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Rational design of anti-freezing electrolytes for extremely low-temperature aqueous batteries

Nature Energy volume 9, pages 839–848 (2024)Cite this article

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Abstract

Designing anti-freezing electrolytes through choosing suitable H2O–solute systems is crucial for low-temperature aqueous batteries (LTABs). However, the lack of an effective guideline for choosing H2O–solute systems based on decisive temperature-limiting factors hinders the development of LTABs. Here we identified two decisive factors: thermodynamic eutectic temperature (Te) and kinetic glass-transition temperature (Tg), with Tg being applicable for LTABs only when H2O–solute systems have strong super-cooling ability. We proposed a general strategy wherein low-Te and strong-super-cooling ability electrolytes can be realized by creating multiple-solute systems via introducing assisted salts with high ionic-potential cations (for example, Al3+, Ca2+) or cosolvents with high donor numbers (for example, ethylene glycol). As a demonstration in Na-based systems, we designed electrolytes with ultralow Te (−53.5 to −72.6 °C) and Tg (−86.1 to −117.1 °C), showcasing battery performances including 80 Wh kg−1 and 5,000 cycles at 25 °C, and 12.5 Wh kg−1 at −85 °C. The work provides effective guidelines for the design of anti-freezing electrolytes for extremely low-temperature applications.

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Fig. 1: Schematic evolution of a dilute solution in the H2O–solute system during cooling process and the difference between traditional and our proposed strategies.
Fig. 2: Design of low-Te and strong-SCA aqueous electrolytes.
Fig. 3: The low-Te mechanisms in designed electrolytes.
Fig. 4: The strong-SCA mechanisms in designed electrolytes.
Fig. 5: Battery demonstrations in designed electrolytes.

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The datasets analysed and generated during the current study are included in the paper and its Supplementary Information.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 52122214 received by Y.L. and 52072370 received by J.Z.), Youth Innovation Promotion Association of the Chinese Academy of Sciences (grant no. 2020006 received by Y.L.), Jiangsu Province Carbon Peak and Neutrality Innovation Program (Industry tackling on prospect and key technology grant no. BE2022002-5 received by Y.-S.H.), Beijing Natural Science Foundation (grant no. 2222078 received by J.Z.), Guangxi Power Grid Project (grant no. GXKJXM20210260 received by Y.-S.H.) and the Research Grant Council of the Hong Kong Special Administrative Region, China (grant nos. CUHK 14308622 and C1002-21G received by Y.-C.L.). We are grateful to B. Dunn for his suggestions on understanding electrolyte performance and mechanisms.

Author information

Author notes

  1. These authors contributed equally: Liwei Jiang, Shuai Han, Yuan-Chao Hu.

Authors and Affiliations

  1. Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Liwei Jiang, Shuai Han, Yang Yang, Yaxiang Lu, Liquan Chen & Yong-Sheng Hu

  2. College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Liwei Jiang, Shuai Han, Yang Yang & Yong-Sheng Hu

  3. Electrochemical Energy and Interfaces Laboratory, Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, Hong Kong, China

    Liwei Jiang & Yi-Chun Lu

  4. Songshan Lake Materials Laboratory, Dongguan, China

    Yuan-Chao Hu

  5. Yangtze River Delta Physics Research Center Co. Ltd, Liyang, China

    Yaxiang Lu & Yong-Sheng Hu

  6. CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Junmei Zhao

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Contributions

L.J., Y.-S.H., J.Z., Y.-C.L. and Y.L. conceived the project. L.J. synthesized the NaFeMnHCF cathode and carried out electrochemical tests, DSC tests, AIMD simulations and DFT calculations. S.H. synthesized the NaTi2(PO4)3 anode and carried out NMR and DSC tests. Y.-C.H. contributed to the electrolyte strong-SCA mechanisms. L.J., S.H., Y.-C.H., Y.L, Y.-C.L., J.Z. and Y.-S.H. wrote the paper. All the authors participated in the preparation of paper.

Corresponding authors

Correspondence to Yaxiang Lu, Yi-Chun Lu, Junmei Zhao or Yong-Sheng Hu.

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Y.-S.H. is employed by HiNa Battery Technology Co., Ltd. The other authors declare no competing interests.

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Nature Energy thanks Xiulei Ji and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–4, Figs. 1–24 and Tables 1–7.

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Jiang, L., Han, S., Hu, YC. et al. Rational design of anti-freezing electrolytes for extremely low-temperature aqueous batteries. Nat Energy 9, 839–848 (2024). https://doi.org/10.1038/s41560-024-01527-5

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