In this study, the oxidation of the V(II) by dissolved oxygen was examined quantitatively using UV-visible spectrophotometry. UV-visible spectrophotometry is an accurate method of determining the concentration of vanadium ions at both the negative and positive half-cell electrolytes. To apply Beer's law, the concentration should be diluted below 0.15 M to achieve a linear relationship between the absorbance and concentration. UV-visible spectrophotometry revealed that the concentration of V(II) in the negative half-cell electrolyte decreases continuously with cycling due to the rapid oxidation of the V(II) by dissolved oxygen. This decrease gives rise to an imbalance between the positive and negative half-cell electrolytes, which results in a significant capacity loss.
The flow field design and material composition of the electrode plays an important role in the performance of redox flow batteries, especially when using highly viscous liquids. To enhance the discharge power density of zinc slurry air flow batteries, an optimum slurry distribution in the cell is key. Hence, several types of flow fields (serpentine, parallel, plastic flow frames) were tested in this study to improve the discharge power density of the battery. The serpentine flow field delivered a power density of 55 mW·cm −2 , while parallel and flow frame resulted in 30 mW·cm −2 and 10 mW·cm −2 , respectively. Moreover, when the anode bipolar plate material was changed from graphite to copper, the power density of the flow frame increased to 65 mW·cm −2 , and further improvement was attained when the bipolar plate material was further changed to copper-nickel. These results show the potential to increase the power density of slurry-based flow batteries by flow field optimization and design of bipolar plate materials.
The membrane is a crucial component of Zn slurry–air flow battery since it provides ionic conductivity between the electrodes while avoiding the mixing of the two compartments. Herein, six commercial membranes (Cellophane™ 350PØØ, Zirfon®, Fumatech® PBI, Celgard® 3501, 3401 and 5550) were first characterized in terms of electrolyte uptake, ion conductivity and zincate ion crossover, and tested in Zn slurry–air flow battery. The peak power density of the battery employing the membranes was found to depend on the in-situ cell resistance. Among them, the cell using Celgard® 3501 membrane, with in-situ area resistance of 2 Ω cm2 at room temperature displayed the highest peak power density (90 mW cm−2). However, due to the porous nature of most of these membranes, a significant crossover of zincate ions was observed. To address this issue, an ion-selective ionomer containing modified poly(phenylene oxide) (PPO) and N-spirocyclic quaternary ammonium monomer was coated on a Celgard® 3501 membrane and crosslinked via UV irradiation (PPO-3.45 + 3501). Moreover, commercial FAA-3 solutions (FAA, Fumatech) were coated for comparison purpose. The successful impregnation of the membrane with the anion-exchange polymers was confirmed by SEM, FTIR and Hg porosimetry. The PPO-3.45 + 3501 membrane exhibited 18 times lower zincate ions crossover compared to that of the pristine membrane (5.2 × 10−13 vs. 9.2 × 10−12 m2 s−1). With low zincate ions crossover and a peak power density of 66 mW cm−2, the prepared membrane is a suitable candidate for rechargeable Zn slurry–air flow batteries.
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