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.

Low-Voltage Nongassing Electroosmotic Pump and Infusion Device with Polyoxometalate-Encapsulated Carbon Nanotubes.

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 ∼1.8 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.

Alkaline all iron redox flow battery with a polyethylene/poly(styrene-co-divinylbenzene) interpolymer cation-exchange membrane.

This work describes the suitability of a polyethylene styrene-DVB based interpolymer cation exchange membrane for use in a highly alkaline redox flow battery (RFB) with a [Fe(TEA)OH]2-/[Fe(TEA)OH]- and Fe(CN)6 3-/Fe(CN)6 4- redox couple. The alkaline stability of the membrane for 1440 h was evaluated in 5 N NaOH containing a 200 mM Fe(CN)6 3-/Fe(CN)6 4- redox couple. It was assessed according to the changes in the electrochemical and physicochemical properties. The performance of the membrane was evaluated over 40 charge-discharge cycles at a current density of 5 mA cm-2 current in a designed RFB cell. The obtained average coulombic efficiency (CE) was 92%, energy efficiency (EE) was 75%, voltage efficiency (VE) was 82% and volumetric efficiency was 34%. Under identical experimental conditions, the values of CE, EE, and VE for Nafion®-112 were 99%, 75%, and 76%, respectively. These results indicate the suitability of the polyethylene styrene-DVB based interpolymer cation exchange membrane for use in an alkaline RFB.

A non-gassing electroosmotic pump with sandwich of poly(2-ethyl aniline)-Prussian blue nanocomposite and PVDF membrane.

Low voltage, non-gassing electroosmotic pump (EOP) was assembled with poly(2-ethyl aniline) (EPANI)-Prussian blue nanocomposite electrode and commercially available hydrophilic PVDF membranes. The nanocomposite material combines excellent oxidation/reduction capacity of EPANI with exceptional stability by shuttling of proton between Prussian blue nanoparticles and EPANI redox matrix. The flow rate was highly dependent on the electrode composition but it was linear with applied voltage. The flow rate at 5 V for different nanocomposite, EPANI, EPANI-A, EPANI-B, and EPANI-C were 127.29, 187.41, 148.51, and 95.47 µL/min cm2 , respectively, which increases substantially with increase in the Prussian blue content. The obtained best electro osmotic flux was 43 µL/min/V/cm2 for EPANI-A. It was higher than most of the EOP assembled using polyquinone and polyanthraquinone redox polymers. The assembled EOP remained exceptionally stable until the electrode charge capacity was fully utilized. The best EOP produces a maximum stall pressure of 1.2 kPa at 2 V. These characteristics make it suitable for a variety of microfluidic/device applications.