Aqueous polysulfide-based redox flow batteries (RFBs) are promising for large-scale energy storage applications due to their low cost and high safety1. However, polysulfide negolyte suffers from poor kinetics, resulting in low operating current density and low energy efficiency2-5. Herein, we proposed a molecular catalyst strategy to transfer the sluggish electrochemical polysulfide reduction reaction to a fast chemical reaction via homogeneous catalysis. Inspired by the electron transport chain in the respiratory process, we selected riboflavin sodium phosphate (FMN-Na) as the molecular catalyst to transfer electrons from electrode to polysulfide with the disulfide bond cleavage6. The reaction rate (or turnover frequency) kobs is determined to be 33 s–1 at 1 M K2S4 solution, and this spontaneous chemical electron transfer process is verified by ultraviolet-visible light spectroscopy. In the polysulfide-ferrocyanide (S-Fe) RFB, the overpotential is dramatically decreased from over 800 mV to 241 mV at 30 mA cm–2 with the assistance of FMN-Na as the molecular catalysts. The catalyzed S-Fe RFB and polysulfide-iodide RFB showed stable operation for over 1,000 cycles at 40 mA cm–2. This work offers a simple but effective method to resolve the bottleneck for aqueous polysulfide-based RFBs, and such a homogeneous catalysis strategy may shed light on other flow battery systems with poor kinetics. We will combine operando spectroscopic techniques and theoretical calculation to discuss the possible reaction mechanism and intermediate.AcknowledgmentThis work is supported by two grants from the Research Grants Council (RGC) T23-713/22-R and RFS2223-4S03. Reference Y. Yao, J. Lei, Y. Shi, F. Ai and Y.-C. Lu, Nat. Energy, 2021, 6, 582-588. Z. Li and Y.-C. Lu, Nat. Energy, 2021, 6, 517-528. X. Wei, G.-G. Xia, B. Kirby, E. Thomsen, B. Li, Z. Nie, G. G. Graff, J. Liu, V. Sprenkle and W. Wang, J. Electrochem. Soc., 2015, 163, A5150. Z. Li, M. S. Pan, L. Su, P.-C. Tsai, A. F. Badel, J. M. Valle, S. L. Eiler, K. Xiang, F. R. Brushett and Y.-M. Chiang, Joule, 2017, 1, 306-327. J. Lei, Y. Yao, Y. Huang and Y.-C. Lu, ACS Energy Lett., 2023, 8, 429-435. J. Lei, Y. Zhang, Y. Yao, Y. Shi, K. L. Leung, J. Fan and Y.-C. Lu, Nat. Energy, 2023, DOI: 10.1038/s41560-023-01370-0.
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