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Electrolyte Stability in Vanadium Flow Batteries

  • D. Noel Buckley (a1) (a2), Daniela Oboroceanu (a1), Nathan Quill (a1), Catherine Lenihan (a1), Deirdre Ní Eidhin (a1) and Robert P. Lynch (a1) (a2)...

Abstract

The stability of VFB catholytes was investigated using both light-scattering measurements and visual observation. V2O5 precipitates after an induction time τ which shows an Arrhenius variation with temperature. The value of τ increases with increasing [S] and with decreasing [VV] but the activation energy remains constant with a value of (1.791±0.020) eV. Plots of ln τ against [S] and [VV] show good linearity and the slopes give values of βS = 2.073 M-1 and βV5 = –3.434 M-1 for the fractional rates of variation of τ with [S] and [VV], respectively. Combining the Arrhenius Equation with the observed log-linear variation of τ with [S] and [VV] provides a model for simulating the stability of catholytes. The addition of H3PO4 has a strong stabilizing effect on catholytes at higher temperatures. For example, at 50°C the induction time for precipitation for a typical catholyte is enhanced ∼ 12.5-fold by 0.1 M added H3PO4. At concentrations of H3PO4 less than ∼0.04 M, the precipitation time increases with increasing concentration at all temperatures investigated (30–70°C). At higher concentrations, induction time begins to decrease with increasing concentration of H3PO4: the changeover concentration depends on the temperature. Experiments at 70°C using other phosphate additives (sodium triphosphate, Na5P3O10, and sodium hexametaphosphate, (NaPO3)6) showed similar results to H3PO4.

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1.Weber, A.Z., Mench, M.M., Meyers, J.P., Ross, P.N., and Gostick, J.T., Liu, Q., J. Appl. Electrochem. 41, 11371164 (2011)
2.de Leon, C.P., Frias-Ferrer, A., Gonzalez-Garcia, J., Szanto, D.A., and Walsh, F.C., J. Power Sources 160, 716732 (2006)
3.Skyllas-Kazacos, M., Chakrabarti, M.H., Hajimolana, S.A., Mjalli, F.S., and Saleem, M., J. Electrochem. Soc. 158, R55R79 (2011)
4.Watt-Smith, M.J., Ridley, P., Wills, R.G.A., Shah, A.A., and Walsh, F.C., J. Chem. Technol. Biotechnol. 88, 126138 (2013)
5.Roe, S., Menictas, C., and Skyllas-Kazacos, M., J. Electrochem. Soc. 163, A5023A5028 (2016)
6.Bourke, A., Miller, M.A., Lynch, R.P., Gao, X., Landon, J., Wainright, J.S., Savinell, R.F., and Buckley, D.N., J. Electrochem. Soc. 163, A5097A5105 (2016)
7.Bourke, A., Miller, M.A., Lynch, R.P., Wainright, J.S., Savinell, R.F., and Buckley, D.N., J. Electrochem. Soc. 162, A1547A1555 (2015)
8.Miller, M.A., Bourke, A., Quill, N., Wainright, J.S., Lynch, R.P., Buckley, D.N., and Savinell, R.F., J. Electrochem. Soc. 163, A2095A2102 (2016)
9.Quill, N., Oboroceanu, D., Buckley, D.N., and Lynch, R.P., ECS Transsaction, 80, 314 (2017)
10.Perry, M.L. and Weber, A.Z., J. Electrochem. Soc. 163, A5064A5067 (2016)
11.Reed, D., Thomsen, E., Li, B., Wang, W., Nie, Z., Koeppel, B., Kizewski, J., and Sprenkle, V., J. Electrochem. Soc. 163, A5211A5219 (2016)
12.Dewage, H.H., Yufit, V., and Brandon, N.P., J. Electrochem. Soc. 163, A5236A5243 (2016)
13.Darling, R.M., Weber, A.Z., Tucker, M.C., and Perry, M.L., J. Electrochem. Soc. 163, A5014A5022 (2016)
14.Manohar, A.K., Kim, K.M., Plichta, E., Hendrickson, M., Rawlings, S., and Narayanan, S.R., J. Electrochem. Soc. 163, A5118A5125 (2016)
15.Tokuda, N., Kanno, T., Hara, T., Shigematsu, T., Tsutsui, Y., Ikeuchi, A., Itou, T., and Kumamoto, T., SEI Tech. Rev., 88-94 (2000)
16.Vynnycky, M., Energy 36, 22422256 (2011)
17.Oboroceanu, D., Quill, N., Lenihan, C., Ní Eidhin, D., Albu, S. P., Lynch, R. P., and Buckley, D. N., ECS Trans. 77, 107115 (2017)
18.Kear, G., Shah, A.A., and Walsh, F.C., Int. J. Energy Res. 36, 11051120 (2012)
19.Petchsingh, C., Quill, N., Joyce, J.T., Ní Eidhin, D., Oboroceanu, D., Lenihan, C., Gao, X., Lynch, R.P., and Buckley, D.N., J. Electrochem. Soc. 163, A5068A5083 (2016)
20.Buckley, D.N., Gao, X., Lynch, R.P., Quill, N., and Leahy, M.J., J. Electrochem. Soc. 161, A524A534 (2014)
21.Buckley, D.N., Gao, X., Lynch, R.P., Leahy, M.J., Bourke, A., and Flynn, G., European Patent EP 13195315, (2 December 2013)
22.Gao, X., Lynch, R.P., Leahy, M.J., and Buckley, D.N., ECS Trans. 45, 2536 (2013)
23.Tang, Z., Aaron, D.S., Papandrew, A.B., and Zawodzinski, T.A., ECS Trans. 41, 19 (2012)
24.Skyllas-Kazacos, M. and Kazacos, M., J. Power Sources 196, 88228827 (2011)
25.Quill, N., Petchsingh, C., Lynch, R. P., Gao, X., Oboroceanu, D., Ní Eidhin, D., O’Mahony, M., Lenihan, C., and Buckley, D. N., ECS Trans. 64, 2339 (2015)
26.Quill, N., Lynch, R.P., Gao, X., and Buckley, D.N., The Electrochemical Society Meeting Abstract, MA2014-01, 389 (2014)
27.Whitehead, A.H. and Harrer, M., J. Power Sources 230, 271276 (2013)
28.Rahman, F. and Skyllas-Kazacos, M., J. Power Sources 189, 12121219 (2009)
29.Vijayakumar, M., Wang, W., Nie, Z., Sprenkle, V., and Hu, J., J. Power Sources 241, 173-177 (2013)
30.Prifti, H., Parasuraman, A., Winardi, S., Lim, T.M., and Skyllas-Kazacos, M., Membranes 2, 275306 (2012)
31.Bourke, A., Lynch, R. P., and Buckley, D.N., ECS Trans. 64, 117 (2015)
32.Bourke, A., Quill, N., Lynch, R.P., and Buckley, D.N., ECS Trans. 61, 1526 (2014)
33.Bourke, A., Quill, N., Lynch, R.P., and Buckley, D.N., Book of Conference Papers, The International Flow Battery Forum 2014 (IFBF, Hamburg, Germany, 2014), p. 16.
34.Zhang, J., Li, L., Nie, Z., Chen, B., Vijayakumar, M., Kim, S., Wang, W., Schwnezer, B., Liu, J., and Yang, Z., J. Appl. Electrochem. 41, 12151221 (2011)
35.Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous Solutions, 2nd ed. (National Association of Corrosion Engineers, Houston, 1974)
36.Wen, Y., Xu, Y., Cheng, J., Cao, G., and Yang, Y., Electrochim. Acta 96, 268273 (2013)
37.Kazacos, M., Cheng, M., and Skyllas-Kazacos, M., J. Appl. Electrochem. 20, 463467 (1990)
38.Skyllas-Kazacos, M., Menictas, C., and Kazacos, M., J. Electrochem. Soc. 143, L86L88 (1996)
39.Vijayakumar, M., Li, L., Graff, G., Liu, J., Zhang, H., Yang, Z., and Hu, J. Z., J. Power Sources 196, 36693672 (2011)
40.Skyllas-Kazacos, M., Rychcik, M., Robins, R. G., Fane, A. G., and Green, M. A., J. Electrochem. Soc. 133, 10571058 (1986)
41.Skyllas-Kazacos, M., and Kazacos, M., U.S. Patent No. 6562514, (13 May 2003)
42.Oboroceanu, D., Quill, N., Lenihan, C., Ní Eidhin, D., Albu, S.P., Lynch, R.P., and Buckley, D.N., J. Electrochem. Soc. 163, A2919A2921 (2016)
43.Oboroceanu, D., Quill, N., Lenihan, C., Ní Eidhin, D., Albu, S.P., Lynch, R.P., and Buckley, D.N., ECS Trans. 75 (18), 4963 (2017)
44.Oboroceanu, D., Quill, N., Lenihan, C., Ní Eidhin, D., Albu, S.P., Lynch, R.P., and Buckley, D.N., MRS Advances 2, 11771182 (2017)
45.Oboroceanu, D., Quill, N., Lenihan, C., Ní Eidhin, D., Albu, S.P., Lynch, R.P., and Buckley, D.N., J. Electrochem. Soc., 164, A2101A2109 (2017)

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