Article | Published:

High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate

Nature Energyvolume 2pages861868 (2017) | Download Citation


Sodium-ion batteries (SIBs) for grid-scale applications need active materials that combine a high energy density with sustainability. Given the high theoretical specific capacity 501 mAh g−1, and Earth abundance of disodium rhodizonate (Na2C6O6), it is one of the most promising cathodes for SIBs. However, substantially lower reversible capacities have been obtained compared with the theoretical value and the understanding of this discrepancy has been limited. Here, we reveal that irreversible phase transformation of Na2C6O6 during cycling is the origin of the deteriorating redox activity of Na2C6O6. The active-particle size and electrolyte conditions were identified as key factors to decrease the activation barrier of the phase transformation during desodiation. On the basis of this understanding, we achieved four-sodium storage in a Na2C6O6 electrode with a reversible capacity of 484 mAh g−1, an energy density of 726 Wh kg−1 cathode, an energy efficiency above 87% and a good cycle retention.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Additional information

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


  1. 1.

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

  2. 2.

    Choi, J. W. & Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 1, 16013 (2016).

  3. 3.

    Kim, H. et al. Recent progress in electrode materials for sodium-ion batteries. Adv. Energy Mater. 6, 1600943 (2016).

  4. 4.

    Kundu, D., Talaie, E., Duffort, V. & Nazar, L. F. The emerging chemistry of sodium ion batteries for electrochemical energy storage. Angew. Chem. Int. Edn 54, 3431–3448 (2015).

  5. 5.

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

  6. 6.

    Muench, S. et al. Polymer-based organic batteries. Chem. Rev. 116, 9438–9484 (2016).

  7. 7.

    Häupler, B., Wild, A. & Schubert, U. S. Carbonyls: powerful organic materials for secondary batteries. Adv. Energy Mater. 5, 1402034 (2015).

  8. 8.

    Song, Z. & Zhou, H. Towards sustainable and versatile energy storage devices: an overview of organic electrode materials. Energy Environ. Sci. 6, 2280–2301 (2013).

  9. 9.

    Zhao, Q. et al. Oxocarbon salts for fast rechargeable batteries. Angew. Chem. Int. Edn 55, 12528–12532 (2016).

  10. 10.

    Chen, H. et al. From biomass to a renewable LiXC6O6 organic electrode for sustainable Li-ion batteries. ChemSusChem 1, 348–355 (2008).

  11. 11.

    Chen, H. et al. Lithium salt of tetrahydroxybenzoquinone: toward the development of a sustainable Li-ion battery. J. Am. Chem. Soc. 131, 8984–8988 (2009).

  12. 12.

    Kim, H. et al. The reaction mechanism and capacity degradation model in lithium insertion organic cathodes, Li2C6O6, using combined experimental and first principle studies. J. Phys. Chem. Lett. 5, 3086–3092 (2014).

  13. 13.

    Chihara, K., Chujo, N., Kitajou, A. & Okada, S. Cathode properties of Na2C6O6 for sodium-ion batteries. Electrochim. Acta 110, 240–246 (2013).

  14. 14.

    Wang, C. et al. Manipulation of disodium rhodizonate: factors for fast-charge and fast-discharge sodium-ion batteries with long-term cyclability. Adv. Funct. Mater. 26, 1777–1786 (2016).

  15. 15.

    Wang, Y. et al. Understanding the size-dependent sodium storage properties of Na2C6O6-based organic electrodes for sodium-ion batteries. Nano Lett. 16, 3329–3334 (2016).

  16. 16.

    Dinnebier, R. E., Nuss, H. & Jansen, M. Disodium rhodizonate: a powder diffraction study. Acta Crystallogr., Sect. E 61, m2148–m2150 (2005).

  17. 17.

    Luo, C. et al. Self-assembled organic nanowires for high power density lithium ion batteries. Nano Lett. 14, 1596–1602 (2014).

  18. 18.

    Yamashita, T., Momida, H. & Oguchi, T. First-principles investigation of a phase transition in NaxC6O6 as an organic cathode material for Na-ion batteries: role of intermolecule bonding of C6O6. J. Phys. Soc. Jpn 84, 074703 (2015).

  19. 19.

    Yamashita, T., Momida, H. & Oguchi, T. Crystal structure predictions of NaxC6O6 for sodium-ion batteries: first-principles calculations with an evolutionary algorithm. Electrochim. Acta 195, 1–8 (2016).

  20. 20.

    Bock, H., Naether, C. & Havlas, Z. Competing Na+ solvation: ether-shared and ether-separated triple ions of perylene dianion. J. Am. Chem. Soc. 117, 3869–3870 (1995).

  21. 21.

    Bock, H., Näther, C., Havlas, Z., John, A. & Arad, C. Ether-solvated sodium ions in salts containing π-hydrocarbon anions: crystallization, structures, and semiempirical solvation energies. Angew. Chem. Int. Ed. Engl. 33, 875–878 (1994).

  22. 22.

    Li, Y. et al. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes. Nat. Energy 1, 15029 (2016).

  23. 23.

    Rui, X., Sun, W., Wu, C., Yu, Y. & Yan, Q. An advanced sodium-ion battery composed of carbon coated Na3V2(PO4)3 in a porous graphene network. Adv. Mater. 27, 6670–6676 (2015).

  24. 24.

    Sakaushi, K. et al. Aromatic porous-honeycomb electrodes for a sodium-organic energy storage device. Nat. Commun. 4, 1485 (2013).

  25. 25.

    Wang, L. et al. A superior low-cost cathode for a Na-ion battery. Angew. Chem. Int. Edn 52, 1964–1967 (2013).

  26. 26.

    Yabuuchi, N. et al. P2-type Nax[Fe1/2Mn1/2]O2 made from earth-abundant elements for rechargeable Na batteries. Nat. Mater. 11, 512–517 (2012).

  27. 27.

    Ramireddy, T. et al. Phosphorus-carbon nanocomposite anodes for lithium-ion and sodium-ion batteries. J. Mater. Chem. A 3, 5572–5584 (2015).

  28. 28.

    Li, W. et al. Amorphous red phosphorus embedded in highly ordered mesoporous carbon with superior lithium and sodium storage capacity. Nano Lett. 16, 1546–1553 (2016).

  29. 29.

    Guo, S. et al. A high-voltage and ultralong-life sodium full cell for stationary energy storage. Angew. Chem. Int. Edn 54, 11701–11705 (2015).

  30. 30.

    Wang, S. et al. All organic sodium-ion batteries with Na4C8H2O6. Angew. Chem. Int. Edn 53, 5892–5896 (2014).

  31. 31.

    Li, H. et al. An advanced high-energy sodium ion full battery based on nanostructured Na2Ti3O7/VOPO4 layered materials. Energy Environ. Sci. 9, 3399–3405 (2016).

  32. 32.

    Xie, X. et al. Sn@CNT nanopillars grown perpendicularly on carbon paper: a novel free-standing anode for sodium ion batteries. Nano Energy 13, 208–217 (2015).

  33. 33.

    Wang, Y., Xiao, R., Hu, Y.-S., Avdeev, M. & Chen, L. P2-Na0.6[Cr0.6Ti0.4]O2 cation-disordered electrode for high-rate symmetric rechargeable sodium-ion batteries. Nat. Commun. 6, 6954 (2015).

  34. 34.

    Zhao, L. et al. Disodium terephthalate (Na2C8H4O4) as high performance anode material for low-cost room-temperature sodium-ion battery. Adv. Energy Mater. 2, 962–965 (2012).

  35. 35.

    Park, Y. et al. Sodium terephthalate as an organic anode material for sodium ion batteries. Adv. Mater. 24, 3562–3567 (2012).

Download references


We acknowledge the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program and Battery500 Consortium. M.L. acknowledges partial support by the Postdoctoral Fellowship from the National Research Foundation of Korea under Grant No. NRF-2017R1A6A3A03007053. J.L. acknowledges support by the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-114747. X-ray measurements were carried out at the Stanford Synchrotron Radiation Laboratory (SSRL), a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. The authors thank C.J. Tassone and T.J. Dunn for assistance during the XRD experiment at SSRL beamline 1–5.

Author information


  1. Department of Chemical Engineering, Stanford University, Stanford, CA, 94305, USA

    • Minah Lee
    • , Jeffrey Lopez
    • , Dawei Feng
    •  & Zhenan Bao
  2. Department of Materials Science and Engineering, Stanford University, Stanford, CA, 94305, USA

    • Jihyun Hong
    • , Yongming Sun
    • , Kipil Lim
    • , William C. Chueh
    •  & Yi Cui
  3. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA

    • Jihyun Hong
    • , Kipil Lim
    •  & Michael F. Toney


  1. Search for Minah Lee in:

  2. Search for Jihyun Hong in:

  3. Search for Jeffrey Lopez in:

  4. Search for Yongming Sun in:

  5. Search for Dawei Feng in:

  6. Search for Kipil Lim in:

  7. Search for William C. Chueh in:

  8. Search for Michael F. Toney in:

  9. Search for Yi Cui in:

  10. Search for Zhenan Bao in:


M.L. carried out materials fabrication, characterization and testing. J.H. and M.L. performed in situ synchrotron XRD. K.L., J.H., M.F.T. and W.C.C. designed and constructed settings for in situ synchrotron XRD. Y.S. prepared the phosphorous/carbon composite. J.L. and D.F. provided constructive advice for experiments. M.L. wrote the first draft. Z.B. and Y.C. revised the manuscript. All authors discussed the results and contributed to preparing the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Yi Cui or Zhenan Bao.

Electronic supplementary material

  1. Supplementary Information

    Supplementary Figures 1–24, Supplementary Tables 1, Supplementary Note 1–2 and Supplementary References

About this article

Publication history