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

Nature Energy volume 2, pages 861–868 (2017)Cite this article

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Abstract

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.

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Fig. 1: Structure of Na2C6O6 and its electrochemical behaviour in Na cells under different conditions showing inconsistent phase transition.
Fig. 2: Phase transformation of Na2C6O6 during sodiation/desodiation processes.
Fig. 3: Voltage profile evolution of Na2C6O6 during sodiation/desodiation processes.
Fig. 4: Morphological changes during reversible phase transformation and proposed redox mechanism for sodium storage of Na2C6O6.
Fig. 5: Electrochemical four-sodium storage of Na2C6O6 electrodes in half-cells and full-cells.

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References

  1. 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 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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

    Article  Google Scholar 

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Acknowledgements

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.

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Authors and Affiliations

  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

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  1. Minah Lee
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Contributions

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.

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Correspondence to Yi Cui or Zhenan Bao.

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

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Lee, M., Hong, J., Lopez, J. et al. High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate. Nat Energy 2, 861–868 (2017). https://doi.org/10.1038/s41560-017-0014-y

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