ABSTRACT
The quest for a cost-effective, chemically-inert, robust and proton conducting membrane for flow batteries is at its paramount. Perfluorinated membranes suffer severe electrolyte diffusion, whereas conductivity and dimensional stability in engineered thermoplastics depend on the degree of functionalization. Herein, we report surface-modified thermally crosslinked polyvinyl alcohol-silica (PVA-SiO2) membranes for the vanadium redox flow battery (VRFB). Hygroscopic, proton-storing metal oxides such as SiO2, ZrO2 and SnO2 were coated on the membranes via the acid-catalyzed sol-gel strategy. The membranes of PVA-SiO2-Si, PVA-SiO2-Zr and PVA-SiO2-Sn demonstrated excellent oxidative stability in 2 M H2SO4 containing 1.5 M VO2+ ions. The metal oxide layer had good influence on conductivity and zeta potential values. The observed trend for conductivity and zeta potential values was PVA-SiO2-Sn > PVA-SiO2-Si > PVA-SiO2-Zr. In VRFB, the membranes showcased higher Coulombic efficiency than Nafion-117 and stable energy efficiencies over 200 cycles at the 100 mA cm-2 current density. The order of average capacity decay per cycle was PVA-SiO2-Zr < PVA-SiO2-Sn < PVA-SiO2-Si < Nafion-117. PVA-SiO2-Sn had the highest power density of 260 mW cm-2, while the self-discharge for PVA-SiO2-Zr was ~3 times higher than Nafion-117. VRFB performance reflects the potential of the facile surface modification technique to design advanced membranes for energy device applications.
ABSTRACT
A low-voltage nongassing electroosmotic pump was assembled by sandwiching a silica frit between two carbon paper electrodes that were dip-coated with a paste consisting of phosphomolybdic acid/phosphotungstic acid (PMA/PTA)-encapsulated multiwalled carbon nanotubes (MWCNTs) and Nafion. The PMA/PTA encapsulation was a combined effect of their thermomigration and nanocapillary action in MWCNTs. The encapsulated MWCNTs retained desirable redox and charge transfer characteristics of PMA/PTA. The stable voltammogram in 1 M H2SO4 solution exhibited 77% charge retention. A total of three different possible pump configurations, namely, PUMP-I = PMA//SiO2//PMA, PUMP-II = PTA//SiO2//PTA, and PUMP-III = PMA//SiO2//PTA were put together. They are in the sequence of the anode, silica frit, and cathode. All pumps showed a linear dependence on the flow rate with a minimum operating voltage of 1 V, which is well below the thermodynamic potential of water splitting. PUMP-I provided an electroosmotic flux of 43.57 µLmin-1 V-1 cm-2 that matched the requirement of an infusion device like an insulin pump. The device was fabricated and its applicability has been demonstrated by delivering â¼1.8 mL of water at a 10 ± 2 µLmin-1 flow rate at 2 V constant applied voltage over a period of 3 h. Such a wearable device can be programed to deliver model insulin or pain medication drugs for chronic diseases.
