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Single-phase local-high-concentration solid polymer electrolytes for lithium-metal batteries

Nature Energy volume 9, pages 386–400 (2024)Cite this article

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Abstract

Solid polymers are promising electrolytes for Li-metal batteries, but they have limitations: they cannot simultaneously achieve high ionic conductivity, good mechanical strength and compatibility with high-voltage cathodes while suppressing Li dendrites. Here, we design a class of locally high-concentration solid polymer electrolytes based on polymer blends, which are termed Li-polymer in F diluter (LPIFD). The Li-polymer (polymer-in-salt) ensures continuous Li-ion conduction channels and contributes to the solid electrolyte interphase (SEI), and the F diluter (inert fluorinated polymer) adds mechanical strength. Studies reveal that a single-phase LPIFD, which is based on a miscible polymer blend, lacks phase boundaries and forms an organic-less and LiF-rich SEI, effectively suppressing lithium dendrites. The single-phase LPIFD delivers ionic conductivity of 3.0 × 10−4 S cm−1, and enables the Li anode to reach a high coulombic efficiency of 99.1% and a critical current density of 3.7 mA cm−2. Furthermore, the ability to form an F-rich cathode electrolyte interphase allows LiNi0.8Co0.1Mn0.1O2||Li cells to achieve a cycle life of 450 cycles at a high operating voltage of 4.5 V. This design will inspire efforts to commercialize polymer electrolytes for high-energy Li-metal batteries.

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Fig. 1: Schematic of the logic for designing single-phase LPIFD SPEs.
Fig. 2: Design of LPIFD electrolytes.
Fig. 3: Properties of phase-separated and single-phase LPIFD.
Fig. 4: SEI composition and electrochemical performance of LPIFD polymer electrolytes with lithium.
Fig. 5: Different Li deposition behaviours of LPIFDs, and summary of design criteria.
Fig. 6: Full-cell performance of single-phase LPIFD.

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Acknowledgements

We acknowledge the advice on the manuscript from B. Dunn at the University of California, Los Angeles, and technical support from the Maryland NanoCenter. STXM was performed at the Canadian Light Source, a national research facility of the University of Saskatchewan. We thank the computational resources provided on Bebop, a high-performance computing cluster operated by the Laboratory Computing Resource Center at Argonne National Laboratory. This work was supported by the US Department of Energy (DOE: Grant No. DE-EE0008856 to C.W.; and Grant No. DE-AC05-76RL01830 to C.W.) and DOE, Office of Energy Efficiency and Renewable Energy (Grant No. DE-EE0009183 to C.W.). The XAS test was supported by DOE, Battery500 Consortium (Grant No. DE-SC0012704 to S.T., X.Y. and E.H.) and DOE, Office of Science User Facilities (Grant No. DE-SC0012704 to Brookhaven National Laboratory). We also thank the Analytical NMR Service & Research Center at the University of Maryland, College Park, for using 600 MHz solution and 500 MHz solid-state NMR spectrometers (supported by the National Science Foundation under Grant No. NSF-1726058).

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Maryland, College Park, MD, USA

    Weiran Zhang & Chunsheng Wang

  2. Materials Science Division, Argonne National Laboratory, Lemont, IL, USA

    Volodymyr Koverga, Naveen K. Dandu & Anh T. Ngo

  3. Department of Chemical Engineering, University of Illinois Chicago, Chicago, IL, USA

    Volodymyr Koverga, Naveen K. Dandu & Anh T. Ngo

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

    Sufu Liu, Panxing Bai, Zeyi Wang, Jiale Xia, Hongli Wan, Xiyue Zhang, Haochen Yang, Ai-Min Li, Srinivasa R. Raghavan & Chunsheng Wang

  5. Canadian Light Source Inc., University of Saskatchewan, Saskatoon, Saskatchewan, Canada

    Jigang Zhou & Jian Wang

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

    Sha Tan, Xiao-Qing Yang & Enyuan Hu

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

    Fu Chen

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

    Brett L. Lucht

Authors
  1. Weiran Zhang
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  2. Volodymyr Koverga
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  3. Sufu Liu
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  4. Jigang Zhou
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  5. Jian Wang
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  6. Panxing Bai
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  7. Sha Tan
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  8. Naveen K. Dandu
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  9. Zeyi Wang
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  10. Fu Chen
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  11. Jiale Xia
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  12. Hongli Wan
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  13. Xiyue Zhang
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  14. Haochen Yang
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  15. Brett L. Lucht
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  16. Ai-Min Li
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  17. Xiao-Qing Yang
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  18. Enyuan Hu
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  19. Srinivasa R. Raghavan
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  20. Anh T. Ngo
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  21. Chunsheng Wang
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Contributions

W.Z. and C.W. proposed the research. W.Z. conceived the idea, performed the electrochemical, SEM and TEM experiments, and wrote the manuscript. V.K. and N.K.D. performed the molecular dynamics simulations and DFT calculations. S.L. helped with the electrochemical experiments and the SEM. P.B. helped with the FTIR. J.Z. and J.W. performed the STXM. S.T., X.Y. and E.H. performed the XAS. Z.W. helped with the analysis of the calculation results. J.X., H.W. and X.Z. helped with editing the manuscript. H.Y. performed the Instron mechanical test. B.L. and A.L. performed the XPS and analysed the results. F.C. performed the NMR spectroscopy. S.R. drew the schematic, edited the manuscript and supervised the analysis of the polymer properties. A.N. supervised the simulations and calculations, and C.W. supervised the study and the manuscript writing. All authors discussed the results.

Corresponding authors

Correspondence to Srinivasa R. Raghavan, Anh T. Ngo or Chunsheng Wang.

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The authors declare no competing interests.

Peer review

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Nature Energy thanks Grazia Accardo, Kan Hatakeyama-Sato and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–8, Figs. 1–63, Table 1 and refs. 1–19.

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Zhang, W., Koverga, V., Liu, S. et al. Single-phase local-high-concentration solid polymer electrolytes for lithium-metal batteries. Nat Energy 9, 386–400 (2024). https://doi.org/10.1038/s41560-023-01443-0

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