Reversible aqueous zinc/manganese oxide energy storage from conversion reactions


Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4-based solution is used as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2, are used as the cathode. We show that a chemical conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This includes an operating voltage of 1.44 V, a capacity of 285 mAh g−1 (MnO2), and capacity retention of 92% over 5,000 cycles. The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-performance rechargeable aqueous batteries.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Structural and morphological characterization of MnO2.
Figure 2: Electrochemical behaviours of Zn/MnO2 batteries with 2 M ZnSO4 as electrolyte.
Figure 3: Improved electrochemical performance of Zn/MnO2 batteries in optimal aqueous electrolyte.
Figure 4: TEM/HRTEM images of MnO2 electrodes during electrochemical process.
Figure 5: Characterization of Zn anode electrodes.


  1. 1

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

    Article  Google Scholar 

  2. 2

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

    Article  Google Scholar 

  3. 3

    Liu, J. et al. Materials science and materials chemistry for large scale electrochemical energy storage: from transportation to electrical grid. Adv. Funct. Mater. 23, 929–946 (2013).

    Article  Google Scholar 

  4. 4

    Larcher, D. & Tarascon, J. M. Towards greener and more sustainable batteries for electrical energy storage. Nature Chem. 7, 19–29 (2015).

    Article  Google Scholar 

  5. 5

    Jiang, J. et al. Recent advances in metal oxide-based electrode architecture design for electrochemical energy storage. Adv. Mater. 24, 5166–5180 (2012).

    Article  Google Scholar 

  6. 6

    Qu, D. Studies of the activated carbons used in double-layer supercapacitors. J. Power Sources 109, 403–411 (2002).

    Article  Google Scholar 

  7. 7

    Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nature Mater. 7, 845–854 (2008).

    Article  Google Scholar 

  8. 8

    Zhai, Y. et al. Carbon materials for chemical capacitive energy storage. Adv. Mater. 23, 4828–4850 (2011).

    Article  Google Scholar 

  9. 9

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

    Article  Google Scholar 

  10. 10

    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. Nature Chem. 2, 760–765 (2010).

    Article  Google Scholar 

  11. 11

    Lu, Y., Goodenough, J. B. & Kim, Y. Aqueous cathode for next-generation alkali-ion batteries. J. Am. Chem. Soc. 133, 5756–5759 (2011).

    Article  Google Scholar 

  12. 12

    Köhler, J., Makihara, H., Uegaito, H., Inoue, H. & Toki, M. LiV3O8: characterization as anode material for an aqueous rechargeable Li-ion battery system. Electrochim. Acta 46, 59–65 (2000).

    Article  Google Scholar 

  13. 13

    Luo, J. Y. & Xia, Y. Y. Aqueous lithium-ion battery LiTi2(PO4)3/LiMn2O4 with high power and energy densities as well as superior cycling stability. Adv. Funct. Mater. 17, 3877–3884 (2007).

    Article  Google Scholar 

  14. 14

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

    Article  Google Scholar 

  15. 15

    Pasta, M., Wessells, C. D., Huggins, R. A. & Cui, Y. A high-rate and long cycle life aqueous electrolyte battery for grid-scale energy storage. Nature Commun. 3, 1149 (2012).

    Article  Google Scholar 

  16. 16

    Chen, L., Zhang, L., Zhou, X. & Liu, Z. Aqueous batteries based on mixed monovalence metal ions: a new battery family. ChemSusChem 7, 2295–2302 (2014).

    Article  Google Scholar 

  17. 17

    Lee, J.-S. et al. Metal–air batteries with high energy density: Li–air versus Zn–air. Adv. Energy Mater. 1, 34–50 (2011).

    Article  Google Scholar 

  18. 18

    Zhang, L., Chen, L., Zhou, X. & Liu, Z. Towards high-voltage aqueous metal-ion batteries beyond 1.5 V: the zinc/zinc hexacyanoferrate system. Adv. Energy Mater. (2015).

  19. 19

    Trócoli, R. & La Mantia, F. An aqueous zinc-ion battery based on copper hexacyanoferrate. ChemSusChem 8, 481–485 (2015).

    Article  Google Scholar 

  20. 20

    Mondoloni, C., Laborde, M., Rioux, J., Andoni, E. & Lévy-Clément, C. Rechargeable alkaline manganese dioxide batteries: I. In situ X-ray diffraction investigation of the (EMD-type) insertion system. J. Electrochem. Soc. 139, 954–959 (1992).

    Article  Google Scholar 

  21. 21

    Hertzberg, B., Sviridov, L., Stach, E. A., Gupta, T. & Steingart, D. A manganese-doped barium carbonate cathode for alkaline batteries. J. Electrochem. Soc. 161, A835–A840 (2014).

    Article  Google Scholar 

  22. 22

    Xu, C., Li, B., Du, H. & Kang, F. Energetic zinc ion chemistry: the rechargeable zinc ion battery. Angew. Chem. 124, 957–959 (2012).

    Article  Google Scholar 

  23. 23

    Xu, C., Du, H., Li, B., Kang, F. & Zeng, Y. Reversible insertion properties of zinc ion into manganese dioxide and its application for energy storage. Electrochem. Solid State Lett. 12, A61–A65 (2009).

    Article  Google Scholar 

  24. 24

    Alfaruqi, M. H. et al. Electrochemically induced structural transformation in a γ-MnO2 cathode of a high capacity zinc-ion battery system. Chem. Mater. 27, 3609–3620 (2015).

    Article  Google Scholar 

  25. 25

    Xu, D. et al. Preparation and characterization of MnO2/acid-treated CNT nanocomposites for energy storage with zinc ions. Electrochim. Acta 133, 254–261 (2014).

    Article  Google Scholar 

  26. 26

    Lee, B. et al. Electrochemically-induced reversible transition from the tunneled to layered polymorphs of manganese dioxide. Sci. Rep. 4, 6066 (2014).

    Article  Google Scholar 

  27. 27

    Alfaruqi, M. H. et al. Enhanced reversible divalent zinc storage in a structurally stable α-MnO2 nanorod electrode. J. Power Sources 288, 320–327 (2015).

    Article  Google Scholar 

  28. 28

    Xu, C., Chiang, S. W., Ma, J. & Kang, F. Investigation on zinc ion storage in alpha manganese dioxide for zinc ion battery by electrochemical impedance spectrum. J. Electrochem. Soc. 160, A93–A97 (2013).

    Article  Google Scholar 

  29. 29

    Lee, B. et al. Elucidating the intercalation mechanism of zinc ions into [α]-MnO2 for rechargeable zinc batteries. Chem. Commun. 51, 9265–9268 (2015).

    Article  Google Scholar 

  30. 30

    Hongen, W., Zhouguang, L., Dong, Q., Yujie, L. & Wei, Z. Single-crystal α-MnO2 nanorods: synthesis and electrochemical properties. Nanotechnology 18, 115616 (2007).

    Article  Google Scholar 

  31. 31

    Cheng, F. Y., Chen, J., Gou, X. L. & Shen, P. W. High-power alkaline Zn–MnO2 batteries using γ-MnO2 nanowires/nanotubes and electrolytic zinc powder. Adv. Mater. 17, 2753–2756 (2005).

    Article  Google Scholar 

  32. 32

    Sun, J. et al. Overpotential and electrochemical impedance analysis on Cr2O3 thin film and powder electrode in rechargeable lithium batteries. Solid State Ion. 179, 2390–2395 (2008).

    Article  Google Scholar 

  33. 33

    Alias, N. & Mohamad, A. A. Advances of aqueous rechargeable lithium-ion battery: a review. J. Power Sources 274, 237–251 (2015).

    Article  Google Scholar 

  34. 34

    Hu, Y. S., Kienle, L., Guo, Y. G. & Maier, J. High lithium electroactivity of nanometer-sized rutile TiO2 . Adv. Mater. 18, 1421–1426 (2006).

    Article  Google Scholar 

  35. 35

    Chan, C. K. et al. High-performance lithium battery anodes using silicon nanowires. Nature Nanotech. 3, 31–35 (2008).

    Article  Google Scholar 

  36. 36

    Lee, H.-W. et al. Ultrathin spinel LiMn2O4 nanowires as high power cathode materials for Li-ion batteries. Nano Lett. 10, 3852–3856 (2010).

    Article  Google Scholar 

  37. 37

    Delmer, O., Balaya, P., Kienle, L. & Maier, J. Enhanced potential of amorphous electrode materials: case study of RuO2 . Adv. Mater. 20, 501–505 (2008).

    Article  Google Scholar 

  38. 38

    Zhong, K. et al. Investigation on porous MnO microsphere anode for lithium ion batteries. J. Power Sources 196, 6802–6808 (2011).

    Article  Google Scholar 

  39. 39

    Pan, H. et al. Sodium storage and transport properties in layered Na2Ti3O7 for room-temperature sodium-ion batteries. Adv. Energy Mater. 3, 1186–1194 (2013).

    Article  Google Scholar 

  40. 40

    Divya, K. C. & Østergaard, J. Battery energy storage technology for power systems—An overview. Electr. Power Syst. Res. 79, 511–520 (2009).

    Article  Google Scholar 

Download references


This work is supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award KC020105-FWP12152. The TEM, NMR and XRD work were performed using EMSL, a National Scientific User Facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL. PNNL is a Multi-Program National Laboratory operated for DOE by Battelle. The work at UW was supported by Inamori Foundation.

Author information




Y.S. and J.L. proposed the research. H.P., Y.S. and J.L. designed the experiments. H.P. and Y.S. performed the material process, characterization, electrochemical measurements and analysed the data. Y.C. synthesized the material. P.Y., Y.C. and C.W. conducted the TEM and STEM mapping. K.S.H. and K.T.M. performed NMR characterization. H.P., Y.S. and J.L. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Yuyan Shao or Jun Liu.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Figures 1–9, Supplementary Discussion, Supplementary References. (PDF 949 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

Further reading


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing