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A manganese–hydrogen battery with potential for grid-scale energy storage


Batteries including lithium-ion, lead–acid, redox-flow and liquid-metal batteries show promise for grid-scale storage, but they are still far from meeting the grid's storage needs such as low cost, long cycle life, reliable safety and reasonable energy density for cost and footprint reduction. Here, we report a rechargeable manganese–hydrogen battery, where the cathode is cycled between soluble Mn2+ and solid MnO2 with a two-electron reaction, and the anode is cycled between H2 gas and H2O through well-known catalytic reactions of hydrogen evolution and oxidation. This battery chemistry exhibits a discharge voltage of ~1.3 V, a rate capability of 100 mA cm−2 (36 s of discharge) and a lifetime of more than 10,000 cycles without decay. We achieve a gravimetric energy density of ~139 Wh kg−1 (volumetric energy density of ~210 Wh l−1), with the theoretical gravimetric energy density of ~174 Wh kg−1 (volumetric energy density of ~263 Wh l−1) in a 4 M MnSO4 electrolyte. The manganese–hydrogen battery involves low-cost abundant materials and has the potential to be scaled up for large-scale energy storage.

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Fig. 1: Schematic and simulation of the Mn–H battery.
Fig. 2: Electrochemical performance of the Swagelok-type Mn–H cell.
Fig. 3: Characterization of the cathode in the Mn–H cell.
Fig. 4: Scale-up of the Mn–H cell.

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  1. Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).

    Article  Google Scholar 

  2. Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  4. Rugolo, J. & Aziz, M. J. Electricity storage for intermittent renewable sources. Energy Environ. Sci. 5, 7151–7160 (2012).

    Article  Google Scholar 

  5. Chen, H. S. et al. Progress in electrical energy storage system: a critical review. Prog. Nat. Sci. 19, 291–312 (2009).

    Article  Google Scholar 

  6. Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359–367 (2001).

    Google Scholar 

  7. Goodenough, J. B. & Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater. 22, 587–603 (2010).

    Article  Google Scholar 

  8. Pavlov, D. Lead–Acid Batteries: Science and Technology: A Handbook of Lead–Acid Battery Technology and its Influence on the Product (Elsevier, Amsterdam, 2011).

  9. Wang, W. et al. Recent progress in redox flow battery research and development. Adv. Func. Mater. 23, 970–986 (2013).

    Article  Google Scholar 

  10. Noack, J., Roznyatovskaya, N., Herr, T. & Fischer, P. The chemistry of redox-flow batteries. Angew. Chem. Int. Ed. 54, 9775–9808 (2015).

    Article  Google Scholar 

  11. Huskinson, B. et al. A metal-free organic–inorganic aqueous flow battery. Nature 505, 195–198 (2014).

    Article  Google Scholar 

  12. Yang, Y., Zheng, G. Y. & Cui, Y. A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage. Energy Environ. Sci. 6, 1552–1558 (2013).

    Article  Google Scholar 

  13. Oshima, T., Kajita, M. & Okuno, A. Development of sodium–sulfur batteries. J. Appl. Ceram. Tech. 1, 269–276 (2004).

    Article  Google Scholar 

  14. Wang, K. L. et al. Lithium–antimony–lead liquid metal battery for grid-level energy storage. Nature 514, 348–350 (2014).

    Article  Google Scholar 

  15. Kim, H. et al. Liquid metal batteries: past, present, and future. Chem. Rev. 113, 2075–2099 (2013).

    Article  Google Scholar 

  16. Ovshinsky, S. R., Fetcenko, M. A. & Ross, J. A nickel metal hydride battery for electric vehicles. Science 260, 176–181 (1993).

    Article  Google Scholar 

  17. Li, W., Dahn, J. R. & Wainwright, D. S. Rechargeable lithium batteries with aqueous electrolytes. Science 264, 1115–1118 (1994).

    Article  Google Scholar 

  18. Beck, F. & Ruetschi, P. Rechargeable batteries with aqueous electrolytes. Electrochim. Acta. 45, 2467–2482 (2000).

    Article  Google Scholar 

  19. Zhang, K. et al. Nanostructured Mn-based oxides for electrochemical energy storage and conversion. Chem. Soc. Rev. 44, 699–728 (2015).

    Article  Google Scholar 

  20. Wei, W. F., Cui, X. W., Chen, W. X. & Ivey, D. G. Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem. Soc. Rev. 40, 1697–1721 (2011).

    Article  Google Scholar 

  21. Pan, H. L. et al. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions. Nat. Energy 1, 16039 (2016).

    Article  Google Scholar 

  22. Cottrell, F. G. On the solubility of manganous sulphate. J. Phys. Chem. 4, 637–656 (1900).

    Article  Google Scholar 

  23. Li, Y. G. et al. MoS2 nanoparticles grown on graphene: an advanced catalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 133, 7296–7299 (2011).

    Article  Google Scholar 

  24. Popczun, E. J. et al. Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction. J. Am. Chem. Soc. 135, 9267–9270 (2013).

    Article  Google Scholar 

  25. Izhar, S. & Nagai, M. Transition metal phosphide catalysts for hydrogen oxidation reaction. Catal. Today 146, 172–176 (2009).

    Article  Google Scholar 

  26. Yang, X. G. & Wang, C. Y. Nanostructured tungsten carbide catalysts for polymer electrolyte fuel cells. Appl. Phys. Lett. 86, 224104 (2005).

    Article  Google Scholar 

  27. Sheng, W. C., Gasteiger, H. A. & Shao-Horn, Y. Hydrogen oxidation and evolution reaction kinetics on platinum: acid vs alkaline electrolytes. J. Electrochem. Soc. 157, B1529–B1536 (2010).

    Article  Google Scholar 

  28. Durst, J. et al. New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism. Energy Environ. Sci. 7, 2255–2260 (2014).

    Article  Google Scholar 

  29. Biswal, A., Tripathy, B. C., Sanjay, K., Subbaiah, T. & Minakshi, M. Electrolytic manganese dioxide (EMD): a perspective on worldwide production, reserves and its role in electrochemistry. RSC Adv. 5, 58255–58283 (2015).

    Article  Google Scholar 

  30. Toupin, M., Brousse, T. & Belanger, D. Charge storage mechanism of MnO2 electrode used in aqueous electrochemical capacitor. Chem. Mater. 16, 3184–3190 (2004).

    Article  Google Scholar 

  31. Sun, M. et al. Controlled synthesis of nanostructured manganese oxide: crystalline evolution and catalytic activities. Cryst. Eng. Comm. 15, 7010–7018 (2013).

    Article  Google Scholar 

  32. Electric Energy Storage Technology Options: A White Paper Primer on Applications, Costs, and Benefits Electric Power Research Institute Technical Report 1020676 (Electric Power Research Institute, 2010).

  33. Roberts, B. P. & Sandberg, C. The role of energy storage in development of smart grids. Proc. IEEE 99, 1139–1144 (2011).

    Article  Google Scholar 

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This work was initiated by the support of the Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract DE-AC02-76-SFO0515.

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Authors and Affiliations



W.C. and Y.C. conceived the idea. W.C. designed the battery cells and conducted the electrochemical measurements. W.C. conducted SEM and XRD characterization. A.P. performed the simulation. Y.L. conducted TEM characterization. H.W. performed the XPS analysis. G.C. helped with the GC measurements. Y.C. supervised the project. W.C. and Y.C. contributed to writing the manuscript. W.C. and G.L. contributed equally to this work. All authors discussed the results and commented on the manuscript.

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Correspondence to Yi Cui.

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Supplementary Figures 1–44, Supplementary Notes 1–8, Supplementary Tables 1–2, Supplementary References

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Chen, W., Li, G., Pei, A. et al. A manganese–hydrogen battery with potential for grid-scale energy storage. Nat Energy 3, 428–435 (2018).

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