Review—Electrode Kinetics and Electrolyte Stability in Vanadium Flow Batteries
Andrea Bourke, Daniela Oboroceanu, Nathan Quill, Catherine Lenihan, Maria Al-Hajji Safi, Mallory A. Miller, Robert F. Savinell, Jesse S. Wainright, Varsha Sasikumar S P, Maria Rybalchenko, Pupak Amini, Niall Dalton, Robert P. Lynch, D. Noel Buckley
Abstract
Two aspects of vanadium flow batteries are reviewed: electrochemical kinetics on carbon electrodes and positive electrolyte stability. There is poor agreement between reported values of kinetic parameters; however, most authors report that kinetic rates are faster for V IV /V V than for V II /V III . Cycling the electrode potential increases the rates of both reactions initially due to roughening but when no further roughening is observed, the V II /V III and V IV /V V reactions are affected oppositely by the pretreatment potential. Anodic pretreatment activates the electrode for the V II /V III reaction, and deactivates it for V IV /V V . Three states of the carbon surface are suggested: reduced and oxidized states R and O, respectively, both with low electrocatalytic activity, and an intermediate state M with higher activity. The role of surface functional groups and the mechanisms of electron transfer for the V II /V III and V IV /V V reactions are still not well understood. The induction time for precipitation of V 2 O 5 from positive electrolytes decreases with temperature, showing an Arrhenius-type dependence with an activation energy of 1.79 eV in agreement with DFT calculations based on a VO(OH) 3 intermediate. It also decreases exponentially with increasing V V concentration and increases exponentially with increasing sulphate concentration. Both arsenate and phosphate are effective additives for improving thermal stability.