Abstract

A hydrogen-vanadium electrochemical system was characterized using extensive experimental tests at different current densities and flow rates of vanadium electrolyte. The maximum peak power density achieved was 2840 W m− 2 along with a limiting current density of over 4200 A m− 2. The cycling performance presented a stable coulombic efficiency over 51 cycles with a mean value of 99.8%, while the voltage efficiency decreased slowly over time from a value of 90.3% to 87.0%. The capacity loss was of 5.6 A s per cycle, which could be related to crossover of ionic species and liquid water. A unit cell model, previously proposed by the authors, was modified to include the effect of species crossover and used to predict the cell potential. Reasonable agreement between the model simulations and the experimental charge-discharge data was observed, with Normalized Root-Mean-Square Errors (NRMSEs) within the range of 0.8–5.3% and 2.9–19.0% for charge and discharge, respectively. Also, a good degree of accuracy was observed in the simulated trend of the polarization and power density, with NRMSEs of 3.1% and 1.0%, and 1.1% and 1.9%, for the operation at a flow rate of vanadium electrolyte of 100 and 50 mL min− 1, respectively, while the voltage efficiency during the cycling test were estimated within a Root-Mean-Square Error (RMSE) of 1.9%. A study of the effect of the component properties on the cell potential was carried out by means of a model sensitivity analysis. The cell potential was sensitive to the cathodic transfer coefficient and the cathode porosity, which are directly related to the cathodic overpotential through the Butler-Volmer equation and the cathodic ohmic overpotential. It was recognized that a kinetic study for the cathodic reaction is needed to obtain more reliable kinetic parameters at practical vanadium concentrations, as well as reliable microstructural parameters of carbon electrodes.

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