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Tailoring polymer electrolyte solvation for 600 Wh kg−1 lithium batteries

Nature volume 646, pages 343–350 (2025)Cite this article

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Abstract

Polymer electrolytes paired with lithium-rich manganese-based layered oxide (LRMO) cathodes and anode-free cell design are considered one of the most promising high-energy-density and high-safety systems1,2,3,4. However, the unstable anode morphological changes and the irreversible anionic reactions at the electrolyte–cathode interfaces induce oxygen escape and catalytic decomposition of polymer electrolytes, resulting in severe interfacial degradation and poor cycling stability. Here we design an in-built fluoropolyether-based polymer electrolyte composed of strongly solvating polyether and weakly solvating fluorohydrocarbon pendants, creating an anion-rich solvation structure and thus anion-derived fluorine-rich interfacial layers on the cathode and anode to resist interfacial issues. The LRMO cathode exhibits improved oxygen redox reversibility with substantially reduced oxygen-involving interfacial side reactions. This quasi-solid-state polymer electrolyte with 30 wt% trimethyl phosphate enables an LRMO cathode with a reversible high-areal-capacity cycling (>8 mAh cm−2) in pouch cells and long-term stability (>500 cycles at 25 °C) in coin cells, respectively. The pouch cells exhibit an energy density of 604 Wh kg−1 (1,027 Wh l−1) and excellent safety under a nail penetration at a fully charged condition. Our work, therefore, provides a promising direction for creating practical high-energy-density and high-safety lithium batteries.

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Fig. 1: Schematic of designing fluoropolyether-based polymer electrolyte with anion-rich solvation structure.
Fig. 2: Design and fabrication of fluoropolyether-based SPEs.
Fig. 3: Characterization of fluoropolyether-based SPEs.
Fig. 4: CEI composition of PE-SPE and PTF-PE-SPE with LRMO.
Fig. 5: Electrochemical and safety performances of PTF-PE-SPE.

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Data availability

The data that support the findings of this study are available from the corresponding author upon request. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program (2021YFB2500300), the National Natural Science Foundation of China (22393900, 22393903, 22409114, 21825501 and T2322015), the Beijing Municipal Natural Science Foundation (L247015, L233004 and L243019), the China Postdoctoral Science Foundation (2023M731920), the Discipline Breakthrough Precursor Project of the Ministry of Education of China and the Tsinghua University Initiative Scientific Research Program.

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Authors and Affiliations

  1. Beijing Key Laboratory of Complex Solid-State Batteries, Department of Chemical Engineering, Tsinghua University, Beijing, China

    Xue-Yan Huang, Chen-Zi Zhao, Wei-Jin Kong, Nan Yao, Zong-Yao Shuang, Pan Xu, Shuo Sun, Yang Lu, Wen-Ze Huang, Jin-Liang Li, Liang Shen, Xiang Chen & Qiang Zhang

  2. School of Materials Science and Engineering, Nanjing Tech University, Nanjing, China

    Shuo Sun

  3. National Energy Metal Resources and New Materials Key Laboratory, School of Metallurgy and Environment, Central South University, Changsha, China

    Yang Lu

  4. School of Interdisciplinary Science, Beijing Institute of Technology, Beijing, China

    Jia-Qi Huang

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

    Jia-Qi Huang

  6. Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY, USA

    Lynden A. Archer

  7. State Key Laboratory of Chemical Engineering and Low-Carbon Technology, Tsinghua University, Beijing, China

    Qiang Zhang

  8. The Innovation Center for Smart Solid-State Batteries, Yibin, China

    Qiang Zhang

  9. Institute for Carbon Neutrality, Tsinghua University, Beijing, China

    Qiang Zhang

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  1. Xue-Yan Huang
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Contributions

X.-Y.H. C.-Z.Z. and Q.Z. proposed the research. X.-Y.H. performed the electrochemical measurements, characterized materials, analysed the data and wrote the paper. W.-J.K. performed the Raman characterization and supervised the analysis of LRMO cathodes. Y.L. helped with the electrochemical experiments. J.-L.L. and L.S. helped with the XPS tests. N.Y. and X.C. performed the theoretical calculations. P.X. helped with the TOF-SIMS tests. Z.-Y.S. and X.-Y.H. assembled the pouch cells. C.-Z.Z., S.S., W.-Z.H., X.C., J.-Q. H., L.A.A. and Q.Z. revised the paper. All authors engaged in the discussion of the results.

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Correspondence to Chen-Zi Zhao or Qiang Zhang.

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Nature thanks Xiulin Fan, Jinsoo Kim, Faezeh Makhlooghiazad and Yingjin Wei for their contribution to the peer review of this work.

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Huang, XY., Zhao, CZ., Kong, WJ. et al. Tailoring polymer electrolyte solvation for 600 Wh kg−1 lithium batteries. Nature 646, 343–350 (2025). https://doi.org/10.1038/s41586-025-09565-z

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