Abstract

The design of Faradaic battery electrodes that exhibit high rate capability and long cycle life equivalent to those of the electrodes of electrical double-layer capacitors is a big challenge. Here we report a strategy to fill this performance gap using the concept of Grotthuss proton conduction, in which proton transfer takes place by means of concerted cleavage and formation of O–H bonds in a hydrogen-bonding network. We show that in a hydrated Prussian blue analogue (Turnbull’s blue) the abundant lattice water molecules with a contiguous hydrogen-bonding network facilitate Grotthuss proton conduction during redox reactions. When using it as a battery electrode, we find high-rate behaviours at 4,000 C (380 A g−1, 508 mA cm−2), and a long cycling life of 0.73 million cycles. These results for diffusion-free Grotthuss topochemistry of protons, in contrast to orthodox battery electrochemistry, which requires ion diffusion inside electrodes, indicate a potential direction to revolutionize electrochemical energy storage for high-power applications.

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Acknowledgements

This work was supported by the US National Science Foundation, Award Number 1551693. J.L. gratefully acknowledges support from the US DOE, Office of Energy Efficiency and Renewable Energy, Vehicle Technologies Office. Argonne National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under contract DE-AC02-06CH11357. This research used resources of the APS (9-BM and 11-ID-D), a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. The work used the XSEDE, which is supported by National Science Foundation grant ACI-1548562. Through XSEDE, computing was performed on Stambede2 at the Texas Advanced Computing Centre through allocation TG-DMR130046. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Author information

Affiliations

  1. Department of Chemistry, Oregon State University, Corvallis, OR, USA

    • Xianyong Wu
    • , Jessica J. Hong
    • , Woochul Shin
    • , Yitong Qi
    • , T. Wesley Surta
    •  & Xiulei Ji
  2. X-ray Science Division, Advanced Photon Sources, Argonne National Laboratory, Lemont, IL, USA

    • Lu Ma
    •  & Tianpin Wu
  3. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL, USA

    • Tongchao Liu
    • , Xuanxuan Bi
    • , Yifei Yuan
    •  & Jun Lu
  4. Materials Science and Engineering, University of California, Riverside, CA, USA

    • Wenxi Huang
    •  & P. Alex Greaney
  5. Oak Ridge National Laboratory, Oak Ridge, TN, USA

    • Joerg Neuefeind

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Contributions

X.J. conceived the idea and designed the research. X.W. conducted the material preparation, electrochemical tests and data analyses with assistance from Y.Q. J.J.H. and T.W.S. performed Rietveld refinements of the synchrotron X-ray and neutron diffraction results. P.A.G. supervised the DFT calculations that W.S. and W.H. carried out. J.L. and T.W. supervised the synchrotron-based characterization and transmission electron microscopy measurements that L.M., T.L., X.B. and Y.Y. performed. J.N. collected the neutron diffraction data. All authors discussed the data and reviewed the final draft.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to P. Alex Greaney or Jun Lu or Xiulei Ji.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–27, Supplementary Tables 1–2, Supplementary References

  2. Supplementary Video 1

    The relaxation process of the proton conduction

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https://doi.org/10.1038/s41560-018-0309-7