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Fire-extinguishing, recyclable liquefied gas electrolytes for temperature-resilient lithium-metal batteries

Nature Energy volume 7, pages 548–559 (2022)Cite this article

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Abstract

High-energy density, improved safety, temperature resilience and sustainability are desirable properties for lithium-battery electrolytes, yet these metrics are rarely achieved simultaneously. Inspired by the compositions of clean fire-extinguishing agents, we demonstrate inherently safe liquefied gas electrolytes based on 1,1,1,2-tetrafluoroethane and pentafluoroethane that maintain >3 mS cm−1 ionic conductivity from −78 to +80 °C. As a result of beneficial solvation chemistry and a fluorine-rich environment, lithium cycling at >99% Coulombic efficiency for over 200 cycles at 3 mA cm−2 and 3 mAh cm−2 was demonstrated in addition to stable cycling of Li/NMC622 full batteries from −60 to +55 °C. In addition, we demonstrate a one-step solvent-recycling process based on the vapour pressure difference at different temperatures of the liquefied gas electrolytes, which promises sustainable operation at scale. This work provides a route to sustainable, temperature-resilient lithium-metal batteries with fire-extinguishing properties that maintain state-of-the-art electrochemical performance.

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Fig. 1: Design of LGEs.
Fig. 2: Properties of LGEs.
Fig. 3: Bulk structure and MD simulation results of the formulated electrolytes.
Fig. 4: Electrochemical performance of Li-metal anode and Li/NMC622 cells in different electrolytes.
Fig. 5: Visualization of Li morphology and SEI.
Fig. 6: SEI information obtained by XPS measurements with electrolytes.
Fig. 7: Recycling concept and demonstration of LGEs.

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Data availability

All the data generated in this study are included in the Article and its Supplementary Information. Source data are provided with this paper.

Code availability

The MD simulation code is available in Supplementary Data 1.

References

  1. Hesse, H. C., Schimpe, M., Kucevic, D. & Jossen, A. Lithium-ion battery storage for the grid—a review of stationary battery storage system design tailored for applications in modern power grids. Energies 10, 2107 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  5. Liu, Y. et al. Making Li-metal electrodes rechargeable by controlling the dendrite growth direction. Nat. Energy 2, 17083 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  7. Wang, J. et al. Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy. Nat. Energy 4, 664–670 (2019).

    Article  Google Scholar 

  8. Hess, S., Wohlfahrt-Mehrens, M. & Wachtler, M. Flammability of Li-ion battery electrolytes: flash point and self-extinguishing time measurements. J. Electrochem. Soc. 162, A3084–A3097 (2015).

    Article  Google Scholar 

  9. Xu, K., Zhang, S., Allen, J. L. & Jow, T. R. Evaluation of fluorinated alkyl phosphates as flame retardants in electrolytes for Li-ion batteries: II. Performance in cell. J. Electrochem. Soc. 150, A170 (2003).

    Article  Google Scholar 

  10. Xu, P. et al. Efficient direct recycling of lithium-ion battery cathodes by targeted healing. Joule 4, 2609–2626 (2020).

    Article  Google Scholar 

  11. Xu, P., Tan, D. H. S. & Chen, Z. Emerging trends in sustainable battery chemistries. Trends Chem. 3, 620–630 (2021).

    Article  Google Scholar 

  12. Tan, D. H., Banerjee, A., Chen, Z. & Meng, Y. S. From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. 15, 170–180 (2020).

    Article  Google Scholar 

  13. Sun, H. et al. High-safety and high-energy-density lithium metal batteries in a novel ionic-liquid electrolyte. Adv. Mater. 32, 2001741 (2020).

    Article  Google Scholar 

  14. Banerjee, A., Wang, X., Fang, C., Wu, E. A. & Meng, Y. S. Interfaces and interphases in all-solid-state batteries with inorganic solid electrolytes. Chem. Rev. 120, 6878–6933 (2020).

    Article  Google Scholar 

  15. Wu, L. et al. A new phosphate-based nonflammable electrolyte solvent for Li-ion batteries. J. Power Sources 188, 570–573 (2009).

    Article  Google Scholar 

  16. Zeng, Z. et al. Safer lithium ion batteries based on nonflammable electrolyte. J. Power Sources 279, 6–12 (2015).

    Article  Google Scholar 

  17. Shiga, T., Kato, Y., Kondo, H. & Okuda, C.-A. Self-extinguishing electrolytes using fluorinated alkyl phosphates for lithium batteries. J. Mater. Chem. A 5, 5156–5162 (2017).

    Article  Google Scholar 

  18. Ota, H., Kominato, A., Chun, W.-J., Yasukawa, E. & Kasuya, S. Effect of cyclic phosphate additive in non-flammable electrolyte. J. Power Sources 119–121, 393–398 (2003).

    Article  Google Scholar 

  19. Wang, J. et al. Fire-extinguishing organic electrolytes for safe batteries. Nat. Energy 3, 22–29 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  21. Ren, X. et al. Localized high-concentration sulfone electrolytes for high-efficiency lithium-metal batteries. Chem 4, 1877–1892 (2018).

    Article  Google Scholar 

  22. Cao, X. et al. Nonflammable electrolytes for lithium ion batteries enabled by ultraconformal passivation interphases. ACS Energy Lett. 4, 2529–2534 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

  24. Fan, X. et al. All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents. Nat. Energy 4, 882–890 (2019).

    Article  Google Scholar 

  25. Wang, Q., Mao, B., Stoliarov, S. I. & Sun, J. A review of lithium ion battery failure mechanisms and fire prevention strategies. Prog. Energy Combust. Sci. 73, 95–131 (2019).

    Article  Google Scholar 

  26. Rustomji, C. S. et al. Liquefied gas electrolytes for electrochemical energy storage devices. Science, https://doi.org/10.1126/science.aal4263 (2017).

  27. Yang, Y. et al. High-efficiency lithium-metal anode enabled by liquefied gas electrolytes. Joule 3, 1986–2000 (2019).

    Article  Google Scholar 

  28. Yang, Y. et al. Liquefied gas electrolytes for wide-temperature lithium metal batteries. Energy Environ. Sci. 13, 2209–2219 (2020).

    Article  Google Scholar 

  29. Wu, J., Liu, Z., Bi, S. & Meng, X. Viscosity of saturated liquid dimethyl ether from (227 to 343) K. J. Chem. Eng. Data 48, 426–429 (2003).

    Article  Google Scholar 

  30. Wu, J. & Yin, J. Vapor pressure measurements of dimethyl ether from (213 to 393) K. J. Chem. Eng. Data 53, 2247–2249 (2008).

    Article  Google Scholar 

  31. Prince, J. C. & Williams, F. A. A short reaction mechanism for the combustion of dimethyl-ether. Combust. Flame 162, 3589–3595 (2015).

    Article  Google Scholar 

  32. Westmoreland, P. R., Burgess, D. R. F., Zachariah, M. R. & Tsang, W. Fluoromethane chemistry and its role in flame suppression. Symp. (Int.) Combust. 25, 1505–1511 (1994).

    Article  Google Scholar 

  33. Holcomb, C. D., Magee, J. W., Scott, J. L., Outcalt, S. L. & Haynes, W. M. Selected Thermodynamic Properties for Mixtures of R-32 (Difluoromethane), R-125 (Pentafluoroethane), R-134A (1,1,1,2-Tetrafluoroethane), R-143A (1,1,1-Trifluoroethane), R-41 (Fluoromethane), R-290 (Propane), and R-744 (Carbon Dioxide) (NIST, 1997).

  34. Sun, L.-Q., Zhu, M.-S., Han, L.-Z. & Lin, Z.-Z. Viscosity of difluoromethane and pentafluoroethane along the saturation line. J. Chem. Eng. Data 41, 292–296 (1996).

    Article  Google Scholar 

  35. Wang, T., Hu, Y.-j, Zhang, P. & Pan, R.-m Study on thermal decomposition properties and its decomposition mechanism of pentafluoroethane (HFC-125) fire extinguishing agent. J. Fluor. Chem. 190, 48–55 (2016).

    Article  Google Scholar 

  36. von Aspern, N., Röschenthaler, G.-V., Winter, M. & Cekic-Laskovic, I. Fluorine and lithium: ideal partners for high-performance rechargeable battery electrolytes. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.201901381 (2019).

  37. Holoubek, J. et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature. Nat. Energy 6, 303–313 (2021).

    Article  Google Scholar 

  38. Cai, G. et al. Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries. Nat. Commun. 12, 3395 (2021).

    Article  Google Scholar 

  39. Davies, D. M. et al. A safer, wide-temperature liquefied gas electrolyte based on difluoromethane. J. Power Sources 493, 229668 (2021).

    Article  Google Scholar 

  40. Dong, X. et al. High‐energy rechargeable metallic lithium battery at −70 °C enabled by a cosolvent electrolyte. Angew. Chem. Int. Ed. 58, 5623–5627 (2019).

    Article  Google Scholar 

  41. Wang, X., Li, Y. & Meng, Y. S. Cryogenic electron microscopy for characterizing and diagnosing batteries. Joule 2, 2225–2234 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  43. 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  Google Scholar 

  44. Chen, H. et al. Uniform high ionic conducting lithium sulfide protection layer for stable lithium metal anode. Adv. Energy Mater. 9, 1900858 (2019).

    Article  Google Scholar 

  45. Kim, M. S. et al. Suspension electrolyte with modified Li+ solvation environment for lithium metal batteries. Nat. Mater. 21, 445–454 (2022).

    Article  Google Scholar 

  46. Lain, M. J. Recycling of lithium ion cells and batteries. J. Power Sources 97, 736–738 (2001).

    Article  Google Scholar 

  47. Georgi-Maschler, T., Friedrich, B., Weyhe, R., Heegn, H. & Rutz, M. Development of a recycling process for Li-ion batteries. J. Power Sources 207, 173–182 (2012).

    Article  Google Scholar 

  48. Sloop, S. et al. A direct recycling case study from a lithium-ion battery recall. Sustain. Mater. Technol. 25, e00152 (2020).

    Google Scholar 

  49. Nowak, S. & Winter, M. The role of sub- and supercritical CO2 as ‘processing solvent’ for the recycling and sample preparation of lithium ion battery electrolytes. Molecules 22, 403 (2017).

    Article  Google Scholar 

  50. Hehre, W. Radom, L., Pople, J. & v. R. Schleyer, P. Ab Initio Molecular Orbital Theory (Wiley, 1986).

  51. Laming, G. J., Termath, V. & Handy, N. C. A general purpose exchange‐correlation energy functional. J. Chem. Phys. 99, 8765–8773 (1993).

    Article  Google Scholar 

  52. Borodin, O. Polarizable force field development and molecular dynamics simulations of ionic liquids. J. Phys. Chem. B 113, 11463–11478 (2009).

    Article  Google Scholar 

  53. Suo, L. et al. ‘Water-in-salt’ electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).

    Article  Google Scholar 

Download references

Acknowledgements

Y. Yin and Y.S.M. thank C. Rustomji from South 8 Technologies for the fruitful discussions. The experimental part of the work performed at UCSD was supported by Sustainable Power and Energy Center (SPEC) and Zable endowed chair fund for energy technologies. The molecular modelling performed at ARL was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. DOE through Applied Battery Research for Transportation (ABRT) program via interagency agreement 89243319SEE000004 supporting contract No. DE-SC0012704. The cryo-FIB and SEM were developed and performed in part at the San Diego Nanotechnology Infrastructure (SDNI) of UCSD, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (Grant ECCS-1542148). Y. Yin thanks I. C. Tran for their help regarding XPS experiments performed at the University of California Irvine Materials Research Institute (IMRI) using instrumentation funded in part by the National Science Foundation Major Research Instrumentation Program (grant CHE-1338173). The authors acknowledge the use of Raman instrumentation supported by NSF through the UC San Diego Materials Research Science and Engineering Center (UCSD MRSEC), grant number DMR-2011924. We appreciate the supply of 20 μm lithium foils from Applied Materials.

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Author notes

  1. These authors contributed equally: Yijie Yin, Yangyuchen Yang.

Authors and Affiliations

  1. Materials Science and Engineering Program, University of California, San Diego, La Jolla, CA, USA

    Yijie Yin, Yangyuchen Yang, Diyi Cheng, Zheng Chen & Y. Shirley Meng

  2. Department of NanoEngineering, University of California, San Diego, La Jolla, CA, USA

    Matthew Mayer, John Holoubek, Weikang Li, Ganesh Raghavendran, Alex Liu, Bingyu Lu, Daniel M. Davies, Zheng Chen & Y. Shirley Meng

  3. Sustainable Power and Energy Center, University of California, San Diego, La Jolla, CA, USA

    Zheng Chen & Y. Shirley Meng

  4. Battery Science Branch, US Army Combat Capabilities Development Command Army Research Laboratory, Adelphi, MD, USA

    Oleg Borodin

  5. Pritzker School of Molecular Engineering, University of Chicago, Chicago, IL, USA

    Y. Shirley Meng

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Contributions

Y. Yin, Y. Yang and Y.S.M. formulated the electrolytes and designed the experiments. Y.S.M., M.M. and Y. Yang conceived the recycling process. Y. Yin and Y. Yang designed and performed the demonstration experiments. Y.S.M. and Y. Yang supervised the project. Y. Yin and Y. Yang conducted the electrochemical experiments. Y. Yin, D.C. and A.L. performed the flame-extinguishing tests with some guidance from Z.C. Raman spectroscopy was performed by Y. Yin based on cells designed by D.M.D. The force field was developed by O.B., who also carried out the MD simulations. D.C. performed the cryo-FIB. W.L. and Y. Yin performed the XPS characterization and analysis. J.H. performed the DFT calculations. G.R. and A.L. helped with control experiments. B.L. performed the cryo-TEM. Y. Yin, Y. Yang, D.C., O.B. and M.M. prepared the manuscript with input from all co-authors. All authors have given approval to the final version of the manuscript.

Corresponding authors

Correspondence to Yangyuchen Yang, Oleg Borodin or Y. Shirley Meng.

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Competing interests

Y. Yin, Y. Yang, M.M. and Y.S.M. declare that this work has been filed as US Provisional Patent Application No. 63/268,910. The remaining authors declare no competing interests. Y.S.M. is a member of the scientific advisory board for South 8 Technologies.

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Nature Energy thanks Jinkui Feng, Jang-Kyo Kim and Matthew McDowell for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–32, Notes 1–6 and Tables 1–4.

Supplementary Video 1

Fire-douse test of air to check the fire-extinguishing effect.

Supplementary Video 2

Fire-douse test of CO2 to check the fire-extinguishing effect.

Supplementary Video 3

Fire-douse test of TFE to check the fire-extinguishing effect.

Supplementary Video 4

Fire-douse test of PFE to check the fire-extinguishing effect.

Supplementary Video 5

Fire-douse test of Me2O to check the fire-extinguishing effect.

Supplementary Video 6

Fire-douse test of 1 M LiFSI-Me2O-TFE-PFE to check the fire-extinguishing effect.

Supplementary Video 7

Gas-venting test of cycled Li/NMC622 after 100 cycles and then charged at 4.05 V to check the fire-extinguishing effect of cycled electrolytes inside the cell.

Supplementary Data 1

MD simulation code and the associated force-field files needed to perform MD simulations.

Supplementary Data 2

Source data for Supplementary Fig. 23a.

Source data

Source Data Fig. 4

Source data for main text figure 4

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Yin, Y., Yang, Y., Cheng, D. et al. Fire-extinguishing, recyclable liquefied gas electrolytes for temperature-resilient lithium-metal batteries. Nat Energy 7, 548–559 (2022). https://doi.org/10.1038/s41560-022-01051-4

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