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Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature

Nature Energy volume 6, pages 303–313 (2021)Cite this article

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Abstract

Lithium metal batteries hold promise for pushing cell-level energy densities beyond 300 Wh kg−1 while operating at ultra-low temperatures (below −30 °C). Batteries capable of both charging and discharging at these temperature extremes are highly desirable due to their inherent reduction in the need for external warming. Here we demonstrate that the local solvation structure of the electrolyte defines the charge-transfer behaviour at ultra-low temperature, which is crucial for achieving high Li metal Coulombic efficiency and avoiding dendritic growth. These insights were applied to Li metal full-cells, where a high-loading 3.5 mAh cm−2 sulfurized polyacrylonitrile (SPAN) cathode was paired with a onefold excess Li metal anode. The cell retained 84% and 76% of its room temperature capacity when cycled at −40 and −60 °C, respectively, which presented stable performance over 50 cycles. This work provides design criteria for ultra-low-temperature lithium metal battery electrolytes, and represents a defining step for the performance of low-temperature batteries.

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Fig. 1: Operational schemes of low-temperature LMBs and the significance of their electrolyte structure for ultra-low Li plating.
Fig. 2: Li metal performance and characterization at benign and ultra-low temperatures.
Fig. 3: Lithium SEI and ionic conductivity study of electrolytes.
Fig. 4: Theoretical and experimental analysis of electrolyte structure.
Fig. 5: Proposed relationship between electrolyte structure and desolvation.
Fig. 6: 1× Li||SPAN full-cell performance at benign and ultra-low temperature.
Fig. 7: The historical context of this work.

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All relevant data are included in the paper and its Supplementary Information.

References

  1. Zhang, S. S., Xu, K. & Jow, T. R. The low temperature performance of Li-ion batteries. J. Power Sources 115, 137–140 (2003).

    Article  Google Scholar 

  2. Smart, M. C. et al. The use of lithium-ion batteries for JPL’s Mars missions. Electrochim. Acta 268, 27–40 (2018).

    Article  Google Scholar 

  3. Gupta, A. & Manthiram, A. Designing advanced lithium-based batteries for low-temperature conditions. Adv. Energy Mater. 10, 2001972 (2020).

    Article  Google Scholar 

  4. Huang, C.-K., Sakamoto, J. S., Wolfenstine, J. & Surampudi, S. The limits of low‐temperature performance of Li‐ion cells. J. Electrochem. Soc. 147, 2893–2896 (2000).

    Article  Google Scholar 

  5. Plichta, E. J. et al. Development of low temperature Li-ion electrolytes for NASA and DoD applications. J. Power Sources 94, 160–162 (2001).

    Article  Google Scholar 

  6. Li, Q. et al. Wide-temperature electrolytes for lithium-ion batteries. ACS Appl. Mater. Interfaces 9, 18826–18835 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  9. Li, S. et al. Developing high-performance lithium metal anode in liquid electrolytes: challenges and progress. Adv. Mater. 30, 1706375 (2018).

    Article  Google Scholar 

  10. Zhou, H., Yu, S., Liu, H. & Liu, P. Protective coatings for lithium metal anodes: recent progress and future perspectives. J. Power Sources 450, 227632 (2020).

    Article  Google Scholar 

  11. Xu, K., von Cresce, A. & Lee, U. Differentiating contributions to “ion transfer” barrier from interphasial resistance and Li+ desolvation at electrolyte/graphite interface. Langmuir 26, 11538–11543 (2010).

    Article  Google Scholar 

  12. Li, Q. et al. Li+-desolvation dictating lithium-ion battery’s low-temperature performances. ACS Appl. Mater. Interfaces 9, 42761–42768 (2017).

    Article  Google Scholar 

  13. Holoubek, J. et al. Exploiting mechanistic solvation kinetics for dual-graphite batteries with high power output at extremely low temperature. Angew. Chem. Int. Ed. 58, 18892–18897 (2019).

    Article  Google Scholar 

  14. Rustomji, C. S. et al. Liquefied gas electrolytes for electrochemical energy storage devices. Science 356, eaal4263 (2017).

    Article  Google Scholar 

  15. 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 

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

    Article  Google Scholar 

  17. Dong, X., Guo, Z., Guo, Z., Wang, Y. & Xia, Y. Organic batteries operated at −70 °C. Joule 2, 902–913 (2018).

    Article  Google Scholar 

  18. Smart, M. C., Ratnakumar, B. V., Chin, K. B. & Whitcanack, L. D. Lithium-ion electrolytes containing ester cosolvents for improved low temperature performance. J. Electrochem. Soc. 157, A1361–A1374 (2010).

    Article  Google Scholar 

  19. Smart, M. C. et al. Gel polymer electrolyte lithium-ion cells with improved low temperature performance. J. Power Sources 165, 535–543 (2007).

    Article  Google Scholar 

  20. Plichta, E. J. & Behl, W. K. A low-temperature electrolyte for lithium and lithium-ion batteries. J. Power Sources 88, 192–196 (2000).

    Article  Google Scholar 

  21. Smart, M. C., Lucht, B. L., Dalavi, S., Krause, F. C. & Ratnakumar, B. V. The effect of additives upon the performance of MCMB/LiNixCo1−xO2 Li-ion cells containing methyl butyrate-based wide operating temperature range electrolytes. J. Electrochem. Soc. 159, A739–A751 (2012).

    Article  Google Scholar 

  22. Zhang, S. S., Xu, K. & Jow, T. R. A new approach toward improved low temperature performance of Li-ion battery. Electrochem. Commun. 4, 928–932 (2002).

    Article  Google Scholar 

  23. Liao, B. et al. Designing low impedance interface films simultaneously on anode and cathode for high energy batteries. Adv. Energy Mater. 8, 1800802 (2018).

    Article  Google Scholar 

  24. Gao, Y. et al. Low-temperature and high-rate-charging lithium metal batteries enabled by an electrochemically active monolayer-regulated interface. Nat. Energy 5, 534–542 (2020).

    Article  Google Scholar 

  25. Wang, C.-Y. et al. Lithium-ion battery structure that self-heats at low temperatures. Nature 529, 515–518 (2016).

    Article  Google Scholar 

  26. Ji, Y. & Wang, C. Y. Heating strategies for Li-ion batteries operated from subzero temperatures. Electrochim. Acta 107, 664–674 (2013).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  29. 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 

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

    Article  Google Scholar 

  31. 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).

    Article  Google Scholar 

  32. Thenuwara, A. C., Shetty, P. P. & McDowell, M. T. Distinct nanoscale interphases and morphology of lithium metal electrodes operating at low temperatures. Nano Lett. 19, 8664–8672 (2019).

    Article  Google Scholar 

  33. 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 

  34. Adams, B. D., Zheng, J., Ren, X., Xu, W. & Zhang, J.-G. Accurate determination of Coulombic efficiency for lithium metal anodes and lithium metal batteries. Adv. Energy Mater. 8, 1702097 (2018).

    Article  Google Scholar 

  35. Bai, P., Li, J., R. Brushett, F. & Bazant, Z. M. Transition of lithium growth mechanisms in liquid electrolytes. Energy Environ. Sci. 9, 3221–3229 (2016).

    Article  Google Scholar 

  36. Park, C. et al. Molecular simulations of electrolyte structure and dynamics in lithium–sulfur battery solvents. J. Power Sources 373, 70–78 (2018).

    Article  Google Scholar 

  37. Callsen, M., Sodeyama, K., Futera, Z., Tateyama, Y. & Hamada, I. The solvation structure of lithium ions in an ether based electrolyte solution from first-principles molecular dynamics. J. Phys. Chem. B 121, 180–188 (2017).

    Article  Google Scholar 

  38. Chaban, V. Solvation of lithium ion in dimethoxyethane and propylene carbonate. Chem. Phys. Lett. 631–632, 1–5 (2015).

    Article  Google Scholar 

  39. Ueno, K. et al. Glyme–lithium salt equimolar molten mixtures: concentrated solutions or solvate ionic liquids? J. Phys. Chem. B 116, 11323–11331 (2012).

    Article  Google Scholar 

  40. Suo, L., Zheng, F., Hu, Y.-S. & Chen, L. FT-Raman spectroscopy study of solvent-in-salt electrolytes. Chin. Phys. B 25, 016101 (2016).

    Article  Google Scholar 

  41. Sand, H. J. S. III On the concentration at the electrodes in a solution, with special reference to the liberation of hydrogen by electrolysis of a mixture of copper sulphate and sulphuric acid. Philos. Mag. 1, 45–79 (1901).

    Article  MATH  Google Scholar 

  42. Borodin, O. et al. Competitive lithium solvation of linear and cyclic carbonates from quantum chemistry. Phys. Chem. Chem. Phys. 18, 164–175 (2016).

    Article  Google Scholar 

  43. Wei, S., Ma, L., Hendrickson, K. E., Tu, Z. & Archer, L. A. Metal–sulfur battery cathodes based on PAN–sulfur composites. J. Am. Chem. Soc. 137, 12143–12152 (2015).

    Article  Google Scholar 

  44. Yang, H., Chen, J., Yang, J. & Wang, J. Prospect of sulfurized pyrolyzed poly(acrylonitrile) (S@pPAN) cathode materials for rechargeable lithium batteries. Angew. Chem. Int. Ed. 59, 7306–7318 (2019).

    Article  Google Scholar 

  45. Xing, X. et al. Cathode electrolyte interface enabling stable Li–S batteries. Energy Storage Mater. 21, 474–480 (2019).

    Article  Google Scholar 

  46. Chen, X. et al. Ether-compatible sulfurized polyacrylonitrile cathode with excellent performance enabled by fast kinetics via selenium doping. Nat. Commun. 10, 1021 (2019).

    Article  Google Scholar 

  47. Zhou, J. et al. A new ether-based electrolyte for lithium sulfur batteries using a S@pPAN cathode. Chem. Commun. 54, 5478–5481 (2018).

    Article  Google Scholar 

  48. Betz, J. et al. Theoretical versus practical energy: a plea for more transparency in the energy calculation of different rechargeable battery systems. Adv. Energy Mater. 9, 1803170 (2019).

    Article  Google Scholar 

  49. Cho, Y.-G., Kim, Y.-S., Sung, D.-G., Seo, M.-S. & Song, H.-K. Nitrile-assistant eutectic electrolytes for cryogenic operation of lithium ion batteries at fast charges and discharges. Energy Environ. Sci. 7, 1737–1743 (2014).

    Article  Google Scholar 

  50. Holoubek, J. et al. An all-fluorinated ester electrolyte for stable high-voltage Li metal batteries capable of ultra-low-temperature operation. ACS Energy Lett. 5, 1438–1447 (2020).

    Article  Google Scholar 

  51. Kaminski, G. A., Friesner, R. A., Tirado-Rives, J. & Jorgensen, W. L. Evaluation and reparametrization of the OPLS-AA force field for proteins via comparison with accurate quantum chemical calculations on peptides. J. Phys. Chem. B 105, 6474–6487 (2001).

    Article  Google Scholar 

  52. Gouveia, A. S. L. et al. Ionic liquids with anions based on fluorosulfonyl derivatives: from asymmetrical substitutions to a consistent force field model. Phys. Chem. Chem. Phys. 19, 29617–29624 (2017).

    Article  Google Scholar 

  53. Towns, J. et al. XSEDE: accelerating scientific discovery. Comput. Sci. Eng. 16, 62–74 (2014).

    Article  Google Scholar 

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Acknowledgements

This work was supported by a NASA Space Technology Graduate Research Opportunity. This work was also partially supported by the Office of Vehicle Technologies of the US Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery500 Consortium) under contract no. DE-EE0007764 to P.L. This work was also partially supported by an Early Career Faculty grant from NASA’s Space Technology Research Grants Program (ECF 80NSSC18K1512) to Z.C. Part of the work used the UCSD-MTI Battery Fabrication Facility and the UCSD-Arbin Battery Testing Facility. Electron microscopic characterization was performed 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). Computational support for this work was provided by the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231. This work also used the Extreme Science and Engineering Discovery Environment (XSEDE)53 on the Comet supercomputer at the San Diego Supercomputing Center, which is supported by National Science Foundation grant no. ACI-1548562.

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Authors and Affiliations

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

    John Holoubek, Haodong Liu, Guorui Cai, Hongyao Zhou, Tod A. Pascal, Zheng Chen & Ping Liu

  2. Program of Materials Science, University of California, San Diego, La Jolla, CA, USA

    Yijie Yin, Xing Xing, Sicen Yu, Tod A. Pascal, Zheng Chen & Ping Liu

  3. Program of Chemical Engineering, University of California, San Diego, La Jolla, CA, USA

    Zhaohui Wu, Tod A. Pascal, Zheng Chen & Ping Liu

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

    Tod A. Pascal, Zheng Chen & Ping Liu

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Contributions

J.H. conceived the original idea. P.L. and Z.C. directed the project. J.H., H.L. and Z.W. carried out the experiments. Z.W., X.X., S.Y., G.C. and Y.Y. assisted with characterization. T.A.P. directed the computational experiments. J.H., H.L., Z.C. and P.L. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Tod A. Pascal, Zheng Chen or Ping Liu.

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Peer review information Nature Energy thanks Kevin Leung and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–23, Discussion 1–5, Tables 1–3 and references.

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Holoubek, J., Liu, H., Wu, Z. et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature. Nat Energy 6, 303–313 (2021). https://doi.org/10.1038/s41560-021-00783-z

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