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At least 37 records · Page 2

Electrochemically active surface area controls HER activity for Fe x Ni 100–x films in alkaline electrolyte

We report the synthesis and electrocatalytic activity of Fe x Ni 100-x electrochemically deposited films were investigated. Films were evaluated for the hydrogen evolution reaction (HER) in alkaline media with respect to composition and electrochemically active surface area (ECSA). Results demonstrate that films of higher or equal Fe content had an ECSA tenfold greater than films with higher Ni. When normalized by geometric surface area, Fe 50 Ni 50 films required the lowest overpotential of -390 mV to reach a current density of -10 mA cm -2 . However, when normalized by the ECSA, intrinsic HER activity increases as Ni content increases. Tafel slope, ECSA, microscopy, and impedance spectroscopy analyses allow a decoupled analysis of surface area versus activity effects on overall measured HER activity. Furthermore, these analyses collectively demonstrate that the increase in electrocatalytic activity is attributed to the increase in ECSA and not to an enhancement in the intrinsic activity by Fe and Ni component interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Platinum and Gold Supported on Transition Metal Nitrides for Hydrogen Evolution in an Alkaline Electrolyte

Here, as the urgency to reduce reliance on fossil fuels increases due to carbon dioxide emissions, hydrogen produced by renewably powered water electrolysis has emerged as a promising technology. Alkaline electrolyzers typically exhibit lower current densities than acidic electrolyzers due to the slow kinetics of the hydrogen evolution reaction (HER) under alkaline conditions. This work developed Pt- and Au-modified transition metal nitride (TMN) thin films for improving alkaline HER kinetics. One monolayer Pt–VN, Pt–Mo 2 N, and Pt–TiN were the most promising thin-film catalysts, with alkaline HER activity approaching that of a bulk Pt foil. Additionally, the Gibbs free energy of adsorbed hydrogen was identified as a useful descriptor for alkaline HER activity on TMN and TMN-supported catalysts and has the potential to guide future studies on TMN-based catalysts for enhancing alkaline HER. For practical applications, the thin-film catalysts were then extended to Pt- and Au-modified TMN powders for alkaline HER. Both 5 wt % Pt/TiN and 2 wt % Pt/TiN powders exhibited lower overpotentials at 5 mA/cm 2 when normalized by the Pt electrochemical surface area than the commercial 5 wt % Pt/C benchmark, suggesting a Pt–TiN synergy that creates opportunities for more cost-effective alkaline HER cathodes. Moreover, 20 wt % Au/Mo 2 N also displayed an enhancement in HER activity when compared to the commercial 20 wt % Au/C benchmark.

58 GEOSCIENCES↗

Bismuth Detection in Alkaline Electrolyte via Anodic Stripping Voltammetry for Battery Separator Evaluation

Abstract Anodic stripping voltammetry (ASV) has been widely used for the detection of several heavy metal ions in neutral and acidic solution, in many cases employing electrodes and/or solutions incorporating Bi. In this work we demonstrate that Bi(OH) 4 − ion concentration can be measured in highly alkaline 8.5 M KOH solution using ASV. The addition of Pb in similar concentrations to the Bi(OH) 4 − being measured is shown to improve both the sensitivity and precision of the method. When the Pb additive is employed, a formal limit of detection of 8.5 ppb is achieved, compared to 17.3 ppb when the Pb additive is not used. Due to the use of Bi additives in alkaline battery chemistries, it follows that separators which limit Bi(OH) 4 − diffusion into the bulk electrolyte and away from the electrodes are of interest. For this purpose, we utilize ASV to determine Bi(OH) 4 − diffusion rates through Celgard 3501, cellophane 350P00, and Nafion 211. Bi(OH) 4 − crossover rates, as determined by ASV, are shown to be repeatable and consistent with expectations from the known separator structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chapter 7: Recent Advances in Electrocatalysts for Hydrogen Oxidation Reaction in Alkaline Electrolytes

The recent development in electrocatalysts for the hydrogen oxidation reaction (HOR) attracted significant attention. In this sense, this chapter provides a fundamental understanding of the state-of-the-art PGM and non-PGM-based electrocatalysts for the HOR in alkaline conditions. Moreover, a strong focus has been made on the strategies to overcome the slow kinetics of the HOR to commercialize anion-exchange membrane fuel cells.

anion-exchange membrane↗

Porous matrix structures for alkaline electrolyte fuel cells

A number of advancements have been realized by a continuing research program to develop higher chemically stable porous matrix structures with high bubble pressure (crossover resistance) for use as separators in potassium hydroxide electrolyte fuel cells. More uniform, higher-bubble-pressure asbestos matrices were produced by reconstituting Johns-Manville asbestos paper; Fybex potassium titanate which was found compatible with 42% KOH at 250 F for up to 3000 hr; good agreement was found between bubble pressures predicted by an analytical study and those measured with filtered structures; Teflon-bonded Fybex matrices with bubble pressures greater than 30 psi were obtained by filtering a water slurry of the mixture directly onto fuel cell electrodes; and PBI fibers have satisfactory compatibility with 42% KOH at 250 F.

Vine, R. W.↗

Development of gold alloy catalyst cathode for alkaline electrolyte fuel cells

A program for the development of improved catalyst and Teflon-bonded electrode structures using this improved catalyst is described, for use in fuel cell cathodes. It was found that Au-Pt was superior to the traditional platinum black as a catalyst. The impetus to the program was provided by the discovery that a life-limiting mechanism on the old catalyst was the gradual dissolution of platinum from the cathode and subsequent redeposition in the electrolyte-containing matrix.

Freed, M. S.↗

Unlocking High Capacity and Reversible Alkaline Iron Redox Using Silicate-Sodium Hydroxide Hybrid Electrolytes

Alkaline iron (Fe) batteries are attractive due to the high abundance, low cost, and multiple valent states of Fe but show limited columbic efficiency and storage capacity when forming electrochemically inert Fe 3 O 4 on discharging and parasitic H 2 on charging. Herein, sodium silicate is found to promote Fe(OH) 2 /FeOOH against Fe(OH) 2 /Fe 3 O 4 conversions. Electrochemical experiments, operando X-ray characterization, and atomistic simulations reveal that improved Fe(OH) 2 /FeOOH conversion originates from (i) strong interaction between sodium silicate and iron oxide and (ii) silicate-induced strengthening of hydrogen-bond networks in electrolytes that inhibits water transport. Furthermore, the silicate additive suppresses hydrogen evolution by impairing energetics of water dissociation and hydroxyl de-sorption on iron surfaces. In conclusion, this new silicate-assisted redox chemistry mitigates H 2 and Fe 3 O 4 formation, improving storage capacity (199 mAh g -1 in half-cells) and coulombic efficiency (94 % after 400 full-cell cycles), paving a path to realizing green battery systems built from earth-abundant materials.

36 MATERIALS SCIENCE↗

Toward the Understanding of the Reaction Mechanism of Zn/MnO2 Batteries Using Non-alkaline Aqueous Electrolytes

Zn/MnO 2 systems using non-alkaline aqueous electrolytes have attracted tremendous interest as rechargeable aqueous Zn ion batteries due to their safety and high specific capacities. Despite their promising electrochemical performance, however, their reaction mechanism has remained elusive. Here in this paper, we examined the structural evolution of cryptomelane α-MnO 2 cathode by ex situ transmission electron microscopy after electrochemical testing using two different non-alkaline aqueous Zn electrolytes with acetate and triflate salts of different pH values. We have discovered that the systems tested in both electrolytes exhibit a dissolution–deposition reaction mechanism through dissolution–deposition of Mn 2+ ions from/on the cathodes with a display of similar discharge/charge product formation. We have also found that the cell tested using the acetate electrolyte shows evidence of structural irreversibility that might contribute to its rapid capacity degradation. This finding offers an important insight into optimizing the cathode design for enhanced electrochemical function of aqueous Zn/MnO 2 batteries.

25 ENERGY STORAGE↗

Regenerative fuel cell energy storage system for a low earth orbit space station

A study was conducted to define characteristics of a Regenerative Fuel Cell System (RFCS) for low earth orbit Space Station missions. The RFCS's were defined and characterized based on both an alkaline electrolyte fuel cell integrated with an alkaline electrolyte water electrolyzer and an alkaline electrolyte fuel cell integrated with an acid solid polymer electrolyte (SPE) water electrolyzer. The study defined the operating characteristics of the systems including system weight, volume, and efficiency. A maintenance philosophy was defined and the implications of system reliability requirements and modularization were determined. Finally, an Engineering Model System was defined and a program to develop and demonstrate the EMS and pacing technology items that should be developed in parallel with the EMS were identified. The specific weight of an optimized RFCS operating at 140 F was defined as a function of system efficiency for a range of module sizes. An EMS operating at a nominal temperature of 180 F and capable of delivery of 10 kW at an overall efficiency of 55.4 percent is described. A program to develop the EMS is described including a technology development effort for pacing technology items.

Martin, R. E.↗