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:

Homogeneous and mechanically stable solid–electrolyte interphase enabled by trioxane-modulated electrolytes for lithium metal batteries

Nature Energy volume 8, pages 725–735 (2023)Cite this article

Subjects

Abstract

The solid–electrolyte interphase (SEI) in lithium (Li) metal batteries is often heterogeneous, containing a diverse range of species and has poor mechanical stability. The SEI undergoes constant cracking and reconstruction during electrochemical cycling, which is accompanied by the exhaustion of active Li and electrolytes, hindering practical applications of the batteries. Here we propose an in situ structural design of SEI to promote its homogeneity and improve its mechanical stability. A bilayer structure of SEI is tailored through trioxane-modulated electrolytes: the inner layer is dominated by LiF to improve homogeneity while the outer layer contains Li polyoxymethylene to improve mechanical stability, synergistically leading to mitigated reconstruction of SEI and reversible Li plating/stripping. The coin cell consisting of an ultrathin Li metal anode (50 μm) and a high-loading cathode (3.0 mAh cm−2)—with the tailored bilayer SEI—achieves 430 cycles tested at 1.2 mA cm−2, while the cell with an anion-derived SEI undergoes only 200 cycles under same conditions. A prototype 440 Wh kg−1 pouch cell (5.3 Ah), with a low negative/positive capacity ratio of 1.8 and lean electrolytes of 2.1 g Ah−1, achieves 130 cycles.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Schematic diagram of the structural evolution of single-layer and tailored bilayer SEIs during Li plating.
Fig. 2: The solvation structure and reduction behaviour of DME- and TO-based electrolytes.
Fig. 3: The 3D nanostructure of SEI resolved by ToF-SIMS.
Fig. 4: The formation process and mechanical stability of SEI resolved by in situ electrochemical AFM.
Fig. 5: The effects of various SEIs on cycling stability of Li metal coin cells, Li morphology and interfacial kinetics.
Fig. 6: The performance of 440 Wh kg−1 Li metal pouch cells enabled by tailored bilayer SEI.

Similar content being viewed by others

Data availability

The data supporting the findings of this study are available within the article and its supplementary information files.

References

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

    Google Scholar 

  2. Winter, M., Barnett, B. & Xu, K. Before Li ion batteries. Chem. Rev. 118, 11433–11456 (2018).

    Google Scholar 

  3. Cheng, X.-B. et al. Toward safe lithium metal anode in rechargeable batteries: a review. Chem. Rev. 117, 10403–10473 (2017).

    Google Scholar 

  4. Louli, A. J. et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis. Nat. Energy 5, 693–702 (2020).

    Google Scholar 

  5. Zhou, M. Y. et al. Quantifying the apparent electron transfer number of electrolyte decomposition reactions in anode-free batteries. Joule 6, 2122–2137 (2022).

    Google Scholar 

  6. Liu, J. et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nat. Energy 4, 180–186 (2019).

    Google Scholar 

  7. Chen, S. et al. Critical parameters for evaluating coin cells and pouch cells of rechargeable Li-metal batteries. Joule 3, 1094–1105 (2019).

    Google Scholar 

  8. 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).

    Google Scholar 

  9. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 104, 4303–4418 (2004).

    Google Scholar 

  10. Tikekar, M. D. et al. Design principles for electrolytes and interfaces for stable lithium-metal batteries. Nat. Energy 1, 16114 (2016).

    Google Scholar 

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

    Google Scholar 

  12. Yoon, I. et al. Measurement of mechanical and fracture properties of solid electrolyte interphase on lithium metal anodes in lithium ion batteries. Energy Storage Mater. 25, 296–304 (2020).

    Google Scholar 

  13. Gao, Y. et al. Unraveling the mechanical origin of stable solid electrolyte interphase. Joule 5, 1860–1872 (2021).

    Google Scholar 

  14. Li, Y. et al. Correlating structure and function of battery interphases at atomic resolution using cryoelectron microscopy. Joule 2, 2167–2177 (2018).

    Google Scholar 

  15. Wang, W. W. et al. Evaluating solid-electrolyte interphases for lithium and lithium-free anodes from nanoindentation features. Chem 6, 2728–2745 (2020).

    Google Scholar 

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

    Google Scholar 

  17. Zhang, X. Q. et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries. Adv. Funct. Mater. 27, 1605989 (2017).

    Google Scholar 

  18. Aurbach, D. et al. On the surface chemical aspects of very high energy density, rechargeable Li–sulfur batteries. J. Electrochem. Soc. 156, A694–A702 (2009).

    Google Scholar 

  19. Liu, Y. et al. Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode. Nat. Commun. 9, 3656 (2018).

    Google Scholar 

  20. Zhang, X. Q. et al. Highly stable lithium metal batteries enabled by regulating the solvation of lithium ions in nonaqueous electrolytes. Angew. Chem. Int. Ed. 57, 5301–5305 (2018).

    Google Scholar 

  21. Ramasubramanian, A. et al. Lithium diffusion mechanism through solid–electrolyte interphase in rechargeable lithium batteries. J. Phys. Chem. C. 123, 10237–10245 (2019).

    Google Scholar 

  22. Chen, S. et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018).

    Google Scholar 

  23. Wang, H. et al. Dual-solvent Li-ion solvation enables high-performance Li-metal batteries. Adv. Mater. 33, 2008619 (2021).

    Google Scholar 

  24. Cao, X. et al. Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization. Nat. Energy 4, 796–805 (2019).

    Google Scholar 

  25. 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).

    Google Scholar 

  26. Zhang, Z. et al. Operando electrochemical atomic force microscopy of solid–electrolyte interphase formation on graphite anodes: the evolution of SEI morphology and mechanical properties. ACS Appl. Mater. Interfaces 12, 35132–35141 (2020).

    Google Scholar 

  27. Gao, Y. & Zhang, B. Probing the mechanically stable solid electrolyte interphase and the implications in design strategies. Adv. Mater. 34, e2205421 (2022).

    Google Scholar 

  28. Zhang, D. et al. Atomic-resolution transmission electron microscopy of electron beam-sensitive crystalline materials. Science 359, 675–679 (2018).

    Google Scholar 

  29. Peled, E., Golodnitsky, D. & Ardel, G. Advanced model for solid electrolyte interphase electrodes in liquid and polymer electrolytes. J. Electrochem. Soc. 144, L208–L210 (1997).

    Google Scholar 

  30. Weissermel, K. et al. Polymerization of trioxane. Angew. Chem. Int. Ed. 6, 526–533 (1967).

    Google Scholar 

  31. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 114, 11503–11618 (2014).

    Google Scholar 

  32. Aurbach, D., Youngman, O. & Dan, P. The electrochemical behavior of 1,3-dioxolane—LiClO4 solutions—II. contaminated solutions. Electrochim. Acta 35, 639–655 (1990).

    Google Scholar 

  33. Greene, J. P. in Automotive Plastics and Composites Ch. 8 (William Andrew Publishing, 2021).

  34. Han, J. et al. Calculated reduction potentials of electrolyte species in lithium–sulfur batteries. J. Phys. Chem. C. 124, 20654–20670 (2020).

    Google Scholar 

  35. Wang, Y. et al. Theoretical studies to understand surface chemistry on carbon anodes for lithium-ion batteries: how does vinylene carbonate play its role as an electrolyte additive? J. Am. Chem. Soc. 124, 4408–4421 (2002).

    Google Scholar 

  36. Zhang, X. Q. et al. Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries. ACS Energy Lett. 4, 411–416 (2019).

    Google Scholar 

  37. Deng, X. et al. Morphology and modulus evolution of graphite anode in lithium ion battery: an in situ AFM investigation. Sci. China Chem. 57, 178–183 (2014).

    Google Scholar 

  38. Zhang, Z. et al. Characterizing batteries by in situ electrochemical atomic force microscopy: a critical review. Adv. Energy Mater. 11, 2101518 (2021).

    Google Scholar 

  39. Lu, Y. et al. The timescale identification decoupling complicated kinetic processes in lithium batteries. Joule 6, 1172–1198 (2022).

    Google Scholar 

  40. Wan, T. H., Saccoccio, M., Chen, C. & Ciucci, F. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015).

    Google Scholar 

  41. Zhao, Q. et al. Upgrading carbonate electrolytes for ultra-stable practical lithium metal batteries. Angew. Chem. Int. Ed. 61, e202116214 (2022).

    Google Scholar 

  42. Niu, C. et al. High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019).

    Google Scholar 

  43. Qiao, Y. et al. A high-energy-density and long-life initial-anode-free lithium battery enabled by a Li2O sacrificial agent. Nat. Energy 6, 653–662 (2021).

    Google Scholar 

  44. Gao, Y. et al. Effect of the supergravity on the formation and cycle life of non-aqueous lithium metal batteries. Nat. Commun. 13, 5 (2022).

    Google Scholar 

  45. Niu, C. et al. Balancing interfacial reactions to achieve long cycle life in high-energy lithium metal batteries. Nat. Energy 6, 723–732 (2021).

    Google Scholar 

  46. Zhang, L. et al. Practical 4.4 V Li||NCM811 batteries enabled by a thermal stable and HF free carbonate-based electrolyte. Nano Energy 96, 107122 (2022).

    Google Scholar 

  47. He, B. et al. Scalable fabrication of a large-area lithium/graphene anode towards a long-life 350 W h kg−1 lithium metal pouch cell. J. Mater. Chem. A 9, 25558–25566 (2021).

    Google Scholar 

  48. Tang, Y. et al. Metal carbodiimides-derived organic–inorganic interface protective layer for practical high energy lithium metal batteries. J. Power Sources 536, 231479 (2022).

    Google Scholar 

  49. Becke, A. D. Density-functional thermochemistry. III. the role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).

    Google Scholar 

  50. Frisch, M. J. et al. Gaussian 09 Revision A.02 (Gaussian Inc., 2009).

  51. Marenich, A. V., Cramer, C. J. & Truhlar, D. G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. B 113, 6378–6396 (2009).

    Google Scholar 

  52. Steve, P. Fast parallel algorithms for short-range molecular-dynamics. J. Comput. Phys. 117, 1–19 (1995).

    MATH  Google Scholar 

  53. Jorgensen, W. L., Maxwell, D. S. & Tirado-Rives, J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. J. Am. Chem. Soc. 118, 11225–11236 (1996).

    Google Scholar 

  54. Schauperl, M. et al. Non-bonded force field model with advanced restrained electrostatic potential charges (RESP2). Commun. Chem. 3, 44 (2020).

    Google Scholar 

  55. Lu, T. & Chen, F.-W. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).

    Google Scholar 

  56. Jensen, K. P. & Jorgensen, W. L. Halide, ammonium, and alkali metal ion parameters for modeling aqueous solutions. J. Chem. Theory Comput. 2, 1499–1509 (2006).

    Google Scholar 

  57. Canongia Lopes, J. N. et al. Potential energy landscape of bis(fluorosulfonyl)amide. J. Phys. Chem. B 112, 9449–9455 (2008).

    Google Scholar 

  58. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).

    Google Scholar 

Download references

Acknowledgements

J.-Q.H. acknowledges support by the National Key Research and Development Program (2021YFB2400300 and 2021YFB2500300) and Beijing Natural Science Foundation (JQ20004). X.-Q.Z. acknowledges support by the National Natural Science Foundation of China (22209010), China Postdoctoral Science Foundation (2021M700404) and Beijing Institute of Technology Research Fund Program for Young Scholars. X.C. acknowledges support by National Natural Science Foundation of China (22109086). We also acknowledge the support from Tsinghua National Laboratory for Information Science and Technology for theoretical simulations. We thank G.-X. Liu, J.-X. Tian, S.-Y. Sun, X.-Q. Ding and Y.-Q. Li for their helpful discussions.

Author information

Author notes

  1. These authors contributed equally: Qian-Kui Zhang, Xue-Qiang Zhang.

Authors and Affiliations

  1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, China

    Qian-Kui Zhang, Xue-Qiang Zhang, Ting-Lu Song, Bo-Quan Li & Jia-Qi Huang

  2. Advanced Research Institute of Multidisciplinary Science, Beijing Institute of Technology, Beijing, China

    Qian-Kui Zhang, Xue-Qiang Zhang, Bo-Quan Li & Jia-Qi Huang

  3. Key Laboratory of Molecular Nanostructure and Nanotechnology and Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China

    Jing Wan & Rui Wen

  4. University of Chinese Academy of Sciences, Beijing, China

    Jing Wan & Rui Wen

  5. Beijing Key Laboratory of Green Chemical, Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Nan Yao, Jin Xie, Li-Peng Hou, Ming-Yue Zhou, Xiang Chen & Qiang Zhang

  6. Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, China

    Hong-Jie Peng

Authors
  1. Qian-Kui Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xue-Qiang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jing Wan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nan Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ting-Lu Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jin Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Li-Peng Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Ming-Yue Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Xiang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Bo-Quan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Rui Wen
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Hong-Jie Peng
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Qiang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Jia-Qi Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.-Q.H. and X.-Q.Z. conceived and designed the experiments. Q.-K.Z. assembled the coin cells and pouch cells. Q.-K.Z., X.-Q.Z., J.X., L.-P.H. and B.-Q.L. carried out material characterizations and electrochemical measurements. J.W. and R.W. performed in situ AFM characterization. T.-L.S carried out the ToF-SIMS tests. N.Y. and X.C. performed the MD simulations. J.-Q.H. supervised this project. All authors engaged in result discussions. X.-Q.Z, M.-Y.Z, H.-J.P., Q.Z. and J.-Q.H. co-wrote the paper with input from all authors.

Corresponding author

Correspondence to Jia-Qi Huang.

Ethics declarations

Competing interests

A patent related to the work has been submitted (application number CN202210942310.X) by Beijing Institute of Technology. The inventors are Jia-Qi Huang, Qian-Kui Zhang and Xue-Qiang Zhang. The patent refers to the methodology in this paper but provides more analogous additives than this work. The other authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Chaojiang Niu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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 Figs. 1–33 and Tables 1–4.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, QK., Zhang, XQ., Wan, J. et al. Homogeneous and mechanically stable solid–electrolyte interphase enabled by trioxane-modulated electrolytes for lithium metal batteries. Nat Energy 8, 725–735 (2023). https://doi.org/10.1038/s41560-023-01275-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-023-01275-y

This article is cited by

Search

Advanced 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