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At least 163 records · Page 9

Uniformity, performance, and durability of roll-to-roll-coated iridium oxide electrolyzer catalyst layers

This work investigates the use of roll-to-roll coating methods for the production of iridium oxide catalyst layers for proton exchange membrane water electrolyzers. Catalyst layers were produced using two coating methods: slot die and gravure. By varying the solids content of the catalyst ink and coating process variables loadings between 0.08 and 0.64 mg Ir cm −2 were prepared with relatively high spatial uniformity. However, at loadings below 0.2 mg Ir cm −2 microscopy reveals voids in the catalyst layer due to similar length scales of catalyst agglomerates and overall layer thickness. Electrochemical testing shows that these voids do not impact initial membrane electrode assembly performance but lead to increased performance losses after potential cycling compared to spray coated catalyst layers.

08 HYDROGEN↗

Advanced Electrocatalysis for Energy and Environmental Sustainability via Water and Nitrogen Reactions

Abstract Clean and efficient energy storage and conversion via sustainable water and nitrogen reactions have attracted substantial attention to address the energy and environmental issues due to the overwhelming use of fossil fuels. These electrochemical reactions are crucial for desirable clean energy technologies, including advanced water electrolyzers, hydrogen fuel cells, and ammonia electrosynthesis and utilization. Their sluggish reaction kinetics lead to inefficient energy conversion. Innovative electrocatalysis, i.e., catalysis at the interface between the electrode and electrolyte to facilitate charge transfer and mass transport, plays a vital role in boosting energy conversion efficiency and providing sufficient performance and durability for these energy technologies. Herein, a comprehensive review on recent progress, achievements, and remaining challenges for these electrocatalysis processes related to water (i.e., oxygen evolution reaction, OER, and oxygen reduction reaction, ORR) and nitrogen (i.e., nitrogen reduction reaction, NRR, for ammonia synthesis and ammonia oxidation reaction, AOR, for energy utilization) is provided. Catalysts, electrolytes, and interfaces between the two within electrodes for these electrocatalysis processes are discussed. The primary emphasis is device performance of OER‐related proton exchange membrane (PEM) electrolyzers, ORR‐related PEM fuel cells, NRR‐driven ammonia electrosynthesis from water and nitrogen, and AOR‐related direct ammonia fuel cells.

Li, Yi↗

A Discussion of Oxygen Recovery Definitions and Key Performance Parameters for Closed-Loop Atmosphere Revitalization Life Support Technology Development

Over the last 55 years, NASA has evolved life support for crewed space exploration vehicles from simple resupply during Project Mercury to the complex and highly integrated system of systems aboard the International Space Station. As NASA targets exploration destinations farther from low Earth orbit and mission durations of 500 to 1000 days, life support systems must evolve to meet new requirements. In addition to having more robust, reliable, and maintainable hardware, limiting resupply becomes critical for managing mission logistics and cost. Supplying a crew with the basics of food, water, and oxygen become more challenging as the destination ventures further from Earth. Aboard ISS the Atmosphere Revitalization Subsystem (ARS) supplies the crew's oxygen demand by electrolyzing water. This approach makes water a primary logistics commodity that must be managed carefully. Chemical reduction of metabolic carbon dioxide (CO2) provides a method of recycling oxygen thereby reducing the net ARS water demand and therefore minimizing logistics needs. Multiple methods have been proposed to achieve this recovery and have been reported in the literature. However, depending on the architecture and the technology approach, "oxygen recovery" can be defined in various ways. This discontinuity makes it difficult to compare technologies directly. In an effort to clarify community discussions of Oxygen Recovery, we propose specific definitions and describe the methodology used to arrive at those definitions. Additionally, we discuss key performance parameters for Oxygen Recovery technology development including challenges with comparisons to state-of-the-art.

Abney, Morgan B.↗

KOH vs Deionized Water Operation in Anion Exchange Membrane Electrolyzers

Anion exchange membrane water electrolyzers (AEMELs) have recently received significant attention due to their potential advantages over proton exchange membrane electrolyzers (PEMELs). However, some AEMELs feed an aqueous salt solution to the cell where PEMELs typically feed deionized (DI) water. DI water is preferred to keep the system and maintenance costs low. Because of this, many AEMEL researchers report performance both in the salt solution (typically KOH) and DI water. However, the methodology for switching between KOH and DI water is often poorly defined, and it is unclear what impact the residual salt has on cell performance after switching from salt to DI water. Having a fully deionized environment is important because the presence of salts in the water feed increase the effective electrochemical surface area of the catalyst in the three-dimensional electrode and residual salt remaining after switching to DI water feed can have a misleading transient effect on cell performance. This paper focuses on understanding the transition from KOH to DI water testing in AEMELs. It is shown that when switching from salt to DI water feed, a large volume of DI water must be fed over several hours to achieve true DI-water performance. It is also shown that starting AEMELs from the beginning with DI water feed (without any KOH ever being fed to the cell) results in better cell durability. Lastly, a cell is demonstrated having operated exclusively on DI water at 1.0 A cm −2 for 500 h at an operating voltage of ca. 2 V and a low degradation rate.

08 HYDROGEN↗

ISRU Advanced Alkaline Electrolyzer (AAE) BAA

This is the one-page status update for the Game Changing Development (GCD) Advanced Alkaline Electrolyzer (AAE) Broad Agency Announcement (BAA) contract with Teledyne Energy Systems, Inc (TESI) to be presented at the fiscal year 2020 (FY20) GCD Annual Review. This activity to develop and demonstrate a contamination-tolerant liquid water electrolyzer for use in in-situ resource utilization (ISRU) applications to generate gaseous hydrogen and oxygen.

Electrolyzer↗

Regenerative solid oxide stack

An individual solid oxide cell (SOC) constructed of a sandwich configuration including in the following order: an oxygen electrode, a solid oxide electrolyte, a fuel electrode, a fuel manifold, and at least one layer of mesh. In one embodiment, the mesh supports a reforming catalyst resulting in a solid oxide fuel cell (SOFC) having a reformer embedded therein. The reformer-modified SOFC functions internally to steam reform or partially oxidize a gaseous hydrocarbon, e.g. methane, to a gaseous reformate of hydrogen and carbon monoxide, which is converted in the SOC to water, carbon dioxide, or a mixture thereof, and an electrical current. In another embodiment, an electrical insulator is disposed between the fuel manifold and the mesh resulting in a solid oxide electrolysis cell (SOEC), which functions to electrolyze water and/or carbon dioxide.

30 DIRECT ENERGY CONVERSION↗

Electrolytic production of oxygen from lunar resources

Oxygen is a valuable commodity in space. Substantial savings have been projected for future missions if oxygen could be produced on the moon from local resources. Some of the most promising approaches to extract oxygen from lunar resources involve electrochemical oxygen generation. In a straight-forward concept called "magma electrolysis", suitable oxides (silicates) are molten at 1300-1500 °C and the melt electrolyzed. Residual melt can be discarded after partial electrolysis. Alternatively, lunar soil may be dissolved in a molten salt and electrolyzed. In this approach, temperatures are lower and melt conductances higher, but electrolyte constituents need to be preserved. Both possibilities are being studied in the laboratory. In a different approach, ilmenite is reduced by hydrogen and the resulting water electrolyzed (Carbotek Process TM). Although know-how from terrestrial technology can be applied, the process task is unconventional and requires many innovative solutions. Time and effort needed for successful development should not be underestimated.

Rudolf Keller↗

Gas Permeability Test Protocol for Ion-Exchange Membranes

The membrane-based electrolysis of water is a growing topic of interest due to the advantages of employing membranes in hydrogen production efficiency and system safety over the traditional alkaline water electrolysis. Ion-exchange membranes with low gas permeability are highly desirable for stable and safe operation of membrane-based water-splitting technologies, hence gas permeability through ion-exchange membranes needs to be properly assessed with standardized methods. We addressed three methods to measure gas permeability of ion-exchange membranes, a pressure permeation cell, chronoamperometry microelectrodes, and in situ testing of the membrane electrode assembly, and provide a guideline for choosing the appropriate method for the targeted operating conditions of the water electrolyzers.

08 HYDROGEN↗

Controlled phosphate doping into nanoscopic SiO 2 proton conducting membranes

This article describes a method to introduce phosphate (PO 4 ) into SiO 2 atomic layer deposition (ALD) films in a self-limiting fashion. The method involves the use of a less common phosphate precursor, trimethyl phosphite [P(OMe) 3 ], to introduce PO 4 as a low-level dopant, <1 at. %, into a SiO 2 ALD process using bis(ethylmethylamino)silane and a modified O 3 conversion. P(OMe) 3 does not deposit a film with typical oxygen sources but incorporates as PO 4 in an ABC-type ALD scheme at deposition temperatures ranging from 100 to 300 °C. Addition of up to ∼1 at. % of PO 4 does not significantly impact the film density or concentrations of carbon and nitrogen impurities, which are both <0.4 at. %. Despite the relatively low dopant concentrations, PO 4 incorporation is shown to have a large impact on transport properties of the film. When explored as proton (H + )-conducting membranes, undoped SiO 2 ALD films showed H + conductivities (3 × 10 −6 –8 × 10 −5 S cm −1 ) and low H 2 permeabilities (<10 −9 cm 2 s −1 ) when measured at room temperature. The addition of PO 4 is shown to increase H + conductivity to 2 × 10 −4 S cm −1 , while maintaining low H 2 permeability of <10 −9 cm 2 s −1 . The ratio of H + conductivity to H 2 permeability, a key performance metric for H + -conducting membranes used in water electrolyzers, exceeds that of commercial Nafion-117 membranes. Here, the moderate H + conductivity and very low H 2 permeability of PO 4 -doped SiO 2 films make them promising candidates as fluorine-free replacements for Nafion in applications such as water electrolysis, hydrogen fuel cells, and redox flow batteries.

Atomic layer deposition↗

Effects of the Hydrophobic Block Length Ratio of Poly(vinylbenzyl N -methylpiperidinium carbonate)- b -polyethylene- b -poly(vinylbenzyl N -methylpiperidinium carbonate) Block Copolymers for Anion Exchange Membrane Electrolysis

Electrolysis of water to produce hydrogen from renewable electricity is an extremely attractive strategy to reduce energy dependence on fossil fuels. Development of membrane and ionomer materials that maintain high performance with long lifetimes is needed. We developed and investigated the performance and durability of a series of polyethylene-based ABA triblock copolymer anion exchange ionomer and membrane (AEI, AEM) materials for anion exchange membrane water electrolysis. Poly(vinylbenzyl N-methylpiperidinium carbonate)-b-polyethylene-b-poly(vinylbenzyl N-methylpiperidinium carbonate) was synthesized with different hydrophobic/hydrophilic block ratios (1.02:1, 2.58:1, and 4.46:1) resulting in a range of ion exchange capacities (1.1–1.8 meq g –1 ) and water swelling (23–154%) characteristics. All AEMs showed full anionic dissociation, as evidenced by linear Arrhenius correlations, and excellent carbonate conductivity of 8–94 mS cm –1 at 50 °C. Hydrophilic phase separation may offer superior chemical durability by only wetting the ion-conducting region of the polymer and avoiding attack at the nonwetted backbone. We evaluated the performance and durability of these AEMs as a function of hydrophobic polyethylene (PE) content. The AEM containing the least amount of PE displayed the highest performance of 1 A cm –2 at 2.3 V but degraded at 40 mV h –1 before catastrophically failing after <3 h at 0.5 A cm –2 . With greater PE-containing AEMs, the degradation rate was reduced by 3 orders of magnitude with only a 0.2 V increase in voltage. Constant current electrolysis for 50 h resulted in a voltage change of 0.3 mV h –1 in a single-cell water electrolyzer and 1 M potassium carbonate. In a 600 h test, the voltage change in the final 200 h was impressively low for an experimental film, 58 μV h –1 . Postmortem analysis indicated that the membrane did not thin and that water becomes more tightly hydrogen-bound in the polymer after electrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Orbital engineering of C 3 N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution

Alkaline water electrolyzer (AWE) is one of the promising technologies for hydrogen production at the industrial level. However, energetic inefficiency and low current density impede the development of AWE. Compared with acidic conditions, the Volmer step in alkaline hydrogen evolution reaction (HER) involves extra water dissociation, whose barrier is one of the most vital reasons for the sluggish kinetics of alkaline HER. Herein, choosing C 3 N monolayer as an ideal theoretical model, we design several empty orbitals through intentional metal doping, and further construct synergistic sites on the C 3 N monolayer to accelerate both water dissociation and hydrogen adsorption for alkaline HER. Furthermore, the as-designed Be-doped and Cr-doped C 3 N monolayers exhibit rather low theoretical overpotential of 0.476 eV and 0.216 eV for alkaline HER, respectively, which are even lower than Pt (1 1 1) surface. Moreover, by comparing the water dissociation behaviors on metal-doped C3N monolayer, we find that the empty orbitals with suitable orientation and energy level are useful for promoting the water dissociation process, indicating that we can use orbital engineering strategy to regulate the adsorption strength between adsorbate and surface site. Consequently, it is reasonable to suggest that our orbital engineering strategy would significantly benefit the design of highly efficient alkaline HER electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fuel Cell Technologies for Energy Storage

This presentation provides an overview of primary fuel cells, regenerative fuel cells, and water electrolyzers as well as how the local environment influences the designs and operations of these systems.

Fuel Cell↗

Dynamics of precatalyst conversion and iron incorporation in nickel-based alkaline oxygen evolution reaction catalysts

The efficiency of alkaline water electrolyzers is limited by the oxygen evolution reaction (OER). The design of improved OER catalysts requires understanding of material changes induced by the electrolyte under oxidizing potentials. We compare four Ni-based thin-film precatalysts—Ni, NiO, Ni(OH) 2 , and NiS x —in 0.1 M KOH with and without Fe impurities. Precatalyst conversion to the active oxyhydroxide catalysts and their OER performance are induced and followed using cyclic voltammetry. Without Fe electrolyte impurities, the precatalysts convert at different rates to a similar, modestly active NiOOH catalyst. Added Fe impurities are incorporated concurrently with the oxyhydroxide formation leading to active Ni 1-x Fe x OOH catalysts. The NiS x and Ni(OH) 2 precatalysts rapidly convert to oxyhydroxides both with and without Fe, while conversion of Ni and especially NiO is slowed down by Fe impurities. Choice of the precatalyst and presence of Fe impurities are key factors in designing active Ni 1-x Fe x OOH OER catalysts for electrolyzers.

alkaline electrolysis↗

Voltage breakdown analyses in anion exchange membrane water electrolysis – the contributions of catalyst layer resistance on overall overpotentials

Despite many recent advances, overpotentials remain high for anion exchange membrane water electrolyzers (AEMWEs). Voltage breakdown analyses (VBA) can help decouple the origins of overpotentials and facilitate design decisions to improve cell performance, but studies investigating how to adapt and apply VBA to AEMWEs are lacking. Specifically, catalyst layer resistances and their contributions to overpotentials are not consistently quantified in water electrolysis and are rarely quantified for AEMWEs. This work presents a systematic methodology for VBA tailored to AEMWEs, including an approach to Tafel analysis in the absence of a reference electrode and under conditions where both the oxygen evolution reaction and hydrogen evolution reaction exhibit significant overpotentials. Catalyst layer resistance contributions are diagnosed via changes in the catalyst layer thickness, transport layer porosity, ionomer content, and electrolyte concentration. In this study, we explain discrepancies between inherent catalytic kinetics and device level performance and identify catalyst layer design strategies to reduce catalyst layer resistances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Space Electrochemical Research and Technology Conference, 2nd, Cleveland, OH, Apr. 11-13, 1989, Proceedings

Attention is given to topics of advanced concepts, hydrogen-oxygen fuel cells and electrolyzers, nickel electrodes, and advanced rechargeable batteries. Papers are presented on human exploration mission studies, advanced rechargeable sodium batteries with novel cathodes, advanced double-layer capacitors, recent advances in solid-polymer electrolyte fuel cell technology with low platinum loading electrodes, electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications, and the corrosion testing of candidates for the alkaline fuel cell cathode. Other papers are on a structural comparison of nickel electodes and precursor phases, the application of electrochemical impedance spectroscopy for characterizing the degradation of Ni(OH)2/NiOOH electrodes, advances in lightweight nickel electrode technology, multimission nickel-hydrogen battery cell for the 1990s, a sodium-sulfur battery flight experiment definition study, and advances in ambient-temperature secondary lithium cells.

O'Donnell, Patricia M.↗

Anion-Exchange-Membrane Electrolysis with Alkali-Free Water Feed

Hydrogen is a green and sustainable energy vector that can facilitate the large-scale integration of intermittent renewable energy, renewable fuels for heavy transport, and deep decarbonization of hard-to-abate industries. Anion-exchange-membrane water electrolyzers (AEM-WEs) have several achieved or expected competitive advantages over other electrolysis technologies, including the use of precious metal-free electrocatalysts at both electrodes, fluorine-free hydrocarbon-based ionomeric membranes and bipolar plates based on inexpensive materials. Contrasting the analogous proton-exchange-membrane system (PEM-WE), where pure water is circulated (no support electrolyte), the current generation of AEM-WEs necessitates the circulation of a dilute aqueous alkaline electrolyte for reaching high energy efficiency and durability. For several reasons, including but not limited to lower cost of balance-of-plant, lower operating cost and improved device's lifetime, achieving high cell efficiency and performance using an alkali-free water feed is highly desirable. In this review, we develop and build a foundational understanding of AEM-WEs operating with pure water, as well as discuss the effects of operating with natural water feeds like seawater. After a discussion of the possible advantages of pure-water-fed AEM-WEs, we cover the thermodynamic and kinetic processes involved in AEM-WE, followed by a detailed review of materials and components and their integration in the device. We highlight the influence of electrolyte composition and alkali/electrolyte-free feed on the membrane-electrode assembly, ionomers, electrocatalysts, porous transport layer, bipolar plates and operating configuration. We provide evidence for how the pure water feed engenders several issues related to the degradation of device components and propose mitigation strategies.

Electrodes↗