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Symmetry-breaking design of an organic iron complex catholyte for a long cyclability aqueous organic redox flow battery

Nature Energy volume 6, pages 873–881 (2021)Cite this article

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Abstract

The limited availability of a high-performance catholyte has hindered the development of aqueous organic redox flow batteries (AORFB) for large-scale energy storage. Here we report a symmetry-breaking design of iron complexes with 2,2′-bipyridine-4,4′-dicarboxylic (Dcbpy) acid and cyanide ligands. By introducing two ligands to the metal centre, the complex compounds (M4[FeII(Dcbpy)2(CN)2], M = Na, K) exhibited up to a 4.2 times higher solubility (1.22 M) than that of M4[FeII(Dcbpy)3] and a 50% increase in potential compared with that of ferrocyanide. The AORFBs with 0.1 M Na4[FeII(Dcbpy)2(CN)2] as the catholyte were demonstrated for 6,000 cycles with a capacity fading rate of 0.00158% per cycle (0.217% per day). Even at a concentration near the solubility limit (1 M Na4[FeII(Dcbpy)2(CN)2]), the flow battery exhibited a capacity fading rate of 0.008% per cycle (0.25% per day) in the first 400 cycles. The AORFB cell with a nearly 1:1 catholyte:anolyte electron ratio achieved a cell voltage of 1.2 V and an energy density of 12.5 Wh l–1.

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Fig. 1: Rational design strategy of an asymmetric iron complex.
Fig. 2: Characterization of metal complexes.
Fig. 3: Electrochemical characterization of metal complexes.
Fig. 4: AORFB testing results with Na4[FeII(Dcbpy)2(CN)2] as catholyte.
Fig. 5: Characterization of electrolytes after cycling.
Fig. 6: Flow battery testing results of high-concentration cells.

Data availability

All the relevant data are included in the paper and its Supplementary Information. Source data are provided with this paper.

References

  1. Leung, P. et al. Recent developments in organic redox flow batteries: a critical review. J. Power Sources 360, 243–283 (2017).

    Article  Google Scholar 

  2. Soloveichik, G. L. Flow batteries: current status and trends. Chem. Rev. 115, 11533–11558 (2015).

    Article  Google Scholar 

  3. Wang, W. et al. Recent progress in redox flow battery research and development. Adv. Funct. Mater. 23, 970–986 (2013).

    Article  Google Scholar 

  4. Winsberg, J., Hagemann, T., Janoschka, T., Hager, M. D. & Schubert, U. S. Redox-flow batteries: from metals to organic redox-active materials. Angew. Chem. Int. Ed. 56, 686–711 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  6. Lin, K. et al. Alkaline quinone flow battery. Science 349, 1529–1532 (2015).

    Article  Google Scholar 

  7. Debruler, C., Hu, B., Moss, J., Luo, J. & Liu, T. L. A sulfonate-functionalized viologen enabling neutral cation exchange, aqueous organic redox flow batteries toward renewable energy storage. ACS Energy Lett. 3, 663–668 (2018).

    Article  Google Scholar 

  8. Lin, K. et al. A redox-flow battery with an alloxazine-based organic electrolyte. Nat. Energy 1, 16102 (2016).

    Article  Google Scholar 

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

    Article  Google Scholar 

  10. Lai, Y. Y. et al. Stable low-cost organic dye anolyte for aqueous organic redox flow battery. ACS Appl. Energy Mater. 3, 2290–2295 (2020).

    Article  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  Google Scholar 

  12. Liu, T., Wei, X., Nie, Z., Sprenkle, V. & Wang, W. A total organic aqueous redox flow battery employing a low cost and sustainable methyl viologen anolyte and 4-HO-TEMPO catholyte. Adv. Energy Mater. 6, 1501449 (2016).

    Article  Google Scholar 

  13. Hagemann, T. et al. (2,2,6,6-tetramethylpiperidin-1-yl)oxyl-containing zwitterionic polymer as catholyte species for high-capacity aqueous polymer redox flow batteries. Chem. Mater. 31, 7987–7999 (2019).

    Article  Google Scholar 

  14. 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  Google Scholar 

  15. Ding, Y., Zhang, C., Zhang, L., Zhou, Y. & Yu, G. Molecular engineering of organic electroactive materials for redox flow batteries. Chem. Soc. Rev. 47, 69–103 (2018).

    Article  Google Scholar 

  16. Wei, X. et al. Materials and systems for organic redox flow batteries: status and challenges. ACS Energy Lett. 2, 2187–2204 (2017).

    Article  Google Scholar 

  17. 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  Google Scholar 

  18. Yang, B. et al. High-performance aqueous organic flow battery with quinone-based redox couples at both electrodes. J. Electrochem. Soc. 163, A1442–A1449 (2016).

    Article  Google Scholar 

  19. Wang, W. Molecular engineering of the redox flow battery technology. In Frontiers in Energy Storage (The Croucher Advanced Study Institute, 2018).

  20. Beh, E. S. et al. A neutral pH aqueous organic–organometallic redox flow battery with extremely high capacity retention. ACS Energy Lett. 2, 639–644 (2017).

    Article  Google Scholar 

  21. Hu, B., Debruler, C., Rhodes, Z. & Liu, T. L. Long-cycling aqueous organic redox flow battery (AORFB) toward sustainable and safe energy storage. J. Am. Chem. Soc. 139, 1207–1214 (2017).

    Article  Google Scholar 

  22. Waters, S. E., Robb, B. H. & Marshak, M. P. Effect of chelation on iron–chromium redox flow batteries. ACS Energy Lett. 5, 1758–1762 (2020).

    Article  Google Scholar 

  23. Luo, J. et al. Unraveling pH dependent cycling stability of ferricyanide/ferrocyanide in redox flow batteries. Nano Energy 42, 215–221 (2017).

    Article  Google Scholar 

  24. Hosseinzadeh, P. & Lu, Y. Design and fine-tuning redox potentials of metalloproteins involved in electron transfer in bioenergetics. Biochim. Biophys. Acta Bioenerg. 1857, 557–581 (2016).

    Article  Google Scholar 

  25. Lever, A. B. P. Electrochemical parametrization of metal complex redox potentials, using the ruthenium(III)/ruthenium(II) couple to generate a ligand electrochemical series. Inorg. Chem. 29, 1271–1285 (1990).

    Article  Google Scholar 

  26. Kaes, C., Katz, A. & Hosseini, M. W. Bipyridine: the most widely used ligand. A review of molecules comprising at least two 2,2′-bipyridine units. Chem. Rev. 100, 3553–3590 (2000).

    Article  Google Scholar 

  27. Cabrera, P. J. et al. Complexes containing redox noninnocent ligands for symmetric, multielectron transfer nonaqueous redox flow batteries. J. Phys. Chem. C 119, 15882–15889 (2015).

    Article  Google Scholar 

  28. Sevov, C. S., Fisher, S. L., Thompson, L. T. & Sanford, M. S. Mechanism-based development of a low-potential, soluble, and cyclable multielectron anolyte for nonaqueous redox flow batteries. J. Am. Chem. Soc. 138, 15378–15384 (2016).

    Article  Google Scholar 

  29. Gavezzotti, A. Molecular symmetry, melting temperatures and melting enthalpies of substituted benzenes and naphthalenes. J. Chem. Soc. Perkin Trans. 1995, 1399–1404 (1995).

    Article  Google Scholar 

  30. Carnelley, T. XIII. Chemical symmetry, or the influence of atomic arrangement on the physical properties of compounds. Lond. Edinb. Dublin Philos. Mag. 13, 112–130 (1882).

    Article  Google Scholar 

  31. Pinal, R. Effect of molecular symmetry on melting temperature and solubility. Org. Biomol. Chem. 2, 2692–2699 (2004).

    Article  Google Scholar 

  32. Yalkowsky, S. H. & Valvani, S. C. Solubility and partitioning I: solubility of nonelectrolytes in water. J. Pharm. Sci. 69, 912–922 (1980).

    Article  Google Scholar 

  33. Machata, P. et al. Redox reactions of nickel, copper, and cobalt complexes with ‘noninnocent’ dithiolate ligands: combined in situ spectroelectrochemical and theoretical study. Organometallics 33, 4846–4859 (2014).

    Article  Google Scholar 

  34. Bakhtchadjian, R. et al. Application of a dioxo-molybdenum(VI) complex anchored on TiO2 for the photochemical oxidative decomposition of 1-chloro-4-ethylbenzene under O2. Transit. Met. Chem. 36, 897–900 (2011).

    Article  Google Scholar 

  35. Ferrere, S. & Gregg, B. A. Photosensitization of TiO2 by [FeII(2,2′-bipyridine-4,4′-dicarboxylic acid)2(CN)2]: band selective electron injection from ultra-short-lived excited states. J. Am. Chem. Soc. 120, 843–844 (1998).

    Article  Google Scholar 

  36. Luo, J. et al. Unprecedented capacity and stability of ammonium ferrocyanide catholyte in pH neutral aqueous redox flow batteries. Joule 3, 149–163 (2019).

    Article  Google Scholar 

  37. Harris, R. K. et al. Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008). Magn. Reson. Chem. 46, 582–598 (2008).

    Article  Google Scholar 

  38. Han, K. S. et al. Preferential solvation of an asymmetric redox molecule. J. Phys. Chem. C 120, 27834–27839 (2016).

    Article  Google Scholar 

  39. Marcus, Y. Ionic radii in aqueous solutions. Chem. Rev. 88, 1475–1498 (1988).

    Article  Google Scholar 

  40. Prampolini, G. et al. Structure and dynamics of ferrocyanide and ferricyanide anions in water and heavy water: an insight by MD simulations and 2D IR spectroscopy. J. Phys. Chem. B 118, 14899–14912 (2014).

    Article  Google Scholar 

  41. Daku, L. M. L. & Hauser, A. Ab initio molecular dynamics study of an aqueous solution of [Fe(bpy)3](Cl)2 in the low-spin and in the high-spin states. J. Phys. Chem. Lett. 1, 1830–1835 (2010).

    Article  Google Scholar 

  42. Gierke, T. D., Munn, G. E. & Wilson, F. The morphology in Nafion perfluorinated membrane products, as determined by wide‐and small‐angle X‐ray studies. J. Polym. Sci. B 19, 1687–1704 (1981).

    Google Scholar 

  43. Hsu, W. Y. & Gierke, T. D. Ion transport and clustering in Nafion perfluorinated membranes. J. Membr. Sci. 13, 307–326 (1983).

    Article  Google Scholar 

  44. Mauritz, K. A. & Moore, R. B. State of understanding of Nafion. Chem. Rev. 104, 4535–4586 (2004).

    Article  Google Scholar 

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

    Article  Google Scholar 

  46. Koutecky, J. & Levich, B. G. The application of the rotating disc electrode to studies of kinetic and catalytic processes. Zh. Fiz. Khim. 32, 1565–1575 (1958).

    Google Scholar 

  47. 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  Google Scholar 

  48. Farrington, J. A., Ledwith, A. & Stam, M. F. Cation–radicals: Oxidation of methoxide ion with 1,1′-dimethyl-4,4′-bipyridylium dichloride (paraquat dichloride). J. Chem. Soc. Chem. Commun. 1969, 259–260 (1969).

    Article  Google Scholar 

  49. Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 38, 3098–3100 (1988).

    Article  Google Scholar 

  50. Perdew, J. P. Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Phys. Rev. B 33, 8822–8824 (1986).

    Article  Google Scholar 

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Acknowledgements

Y.Z., X.L., Y.-Y.L., W.-Y.T., C.-F.C. Y.-T.L. and H.-Y.L. acknowledge the support of the University of Akron. P.G, J.D.B, A.H., V.M., R.F. and W.W. acknowledge joint financial support from the US Department of Energy (DOE) Office of Electricity (OE) Energy Storage Program (under Contract no. 57558) and Energy Storage Materials Initiative, which is a Laboratory Directed Research and Development Project at Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated by Battelle for the US DOE under contract DE-AC05-76RL01830.

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Author notes

  1. These authors contributed equally: Xiang Li, Peiyuan Gao, Yun-Yu Lai.

Authors and Affiliations

  1. School of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH, USA

    Xiang Li, Yun-Yu Lai, Heng-Yi Lin, Shuyuan Zhang, Chung-Fu Cheng, Wei-Yao Tung, Yueh-Ting Lai, Jin Wang & Yu Zhu

  2. Pacific Northwest National Laboratory, Richland, WA, USA

    Peiyuan Gao, J. David Bazak, Aaron Hollas, Vijayakumar Murugesan, Ruozhu Feng & Wei Wang

  3. Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu, Taiwan

    Heng-Yi Lin & Chien-Lung Wang

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Contributions

X.L, P.G. and Y.-Y.L. contributed equally to the work. X.L. and Y.Z. conceived the idea. W.W. and Y.Z. directed the project. X.L. designed the experiments, performed the synthesis, material characterizations, 1H NMR and 13C NMR spectroscopy, electrochemical measurements and capacity-balanced flow battery tests. P.G. performed the DFT calculations, AIMD simulations and classical MD simulations. Y.-Y.L. fabricated and tested all the catholyte capacity-limiting cells and assisted with materials characterization. J.D.B. performed the 23Na NMR and 17O NMR spectroscopy. A.H. and R.F. verified the solubility and prepared the NMR samples, Y-T.L. and H.-Y.L. assisted with the flow battery fabrication and tests. V.M. oversaw the NMR work. C.-F.C. and R.F. assisted with the electrochemical tests. W.-Y.T., J.W. and S.Z. helped with the materials synthesis and characterization. C.-L.W. helped with the materials design. All the authors discussed and analysed the data. X.L., W.W. and Y.Z. wrote and revised the manuscript.

Corresponding authors

Correspondence to Wei Wang or Yu Zhu.

Ethics declarations

Competing interests

The metal complex materials disclosed in this work have been filed as US Provisional Patent Application USPTO: 63/080,374 with Y.Z. as the applicant, and Y.Z and X.L. as inventors. The status of the patent application is pending.

Additional information

Peer review information Nature Energy thanks Michael Aziz and Michael Marshak for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–29 and Tables 1 and 2.

Source data

Source Data Fig. 2

NMR source data.

Source Data Fig. 3

Source data for CV, redox potential, RDE and Levich plot.

Source Data Fig. 4

Source data for Ratability test, low concentration cell.

Source Data Fig. 5

Source data for NMR and CV.

Source Data Fig. 6

Source data for high concentration cell.

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Li, X., Gao, P., Lai, YY. 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). https://doi.org/10.1038/s41560-021-00879-6

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