Initially we investigated the kinetics of V(V)/V(IV) redox couple in sulfuric acid and mixed electrolyte (H2SO4+HCl) using oxidized glassy carbon electrode surface [6]. Cyclic voltammetry and electrochemical impedance spectroscopy techniques were used for the electrochemical investigation. Additionally, the thermal and chemical stability of the V(V) and V(IV) electrolytes in H2SO4 and mixed H2SO4 + HCl were investigated using X-Ray absorption spectroscopy. Detailed knowledge regarding the V(V) coordination sphere in H2SO4 and mixed acids are of significant interest for understanding electrolyte stability but also for elucidating the V(V) electrochemical reduction mechanism. Finally, the change in atomic coordination sphere of V(V) and V(IV) electrolytes in H2SO4 and H2SO4/HCl were investigated in fresh and aged samples using K-edge EXAFS, which is sensitive to both the electronic configuration and the atomic structure around the V, Cl and S atoms.
References
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[2] H.Chen et al., Prog. Nat. Sci. 291, 19 (2009).
[3] M. Skyllas-Kazacos, L. Cao, M. Kazacos, N. Kausar, A. Mousa, ChemSusChem, 9, 1521 (2016).
[4] Vijayakumar et al., Journal of Power Sources, 214, 173 (2013)
[5] M. Bon, T. Laino, A. Curioni, M. Parrinello, The Journal of Physical Chemistry C, 120, 10791 (2016)
[6] S.M. Taylor, A. Patru, D. Streich, M. ElKasi, E. Fabbri, T.J. Schmidt, Carbon, 109, 472 (2016)
Acknowledgements
Financial support of this work by the Commission of Technology and Innovation Switzerland (CTI) and the Swiss Competence Center for Energy Research Heat and Electricity Storage are greatly acknowledged. We acknowledge beam time at the PHOENIX beamline of the Swiss Light Source (Villigen, Switzerland).