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Quantitative and mechanistic insights into proton dynamics for fast energy storage

Nature Materials (2025)Cite this article

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Abstract

Proton conduction in hydrogen-bond-rich protic electrolytes enables fast mass and charge transport, crucial for electrochemical energy storage and power conversion. Such transport can give proton-based batteries exceptional rate capability and low-temperature operation beyond other working ions. Here we show that in phosphoric acid (H3PO4) electrolytes, vehicular and structural proton transport coexist, and their contributions to conductivity can be quantitatively distinguished. We link structural diffusion directly to hydrogen-bond strength, enabling the precise tuning of proton migration. Guided by this, we reveal a double conductivity peak from regulated structural diffusion. The optimal electrolyte (5.8-M H3PO4) achieves high overall (232.9 mS cm−1) and structural (164.9 mS cm−1) conductivity. A MoO3‖CuFe-TBA battery with this electrolyte outperforms a deep-eutectic benchmark (8.3-M H3PO4), delivering >17,474 W kg−1 at room temperature and retaining 15.1 Wh kg−1 at −75 °C. These findings provide a framework for designing advanced protic electrolytes across electrochemical systems.

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Fig. 1: Bulk phase characterizations of electrolytes.
Fig. 2: Quantifying and decoupling two transport mechanisms.
Fig. 3: H-bond evolution and its mathematical relationship with diffusivity.
Fig. 4: Proton transport behaviour and diffusion mechanisms in H3PO4.
Fig. 5: Electrochemical performance of a full H+ battery consisting of MoO3 ‖5.8-M H3PO4 ‖CuFe-TBA.

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All data are available in the article or Supplementary Information. All experimental data reported in this study and Supplementary Information are available from the corresponding authors upon request. Source data are provided with this paper.

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Acknowledgements

We thank F. Wang and X. Qu for technical support. This work was supported by the National Natural Science Foundation of China (numbers 52261135631 and 52103335, F.W.; number 52071083, F.F.), the Science and Technology Commission of Shanghai Municipality (number 23TS1401700, F.W.), the Shanghai Pilot Program for Basic Research—Fudan University 21TQ1400100(25TQ012) (F.W.) and the Shanghai International Science and Technology Partnership Project (number 23520750400, F.W.). Work at Hunter College was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Energy Frontier Research Center ‘Breakthrough Electrolytes for Energy Storage (BEES)’ (Award DE-SC0019409, S.G.G.). Work at the School of Physics and Electronic Engineering was supported by the National Natural Science Foundation of China (number 52202245, Y. Lin), the Natural Science Fund for Colleges and Universities in Jiangsu Province (number 22KJB430004, Y. Lin) and the Jiangsu Special-Term Professor Program (Y. Lin). Work at Zhejiang Laboratory was supported by the Beforehand Research Project of the New Materials Computing Research Center (number 3700-32601, Y. Li).

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Authors and Affiliations

  1. College of Smart Materials and Future Energy, Fudan University, Shanghai, People’s Republic of China

    Ziyue Li, Mochou Liao, Jiafeng Ruan, Qin Li, Dalin Sun, Fang Fang & Fei Wang

  2. School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou, People’s Republic of China

    Yuxiao Lin

  3. Department of Physics and Astronomy, Hunter College, City University of New York, New York, NY, USA

    Mounesha N. Garaga & Steven G. Greenbaum

  4. Zhejiang Laboratory, Hangzhou, People’s Republic of China

    Yunsong Li

  5. SES AI Corp., Woburn, MA, USA

    Kang Xu

Authors
  1. Ziyue Li
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  3. Mounesha N. Garaga
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Contributions

Conceptualization: Z.L., F.W., K.X., S.G.G. Methodology: Z.L., Y. Lin, M.N.G., Y. Li. Investigation: Z.L., F.W., M.N.G., M.L., Q.L. Visualization: Z.L., F.W., F.F., J.R., Y. Lin. Funding acquisition: F.W., F.F., D.S., S.G.G. Project administration: Z.L., F.W., S.G.G. Supervision: F.W., D.S., F.F., S.G.G. Writing—original draft: Z.L., K.X. Writing—review and editing: F.W., K.X., F.F., D.S.

Corresponding authors

Correspondence to Dalin Sun, Kang Xu, Fang Fang or Fei Wang.

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Li, Z., Lin, Y., Garaga, M.N. et al. Quantitative and mechanistic insights into proton dynamics for fast energy storage. Nat. Mater. (2025). https://doi.org/10.1038/s41563-025-02366-9

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