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

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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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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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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