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Air-stable naphthalene derivative-based electrolytes for sustainable aqueous flow batteries

Nature Sustainability volume 7, pages 1273–1282 (2024)Cite this article

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Abstract

The growing global capacity for renewable energy generation necessitates the deployment of energy storage technologies with a combination of low cost, good performance and scalability. With these advantages, aqueous organic flow batteries have the potential to be the system of choice because they could store energy from organic redox-active molecules. Here we report naphthalene derivatives as organic redox-active molecules that exhibit high solubility (~1.5 M) and a stable redox-active framework with no obvious capacity decay over 40 days (50 Ah l−1) in an air atmosphere in flow batteries. We report a battery that runs smoothly even under continuous airflow without obvious capacity decay for ~22 days (more than 600 cycles). A series of spectral analyses and theoretical calculations reveal that the dimethylamine scaffolds improve the water solubility and protect the active centre, ensuring the stability of the molecules during the charge and discharge process. Owing to the success in kilogramme-scale molecular synthesis, pilot-scale stack expansion with notable cycling stability over 270 cycles (~27 days) is attained. The cost benefit evidenced by technoeconomic analysis together with the stability even under open-air conditions indicates the practical value of the present molecular system in grid-scale energy storage.

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Fig. 1: Chemical and electrochemical reaction and battery performance of naphthalene derivatives.
Fig. 2: In situ NMR of TANQ during electrochemical cycling.
Fig. 3: LC‒MS and EPR spectra of TANQ during operation.
Fig. 4: Stable radical intermediates and mechanism.
Fig. 5: Scaled-up TAND synthesis and pilot stacks.

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Data availability

All data generated and/or analysed from this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

References

  1. Zhao, Z. et al. Development of flow battery technologies using the principles of sustainable chemistry. Chem. Soc. Rev. 52, 6031–6074 (2023).

    Article  CAS  Google Scholar 

  2. Cameron, J. M. et al. Molecular redox species for next-generation batteries. Chem. Soc. Rev. 50, 5863–5883 (2021).

    Article  CAS  Google Scholar 

  3. Zhang, C., Yuan, Z. & Li, X. Designing better flow batteries: an overview on fifty years’ research. ACS Energy Lett. 9, 3456–3473 (2024).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  5. Janoschka, T. et al. An aqueous, polymer-based redox-flow battery using non-corrosive, safe, and low-cost materials. Nature 527, 78–81 (2015).

    Article  CAS  Google Scholar 

  6. Wang, J. et al. Conjugated sulfonamides as a class of organic lithium-ion positive electrodes. Nat. Mater. 20, 665–673 (2021).

    Article  CAS  Google Scholar 

  7. Feng, R. et al. Reversible ketone hydrogenation and dehydrogenation for aqueous organic redox flow batteries. Science 372, 836–840 (2021).

    Article  CAS  Google Scholar 

  8. Hollas, A. et al. A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries. Nat. Energy 3, 508–514 (2018).

    Article  CAS  Google Scholar 

  9. Zhang, C. et al. Phenothiazine-based organic catholyte for high-capacity and long-life aqueous redox flow batteries. Adv. Mater. 31, 1901052 (2019).

    Article  Google Scholar 

  10. Nguyen, T. P. et al. Polypeptide organic radical batteries. Nature 593, 61–66 (2021).

    Article  CAS  Google Scholar 

  11. Janoschka, T., Martin, N., Hager, M. D. & Schubert, U. S. An aqueous redox-flow battery with high capacity and power: the TEMPTMA/MV system. Angew. Chem. Int. Ed. 55, 14427–14430 (2016).

    Article  CAS  Google Scholar 

  12. Liu, Y. et al. A long-lifetime all-organic aqueous flow battery utilizing TMAP-TEMPO radical. Chem 5, 1861–1870 (2019).

    Article  CAS  Google Scholar 

  13. Feng, R. et al. Proton-regulated alcohol oxidation for high-capacity ketone-based flow battery anolyte. Joule 7, 1609–1622 (2023).

    Article  CAS  Google Scholar 

  14. Li, X. et al. Symmetry-breaking design of an organic iron complex catholyte for a long cyclability aqueous organic redox flow battery. Nat. Energy 6, 873–881 (2021).

    Article  CAS  Google Scholar 

  15. Luo, J., Hu, B., Hu, M., Zhao, Y. & Liu, T. L. Status and prospects of organic redox flow batteries toward sustainable energy storage. ACS Energy Lett. 4, 2220–2240 (2019).

    Article  CAS  Google Scholar 

  16. Kwabi, D. G., Ji, Y. & Aziz, M. J. Electrolyte lifetime in aqueous organic redox flow batteries: a critical review. Chem. Rev. 120, 6467–6489 (2020).

    Article  CAS  Google Scholar 

  17. Singh, V., Kim, S., Kang, J. & Byon, H. R. Aqueous organic redox flow batteries. Nano Res. 12, 1988–2001 (2019).

    Article  CAS  Google Scholar 

  18. Liu, W. Q. et al. A high potential biphenol derivative cathode: toward a highly stable air-insensitive aqueous organic flow battery. Sci. Bull. 66, 457–463 (2021).

    Article  CAS  Google Scholar 

  19. Wedege, K., Dražević, E., Konya, D. & Bentien, A. Organic redox species in aqueous flow batteries: redox potentials, chemical stability and solubility. Sci. Rep. 6, 39101 (2016).

    Article  CAS  Google Scholar 

  20. Kwabi, D. G. et al. Alkaline quinone flow battery with long lifetime at pH 12. Joule 2, 1894–1906 (2018).

    Article  CAS  Google Scholar 

  21. Wang, C. et al. Molecular design of fused-ring phenazine derivatives for long-cycling alkaline redox flow batteries. ACS Energy Lett. 5, 411–417 (2020).

    Article  CAS  Google Scholar 

  22. Pang, S., Wang, X., Wang, P. & Ji, Y. Biomimetic amino acid functionalized phenazine flow batteries with long lifetime at near-neutral pH. Angew. Chem. Int. Ed. 60, 5289–5298 (2021).

    Article  CAS  Google Scholar 

  23. Zhang, C. & Li, X. Perspective on organic flow batteries for large-scale energy storage. Curr. Opin. Electrochem. 30, 100836 (2021).

    Article  CAS  Google Scholar 

  24. Carrington, M. E. et al. Associative pyridinium electrolytes for air-tolerant redox flow batteries. Nature 623, 949–955 (2023).

    Article  CAS  Google Scholar 

  25. Clark, C. D., Debad, J. D., Yonemoto, E. H., Mallouk, T. E. & Bard, A. J. Effect of oxygen on linked Ru(bpy)32+−Viologen species and methylviologen: a reinterpretation of the electrogenerated chemiluminescence. J. Am. Chem. Soc. 119, 10525–10531 (1997).

    Article  CAS  Google Scholar 

  26. Levey, G. T. & Ebbesen, W. Methyl viologen radical reactions with several oxidizing agents. J. Phys. Chem. 87, 829–832 (1983).

    Article  CAS  Google Scholar 

  27. Zotti, G., Schiavon, G., Zecchin, S. & Favretto, D. Dioxygen-decomposition of ferrocenium molecules in acetonitrile: the nature of the electrode-fouling films during ferrocene electrochemistry. J. Electroanal. Chem. 456, 217–221 (1998).

    Article  CAS  Google Scholar 

  28. Zhao, E. W. et al. Coupled in situ NMR and EPR studies reveal the electron transfer rate and electrolyte decomposition in redox flow batteries. J. Am. Chem. Soc. 143, 1885–1895 (2021).

    Article  CAS  Google Scholar 

  29. Symons, P. Quinones for redox flow batteries. Curr. Opin. Electrochem. 29, 100759 (2021).

    Article  CAS  Google Scholar 

  30. Lu, T. & Chen, Q. Interaction region indicator: a simple real space function clearly revealing both chemical bonds and weak interactions. Chem.–Methods 1, 231–239 (2021).

    Article  CAS  Google Scholar 

  31. Dai, Q. et al. High-performance PBI membranes for flow batteries: from the transport mechanism to the pilot plant. Energy Environ. Sci. 15, 1594–1600 (2022).

    Article  CAS  Google Scholar 

  32. Frisch, M. J. et al. Gaussian 16 Rev. A.03 (Gaussian, Inc., 2016). https://gaussian.com/citation/

  33. Grimme, S. Accurate description of van der Waals complexes by density functional theory including empirical corrections. J. Comput. Chem. 25, 1463–1473 (2004).

    Article  CAS  Google Scholar 

  34. Marenich, A. V., Cramer, C. J. & Truhlar, D. G. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J. Phys. Chem. 113, 6378–6396 (2009).

    Article  CAS  Google Scholar 

  35. Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297–3305 (2005).

    Article  CAS  Google Scholar 

  36. Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580–592 (2012).

    Article  Google Scholar 

  37. Humphrey, W., Dalke, A. & Schulten, K. VMD: visual molecular dynamics. J. Mol. Graph. 14, 33–38 (1996).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We acknowledge financial support from the National Key R&D Programme of China (grant no. 2022YFB2405000), the National Natural Science Foundation of China (grant nos 22279133 and 22393964), the International Partnership Programme of the Chinese Academy of Sciences (grant no. 121421KYSB20210028) and the CAS Strategic Leading Science & Technology Program (A) (grant no. XDA0400201). We thank X. Ai for his help with the in situ NMR measurement and discussions.

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Author notes

  1. These authors contributed equally: Ziming Zhao, Tianyu Li.

Authors and Affiliations

  1. Division of Energy Storage, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Ziming Zhao, Tianyu Li, Changkun Zhang, Mengqi Zhang & Xianfeng Li

  2. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

    Ziming Zhao & Shenghai Li

  3. University of Science and Technology of China, Hefei, China

    Ziming Zhao & Shenghai Li

  4. University of Chinese Academy of Sciences, Beijing, China

    Mengqi Zhang

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Contributions

Z.Z. and C.Z. conceived the idea and designed the experiments. C.Z., S.L. and X.L. supervised the project. Z.Z. conducted the experiments and data analysis. M.Z. and C.Z. helped with battery performance tests. T.L. contributed to the DFT simulation. Z.Z., T.L., C.Z. and X.L. organized and wrote the manuscript. All authors contributed to the discussion and revision of the manuscript.

Corresponding authors

Correspondence to Changkun Zhang, Shenghai Li or Xianfeng Li.

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The authors declare no competing interests.

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Nature Sustainability thanks Qing Chen, Minjoon Park, Xiongwei Wu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information (download PDF )

Supplementary Figs. 1–6, 23–29 and 39 showing spectra analysis, Figs. 7–13, 15–22, 34–37 and 42–44 showing electrochemical or battery analysis, Figs. 14, 30 and 40 presenting digital images, Figs. 31–33 and 38 presenting the theoretical calculations, Fig. 41 showing the cost analysis, Tables 1 and 2 detailing electrochemical or battery properties/performance, Tables 3 and 4 giving cost analysis and Notes 1 and 2 presenting structural stability and battery performance.

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Zhao, Z., Li, T., Zhang, C. et al. Air-stable naphthalene derivative-based electrolytes for sustainable aqueous flow batteries. Nat Sustain 7, 1273–1282 (2024). https://doi.org/10.1038/s41893-024-01415-6

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