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:

Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries

Nature Chemistry (2024)Cite this article

Subjects

Abstract

Lithium metal batteries represent a promising technology for next-generation energy storage, but they still suffer from poor cycle life due to lithium dendrite formation and cathode cracking. Fluorinated solvents can improve battery longevity by improving LiF content in the solid–electrolyte interphase; however, the high cost and environmental concerns of fluorinated solvents limit battery viability. Here we designed a series of fluorine-free solvents through the methylation of 1,2-dimethoxyethane, which promotes inorganic LiF-rich interphase formation through anion reduction and achieves high oxidation stability. The anion-derived LiF interphases suppress lithium dendrite growth on the lithium anode and minimize cathode cracking under high-voltage operation. The Li+-solvent structure is investigated through in situ techniques and simulations to draw correlations between the interphase compositions and electrochemical performances. The methylation strategy provides an alternative pathway for electrolyte engineering towards high-voltage electrolytes while reducing dependence on expensive fluorinated solvents.

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: Methylation design on DME molecules to enhance the electrochemical performance when formulating electrolytes with LiFSI salt.
Fig. 2: Electrochemical performance of 2.0 M LiFSI electrolytes using different solvents.
Fig. 3: Molecular dynamics solvation investigation of the studied electrolytes.
Fig. 4: Lithium plating/stripping in methylated DME/LiFSI electrolytes.
Fig. 5: Scanning electron microscope images illustrating lithium metal morphology after 50 cycles in Li||NCA cells with the investigated electrolytes.
Fig. 6: Li||NCA full cell performance with different areal loadings and N/P ratios.

Similar content being viewed by others

Data availability

We declare that the data supporting the findings of this study are available within the article and its Supplementary Information. An archive containing a final configuration from molecular dynamics simulations, force field, simulation parameters and molecular dynamics code is provided. Source data are provided with this paper.

References

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

    Article  CAS  Google Scholar 

  2. Cao, Y. et al. Bridging the academic and industrial metrics for next-generation practical batteries. Nat. Nanotechnol. 14, 200–207 (2019).

    Article  CAS  PubMed  Google Scholar 

  3. Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

    Article  CAS  Google Scholar 

  4. Albertus, P. et al. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy 3, 16–21 (2017).

    Article  Google Scholar 

  5. 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).

    Article  CAS  Google Scholar 

  6. Fan, X. et al. Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery. Sci. Adv. 4, eaau9245 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  8. McLafferty, F. W. Mass spectrometric analysis of aliphatic ethers. Anal. Chem. 29, 1782–1789 (1957).

    Article  CAS  Google Scholar 

  9. Sun, W. et al. Insights into the oxidation kinetics of a cetane improver—1,2-dimethoxyethane (1,2-DME) with experimental and modeling methods. Proc. Combust. Inst. 37, 555–564 (2019).

    Article  CAS  Google Scholar 

  10. Di Tommaso, S., Rotureau, P. & Adamo, C. Oxidation mechanism of aliphatic ethers: theoretical insights on the main reaction channels. J. Phys. Chem. A 116, 9010–9019 (2012).

    Article  CAS  PubMed  Google Scholar 

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

    Article  CAS  PubMed  Google Scholar 

  12. Jiao, S. et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3, 739–746 (2018).

    Article  CAS  Google Scholar 

  13. Zheng, J. et al. Manipulating electrolyte and solid electrolyte interphase to enable safe and efficient Li–S batteries. Nano Energy 50, 431–440 (2018).

    Article  CAS  Google Scholar 

  14. Suo, L. et al. A new class of solvent-in-salt electrolytes for high-energy rechargeable metallic lithium batteries. Nat. Commun. 4, 1481 (2013).

    Article  PubMed  Google Scholar 

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

    Article  Google Scholar 

  16. 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).

    Article  CAS  Google Scholar 

  17. Cao, X. et al. Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries. Proc. Natl Acad. Sci. USA 118, 2020357118 (2021).

    Article  Google Scholar 

  18. Yu, Z. et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries. Nat. Energy 5, 526–533 (2020).

    Article  CAS  Google Scholar 

  19. Yu, Z. et al. Rational solvent molecule tuning for high-performance lithium metal battery electrolytes. Nat. Energy 7, 94–106 (2022).

    Article  CAS  Google Scholar 

  20. Ajanovic, A. & Haas, R. Economic and environmental prospects for battery electric‐ and fuel cell vehicles: a review. Fuel Cells 19, 515–529 (2019).

    Article  CAS  Google Scholar 

  21. Bai, Y. et al. Energy and environmental aspects in recycling lithium-ion batteries: concept of battery identity global passport. Mater. Today 41, 304–315 (2020).

    Article  CAS  Google Scholar 

  22. Chen, Y. et al. Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery. J. Am. Chem. Soc. 143, 18703–18713 (2021).

    Article  CAS  PubMed  Google Scholar 

  23. Park, E. et al. Exploiting the steric effect and low dielectric constant of 1,2-dimethoxypropane for 4.3 V lithium metal batteries. ACS Energy Lett. 8, 179–188 (2022).

    Article  Google Scholar 

  24. Sharon, D. et al. 2,4-Dimethoxy-2,4-dimethylpentan-3-one: an aprotic solvent designed for stability in Li–O2 cells. J. Am. Chem. Soc. 139, 11690–11693 (2017).

    Article  CAS  PubMed  Google Scholar 

  25. Camacho-Forero, L. E. & Balbuena, P. B. Elucidating electrolyte decomposition under electron-rich environments at the lithium-metal anode. Phys. Chem. Chem. Phys. 19, 30861–30873 (2017).

    Article  CAS  PubMed  Google Scholar 

  26. Freunberger, S. A. et al. The lithium-oxygen battery with ether-based electrolytes. Angew. Chem. Int. Ed. 50, 8609–8613 (2011).

    Article  CAS  Google Scholar 

  27. Bryantsev, V. S. et al. Predicting solvent stability in aprotic electrolyte Li–air batteries: nucleophilic substitution by the superoxide anion radical (O2•–). J. Phys. Chem. A 115, 12399–12409 (2011).

    Article  CAS  PubMed  Google Scholar 

  28. Bryantsev, V. S. et al. The identification of stable solvents for nonaqueous rechargeable Li-air batteries. J. Electrochem. Soc. 160, A160 (2012).

    Article  Google Scholar 

  29. Alvarado, J. et al. Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ. Sci. 12, 780–794 (2019).

    Article  CAS  Google Scholar 

  30. Xie, J. D. et al. Superior Coulombic efficiency of lithium anodes for rechargeable batteries utilizing high-concentration ether electrolytes. Electrochim. Acta 319, 625–633 (2019).

    Article  CAS  Google Scholar 

  31. Chen, S. et al. High-efficiency lithium metal batteries with fire-retardant electrolytes. Joule 2, 1548–1558 (2018).

    Article  CAS  Google Scholar 

  32. Hayashi, K. et al. Dependence of lithium metal secondary cell performance on lithium cation solvation state. J. Power Sources 81, 782–785 (1999).

    Article  Google Scholar 

  33. Thielen, J. et al. Multinuclear NMR study of structure and mobility in cyclic model lithium conducting systems. Appl. Magn. Reson. 45, 1063–1073 (2014).

    Article  CAS  Google Scholar 

  34. Deng, X. et al. Natural abundance 17O nuclear magnetic resonance and computational modeling studies of lithium-based liquid electrolytes. J. Power Sources 285, 146–155 (2015).

    Article  CAS  Google Scholar 

  35. Ma, P., Mirmira, P. & Amanchukwu, C. V. Effect of building block connectivity and ion solvation on electrochemical stability and ionic conductivity in novel fluoroether electrolytes. ACS Cent. Sci. 7, 1232–1244 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  36. Wan, C. et al. Natural abundance 17O, 6Li NMR and molecular modeling studies of the solvation structures of lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane liquid electrolytes. J. Power Sources 307, 231–243 (2016).

    Article  CAS  Google Scholar 

  37. Ren, X. et al. Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019).

    Article  CAS  Google Scholar 

  38. Martin, P. A. et al. Correlating intermolecular cross-relaxation rates with distances and coordination numbers in ionic liquids. J. Phys. Chem. Lett. 9, 7072–7078 (2018).

    Article  CAS  PubMed  Google Scholar 

  39. Kumar, V. et al. Lithium speciation in the LiPF6/PC electrolyte studied by two-dimensional heteronuclear Overhauser enhancement and pulse-field gradient diffusometry NMR. J. Phys. Chem. C 123, 9661–9672 (2019).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  41. Hobold, G. M. et al. Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes. Nat. Energy 6, 951–960 (2021).

    Article  CAS  Google Scholar 

  42. Xue, W. et al. Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte. Nat. Energy 6, 495–505 (2021).

    Article  CAS  Google Scholar 

  43. Fang, C. et al. Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019).

    Article  CAS  PubMed  Google Scholar 

  44. Guo, R. & Gallant, B. M. Li2O solid electrolyte interphase: probing transport properties at the chemical potential of lithium. Chem. Mater. 32, 5525–5533 (2020).

    Article  CAS  Google Scholar 

  45. May, R. et al. Rapid interfacial exchange of Li ions dictates high Coulombic efficiency in Li metal anodes. ACS Energy Lett. 6, 1162–1169 (2021).

    Article  CAS  Google Scholar 

  46. Fairley, N. et al. Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy. Appl. Surf. Sci. 5, 100112 (2021).

    Article  Google Scholar 

  47. Hammersley, A. P. FIT2D: a multi-purpose data reduction, analysis and visualization program. J. Appl. Crystallogr. 49, 646–652 (2016).

    Article  CAS  Google Scholar 

  48. Qiu, X., Thompson, J. W. & Billinge, S. J. L. PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data. J. Appl. Crystallogr. 37, 678 (2004).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the US Department of Energy (DOE) under award no. DE-EE0008202 (C.W.) & DE-SC0023408 (C.W.) at the University of Maryland (UMD). The work at Brookhaven National Laboratory is supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the US Department of Energy (DOE) through the Advanced Battery Materials Research (BMR) Program under contract no. DE-SC0012704 (E.H. and X.-Q.Y.). This research used 28-ID-2 beamline of the National Synchrotron Light Source II, US DOE Office of Science User Facilities, operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704 (E.H. and X.-Q.Y.). Modelling work was supported by DEVCOM ARL and the Center for Research on Extreme Batteries (O.B.).

Author information

Authors and Affiliations

  1. Department of Chemical and Biomolecular Engineering, University of Maryland, College Park, MD, USA

    Ai-Min Li, Weiran Zhang, Nan Zhang & Chunsheng Wang

  2. Battery Science Branch, DEVCOM Army Research Laboratory, Adelphi, MD, USA

    Oleg Borodin & Travis P. Pollard

  3. Chemistry Division, Brookhaven National Laboratory, Upton, NY, USA

    Sha Tan, Enyuan Hu & Xiao-Qing Yang

  4. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, USA

    Fu Chen

  5. Department of Chemistry, University of Rhode Island, Kingston, RI, USA

    Chamithri Jayawardana & Brett L. Lucht

Authors
  1. Ai-Min Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Oleg Borodin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Travis P. Pollard
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Weiran Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Nan Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sha Tan
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Fu Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chamithri Jayawardana
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Brett L. Lucht
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Enyuan Hu
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Xiao-Qing Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Chunsheng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

A.-M.L. and C.W. conceived the idea for the project and wrote the paper. O.B. and T.P.P. conducted and analysed the DFT calculations and molecular dynamics simulations and also assisted with paper revision and mechanism identification. W.Z and N.Z. assisted with electrochemical cell tests. F.C. helped with the NMR set-up. C.J. and B.L.L. helped with the XPS data collection. S.T., E.H. and X.-Q.Y. helped with the synchrotron data collection and analysis. All of the authors discussed the results and analysed the data.

Corresponding author

Correspondence to Chunsheng Wang.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Chemistry thanks JianZhi Hu 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 Notes 1–5, Tables 1–5, Figs. 1–46, synthetic details and references.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Source Data Fig. 6

Statistical source data.

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

Li, AM., Borodin, O., Pollard, T.P. et al. Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01497-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s41557-024-01497-x

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