Modeling electrolyte composition effects on anion-exchange membrane water electrolyzer performance

Anion-exchange membrane (AEM) water electrolysis could allow inexpensive and greener hydrogen production than other alternatives, such as steam methane reforming. To increase performance, hydroxide salts are often added to the water feed, with the tradeoff of corrosivity and complexity. Recently, carbonate salts that are less corrosive have shown promise, but their specific functionality remains unknown. In this paper, we use a mathematical model to compare an AEM electrolyzer with added potassium carbonate to an AEM electrolyzer with added potassium hydroxide. We show that the conductivity of the carbonate-form membrane has little impact on the performance of the device, but that carbonate ions replace hydroxide in the ionomer, which creates a Nernstian voltage difference across the membrane. The replacement of hydroxide anions with carbonate also reduces utilization of the catalyst in the anode, resulting in an additional voltage loss

Mass-transport resistances of acid and alkaline ionomer layers: A microelectrode study part 1 - Microelectrode development

The use of microelectrodes to study localized mass-transport phenomena in fuel-cell catalyst layers is an increasingly valuable tool. However, existing microelectrode cells have been used in static, equilibrated environment modes with poorly controlled interfaces. In this work, we present a microelectrode cell design that expands the experimental space addressable by microelectrodes to include mechanical pressure, gas flow and ionomer medium, and experimental throughput. The feasibility of the design is examined for fuel-cell reactions, with oxygen reduction currents independent of mechanical pressure and gas flowrate. Finally, cell equilibration time and IR drop across the electrolyte are estimated. The new cell design is robust and provides a consistent base from which to perform more complicated studies examining mass-transport properties of ionomers and/or the electrochemical reaction kinetics of hydrogen oxidation and oxygen reduction

Along-the-channel modeling and analysis of PEFCs at low stoichiometry: Development of a 1+2D model

Water management remains a key challenge in polymer-electrolyte fuel cells. In this work, a pseudo 3-D (1+2D) model is developed to account better for changes of water management along the channel, as well as verify the possibilities of using differential cells for data capture and translation to integral cell performance. An accurate 2-D membrane-electrode-assembly model is developed for differential cell modeling, which is combined with an along-the-channel stepping algorithm to account for down the channel changes in pressure, temperature, reactant concentration, and relative humidity. Variations in cell performance along the channel due to changes in operating conditions are characterized quantitatively and optimized, where drier feed conditions demonstratively require such an approach. Overall, the study identifies gaps between differential and integral cells including those related to flow velocity and highlights the need for better models to understand and link integral cell performance and water management

Ice crystallization during cold-start of a proton-exchange-membrane fuel cell

Under subfreezing conditions, ice forms in the gas-diffusion (GDL) and catalyst layers (CL) of proton-exchange-membrane fuel cells (PEMFCs), drastically reducing cell performance. Although a number of strategies exist to prevent ice formation, there is little fundamental understanding of ice-crystallization mechanisms and kinetics within PEMFC components. We incorporate recently developed ice-crystallization kinetic expressions (1-3) within the CL and GDL of a simplified 1-D transient PEMFC cold-start model. To investigate the importance of ice-crystallization kinetics, we compare liquid-water and ice saturations, and cell-failure time predicted using our kinetic rate expression relative to that predicted using a thermodynamic-based approach. We identify conditions under which ice-crystallization kinetics is critical and elucidate the impact of freezing kinetics on low-temperature PEMFC operation. © The Electrochemical Society

A global perspective on marine photosynthetic picoeukaryote community structure

A central goal in ecology is to understand the factors affecting the temporal dynamics and spatial distribution of microorganisms and the underlying processes causing differences in community structure and composition. However, little is known in this respect for photosynthetic picoeukaryotes (PPEs), algae that are now recognised as major players in marine CO2 fixation. Here, we analysed dot blot hybridisation and cloning–sequencing data, using the plastid-encoded 16S rRNA gene, from seven research cruises that encompassed all four ocean biomes. We provide insights into global abundance, α- and β-diversity distribution and the environmental factors shaping PPE community structure and composition. At the class level, the most commonly encountered PPEs were Prymnesiophyceae and Chrysophyceae. These taxa displayed complementary distribution patterns, with peak abundances of Prymnesiophyceae and Chrysophyceae in waters of high (25:1) or low (12:1) nitrogen:phosphorus (N:P) ratio, respectively. Significant differences in phylogenetic composition of PPEs were demonstrated for higher taxonomic levels between ocean basins, using Unifrac analyses of clone library sequence data. Differences in composition were generally greater between basins (interbasins) than within a basin (intrabasin). These differences were primarily linked to taxonomic variation in the composition of Prymnesiophyceae and Prasinophyceae whereas Chrysophyceae were phylogenetically similar in all libraries. These data provide better knowledge of PPE community structure across the world ocean and are crucial in assessing their evolution and contribution to CO2 fixation, especially in the context of global climate change