Perfluorinated Sulfonic Acid based Composite Membranes for Vanadium Redox Flow Battery

바나듐 레독스 흐름 전지를 위한 과불소화 술폰산 복합막

  • Received : 2016.01.21
  • Accepted : 2016.01.27
  • Published : 2016.02.29


Vanadium redox flow batteries (VRFBs) using the electrolytes containing various vanadium ions in sulfuric acid as supporting solution are one of the energy storage devices in alternatively charging and discharging operation modes. The positive electrolyte contains $V^{5+}/V^{4+}$ and the negative electrolyte $V^{2+}/V^{3+}$ depending on the operation mode. To prevent the mixing of two solutions, proton exchange membranes are mainly used in VRFBs. Nafion 117 could be the most promising candidate due to the strong oxidative property of $V^{5+}$ ion, but causes high crossover of electroactive species to result in a decrease in coulombic efficiency. In this study, the composite membranes using Nafion ionomer and porous polyethylene substrate were prepared to keep good chemical stability and to decrease the cost of membranes, and were compared to the properties and performance of the commercially available electrolyte membrane, Nafion 117. As a result, the water uptake and ionic conductivity of the composite membranes increased as the thickness of the composite membranes increased, but those of Nafion 117 slightly decreased. The permeability of vanadium ions for the composite membranes significantly decreased compared to that for Nafion 117. In a single cell test for the composite membranes, the voltage efficiency decreased and the coulombic efficiency increased, finally resulting in the similar energy efficiency. In conclusion, the less cost of the composite membranes by decreasing 6.4 wt.% of the amount of perfluorinated sulfonic acid polymer due to the introduction of porous substrate and lower vanadium ion permeability to decrease self-discharge were achieved than Nafion 117.


Vanadium redox flow battery;Nafion composite membrane;Porous polyethylene substrate


  1. W. Dai, L. Yu, Z. Li, J. Yan, L. Liu, J. Xi, and X. Qiu, 'Sulfonated Poly(Ether Ether Ketone)/Graphene Composite Membrane for Vanadium Redox Flow Battery', Electrochim. Acta, 132, 200 (2014).
  2. X. Teng, J. Dai, F. Bi, and G. Yin, 'Ultra-Thin Polytetrafluoroethene/Nafion/Silica Composite Membrane with High Performance for Vanadium Redox Flow Battery', J. Power Sources, 272, 113 (2014).
  3. B. Yin, Z. Li, W. Dai, L. Wang, L. Yu, and J. Xi, 'Highly Branched Sulfonated Poly (Fluorenyl Ether Ketone Sulfone)s Membrane for Energy Efficient Vanadium Redox Flow Battery', J. Power Sources, 285, 109 (2015).
  4. B. Hwang and K. Kim, 'Redox Pairs in Redox Flow Batteries', J. Korean Electrochem. Soc., 16, 99 (2013).
  5. S. Liu, L. Wang, Y. Ding, B. Liu, X. Han, and Y. Song, 'Novel Sulfonated Poly(Ether Ether Keton)/Polyetherimide Acid-Base Blend Membranes for Vanadium Redox Flow Battery Applications', Electrochim. Acta, 130, 90 (2014).
  6. Y. Li, H. Zhang, H. Zhang, J. Cao, W. Xu, and X. Li, 'Hydrophilic Porous Poly (sulfone) Membranes Modified by UV-Initiated Polymerization for Vanadium Flow Battery Application', J. Membr. Sci., 454, 478 (2014).
  7. S. K. Park, J. Shim, J. H. Yang, C. S. Jin, B. S. Lee, and J. D. Jeon, 'The Influence of Compressed Carbon Felt Electrodes on the Performance of a Vanadium Redox Flow Battery', Electrochim. Acta, 116, 447 (2014).
  8. A. Chromik, A. R. dos Santos, T. Turek, U. Kunz, T. Haring, and J. Kerres, 'Stability of Acid-Excess Acid-Base Blend Membranes in All-Vanadium Redox-Flow Batteries', J. Membr. Sci., 476, 148 (2015).
  9. X. Wu, H. Xu, L. Lu, H. Zhao, J. Fu, Y. Shen, and Y. Dong, 'PbO 2-Modified Graphite Felt as the Positive Electrode for an All-Vanadium Redox Flow Battery', J. Power Sources, 250, 274 (2014).
  10. Z. Li, W. Dai, L. Yu, J. Xi, X. Qiu, and L. Chen, 'Sulfonated Poly(Ether Ether Ketone)/Mesoporous Silica Hybrid Membrane for High Performance Vanadium Redox Flow Battery', J. Power Sources, 257, 221 (2014).
  11. J. Xi, Z. Wu, X. Qiu, and L. Chen, 'Nafion/$SiO_2$ Hybrid Membrane for Vanadium Redox Flow Battery', J. Power Sources, 166, 531 (2007).
  12. J. Kim, J. D. Jeon, and S. Y. Kwak, 'Nafion-Based Composite Membrane with a Permselective Layered Silicate Layer for Vanadium Redox Flow Battery', Electrochem. Comm., 38, 68 (2014).
  13. S. S. Sekhon, J.-S. Park, and Y.-W Choi, 'A SAXS Study on Nanostructure Evolution in Water Free Membranes Containing Ionic Liquid: from Dry Membrane to Saturation', Phys. Chem. Chem. Phys., 12, 13763 (2010).
  14. Y. Wang, S. Wang, M. Xiao, S. Song, D. Han, M. A. Hickner, Y. Meng, 'Amphoteric Ion Exchange Membrane Synthesized by Direct Polymerization for Vanadium Redox Flow Battery Application', Int. J. Hydrogen Energy, 39, 16123 (2014).
  15. B. Zhang, E. Zhang, G. Wang, P. Yu, Q. Zhao, and F. Yao, 'Poly(Phenyl Sulfone) Anion Exchange Membranes with Pyridinium Groups for Vanadium Redox Flow Battery Applications', J. Power Sources, 282, 328 (2015).
  16. K.-W. Sung, S.-H. Shin, and S.-H. Moon, 'Characterization of Commercial Membranes for Non-Aqueous Vanadium Redox Flow Battery', Korean Chem. Eng. Res., 51, 615 (2013).

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Supported by : 상명대학교