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At least 253 records · Page 14

Physical model and experimental validation of a high temperature proton exchange membrane electrochemical hydrogen pump cell for efficient single-stage extraction of low concentration hydrogen gas

There is interest in valorization of existing natural gas infrastructure to facilitate the co-transportation of hydrogen via blending of hydrogen gas initially at limited concentrations of 1–20 vol% H2 and to subsequently extract hydrogen at fuel cell quality standards (SAE J2719/ISO14687-2). High temperature proton exchange membrane electrochemical hydrogen pump (HT-PEM EHP) based on phosphoric acid doped polybenzimidazole (PA-PBI) exhibits good performance at elevated temperatures (>120 °C), which provides desirable tolerance to non-methane natural gas constituents that are problematic for lower temperature based EHP. To better understand the suitability of the HT-PEM EHP for such gas separation processes, a two-dimensional model of EHP based on PA-PBI was developed. The model is validated for several relevant operating conditions and across cells with differing amounts of phosphoric acid content in the electrodes. Operando micro x-ray computed tomography (CT) imaging of an HT-PEM EHP was used to further validate physical parameters and assumptions of the model. The impacts of pressure, relative humidity of the anode feed, and concentration of feed gases on separation performance are investigated. This study shows that a specific energy of separation of 5.1 kWh/kg H2 at a hydrogen recovery factor (HRF) of 50 vol% can be achieved in a single stage with the EHP, producing fuel cell quality hydrogen purity of 99.99 vol% H2 from a 2 vol% H2/CH4 feed blend, while pressurizing the product H2 at a pressure ratio of 1.3 relative to feed pressure.

Stansberry, John M↗

A review of functions, attributes, properties and measurements for the quality control of proton exchange membrane fuel cell components

Quality control (QC) is an essential part of fuel cell technology industrialization, providing means to reduce cost of components, enhancing the reliability of the final product, and offering specification guidance for new entrants in the supply chain. The membrane electrode assembly (MEA), including membrane, catalyst layer (CL), and gas diffusion layer (GDL), as well as bipolar plate (BP), are key components of a proton exchange membrane (PEM) fuel cell, and the attributes of each component strongly correlate with the cell performance and longevity. To ensure the quality of the fuel cell, it is of great importance to characterize the properties with respect to the standardization of component/sub-component specifications. In collaboration with the fuel cell industry, this work aims at establishing compendiums of attributes, or so-called books of attributes, of key fuel cell components for the QC of PEM fuel cells through reviewing, identifying, categorizing, and prioritizing the main attributes/properties that determine their functionalities. The books of attributes for the major PEM fuel cell components include catalyst coated membrane (CCM) as a sub-assembly, GDL, and BP. To address the full spectrum of fuel cell components, gaskets and sub-gaskets are also included.

25 ENERGY STORAGE↗

Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures

Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. Here, in this study, we developed a series of non-fluorinated PEMs from poly(terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25% at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm 2 for PFLSH60 compared to 1.83 mA/cm 2 for Nafion 212) under testing conditions of 80 °C and 100% RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray Photoelectron Spectroscopy Analysis of Nafion-Containing Samples: Pitfalls, Protocols, and Perceptions of Physicochemical Properties

X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the Case for Reduced Precious Metal Catalysts in Proton Exchange Membrane Electrolyzers

Proton exchange membrane (PEM) water electrolyzers are a key technology in decarbonizing hydrogen production. Though the market for PEM electrolyzer systems is growing, there are concerns that the cost and availability of precious metal catalysts utilized in today’s commercial systems can limit deployment. Herein, we show that while the availability of Ir should not impede deployment in the near term, the inelasticity of the Ir commodity price is cause for immediate concern. Here we emphasize that diversifying catalyst materials, even with other precious metals, can reduce system costs and mitigate supply chain risk. Furthermore, we analyze the trade-offs between catalyst capital cost and catalyst activity for a range of operating conditions (i.e., capacity factor, electricity price). The framework presented herein is a first step toward establishing performance targets (i.e., activity, stability, material cost) for reduced precious metal and non-precious metal catalysts as a function of PEM electrolyzer operating conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis

Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, in this study, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO 2 ) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO 2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO 2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO 2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm -2 , suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO 2 , as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-iridium stabilized ruthenium oxide anode catalyst for durable proton-exchange membrane water electrolysis

While mixing iridium (Ir) with ruthenium oxide (RuO 2 ) has proven to be an effective strategy for reducing Ir loading in anode catalysts for proton-exchange membrane (PEM) water electrolysers, achieving industrially relevant long-term stability typically requires an Ir-rich, Ru-lean combination. Here, in this study, by combining density functional theory with Metropolis Monte Carlo methods, we discovered that sufficient stabilization in the RuO 2 lattice could be achieved with less than 50 at.% of Ir, and that Ir in the first subsurface layer plays a critical role. By effectively dispersing Ir dopants within the RuO 2 lattice, we demonstrated an Ir:Ru atomic ratio of only 1:6 that exhibited exceptional stability for over 1,500 h of continuous water electrolysis at 2 A cm −2 . Our Ru 6 IrO x catalyst has the potential to reduce Ir loading by 80% compared with current commercial PEM water electrolysers, and its stability was further validated under industrial testing conditions in a 25-cm 2 PEM electrolyser.

36 MATERIALS SCIENCE↗

Deconvoluting charge-transfer, mass transfer, and ohmic resistances in phosphonic acid–sulfonic acid ionomer binders used in electrochemical hydrogen pumps

Ion-pair high-temperature polymer electrolyte membranes (HT-PEMs) paired with phosphonic acid ionomer electrode binders have substantially improved the performance of HT-PEM electrochemical hydrogen pumps (EHPs) and fuel cells. Here, blending poly(pentafluorstyrene-co-tetrafluorostyrene phosphonic acid) (PTFSPA) with Nafion™, and using this blend as an electrode binder, improved proton conductivity in the electrode layer resulting in a 2 W cm –2 peak power density of fuel cells at 240 °C (a HT-PEM fuel cell record). However, much is unknown about how phosphonic acid ionomers blended with perfluorosulfonic acid materials affect electrode kinetics and gas transport in porous electrodes. In this work, we studied the proton conductivity, electrode kinetics, and gas transport resistances of 3 types of phosphonic acid ionomers, poly(vinyl phosphonic acid), poly(vinyl benzyl phosphonic acid), and PTFSPA by themselves and when blended with Aquivion® (a perfluorosulfonic acid material).

08 HYDROGEN↗

Enrichment of H2 to CO2 ratio using formic acid as a hydrogen carrier - CRADA 581 (Abstract)

The collaboration between PNNL and OCOchem will investigate approaches to enhance the hydrogen (H2) content from a stream of H2 and carbon dioxide (CO2) gases produced in the catalytic decomposition of aqueous formic acid (FA85). OCOchem uses an electrochemical process to generate FA85 from captured CO2 using electricity from renewable resources. The FA85 is a liquid organic hydrogen carrier (LOHC) that provides the opportunity to transport and store hydrogen, in liquid form, at volumetric densities significantly greater than compressed H2 gas, i.e., 50 grams H2/liter FA. PNNL has developed and tested catalytic reactors to release H2 from LOHCs like FA and aqueous formate salts (FS). The H2 released from the LOHC can be oxidized in a proton-exchange membrane fuel cell (PEM-FC) to generate electricity with water as the only by-product. The purpose of the proposed project is to increase the purity of the hydrogen released from the LOHC to enhance the operation efficiency of the PEM FC. The PEM FC in combination with the LOHC provides an approach to demonstrate a portable generator that utilizes hydrogen as the energy carrier instead of conventional diesel generator. The ‘hydrogen generator’ can be used to supply emergency backup power and significantly reduce CO2 emissions relative to a diesel generator.

30 DIRECT ENERGY CONVERSION↗

Towards a Unified Low-Cost Flow Plate, Flow-Field, PTL Solution for Proton Exchange Membrane Electrolyzers

Proton exchange membrane (PEM) water electrolysis is a highly efficient method for hydrogen production. Research cells typically consist of one proton exchange membrane, two catalyst layers, two porous transport layers, two flow-field plates, and two endplates. In commercial systems, the machined flow-field plates that are employed in research cells are typically replaced by stamped parts or open mesh material solutions to reduce manufacturing cost at scale. Nonetheless, the cell contains about 8 total interfaces: bipolar plate / flow plate material / porous transport medium / electrode / membrane / electrode / porous transport medium / flow plate material / bipolar plate. All these materials and interfaces need to be optimized for maximum performance and efficiency. Reducing the amount of interfaces by combining individual cell components directly benefits the fabrication cost (by reducing the parts count and the needs for surface coatings) and the electrochemical performance (by reducing ohmic losses). We have designed a novel PEM electrolysis cell with a piece of channeled titanium felt functioning as both the anode flow-field and the PTL, referred to as the channeled diffusion layer (CDL). The pores of the felt facilitate both in-plane and through-plane diffusion, ensuring maximum catalyst utilization while also minimizing mass transport loss. The titanium felt can be mass manufactured with existing stamping and forming methods and is therefore a promising candidate to reduce the capital cost of PEM electrolyzers whilst improving hydrogen production efficiency. Experiments conducted with 3mg IrOx/cm2 loading MEAs have shown a approximately 40% boost in peak current by implementing the CDL design. Low catalyst-loading MEAs are being tested in ongoing experiments and their results will be discussed and compared.

08 HYDROGEN↗

Electrospun Composite Proton-Exchange and Anion-Exchange Membranes for Fuel Cells

A fuel cell is an electrochemical device that converts the chemical energy of a fuel and oxidant into electricity. Cation-exchange and anion-exchange membranes play an important role in hydrogen fed proton-exchange membrane (PEM) and anion-exchange membrane (AEM) fuel cells, respectively. Over the past 10 years, there has been growing interest in using nanofiber electrospinning to fabricate fuel cell PEMs and AEMs with improved properties, e.g., a high ion conductivity with low in-plane water swelling and good mechanical strength under wet and dry conditions. Electrospinning is used to create either reinforcing scaffolds that can be pore-filled with an ionomer or precursor mats of interwoven ionomer and reinforcing polymers, which after suitable processing (densification) form a functional membrane. In this review paper, methods of nanofiber composite PEMs and AEMs fabrication are reviewed and the properties of these membranes are discussed and contrasted with the properties of fuel cell membranes prepared using conventional methods. The information and discussions contained herein are intended to provide inspiration for the design of high-performance next-generation fuel cell ion-exchange membranes.

25 ENERGY STORAGE↗

High energy efficiency and high power density proton exchange membrane fuel cells: Electrode kinetics and mass transport

The development of proton exchange membrane (PEM) fuel cell power plants with high energy efficiencies and high power densities is gaining momentum because of the vital need of such high levels of performance for extraterrestrial (space, underwater) and terrestrial (power source for electric vehicles) applications. Since 1987, considerable progress has been made in achieving energy efficiencies of about 60 percent at a current density of 200 mA/sq cm and high power densities (greater than 1 W/sq cm) in PEM fuel cells with high (4 mg/sq cm) or low (0.4 mg/sq cm) platinum loadings in electrodes. The following areas are discussed: (1) methods to obtain these high levels of performance with low Pt loading electrodes - by proton conductor impregnation into electrodes, localization of Pt near front surface; (2) a novel microelectrode technique which yields electrode kinetic parameters for oxygen reduction and mass transport parameters; (3) demonstration of lack of water transport from anode to cathode; (4) modeling analysis of PEM fuel cell for comparison with experimental results and predicting further improvements in performance; and (5) recommendations of needed research and development for achieving the above goals.

Supramaniam Srinivasan↗

High power density proton exchange membrane fuel cells

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Murphy, Oliver J.↗

Critical concerns, solutions and guidelines for use of plastic encapsulated microcircuits for space flight applications

Some of the concerns and risk mitigation procedures for using plastic encapsulated microcircuits (PEMs) for space applications are discussed. Despite their advantages, PEMs cannot be implemented in all space applications by replacing military parts numbers with their commercial counterparts in product designs and part lists. The technical and procurement concerns are summarized, and suggestions for high reliability procurements are given. The ability to withstand deleterious environmental effects and to meet mission critical reliability is the key to the successful use of PEMs for space applications.

Virmani, Nick↗

Global Troposphere Experiment Project

For the Global Troposphere Experiment project Pacific Exploratory Measurements West B (PEM West B), we made determinations of sulfur dioxide (SO2) and dimethyl sulfide (DMS) using gas chromatography-mass spectrometry with isotopically labelled internal standards. This technique provides measurements with precision of 1 part-per-trillion by volume below 20 pptv and 1% above 20 pptv. Measurement of DMS and SO2 were performed with a time cycle of 5-6 minutes with intermittent zero checks. The detection limits were about 1 pptv for SO2 and 2 pptv for DMS. Over 700 measurements of each compound were made in flight. Volcanic impacts on the upper troposphere were again found as a result of deep convection in the tropics. Extensive emission of SO2 from the Pacific Rim land masses were primarily observed in the lower well-mixed part of the boundary layer but also in the upper part of the boundary layer. Analyses of the SO2 data with aerosol sulfate, beryllium-7, and lead-210 indicated that SO2, contributed to half or more of the observed total oxidized sulfur (SO2 plus aerosol sulfate) in free tropospheric air. Cloud processing and rain appeared to be responsible for lower SO2 levels between 3 and 8.5 km than above or below this region. During both phases of PEM-West, dimethyl sulfide did not appear to be a major source of sulfur dioxide in the upper free troposphere over the western Pacific Ocean. In 1991 the sources Of SO2 at high altitude appeared to be both anthropogenic and volcanic with an estimated 1% being solely from DMS. The primary difference for the increase in the DMS source was the very low concentration of SO2 at high altitude. In the midlatitude region near the Asian land masses, DMS in the mixed layer was lower than in the tropical region of the western Pacific. Convective cloud systems near volcanoes in the tropical convergence in the western Pacific troposphere were a major source of SO2 at high altitudes during PEM-West B. High levels of SO2 were observed in several instances with large number concentrations of ultrafine CN above 9 km in the tropical convergence zone. Conversion of SO2, by OH to SO3 and subsequently to sulfuric acid may have been enhanced by lightning-produced NO levels exceeding 1 part per billion. Coupling of strong convection and volcanic sources of SO2 apparently is an important source of new particle formation at high altitude in the tropical convergence zone.

Bandy, Alan R.↗

Combining data from lidar and in situ instruments to characterize the vertical structure of aerosol optical properties

Over the last decade, the quantification of tropospheric aerosol abundance, composition and radiative impacts has become an important research endeavor. For the most part, the interest in tropospheric aerosols is derived from questions related to the global and local (instantaneous) radiative forcing of climate due to these aerosols. One approach is to study local forcing under well-defined conditions, and to extrapolate such results to global scales. To estimate local aerosol forcing, appropriate radiative transfer models can be employed (e.g., the Fu-Liou radiative transfer code, [Fu and Liou, 1993]). In general, such models require information on derived aerosol properties [Toon, 1994]; namely the aerosol optical depth, single-scattering albedo, and asymmetry factor (phase function), all of which appear in the equations of radiative transfer. In this paper, we report on a method that utilizes lidar data and in situ aerosol size distribution measurements to deduce the vertical structure of the aerosol complex index of refraction in the near IR, thus identifying the aerosol type. Together with aerosol size distributions obtained in situ, the aerosol refractive index can be used to calculate the necessary derived aerosol properties. The data analyzed here were collected during NASA's PEM West-B (Pacific Exploratory Mission) experiment, which took place in February/March 1994. The platform for the measurements was the NASA DC-8 aircraft. The primary goal of the PEM West missions [Browell et al., 1996] was the assessment of potential anthropogenic perturbations of the chemistry in the Pacific Basin troposphere. For this purpose the timing of PEM West-B corresponded to the seasonal peak in transport from the Asian continent into the Pacific basin [Merrill et al., in press]. This period normally occurs during Northern Hemisphere spring, when the Japan jet is well developed.

Redemann, J.↗

Fuel Cell Activities at the NASA Glenn Research Center

Fuel cells have a long history in space applications and may have potential application in aeronautics as well. A fuel cell is an electrochemical energy conversion device that directly transforms the chemical energy of a fuel and oxidant into electrical energy. Alkaline fuel cells have been the mainstay of the U.S. space program, providing power for the Apollo missions and the Space Shuttle. However, Proton Exchange Membrane (PEM) fuel cells offer potential benefits over alkaline systems and are currently under development for the next generation Reusable Launch Vehicle (RLV). Furthermore, primary and regenerative systems utilizing PEM technology are also being considered for future space applications such as surface power and planetary aircraft. In addition to these applications, the NASA Glenn Research Center is currently studying the feasibility of the use of both PEM and solid oxide fuel cells for low- or zero-emission electric aircraft propulsion. These types of systems have potential applications for high altitude environmental aircraft, general aviation and commercial aircraft, and high attitude airships. NASA Glenn has a unique set of capabilities and expertise essential to the successful development of advanced fuel cell power systems for space and aeronautics applications. NASA Glenn's role in past fuel cell development programs as well as current activities to meet these new challenges will be presented

Kohout, Lisa L.↗