Article | Published:

Diffusion-free Grotthuss topochemistry for high-rate and long-life proton batteries


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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Data availability

The additional data related to this study are available from the corresponding authors upon request.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.


  1. 1.

    Armand, M. & Tarascon, J. M. Building better batteries. Nature 451, 652–657 (2008).

  2. 2.

    Dunn, B., Kamath, H. & Tarascon, J.-M. Electrical energy storage for the grid: a battery of choices. Science 334, 928–935 (2011).

  3. 3.

    Simon, P., Gogotsi, Y. & Dunn, B. Where do batteries end and supercapacitors begin? Science 343, 1210–1211 (2014).

  4. 4.

    Yang, Z. et al. Electrochemical energy storage for green grid. Chem. Rev. 111, 3577–3613 (2011).

  5. 5.

    Kang, B. & Ceder, G. Battery materials for ultrafast charging and discharging. Nature 458, 190–193 (2009).

  6. 6.

    Evanko, B. et al. Efficient charge storage in dual-redox electrochemical capacitors through reversible counterion-induced solid complexation. J. Am. Chem. Soc. 138, 9373–9376 (2016).

  7. 7.

    Goodenough, J. B. & Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 135, 1167–1176 (2013).

  8. 8.

    Li, W., Dahn, J. R. & Wainwright, D. S. Rechargeable lithium batteries with aqueous electrolytes. Science 264, 1115–1117 (1994).

  9. 9.

    Luo, J.-Y., Cui, W.-J., He, P. & Xia, Y.-Y. Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. Nat. Chem. 2, 760–765 (2010).

  10. 10.

    Suo, L. et al. “Water-in-salt” electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 350, 938–943 (2015).

  11. 11.

    Yabuuchi, N., Kubota, K., Dahbi, M. & Komaba, S. Research development on sodium-ion batteries. Chem. Rev. 114, 11636–11682 (2014).

  12. 12.

    Komaba, S., Hasegawa, T., Dahbi, M. & Kubota, K. Potassium intercalation into graphite to realize high-voltage/high-power potassium-ion batteries and potassium-ion capacitors. Electrochem. Commun. 60, 172–175 (2015).

  13. 13.

    Aurbach, D. et al. Prototype systems for rechargeable magnesium batteries. Nature 407, 724–727 (2000).

  14. 14.

    Lin, M.-C. et al. An ultrafast rechargeable aluminium-ion battery. Nature 520, 324–328 (2015).

  15. 15.

    Kundu, D., Adams, B. D., Duffort, V., Vajargah, S. H. & Nazar, L. F. A high-capacity and long-life aqueous rechargeable zinc battery using a metal oxide intercalation cathode. Nat. Energy 1, 16119 (2016).

  16. 16.

    Ardizzone, S., Fregonara, G. & Trasatti, S. “Inner” and “outer” active surface of RuO2 electrodes. Electrochim. Acta 35, 263–267 (1990).

  17. 17.

    Emanuelsson, R., Sterby, M., Strømme, M. & Sjödin, M. An all-organic proton battery. J. Am. Chem. Soc. 139, 4828–4834 (2017).

  18. 18.

    Sun, W. et al. Zn/MnO2 battery chemistry with H+ and Zn2+ coinsertion. J. Am. Chem. Soc. 139, 9775–9778 (2017).

  19. 19.

    Lee, J. H., Ali, G., Kim, D. H. & Chung, K. Y. Metal–organic framework cathodes based on a vanadium hexacyanoferrate Prussian blue analogue for high-performance aqueous rechargeable batteries. Adv. Energy Mater. 7, 1601491 (2017).

  20. 20.

    Lukatskaya, M. R. et al. Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides. Nat. Energy 2, 17105 (2017).

  21. 21.

    Carlson, C. E. The proton radius puzzle. Prog. Part. Nucl. Phys. 82, 59–77 (2015).

  22. 22.

    Grotthuss, C. J. T. Sur la decomposition de l’eau et des corps q’uelle tient en dissolution à l’aide de l'électricité galvanique. Ann. Chim. LVIII, 54–74 (1806).

  23. 23.

    Wolke, C. T. et al. Spectroscopic snapshots of the proton-transfer mechanism in water. Science 354, 1131–1135 (2016).

  24. 24.

    Knight, C. & Voth, G. A. The curious case of the hydrated proton. Acc. Chem. Res. 45, 101–109 (2011).

  25. 25.

    Agmon, N. The Grotthuss mechanism. Chem. Phys. Lett. 244, 456–462 (1995).

  26. 26.

    Thämer, M., De Marco, L., Ramasesha, K., Mandal, A. & Tokmakoff, A. Ultrafast 2D IR spectroscopy of the excess proton in liquid water. Science 350, 78–82 (2015).

  27. 27.

    Marx, D., Tuckerman, M. E., Hutter, J. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397, 601–604 (1999).

  28. 28.

    Gileadi, E. & Kirowa-Eisner, E. Electrolytic conductivity—the hopping mechanism of the proton and beyond. Electrochim. Acta 51, 6003–6011 (2006).

  29. 29.

    Shimizu, G. K., Taylor, J. M. & Kim, S. Proton conduction with metal–organic frameworks. Science 341, 354–355 (2013).

  30. 30.

    Ohkoshi, S.-i et al. High proton conductivity in Prussian blue analogues and the interference effect by magnetic ordering. J. Am. Chem. Soc. 132, 6620–6621 (2010).

  31. 31.

    Kaye, S. S. & Long, J. R. Hydrogen storage in the dehydrated Prussian blue analogues M3[Co(CN)6]2 (M = Mn, Fe, Co, Ni, Cu, Zn). J. Am. Chem. Soc. 127, 6506–6507 (2005).

  32. 32.

    Wessells, C. D., Huggins, R. A. & Cui, Y. Copper hexacyanoferrate battery electrodes with long cycle life and high power. Nat. Commun. 2, 550 (2011).

  33. 33.

    Wessells, C. D., Peddada, S. V., Huggins, R. A. & Cui, Y. Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. Nano Lett. 11, 5421–5425 (2011).

  34. 34.

    Herren, F., Fischer, P., Ludi, A. & Hälg, W. Neutron diffraction study of Prussian blue, Fe4[Fe(CN)6]3xH2O. Location of water molecules and long-range magnetic order. Inorg. Chem. 19, 956–959 (1980).

  35. 35.

    Asakura, D. et al. Bimetallic cyanide-bridged coordination polymers as lithium ion cathode materials: core@shell nanoparticles with enhanced cyclability. J. Am. Chem. Soc. 135, 2793–2799 (2013).

  36. 36.

    Sun, H. et al. Three-dimensional holey-graphene/niobia composite architectures for ultrahigh-rate energy storage. Science 356, 599–604 (2017).

  37. 37.

    Liu, C., Li, F., Ma, L. P. & Cheng, H. M. Advanced materials for energy storage. Adv. Mater. 22, 28–62 (2010).

  38. 38.

    Zhang, H., Yu, X. & Braun, P. V. Three-dimensional bicontinuous ultrafast-charge and -discharge bulk battery electrodes. Nat. Nanotech. 6, 277–281 (2011).

  39. 39.

    Augustyn, V. et al. High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. Nat. Mater. 12, 518–522 (2013).

  40. 40.

    Zheng, J. et al. Janus solid–liquid interface enabling ultrahigh charging and discharging rate for advanced Lithium-ion batteries. Nano. Lett. 15, 6102–6109 (2015).

  41. 41.

    Lee, S. W. et al. High-power lithium batteries from functionalized carbon-nanotube electrodes. Nat. Nanotech. 5, 531–537 (2010).

  42. 42.

    Augustyn, V. & Gogotsi, Y. 2D materials with nanoconfined fluids for electrochemical energy storage. Joule 1, 443–452 (2017).

  43. 43.

    Zwier, T. S. The structure of protonated water clusters. Science 304, 1119–1120 (2004).

  44. 44.

    Wei, M. et al. A large protonated water cluster H+(H2O)27 in a 3D metal–organic framework. J. Am. Chem. Soc. 128, 13318–13319 (2006).

  45. 45.

    Wang, J., Polleux, J., Lim, J. & Dunn, B. Pseudocapacitive contributions to electrochemical energy storage in TiO2 (anatase) nanoparticles. J. Phys. Chem. C 111, 14925–14931 (2007).

  46. 46.

    Tuckerman, M. E., Marx, D. & Parrinello, M. The nature and transport mechanism of hydrated hydroxide ions in aqueous solution. Nature 417, 925–929 (2002).

  47. 47.

    Bai, Y. et al. High-performance dye-sensitized solar cells based on solvent-free electrolytes produced from eutectic melts. Nat. Mater. 7, 626–630 (2008).

  48. 48.

    Wu, X. et al. Low defect FeFe(CN)6 framework as stable host material for high performance Li-ion batteries. ACS Appl. Mater. Interfaces 8, 23706–23712 (2016).

  49. 49.

    Asakura, D. et al. Fabrication of a cyanide-bridged coordination polymer electrode for enhanced electrochemical ion storage ability. J. Phys. Chem. C 116, 8364–8369 (2012).

  50. 50.

    Ono, K. et al. Grain-boundary-free super-proton conduction of a solution-processed Prussian-blue nanoparticle film. Angew. Chem. Int. Ed. 56, 5531–5535 (2017).

  51. 51.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558 (1993).

  52. 52.

    Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251 (1994).

  53. 53.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).

  54. 54.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

  55. 55.

    Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188 (1976).

  56. 56.

    Dudarev, S., Botton, G., Savrasov, S., Humphreys, C. & Sutton, A. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys. Rev. B 57, 1505 (1998).

  57. 57.

    Ling, C., Chen, J. & Mizuno, F. First-principles study of alkali and alkaline earth ion intercalation in iron hexacyanoferrate: the important role of ionic radius. J. Phys. Chem. C 117, 21158–21165 (2013).

  58. 58.

    Plimpton, S. Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117, 1–19 (1995).

  59. 59.

    Robert, C. P. Casella Monte Carlo Statistical Methods 2nd edn (Springer, New York, 2004).

  60. 60.

    Stukowski, A. Visualization and analysis of atomistic simulation data with OVITO—the Open Visualization Tool. Model. Simul. Mater. Sci. Eng. 18, 015012 (2010).

  61. 61.

    Henkelman, G., Uberuaga, B. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

  62. 62.

    Henkelman, G. & Jonsson, H. Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J. Chem. Phys. 113, 9978–9985 (2000).––

Download references


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

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.

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

Supplementary information

Supplementary Information

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

Supplementary Video 1

The relaxation process of the proton conduction

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Further reading

Fig. 1: Transfer of charges and energy, and three classes of PBAs.
Fig. 2: Electrochemical performance of CuFe-TBA.
Fig. 3: Structural studies of CuFe-TBA.
Fig. 4: DFT calculations of the proton-binding sites.
Fig. 5: Structural evolution during proton (de)insertion.