Proton Conducting Organic-Inorganic Composite Membranes for All-Vanadium Redox Flow Battery.

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.

Fabrication of Alkaline Electrolyzer Using Ni@MWCNT as an Effective Electrocatalyst and Composite Anion Exchange Membrane.

Here, we report the synthesis of nickel nanoparticles thermally encapsulated in multiwalled carbon nanotubes (MWCNTs) and its utility in alkaline water splitting by combining with composite thermoset anion-exchange membrane. Ni@MWCNT displayed both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). It provided 10 mA cm-2 current density at an overpotential of 300 mV for OER and 254 mV for HER on a glassy carbon electrode, respectively. Base-catalyzed N-methly-4-piperidone-formaldehyde-based prepolymer was grafted on to poly(vinyl alcohol) and cross-linked via thermal annealing followed by quaternization using methyl iodide to obtain thermoset anion exchange membrane (NMPi). Composite NMPi membranes were synthesized using additives tetraethyl orthosilicate (TEOS) and zirconium oxychloride. The water splitting performance on the fabricated membrane electrode assembly was tested and compared with commercially available Neosepta membrane. The obtained faradic efficacy of the water splitting was 94.33% for ZrO2-NMPi membrane followed by 80.23%, 77.70%, and 65.10% for SiO2-NMPi, NMPi, and Neosepta membranes, respectively. The best membrane ZrO2-NMPi achieved maximum current density of ∼0.776 A cm-2 in 5 M KOH electrolyte at 80 °C and 2 V applied constant voltage. The excellent alkaline stability of MEA indicates its potential utility in hydrogen generation applications.