Novel Anion Exchange Membrane Based on Poly(Pentafluorostyrene) Substituted with Mercaptotetrazole Pendant Groups and Its Blend with Polybenzimidazole for Vanadium Redox Flow Battery Applications.

In order to evaluate the performance of the anion exchange membranes in a vanadium redox flow battery, a novel anion exchange polymer was synthesized via a three step process. Firstly, 1-(2-dimethylaminoethyl)-5-mercaptotetrazole was grafted onto poly(pentafluorostyrene) by nucleophilic F/S exchange. Secondly, the tertiary amino groups were quaternized by using iodomethane to provide anion exchange sites. Finally, the synthesized polymer was blended with polybenzimidazole to be applied in vanadium redox flow battery. The blend membranes exhibited better single cell battery performance in terms of efficiencies, open circuit voltage test and charge-discharge cycling test than that of a Nafion 212 membrane. The battery performance results of synthesized blend membranes suggest that those novel anion exchange membranes are promising candidates for vanadium redox flow batteries.

Electrowinning of Iron from Spent Leaching Solutions Using Novel Anion Exchange Membranes.

In the Pyror process, electrowinning (EW) is used to recover acid and iron from spent leaching solutions (SLS), where a porous Terylene membrane acts as a separator between the cathode and anode. In this study, a novel anion exchange membrane (AEM)-based EW process is benchmarked against a process without and with a porous Terylene membrane by comparing the current efficiency, specific energy consumption (SEC), and sulfuric acid generation using an in-house constructed EW flow cell. Using an FAP-PK-130 commercial AEM, it was shown that the AEM-based process was more efficient than the traditional processes. Subsequently, 11 novel polybenzimidazole (PBI)-based blend AEMs were compared with the commercial AEM. The best performing novel AEM (BM-5), yielded a current efficiency of 95% at an SEC of 3.53 kWh/kg Fe, which is a 10% increase in current efficiency and a 0.72 kWh/kg Fe decrease in SEC when compared to the existing Pyror process. Furthermore, the use of the novel BM-5 AEM resulted in a 0.22 kWh/kg Fe lower SEC than that obtained with the commercial AEM, also showing mechanical stability in the EW flow cell. Finally, it was shown that below 5 g/L Fe, side reactions at the cathode resulted in a decrease in process efficiency, while 40 g/L yielded the highest efficiency and lowest SECs.

Performances of Anion-Exchange Blend Membranes on Vanadium Redox Flow Batteries.

Anion exchange blend membranes (AEBMs) were prepared for use in Vanadium Redox Flow Batteries (VRFBs). These AEBMs consisted of 3 polymer components. Firstly, PBI-OO (nonfluorinated PBI) or F6-PBI (partially fluorinated PBI) were used as a matrix polymer. The second polymer, a bromomethylated PPO, was quaternized with 1,2,4,5-tetramethylimidazole (TMIm) which provided the anion exchange sites. Thirdly, a partially fluorinated polyether or a non-fluorinated poly (ether sulfone) was used as an ionical cross-linker. While the AEBMs were prepared with different combinations of the blend polymers, the same weight ratios of the three components were used. The AEBMs showed similar membrane properties such as ion exchange capacity, dimensional stability and thermal stability. For the VRFB application, comparable or better energy efficiencies were obtained when using the AEBMs compared to the commercial membranes included in this study, that is, Nafion (cation exchange membrane) and FAP 450 (anion exchange membrane). One of the blend membranes showed no capacity decay during a charge-discharge cycles test for 550 cycles run at 40 mA/cm² indicating superior performance compared to the commercial membranes tested.

Density functional theory study with and without COSMO of H2 SO4 reactions in an aqueous environment for metal extraction.

In a recent study investigating the suitability of solvent extraction (SX) for the separation of Ta and Nb, it was shown that speciation data would be required to help explain the data obtained. As traditional speciation techniques cannot be readily applied for Ta and Nb, it was decided to determine the suitability of molecular modeling for this purpose. During the SX experiments the aqueous phase consisted of sulfuric acid (H2 SO4 ), water, and metal species. In this study density functional theory (DFT) modeling was used to calculate the formation energy of five possible reactions of H2 SO4 and H2 O. Different functional and basis set combinations were compared as well as the effect of infinite dilution by using the conductor-like screening model (COSMO), which simulates infinite dilution of solvents of varying polarity and includes the short-range interactions of the solute particles. The results obtained were used to determine whether it is possible to predict the reactions and mechanism when H2 SO4 and H2 O interact during SX. According to the results, the deprotonation of H2 SO4 was endothermic in a 1:1 acid-water ratio, while being both exothermic in the 1:5 and 1:10 acid-water ratio forming HSO4 - and SO4 2- respectively. Furthermore, it was seen that the hydration and dehydration of H2 SO4 in a bulk H2 O solution was a continuous process. From the energy calculations it was determined that although the H2 SO4 ●H2 O, HSO4 - ●H2 O, and H2 SO4 ●2H2 O species could form, they would most likely react with H2 O molecules to form HSO4 - , H3 O+ , and H2 O. © 2018 Wiley Periodicals, Inc.

Application of Novel Anion-Exchange Blend Membranes (AEBMs) to Vanadium Redox Flow Batteries.

Both cation-exchange membranes and anion-exchange membranes are used as ion conducting membranes in vanadium redox flow batteries (VRFBs). Anion-exchange membranes (AEMs) are applied in vanadium redox flow batteries due to the high blocking property of vanadium ions via the Donnan exclusion effect. In this study, novel anion-exchange blend membranes (AEBMs) were prepared, characterized, and applied in VRFBs. Bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide), poly[(1-(4,4′-diphenylether)-5-oxybenzimidazole)-benzimidazole] (PBI-OO) and sulfonated polyether sulfone polymer were combined to prepare 3-component AEBMs with 1,2,4,5-tetramethylimidazole (TMIm) for quaternization. 3-component AEBMs showed significantly enhanced chemical and mechanical properties compared with those of 2-component AEBMs, resulting in an improved performance in VRFBs. The compositions of the anion-exchange polymers in 3-component AEBMs were systematically varied to optimize the AEBMs for the redox-flow battery application. While the 3-component AEBMs showed comparable efficiencies with Nafion® 212 membranes, they displayed improved vanadium ions cross-over as was confirmed by open circuit voltage tests and capacity fade tests conducted in VRFBs. In addition, one of the synthesized 3-component AEBM had a superior coulombic efficiency and capacity retention in a charging⁻discharging test over 300 cycles at a current density of 40 mA/cm². It can thus be concluded that 3-component AEBMs are promising candidates for long-term operation in VRFBs.

Poly(vinylbenzylchloride) Based Anion-Exchange Blend Membranes (AEBMs): Influence of PEG Additive on Conductivity and Stability.

In view of the many possible applications such as fuel cells and electrolysers, recent interest in novel anion exchange membranes (AEMs) has increased significantly. However, their low conductivity and chemical stability limits their current suitability. In this study, the synthesis and characterization of several three- and four-component anion exchange blend membranes (AEBMs) is described, where the compositions have been systematically varied to study the influence of the AEBM's composition on the anion conductivities as well as chemical and thermal stabilities under strongly alkaline conditions. It was shown that the epoxide-functionalized poly(ethylene glycol)s that were introduced into the four-component AEBMs resulted in increased conductivity as well as a marked improvement in the stability of the AEBMs in an alkaline environment. In addition, the thermal stability of the novel AEBMs was excellent showing the suitability of these membranes for several electrochemical applications.