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Polysulfide-based redox flow batteries with long life and low levelized cost enabled by charge-reinforced ion-selective membranes

Abstract

Polysulfide is one of the most promising aqueous redox chemistries for grid storage owing to its inherent safety, high energy and low cost. However, its poor cycle life resulting from polysulfide cross-over has prohibited its successful commercialization. To exploit low-cost and high-capacity polysulfide flow batteries with industrial-relevant cycling stability, we develop a charge-reinforced ion-selective membrane to retain polysulfide/iodide, restrain membrane swelling and prevent water/OH migration. The polysulfide/polyiodide static cell demonstrates a low capacity decay rate (0.005% per day and 0.0004% per cycle) over 2.9 months (1,200 cycles) at a 100% state of charge. A flow cell containing 4.0 M KI/2.0 M K2S2 demonstrated stable cycling at 17.9 Ah l−1posolyte+negolyte over 3.1 months (500 cycles). Small-angle X-ray scattering and in-situ attenuated total reflectance–Fourier transform infrared/solid-state NMR revealed reduced water cluster size and restrained water movement in the charge-reinforced ion-selective membrane compared to commercial Nafion membrane. Techno-economic analysis shows that the developed polysulfide flow battery promises competitive levelized cost of storage for long-duration energy storage.

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Fig. 1: Different processes in PSIBs with a Nafion and CRIS membrane.
Fig. 2: Permeability and self-discharge.
Fig. 3: Long-term galvanostatic cycling measurements of PSIBs at static mode.
Fig. 4: Electrochemical performance of scale-up PSIBs under continuous flow mode.
Fig. 5: Mechanism of water migration through N117 and CRIS membrane.
Fig. 6: Cost analysis of emerging RFBs.

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

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

    Article  Google Scholar 

  3. Noack, J., Roznyatovskaya, N., Herr, T. & Fischer, P. The chemistry of redox‐flow batteries. Angew. Chem. Int. Ed. Engl. 54, 9776–9809 (2015).

    Article  Google Scholar 

  4. Park, M., Ryu, J., Wang, W. & Cho, J. Material design and engineering of next-generation flow-battery technologies. Nat. Rev. Mater. 2, 16080 (2017).

    Article  Google Scholar 

  5. Ulaganathan, M. et al. Recent advancements in all-vanadium redox flow batteries. Adv. Mater. Interfaces 3, 1500309 (2016).

    Article  Google Scholar 

  6. Li, Z. et al. Air-breathing aqueous sulfur flow battery for ultralow-cost long-duration electrical storage. Joule 1, 306–327 (2017).

    Article  Google Scholar 

  7. 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. Engl. 56, 686–711 (2017).

    Article  Google Scholar 

  8. 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 

  9. Li, B. et al. Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery. Nat. Commun. 6, 6303 (2015).

    Article  Google Scholar 

  10. Zhang, J. et al. An all-aqueous redox flow battery with unprecedented energy density. Energy Environ. Sci. 11, 2010–2015 (2018).

    Article  Google Scholar 

  11. Schmidt, O., Melchior, S., Hawkes, A. & Staffell, I. Projecting the future levelized cost of electricity storage technologies. Joule 3, 81–100 (2019).

    Article  Google Scholar 

  12. Schmidt, O., Hawkes, A., Gambhir, A. & Staffell, I. The future cost of electrical energy storage based on experience rates. Nat. Energy 2, 17110 (2017).

    Article  Google Scholar 

  13. Zakeri, B. & Syri, S. Electrical energy storage systems: a comparative life cycle cost analysis. Renew. Sustain. Energy Rev. 42, 569–596 (2015).

    Article  Google Scholar 

  14. Jülch, V. Comparison of electricity storage options using levelized cost of storage (LCOS) method. Appl. Energy 183, 1594–1606 (2016).

    Article  Google Scholar 

  15. Su, L., Badel, A. F., Cao, C., Hinricher, J. J. & Brushett, F. R. Toward an inexpensive aqueous polysulfide-polyiodide redox flow battery. Ind. Eng. Chem. Res. 56, 9783–9792 (2017).

    Article  Google Scholar 

  16. Remick, R. & Ang, P. Electrically rechargeable anionically active reduction-oxidation electrical storage-supply system. US patent US4485154A (1984).

  17. Zhang, S. et al. Recent progress in polysulfide redox-flow batteries. Batteries Supercaps 2, 627–637 (2019).

    Article  Google Scholar 

  18. Zhou, H., Zhang, H., Zhao, P. & Yi, B. A comparative study of carbon felt and activated carbon based electrodes for sodium polysulfide/bromine redox flow battery. Electrochim. Acta 51, 6304–6312 (2006).

    Article  Google Scholar 

  19. Zhao, P., Zhang, H., Zhou, H. & Yi, B. Nickel foam and carbon felt applications for sodium polysulfide/bromine redox flow battery electrodes. Electrochim. Acta 51, 1091–1098 (2005).

    Article  Google Scholar 

  20. Ge, S., Yi, B. & Zhang, H. Study of a high power density sodium polysulfide/bromine energy storage cell. J. Appl. Electrochem. 34, 181–185 (2004).

    Article  Google Scholar 

  21. Li, Z., Weng, G., Zou, Q., Cong, G. & Lu, Y.-C. A high-energy and low-cost polysulfide/iodide redox flow battery. Nano Energy 30, 283–292 (2016).

    Article  Google Scholar 

  22. Ma, D. et al. Highly active nanostructured CoS2/CoS heterojunction electrocatalysts for aqueous polysulfide/iodide redox flow batteries. Nat. Commun. 10, 3367 (2019).

    Article  Google Scholar 

  23. Gross, M. M. & Manthiram, A. Long-life polysulfide-polyhalide batteries with a mediator-ion solid electrolyte. ACS Appl. Energy Mater. 2, 3445–3451 (2019).

    Article  Google Scholar 

  24. Gross, M. M. & Manthiram, A. Aqueous polysulfide–air battery with a mediator-ion solid electrolyte and a copper sulfide catalyst for polysulfide redox. ACS Appl. Energy Mater. 1, 7230–7236 (2018).

    Article  Google Scholar 

  25. Sun, C., Chen, J., Zhang, H., Han, X. & Luo, Q. Investigations on transfer of water and vanadium ions across Nafion membrane in an operating vanadium redox flow battery. J. Power Sources 195, 890–897 (2010).

    Article  Google Scholar 

  26. Eckert, B. et al. Elemental sulfur and sulfur-rich compounds II. Top. Curr. Chem. 231, 32–98 (2003).

    Google Scholar 

  27. Sukkar, T. & Skyllas-Kazacos, M. Water transfer behaviour across cation exchange membranes in the vanadium redox battery. J. Membr. Sci. 222, 235–247 (2003).

    Article  Google Scholar 

  28. Wan, L. & Xu, Y. Iodine-sensitized oxidation of ferrous ions under UV and visible light: the influencing factors and reaction mechanism. Photochem. Photobiol. Sci. 12, 2084–2088 (2013).

    Article  Google Scholar 

  29. Gao, Y. et al. Heavy doping of S2 in Cu7.2S4 lattice into chemically homogeneous superlattice Cu7.2Sx nanowires: strong photoelectric response. J. Mater. Chem. C 3, 2575–2581 (2015).

    Article  Google Scholar 

  30. Li, N., Wang, Y., Tang, D. & Zhou, H. Integrating a photocatalyst into a hybrid lithium–sulfur battery for direct storage of solar energy. Angew. Chem. Int. Ed. Engl. 54, 9271–9274 (2015).

    Article  Google Scholar 

  31. Gyenes, B., Stevens, D., Chevrier, V. & Dahn, J. Understanding anomalous behavior in coulombic efficiency measurements on Li-ion batteries. J. Electrochem. Soc. 162, A278–A283 (2015).

    Article  Google Scholar 

  32. Yang, F., Wang, D., Zhao, Y., Tsui, K.-L. & Bae, S. J. A study of the relationship between coulombic efficiency and capacity degradation of commercial lithium-ion batteries. Energy 145, 486–495 (2018).

    Article  Google Scholar 

  33. Sun, C.-N. et al. Probing electrode losses in all-vanadium redox flow batteries with impedance spectroscopy. ECS Electrochem. Lett. 2, A43–A45 (2013).

    Article  Google Scholar 

  34. Orazem, M. & Tribollet, B. Electrochemical Impedance Spectroscopy (Wiley, 2008).

  35. Mazur, P. et al. A complex four-point method for the evaluation of ohmic and faradaic losses within a redox flow battery single-cell. MethodsX 6, 534–539 (2019).

    Article  Google Scholar 

  36. Bauer, F., Denneler, S. & Willert-Porada, M. Influence of temperature and humidity on the mechanical properties of Nafion® 117 polymer electrolyte membrane. J. Polym. Sci. B 43, 786–795 (2005).

    Article  Google Scholar 

  37. Li, Z., Jiang, H., Lai, N.-C., Zhao, T. & Lu, Y.-C. Designing effective solvent-catalyst interface for catalytic sulfur conversion in lithium-sulfur batteries. Chem. Mater. 31, 10186–10196 (2019).

    Article  Google Scholar 

  38. Schmidt-Rohr, K. & Chen, Q. Parallel cylindrical water nanochannels in Nafion fuel-cell membranes. Nat. Mater. 7, 75–83 (2008).

    Article  Google Scholar 

  39. Kusoglu, A. & Weber, A. Z. New insights into perfluorinated sulfonic-acid ionomers. Chem. Rev. 117, 987–1104 (2017).

    Article  Google Scholar 

  40. Bender, P. et al. Using the singular value decomposition to extract 2D correlation functions from scattering patterns. Acta Crystallogr. A 75, 766–771 (2019).

    Article  Google Scholar 

  41. Laporta, M., Pegoraro, M. & Zanderighi, L. Perfluorosulfonated membrane (Nafion): FT–IR study of the state of water with increasing humidity. Phys. Chem. Chem. Phys. 1, 4619–4628 (1999).

    Article  Google Scholar 

  42. Falk, M. The frequency of the H-O-H bending fundamental in solids and liquids. Spectrochim. Acta A 40, 43–48 (1984).

    Article  Google Scholar 

  43. Kunimatsu, K., Bae, B., Miyatake, K., Uchida, H. & Watanabe, M. ATR–FTIR study of water in Nafion membrane combined with proton conductivity measurements during hydration/dehydration cycle. J. Phys. Chem. B 115, 4315–4321 (2011).

    Article  Google Scholar 

  44. Hammer, R., Schönhoff, M. & Hansen, M. R. Comprehensive picture of water dynamics in Nafion membranes at different levels of hydration. J. Phys. Chem. B 123, 8313–8324 (2019).

    Article  Google Scholar 

  45. Darling, R. M., Gallagher, K. G., Kowalski, J. A., Ha, S. & Brushett, F. R. Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries. Energy Environ. Sci. 7, 3459–3477 (2014).

    Article  Google Scholar 

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

    Article  Google Scholar 

  47. Qiu, X., Li, W., Zhang, S., Liang, H. & Zhu, W. The microstructure and character of the PVDF-g-PSSA membrane prepared by solution grafting. J. Electrochem. Soc. 150, A917–A921 (2003).

    Article  Google Scholar 

  48. El Kaddouri, A., Perrin, L., Jean, B., Flandin, L. & Bas, C. Investigation of perfluorosulfonic acid ionomer solutions by 19F NMR and DLS: establishment of an accurate quantification protocol. J. Polym. Sci. B 54, 2210–2222 (2016).

    Article  Google Scholar 

  49. Moukheiber, E., De Moor, G., Flandin, L. & Bas, C. Investigation of ionomer structure through its dependence on ion exchange capacity (IEC). J. Membr. Sci. 389, 294–304 (2012).

    Article  Google Scholar 

  50. Yuan, Z., Duan, Y., Liu, T., Zhang, H. & Li, X. Toward a low-cost alkaline zinc-iron flow battery with a polybenzimidazole custom membrane for stationary energy storage. iScience 3, 40–49 (2018).

    Article  Google Scholar 

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Acknowledgements

The work described herein was supported by two grants from the Research Grant Council (RGC) of the Hong Kong Special Administrative Region, China (project no. T23-601/17-R and N_CUHK435/18, received by Y.-C.L.). We thank B. T. W. Lo and the University Research Facility in Chemical and Environmental Analysis (UCEA) from Hong Kong Polytechnic University for assisting with ssNMR measurements, J. Lei for assistance in building up the flow system and W. Wang for assisting with SEM image collection.

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Z.L. and Y.-C.L. conceived the project. Z.L. designed and conducted the experiments and performed the electrochemical and characterization tests. Both authors analysed the data, discussed the results and wrote the manuscript.

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Correspondence to Yi-Chun Lu.

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Peer review information Nature Energy thanks Wei Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–23, Tables 1–7, Notes 1–7 and ref.

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Source data of bar chart in Fig. 6b and pie chart in Fig. 6c.

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Li, Z., Lu, YC. Polysulfide-based redox flow batteries with long life and low levelized cost enabled by charge-reinforced ion-selective membranes. Nat Energy 6, 517–528 (2021). https://doi.org/10.1038/s41560-021-00804-x

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