Effect of Polarization Pretreatment of Glassy Carbon on the Kinetics of the Redox Reactions in Vanadium Redox Flow Batteries

Vanadium redox flow batteries (VRFBs) are a promising technology to meet energy storage requirements for large scale and remote area applications.¹ Flow batteries offer a long cycle-life²and the energy capacity can be scaled separately from the power capacity. This design flexibility makes them suitable for a wide range of applications. VRFBs have the additional advantage of having the same element on both sides of the membrane which eliminates cross-contamination issues that arise in mixed-element flow batteries. As a result electrolyte maintenance issues are reduced; in theory, the electrolyte is indefinitely reusable.

In a VRFB the electroactive species are dissolved in the electrolyte. The electrode reactions may be written as:

V³⁺ + e^- ↔ V²⁺

VO²⁺ + H₂O ↔ VO₂⁺ + 2H⁺ + e^-

The negative half-cell reaction appears to be a simple one-electron transfer reaction while the positive half-cell reaction appears to involve bond breaking. Thus the kinetics would be expected to be faster at the negative electrode than at the positive. However, in actual flow cells, the overpotential is much larger at the negative electrode than at the positive.³

The detailed kinetics of the redox processes occurring at the positive and negative electrode in a VRFB are not well established in the literature and there is some disagreement between results obtained on various substrates at fixed and rotating disk electrodes.^4-11

As part of an investigation of the kinetics of electrode processes in VRFBs, we have examined the kinetics of the VO²⁺/VO₂⁺ and V²⁺/V³⁺ couples on glassy carbon electrodes. We have found that polarization pretreatment of glassy carbon has an effect on the activity of the surface for oxidation and reduction of the VO²⁺/VO₂⁺ and V²⁺/V³⁺ couples. When glassy carbon electrodes are pretreated by polarization at potentials more positive than 0.5 V (sat. Hg/Hg₂SO₄) they are subsequently less active for oxidation of VO²⁺ and reduction of VO₂⁺. The activity of the electrode is recovered by polarization at negative potentials.¹¹ However, when glassy carbon electrodes are pretreated by polarization at potentials more positive than 0.5 V (sat. Hg/Hg₂SO₄) they are subsequently more active for oxidation of V²⁺ and reduction of V³⁺. The electrode can be deactivated by polarization pretreatment at negative potentials.

The results of this investigation will be presented and discussed. 

Acknowledgements

A. Bourke wishes to thank the Irish Research Council (IRC) for a postgraduate scholarship to perform this research.

References

1. C. Ponce de León, A. Frías-Ferrer, J. González-García, D. A. Szánto and F. C. Walsh, J. Power Sources, 160, 716, (2006)
2. N. Tokuda, T. Kanno, T. Hara, T. Shigematsu, Y. Tsutsui, A. Ikeuchi, T. Itou, T. Kumamoto, SEI Tech. Rev., p.88-94 (2000)
3. Z. Tang, D.S. Aaron, A.B. Papandrew and T.A. Zawodzinski, Jr., ECS Trans., 41 (23), 1 (2012)
4. G. Oriji, Y. Katayama, T. Miura,  J. Power Sources., 139, (2005)
5. E. Sum, M. Rychcik, M. Skyllas-Kazacos, J. Power Sources., 16, (1985).
6. T. Yamamura, N. Watanabe, T. Yano, Y. Shiokawa, J. Electrochem. Soc., 152, 4 (2005)
7. M. P. Manahan, Q. H. Liu, M. L. Gross, M. M. Mench, J. Power Sources., 222, 498-502 (2013)
8. M. Gattrell, J. Park, B. MacDougall, J. Apte, S. McCarthy, and C. W. Wu., J. Electrochem. Soc., 151, 1 (2004)
9. Ch. Fabjan, J. Garche, B. Harrer, L. Jörissen, C. Kolbeck, F. Philippi, G. Tomazic, F. Wagner, Electrochim. Acta, 47, 825 (2001)
10. X. Wu, T. Yamamura, S. Ohta,  Q. Zhang, F. Lv, C. Liu, K. Shirasaki, I. Satoh, T. Shikama, D. Lu, S. Liu, J. Applied Electrochemistry, 41, 10 (2011)
11. A. Bourke, R. P. Lynch, D. N. Buckley, ECS Trans, 53 (30) 59-67 (2013)