal sulfur loading for Li–S batteries. Adv. Mater. 28, 3374–3382 (2016).

    Article  Google Scholar 

  36. Zhang, S. S. New insight into liquid electrolyte of rechargeable lithium/sulfur battery. Electrochim. Acta 97, 226–230 (2013).

    Article  Google Scholar 

  37. Kim, H., Lee, J., Ahn, H., Kim, O. & Park, M. J. Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries. Nat. Commun. 6, 7278 (2015).

    Article  Google Scholar 

  38. Zhao, M.-Q. et al. Hierarchical vine-tree-like carbon nanotube architectures: in-situ CVD self-assembly and their use as robust scaffolds for lithium-sulfur batteries. Adv. Mater. 26, 7051–7058 (2014).

    Article  Google Scholar 

  39. Song, M.-K., Zhang, Y. & Cairns, E. J. A long-life, high-rate lithium/sulfur cell: a multifaceted approach to enhancing cell performance. Nano Lett. 13, 5891–5899 (2013).

    Article  Google Scholar 

  40. Zhao, M.-Q. et al. Unstacked double layer templated graphene for high-rate lithium–sulphur batteries. Nat. Commun. 5, 3410 (2014).

    Google Scholar 

  41. Zhou, Y. et al. Enabling prominent high-rate and cycle performances in one lithium–sulfur battery: designing perm-selective gateways for Li+ transportation in holey-CNT/S cathodes. Adv. Mater. 27, 3774–3781 (2015).

    Article  Google Scholar 

  42. Liu, Q.-C. et al. Artificial protection film on lithium metal anode toward long-cycle-life lithium–oxygen batteries. Adv. Mater. 27, 5241–5247 (2015).

    Article  Google Scholar 

  43. Cheng, X.-B. et al. Implantable solid electrolyte interphase in lithium-metal batteries. Chem 2, 258–270 (2017).

    Article  Google Scholar 

  44. Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. 136, B864–B871 (1964).

    Article  Google Scholar 

  45. Kresse, G. & Joubert, D. From ultra-soft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999).

    Article  Google Scholar 

  46. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  47. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  48. Petrova, N. V., Yakovkin, I. N. & Zeze, D. A. Metallization and stiffness of the Li-intercalated MoS2 bilayer. Appl. Surf. Sci. 353, 333–337 (2015).

    Article  Google Scholar 

  49. Sheppard, D., Xiao, P., Chemelewski, W., Johnson, D. D. & Henkelman, G. A generalized solid-state nudged elastic band method. J. Chem. Phys. 136, 074103 (2012).

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank J. Tour for discussions. We also thank KIST Jeonbuk (Korea Institute of Science and Technology at Jeonbuk) for providing the facility to carry out HRTEM and B. Gwalani for helping out with additional EDX analysis. W.C. acknowledges partial financial support from SEED fund at University of North Texas. K.C. acknowledges a part of financial support by the International Energy Joint R & D Program (No. 20168510011350) of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), the Ministry of Knowledge Economy and the National Research Foundation of Creative Materials Discovery Program (2015M3D1A1068062).

Author information

Authors and Affiliations

Authors

Contributions

W.C. conceived the idea and designed the experiments. E.C. performed the cell fabrication, battery testing, SEM and TEM characterizations. W.C. and E.C. wrote the manuscript. M.D.P. performed the EIS measurements and cathode characterization. J.P. performed nano coating and analysed the Raman and XPS data. J.H. and K.C. performed the numerical simulation and provided data analysis. V.P. analysed the materials characterization data and edited the manuscript. All authors have discussed the results, read the manuscript and agreed with its content.

Corresponding author

Correspondence to Wonbong Choi.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Notes 1–4 and Supplementary Figures 1–19, Supplementary Tables 1–2.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cha, E., Patel, M.D., Park, J. et al. 2D MoS2 as an efficient protective layer for lithium metal anodes in high-performance Li–S batteries. Nature Nanotech 13, 337–344 (2018). https://doi.org/10.1038/s41565-018-0061-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41565-018-0061-y

This article is cited by

Search

Quick links

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