Article | Published:

Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions

Nature Materialsvolume 18pages384389 (2019) | Download Citation



The solid–electrolyte interphase (SEI) is pivotal in stabilizing lithium metal anodes for rechargeable batteries. However, the SEI is constantly reforming and consuming electrolyte with cycling. The rational design of a stable SEI is plagued by the failure to control its structure and stability. Here we report a molecular-level SEI design using a reactive polymer composite, which effectively suppresses electrolyte consumption in the formation and maintenance of the SEI. The SEI layer consists of a polymeric lithium salt, lithium fluoride nanoparticles and graphene oxide sheets, as evidenced by cryo-transmission electron microscopy, atomic force microscopy and surface-sensitive spectroscopies. This structure is different from that of a conventional electrolyte-derived SEI and has excellent passivation properties, homogeneity and mechanical strength. The use of the polymer–inorganic SEI enables high-efficiency Li deposition and stable cycling of 4 V Li|LiNi0.5Co0.2Mn0.3O2 cells under lean electrolyte, limited Li excess and high capacity conditions. The same approach was also applied to design stable SEI layers for sodium and zinc anodes.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Data availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

Additional information

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


  1. 1.

    Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

  2. 2.

    Goodenough, J. B. & Park, K.-S. S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).

  3. 3.

    Choi, N. S. et al. Challenges facing lithium batteries and electrical double-layer capacitors. Angew. Chem. Int. Ed. 51, 9994–10024 (2012).

  4. 4.

    Kim, H. et al. Metallic anodes for next generation secondary batteries. Chem. Soc. Rev. 42, 9011–9034 (2013).

  5. 5.

    Peled, E. & Menkin, S. Review—SEI: past, present and future. J. Electrochem. Soc. 164, A1703–A1719 (2017).

  6. 6.

    Aurbach, D. Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries. J. Power Sources 89, 206–218 (2000).

  7. 7.

    Lin, D., Liu, Y. & Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017).

  8. 8.

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

  9. 9.

    Cheng, X. B., Zhang, R., Zhao, C. Z. & Zhang, Q. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).

  10. 10.

    Tikekar, M. D., Choudhury, S., Tu, Z. & Archer, L. A. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).

  11. 11.

    Sacci, R. L. et al. Direct visualization of initial SEI morphology and growth kinetics during lithium deposition by in situ electrochemical transmission electron microscopy. Chem. Commun. 50, 2104 (2014).

  12. 12.

    Lin, D. et al. Layered reduced graphene oxide with nanoscale interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 11, 626–632 (2016).

  13. 13.

    Ye, H. et al. Stable Li plating/stripping electrochemistry realized by a hybrid Li reservoir in spherical carbon granules with 3D conducting skeletons. J. Am. Chem. Soc. 139, 5916–5922 (2017).

  14. 14.

    Yan, K. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat. Energy 1, 16010 (2016).

  15. 15.

    Li, G. et al. Stable metal battery anodes enabled by polyethylenimine sponge hosts by way of electrokinetic effects. Nat. Energy 3, 1076–1083 (2018).

  16. 16.

    Tung, S.-O., Ho, S., Yang, M., Zhang, R. & Kotov, N. A. A dendrite-suppressing composite ion conductor from aramid nanofibres. Nat. Commun. 6, 6152 (2015).

  17. 17.

    Cheng, X.-B. et al. Nanodiamonds suppress the growth of lithium dendrites. Nat. Commun. 8, 336 (2017).

  18. 18.

    Li, N.-W., Yin, Y.-X., Yang, C.-P. & Guo, Y.-G. An artificial solid electrolyte interphase layer for stable lithium metal anodes. Adv. Mater. 28, 1853–1858 (2016).

  19. 19.

    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).

  20. 20.

    Kazyak, E., Wood, K. N. & Dasgupta, N. P. Improved cycle life and stability of lithium metal anodes through ultrathin atomic layer deposition surface treatments. Chem. Mater. 27, 6457–6462 (2015).

  21. 21.

    Zhao, J. et al. Surface fluorination of reactive battery anode materials for enhanced stability. J. Am. Chem. Soc. 139, 11550–11558 (2017).

  22. 22.

    Liang, X. et al. A facile surface chemistry route to a stabilized lithium metal anode. Nat. Energy 6, 17119 (2017).

  23. 23.

    Tu, Z. et al. Designing artificial solid–electrolyte interphases for single-ion and high-efficiency transport in batteries. Joule 1, 394–406 (2017).

  24. 24.

    Liu, K. et al. Lithium metal anodes with an adaptive “Solid–liquid” interfacial protective layer. J. Am. Chem. Soc. 139, 4815–4820 (2017).

  25. 25.

    Choi, S. M. et al. Cycling characteristics of lithium metal batteries assembled with a surface modified lithium electrode. J. Power Sources 244, 363–368 (2013).

  26. 26.

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

  27. 27.

    Suo, L., Hu, Y.-S., Li, H., Armand, M. & Chen, L. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).

  28. 28.

    Basile, A., Bhatt, A. I. & O’Mullane, A. P. Stabilizing lithium metal using ionic liquids for long-lived batteries. Nat. Commun. 7, ncomms11794 (2016).

  29. 29.

    Lu, Y., Korf, K., Kambe, Y., Tu, Z. & Archer, L. A. Ionic–liquid–nanoparticle hybrid electrolytes: applications in lithium metal batteries. Angew. Chem. Int. Ed. 53, 488–492 (2014).

  30. 30.

    Fan, X. et al. Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018).

  31. 31.

    Zheng, J. et al. Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017).

  32. 32.

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

  33. 33.

    Markevich, E., Salitra, G. & Aurbach, D. Fluoroethylene carbonate as an important component for the formation of an effective solid electrolyte interphase on anodes and cathodes for advanced Li-ion batteries. ACS Energy Lett. 2, 1337–1345 (2017).

  34. 34.

    Zhang, Y. et al. Dendrite-free lithium deposition with self-aligned nanorod structure. Nano Lett. 14, 6889–6896 (2014).

  35. 35.

    Chen, S. et al. Functional organosulfide electrolyte promotes an alternate reaction pathway to achieve high performance in lithium-sulfur batteries. Angew. Chem. Int. Ed. 55, 4231–4235 (2016).

  36. 36.

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

  37. 37.

    Li, G. et al. Organosulfide-plasticized solid–electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries. Nat. Commun. 8, 850 (2017).

  38. 38.

    Zhang, H. et al. Electrolyte additives for lithium metal anodes and rechargeable lithium metal batteries: progress and perspectives. Angew. Chem. Int. Ed. 57, 15002–15027 (2018).

  39. 39.

    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).

  40. 40.

    Gao, Y. et al. Interfacial chemistry regulation via a skin-grafting strategy enables high-performance lithium-metal batteries. J. Am. Chem. Soc. 139, 15288–15291 (2017).

  41. 41.

    Gao, Y. et al. Salt-based organic–inorganic nanocomposites: towards a stable lithium metal/Li10GeP2S12 solid electrolyte interface. Angew. Chem. Int. Ed. 57, 13608–13612 (2018).

  42. 42.

    Li, Y. et al. Atomic structure of sensitive battery materials and interfaces revealed by cryo-electron microscopy. Science 358, 506–510 (2017).

  43. 43.

    Wang, X. et al. New insights on the structure of electrochemically deposited lithium metal and its solid electrolyte interphases via cryogenic TEM. Nano Lett. 17, 7606–7612 (2017).

  44. 44.

    Zachman, M. J., Tu, Z., Choudhury, S., Archer, L. A. & Kourkoutis, L. F. Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries. Nature 560, 345–349 (2018).

  45. 45.

    Foroozan, T. et al. Synergistic effect of graphene oxide for impeding the dendritic plating of Li. Adv. Funct. Mater. 28, 1705917 (2018).

  46. 46.

    Kovtyukhova, N. I. et al. Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations. Chem. Mater. 11, 771–778 (1999).

  47. 47.

    Green, C. P. & Sader, J. E. Frequency response of cantilever beams immersed in viscous fluids near a solid surface with applications to the atomic force microscope. J. Appl. Phys. 98, 114913 (2005).

  48. 48.

    Kuznetsov, V. et al. Wet nanoindentation of the solid electrolyte interphase on thin film Si electrodes. ACS Appl. Mater. Interfaces 7, 23554–23563 (2015).

  49. 49.

    Greaves, G. N., Greer, A. L., Lakes, R. S. & Rouxel, T. Poisson’s ratio and modern materials. Nat. Mater. 10, 823–837 (2011).

  50. 50.

    Carpick, R. W., Ogletree, D. F. & Salmeron, M. A General equation for fitting contact area and friction vs load measurements. J Colloid Interface Sci. 400, 395–400 (1999).

  51. 51.

    Piétrement, O. & Troyon, M. General equations describing elastic indentation depth and normal contact stiffness versus load. J. Colloid Interface Sci. 226, 166–171 (2000).

  52. 52.

    Ebenstein, D. M. & Wahl, K. J. A comparison of JKR-based methods to analyze quasi-static and dynamic indentation force curves. J. Colloid Interface Sci. 298, 652–662 (2006).

Download references


This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy, through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) award no. DE-EE0008198. Z.Y., Y.C.L. and T.E.M. acknowledge support from the National Science Foundation under grant DMR-1807116. X.H. and S.H.K. acknowledge support from the National Science Foundation under grant CMMI-1435766.

Author information


  1. Department of Chemistry, The Pennsylvania State University, University Park, PA, USA

    • Yue Gao
    • , Zhifei Yan
    • , Yuguang C. Li
    •  & Thomas E. Mallouk
  2. Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    • Jennifer L. Gray
    •  & Haiying Wang
  3. Department of Chemical Engineering and Materials Research Institute, The Pennsylvania State University, University Park, PA, USA

    • Xin He
    •  & Seong H. Kim
  4. Department of Mechanical and Nuclear Engineering, The Pennsylvania State University, University Park, PA, USA

    • Daiwei Wang
    • , Tianhang Chen
    • , Qingquan Huang
    •  & Donghai Wang


  1. Search for Yue Gao in:

  2. Search for Zhifei Yan in:

  3. Search for Jennifer L. Gray in:

  4. Search for Xin He in:

  5. Search for Daiwei Wang in:

  6. Search for Tianhang Chen in:

  7. Search for Qingquan Huang in:

  8. Search for Yuguang C. Li in:

  9. Search for Haiying Wang in:

  10. Search for Seong H. Kim in:

  11. Search for Thomas E. Mallouk in:

  12. Search for Donghai Wang in:


Y.G., T.E.M. and Do.W. conceived the idea, Y.G. and Do.W. designed the experiments, and Do.W. directed the project. Y.G. performed the material preparation and chemical and morphological characterization. Z.Y. prepared the graphene oxide materials. H.W. prepared the samples for cryo-TEM experiments. J.L.G. performed the cryo-TEM experiments. Y.G. and T.C. performed the battery tests. X.H. conducted the AFM indentation test. Y.G. and Y.C.L. performed the electrochemical impedance spectroscopy test. Y.G. and Da.W. conducted the SEM test. All authors discussed and analysed the data. Y.G., S.H.K, T.E.M. and Do.W. wrote the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Donghai Wang.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–42, Supplementary Table 1, Supplementary References 1–9

About this article

Publication history




Issue Date