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Designing phosphazene-derivative electrolyte matrices to enable high-voltage lithium metal batteries for extreme working conditions

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Abstract

The current high-energy lithium metal batteries are limited by their safety and lifespan owing to the lack of suitable electrolyte solutions. Here we report a synergy of fluorinated co-solvent and gelation treatment by a butenoxycyclotriphosphazene (BCPN) monomer, which facilitates the use of ether-based electrolyte solutions for high-energy lithium metal batteries. We show that the safety risks of fire and electrolyte leakage are eliminated by the fluorinated co-solvent and fireproof polymeric matrices. The compatibility with high-energy cathodes is realized by a well-tailored Li+ solvation sheath, along with BCPN-derived protective surface films developed on the cathodes. Our Li | |LiNi0.8Co0.1Mn0.1O2 cells reach high-capacity retention, superior low-temperature performance, good cyclability under high pressure and steady power supply under abusive conditions. Our electrolyte design concept provides a promising path for high energetic, durable and safe rechargeable Li batteries.

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Fig. 1: Design of NGPE and investigation on the solvation structures.
Fig. 2: Safety of the NGPE.
Fig. 3: Interfacial compatibility between NGPE and electrodes.
Fig. 4: Li | NGPE | NCM811 coin cell performance under extreme operating environments.
Fig. 5: Li | NGPE | NCM811 pouch cells performance under abuse conditions.
Fig. 6: 500 mAh pouch cell performance under abuse conditions.

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Data availability

All data are available in the main text or the Supplementary Information.

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Acknowledgements

B.L. acknowledges support by the National Natural Science Foundation of China (number 52072208 and number 52261160384), Shenzhen Science and Technology Program (KCXFZ20211020163810015), the Fundamental Research Project of Shenzhen (number JCYJ20220818101004009), Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01N111) and Shenzhen Outstanding Talents Training Fund. G.W. acknowledges the support from Australian Research Council (ARC) Discovery Projects (DP200101249 and DP210101389) and the ARC Research Hub for Integrated Energy Storage Solutions (IH180100020). B.S. acknowledges the financial support from the Australian Research Council (ARC) through the ARC Future Fellowship (FT220100561).

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Author notes

  1. These authors contributed equally: Yuefeng Meng, Dong Zhou.

Authors and Affiliations

  1. Tsinghua Shenzhen International Graduate School, Tsinghua University, Shenzhen, China

    Yuefeng Meng, Dong Zhou, Yao Tian, Yifu Gao, Yao Wang, Feiyu Kang & Baohua Li

  2. School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Yuefeng Meng, Yifu Gao & Feiyu Kang

  3. School of Chemistry and Materials Science, Guangdong University of Education, Guangzhou, China

    Ruliang Liu

  4. Centre for Clean Energy Technology, School of Mathematical and Physical Sciences, Faculty of Science, University of Technology Sydney, Sydney, New South Wales, Australia

    Bing Sun & Guoxiu Wang

  5. Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Vitoria-Gasteiz, Spain

    Michel Armand

  6. Department of Chemistry and Institute of Nanotechnology & Advanced Materials (BINA), Bar-Ilan University, Ramat Gan, Israel

    Doron Aurbach

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  1. Yuefeng Meng
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Contributions

D.Z., M.A., B.L. and G.W. conceived and designed this work. Y.M. performed the experiments and wrote the manuscript. Y.G. and Y.T. carried out the computations. R.L., Y.W., B.S., F.K. and D.A. discussed the results and participated in the preparation of the paper.

Corresponding authors

Correspondence to Dong Zhou, Michel Armand, Baohua Li, Guoxiu Wang or Doron Aurbach.

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Nature Energy thanks Feifei Shi, Hsisheng Teng, 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 Figs. 1–48, Tables 1–9 and Notes 1–4.

Supplementary Video 1

Combustion test of pure ether electrolyte.

Supplementary Video 2

Combustion test of ether–SFE electrolyte.

Supplementary Video 3

Combustion test of NGPE.

Supplementary Video 4

Leakage test of liquid electrolyte and NGPE.

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Meng, Y., Zhou, D., Liu, R. et al. Designing phosphazene-derivative electrolyte matrices to enable high-voltage lithium metal batteries for extreme working conditions. Nat Energy 8, 1023–1033 (2023). https://doi.org/10.1038/s41560-023-01339-z

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