Abstract
Understanding mass transfer is of great importance to molten salt electrochemistry. However, natural convection has long been neglected in electrochemical measurements in stagnant molten salt systems due to the complex mathematical treatments. Here we reported the notable natural convection effects in molten LiF-NaF-KF during cyclic voltammetry and chronoamperometry tests. The established model showed that the convection-diffusion layer (CDL) convection dominated mass transfer under long time-scale tests in molten LiF-NaF-KF-EuF3. However, in the case of molten LiF-NaF-KF-K2TiF6, CDL convection predominated at dilute redox concentrations while density-driven convection came into dominance at high redox concentrations, because of the severe coordinate structure change of the redox couple. The derived thickness of the convection-diffusion layer, δconv., ranged from 135 to 183 μm, much higher than that in aqueous solutions (220–250 μm). Moreover, the increase in system temperature greatly enhanced natural convection effects in molten fluorides. Lastly, the use of microelectrode (re<39.7 μm for δconv.=160 μm) was demonstrated to be an effective way to suppress the intense natural convection effects.
Published Version
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