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At least 19 records

Local ionic transport enables selective PGM-free bipolar membrane electrode assembly

Bipolar membranes in electrochemical CO 2 conversion cells enable different reaction environments in the CO 2 -reduction and O 2 -evolution compartments. Under ideal conditions, water-splitting in the bipolar membrane allows for platinum-group-metal-free anode materials and high CO 2 utilizations. In practice, however, even minor unwanted ion crossover limits stability to short time periods. Here we report the vital role of managing ionic species to improve CO 2 conversion efficiency while preventing acidification of the anodic compartment. Through transport modelling, we identify that an anion-exchange ionomer in the catalyst layer improves local bicarbonate availability and increasing the proton transference number in the bipolar membranes increases CO 2 regeneration and limits K + concentration in the cathode region. Through experiments, we show that a uniform local distribution of bicarbonate ions increases the accessibility of reverted CO 2 to the catalyst surface, improving Faradaic efficiency and limiting current densities by twofold. Using these insights, we demonstrate a fully platinum-group-metal-free bipolar membrane electrode assembly CO 2 conversion system exhibiting <1% CO 2 /cation crossover rates and 80-90% CO 2 -to-CO utilization efficiency over 150 h operation at 100 mA cm -2 without anolyte replenishment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pt Nanoparticles on Atomic-Metal-Rich Carbon for Heavy-Duty Fuel Cell Catalysts: Durability Enhancement and Degradation Behavior in Membrane Electrode Assemblies

Proton exchange membrane fuel cells (PEMFCs) are a promising zero-emission power source for heavy-duty vehicles (HDVs). However, long-term durability of up to 25,000 h is challenging because current carbon support, catalyst, membrane, and ionomer developed for traditional light-duty vehicles cannot meet the stringent requirement. Therefore, understanding catalyst degradation mechanisms under the HDV condition is crucial for rationally designing highly active and durable platinum group metal (PGM) catalysts for high-performance membrane electrode assemblies (MEAs). Herein, we report a PGM catalyst consisting of platinum nanoparticles with a high content (40 wt %) on atomic-metal-site (e.g., MnN 4 )-rich carbon support. MEAs with the Pt (40 wt %)/Mn–N–C cathode catalyst achieved significantly enhanced performance and durability, generating 1.41 A cm –2 at 0.7 V under HDV conditions (0.25 mgPt cm –2 and 250 kPa abs pressure) and retaining 1.20 A cm –2 after an extended and accelerated stress test up to 150,000 voltage cycles. Electron microscopy studies indicate that most fine Pt nanoparticles are retained on or/and in the carbon support covered with the ionomer throughout the catalyst layer at the end of life. During the long-term stability test, the observed electrochemical active surface area reduction and performance loss primarily result from Pt depletion in the catalyst layer due to Pt dissolution and redeposition at the interface of the cathode and membrane. Importantly, the first-principle density functional theory calculations further reveal a support entrapment effect of the Mn–N–C, in which the MnN 4 site can specifically adsorb the Pt atom and further retard the Pt dissolution and migration, therefore enhancing long-term MEA durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane electrode assembly for CO x reduction

Provided herein are membrane electrode assemblies (MEAs) for CO x reduction. According to various embodiments, the MEAs are configured to address challenges particular to CO x including managing water in the MEA. Bipolar and anion-exchange membrane (AEM)-only MEAs are described along with components thereof and related methods of fabrication.

Huo, Ziyang↗

Physics-Based Model to Represent Membrane-Electrode Assemblies of Solid-Oxide Fuel Cells Based on Gadolinium-Doped Ceria

This paper reports a physics-based model that predicts membrane-electrode assembly (MEA) performance of solid-oxide fuel cells (SOFCs) with Ce 0.9 Gd 0.1 O 2− δ (GDC10) electrolyte membranes. The paper derives self-consistent thermodynamic and transport properties for GDC1o mobile charged defects (oxide vacancies and reduced-ceria small polarons) by fitting published measurements of oxygen non-stoichiometry and conductivity over ranges of temperature and O 2 partial pressures. The button-cell model is applied to evaluate how mixed ionic-electronic conductivity influences the performance of an SOFC MEA with a GDC10 electrolyte sandwiched between a porous, composite Ni-GDC10 anode and a porous, composite cathode of Sm 0.5 Sr 0.5 CoO 3− δ (i.e., SSC) and GDC10. SSC properties are also derived by fitting published conductivity and oxygen non-stoichiometry measurements. Mixed conductivity of GDC10 and competing charge transfer reactions at both electrodes reduce open circuit voltages due to leakage current and buildup of defect concentrations at electrode-electrolyte interfaces. To fit polarization data, the button-cell model includes heterogeneous reaction rates for defect incorporation on the GDC10 surface along with Butler–Volmer expressions derived for competing charge transfer reaction rates from rigorous analyses assuming rate-limiting, elementary charge transfer reactions for each electrode. The calibrated MEA model can support rigorous SOFC modeling with GDC10 electrolytes over the range of conditions within a fully operating cell.

Electrochemistry↗

Fuel Cell Membrane Electrode Assemblies with Ultra-Low Pt Nanofiber Electrodes (Final Report)

H 2 /air fuel cell membrane-electrode-assemblies (MEAs) were fabricated with electrospun particle/polymer nanofiber mat cathodes (0.1 mg Pt /cm 2 or 0.2 mg Pt /cm 2 Pt/C, PtCo/C or PtNi/C) and anodes (0.1 mg/cm 2 Pt/C), where the binder was a mixture of acid-form perfluorosulfonic acid ionomer (e.g., Nafion™) and poly(acrylic acid) (PAA) carrier polymer or sodium-form PFSA with a carrier polymer of either PAA or polyethylene oxide (PEO). For the latter two cases, the water-soluble carrier was removed from the fibers after electrospinning. MEAs with Pt/C anode/cathode catalyst loadings of 0.1 mg Pt /cm2 each, an 1100 EW PFSA binder (Nafion™ dispersion), and a Nafion 211 membrane produced high power at both high and low relative humidity (RH) conditions, e.g., a maximum power density of 919 mW/cm 2 at 100% RH and 832 mW/cm 2 at 40% RH for a test at 80 °C and 200 kPa abs . The high power at low RH was attributed to nm-size pores within the fibers that trap water via capillary condensation thus maintaining a high proton conductivity of the PFSA binder in the cathode and especially the anode while minimizing/eliminating ionic isolation of catalyst particles in low water content, poorly conductive binder. At the same time, micro-porosity between fibers in the cathode allows for fast removal of electrogenerated water, thus minimizing cathode flooding. Nanofiber MEAs with Pt alloy catalyst cathodes also performed well, where a fibrous PtCo/C catalyst cathode at a loading of 0.1 mg/cm 2 produced 20% more power than a conventional powder cathode MEA, e.g., a maximum power density of 1,045 mW/cm 2 vs. 869 mW/cm 2 at 80 °C, 100% RH, and 200 kPa abs , and a PtNi/C fiber cathode MEAs prepared with Na+-form Nafion + PEO generated a maximum power of 820 mW/cm 2 at 40% RH. Fiber electrode MEAs with a neat Nafion binder (prepared from Na+-form Nafion + PEO or PAA) where the cathode Pt loading was ~0.1 mg/cm 2 exhibited a 25% loss in maximum power at 30,000 metal dissolution cycles, as compared to a 12% loss when the cathode binder was H+-form Nafion + PAA. The performance of a fiber mat electrode MEA with Pt/C catalyst (0.2 mg/cm 2 cathode loading and 0.1 mg/cm 2 anode loading) was excellent. At 80 oC and 200 kPa abs , the maximum power density was 1104 mW/cm 2 . The maximum power was independent of feed gas humidity for 40 < RH < 100%. The power loss after a metal dissolution AST (30,000 voltage cycles) was only 13%.

08 HYDROGEN↗

HSPES membrane electrode assembly

An improved fuel cell electrode, as well as fuel cells and membrane electrode assemblies that include such an electrode, in which the electrode includes a backing layer having a sintered layer thereon, and a non-sintered free-catalyst layer. The invention also features a method of forming the electrode by sintering a backing material with a catalyst material and then applying a free-catalyst layer.

Kindler, Andrew↗

Sulfonated Diels–Alder Poly(Phenylene)s in Membrane Electrode Assemblies for Fuel Cells

The transition to environmentally sustainable materials in fuel cells requires alternatives to persistent polyfluoroalkyl substances (PFAS) like Nafion. This study investigates the performance-limiting factors of membrane electrode assemblies (MEAs) utilizing sulfonated Diels–Alder poly(phenylene)s (sDAPPs) as PFAS-free polymer electrolytes. Among the configurations evaluated, the greatest performance loss occurred when sDAPP is used as the cathode binder, primarily due to phenyl group adsorption on catalyst surfaces, which reduces oxygen reduction reaction activity and impedes oxygen transport. Additional performance degradation arises from membrane-electrode interfacial incompatibility and insufficient ionomer hydrophobicity. By addressing ionomer adsorption and improving interfacial contact, an sDAPP-based cathode achieved a current density of 1.57 A cm −2 at 0.6 V under fully humidified H 2 /air conditions at 80 °C and 150 kPa abs . These results offer key insights for advancing high-performance, PFAS-free fuel cell technologies.

08 HYDROGEN↗

Degradation of Fuel Cell Membrane Electrode Assemblies from Buses Operated More than 25,000 h

This study investigates the performance losses and degradation of proton-exchange-membrane fuel-cell stacks taken from the Alameda Contra Costa Transit District (AC Transit) bus system (Alameda and Contra Costa counties, California, United States) that were operated for over 25,000 h. Here, we focus on the origin of differences in electrochemical performance between beginning-of-life (BOL) and end-of-life states as well as diagnostic data acquired during the lifetime of the buses. In doing so, we employ in- and ex- situ characterization methods such as polarization curves, electrochemical impedance spectroscopy, electron microscopy, and X-ray characterization. Uniform degradation of the catalyst layer including Pt agglomeration/migration and electrode thinning was observed in all of the post-teardown measurements compared to BOL materials resulting from years of field operation. Despite these changes, the measured post-teardown performance suggests a sufficient output for the expected load, which indicate factors other than degradation of the membrane-electrode assemblies (MEAs) are likely responsible for the decommissioning of the stacks. The findings indicate that these MEA materials can enable long lifetime in fuel-cell vehicles, if the MEAs are not subjected to adverse operating conditions. The results also highlight the need for more in-vehicle diagnostics to maximize the lifetime of fuel cell vehicle (FCV) powerplants.

25 ENERGY STORAGE↗

Modeling Planar Electrodes and Zero–Gap Membrane Electrode Assemblies for CO 2 Electrolysis

Multiphysics modeling enables probing of conditions inside a CO 2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one-dimensional model for a zero-gap membrane electrode assembly (MEA) CO 2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO 3 concentration.

30 DIRECT ENERGY CONVERSION↗

Transport–Friendly Microstructure in SSC–MEA: Unveiling the SSC Ionomer–Based Membrane Electrode Assemblies for Enhanced Fuel Cell Performance

The significant role of the cathodic binder in modulating mass transport within the catalyst layer (CL) of fuel cells is essential for optimizing cell performance. This investigation focuses on enhancing the membrane electrode assembly (MEA) through the utilization of a short-side-chain perfluoro-sulfonic acid (SSC-PFSA) ionomer as the cathode binder, referred to as SSC-MEA. This study meticulously visualizes the distinctive interpenetrating networks of ionomers and catalysts, and explicitly clarifies the triple-phase interface, unveiling the transport-friendly microstructure and transport mechanisms inherent in SSC-MEA. The SSC-MEA exhibits advantageous microstructural features, including a better-connected ionomer network and well-organized hierarchical porous structure, culminating in superior mass transfer properties. Relative to the MEA bonded by long-side-chain perfluoro-sulfonic acid (LSC-PFSA) ionomer, noted as LSC-MEA, SSC-MEA exhibits a notable peak power density (1.23 W cm –2 ), efficient O 2 transport, and remarkable proton conductivity (65% improvement) at 65 °C and 70% relativity humidity (RH). These findings establish crucial insights into the intricate morphology-transport-performance relationship in the CL, thereby providing strategic guidance for developing highly efficient MEA.

25 ENERGY STORAGE↗

A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO2 to formic acid

Abstract The electrochemical reduction of carbon dioxide to formic acid is a promising pathway to improve CO 2 utilization and has potential applications as a hydrogen storage medium. In this work, a zero-gap membrane electrode assembly architecture is developed for the direct electrochemical synthesis of formic acid from carbon dioxide. The key technological advancement is a perforated cation exchange membrane, which, when utilized in a forward bias bipolar membrane configuration, allows formic acid generated at the membrane interface to exit through the anode flow field at concentrations up to 0.25 M. Having no additional interlayer components between the anode and cathode this concept is positioned to leverage currently available materials and stack designs ubiquitous in fuel cell and H 2 electrolysis, enabling a more rapid transition to scale and commercialization. The perforated cation exchange membrane configuration can achieve >75% Faradaic efficiency to formic acid at <2 V and 300 mA/cm 2 in a 25 cm 2 cell. More critically, a 55-hour stability test at 200 mA/cm 2 shows stable Faradaic efficiency and cell voltage. Technoeconomic analysis is utilized to illustrate a path towards achieving cost parity with current formic acid production methods.

08 HYDROGEN↗

Exploring CO 2 reduction and crossover in membrane electrode assemblies

Electrochemical CO 2 reduction (CO 2 R) using renewable electricity is a key pathway toward synthesizing fuels and chemicals. In this study, multi-physics modeling is used to interpret experimental data obtained for CO 2 R to CO using Ag catalysts in a membrane electrode assembly. The one-dimensional model is validated using measured CO 2 crossover and product formation rates. The kinetics of CO formation are described by Marcus–Hush–Chidsey kinetics, which enables accurate prediction of the experimental data by accounting for the reorganization of the solvent during CO 2 R. Further, the results show how the performance is dictated by competing phenomena including ion formation and transport, CO 2 solubility, and water management. The model shows that increasing the ion-exchange capacity of the membrane and surface area of the catalyst increases CO formation rates by >100 mA cm –2 without negatively impacting CO 2 utilization. Here we provide insights into how to manage the trade-off between productivity and CO 2 utilization in CO 2 electrolyzers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membrane Electrode Assembly Manufacturing Automation Technology for the Electrochemical Compression of Hydrogen: Cooperative Research and Development (Final Report)

Electrochemical compression has the possibility to outcompete mechanical compression for hydrogen end- use applications. While HyET has a compressor that can output JO kilograms (kg)/day (fully scalable from home-to-industrial application) at up to 700 bar, the energy demand and reliability require top-quality electrochemical hydrogen compression (EHC) membrane electrode assemblies (MEAs), preferably prepared by cost-effective high-capacity manufacturing. High pressure requires a special MEA design, deviating from typical proton exchange membrane fuel cell (PEMFC) MEAs with adapted catalyst layer substrates, asking for a modified coating process. The National Renewable Energy Laboratory (NREL) will help HyET by developing an automated catalyst coating process fit for EHC MEA manufacturing. In addition, inline quality inspection methods will be developed/selected to improve the MBA quality as it is used for EHC stack assembly. In a joint effort, NREL and HyET will even design an automated manufacturing process for the EHC MEA and approach potential United States (US) suppliers of manufacturing equipment.

30 DIRECT ENERGY CONVERSION↗

Membrane electrode assembly for a fuel cell

A catalyst ink for a fuel cell including a catalytic material and poly(vinylidene fluoride). The ink may be applied to a substrate to form an electrode, or bonded with other electrode layers to form a membrane electrode assembly (MEA).

Prakash, Surya↗

Durability of Membrane Electrode Assemblies (MEAs) in PEM Fuel Cells Operated on Pure Hydrogen and Oxygen

Proton exchange membrane (PEM) fuel cells are energy sources that have the potential to replace alkaline fuel cells for space programs. Broad power ranges, high peak-to-nominal power capabilities, low maintenance costs, and the promise of increased life are the major advantages of PEM technology in comparison to alkaline technology. The probability of PEM fuel cells replacing alkaline fuel cells for space applications will increase if the promise of increased life is verified by achieving a minimum of 10,000 hours of operating life. Durability plays an important role in the process of evaluation and selection of MEAs for Teledyne s Phase I contract with the NASA Glenn Research Center entitled Proton Exchange Membrane Fuel cell (PEMFC) Power Plant Technology Development for 2nd Generation Reusable Launch Vehicles (RLVs). For this contract, MEAs that are typically used for H2/air operation were selected as potential candidates for H2/O2 PEM fuel cells because their catalysts have properties suitable for O2 operation. They were purchased from several well-established MEA manufacturers who are world leaders in the manufacturing of diverse products and have committed extensive resources in an attempt to develop and fully commercialize MEA technology. A total of twelve MEAs used in H2/air operation were initially identified from these manufacturers. Based on the manufacturers specifications, nine of these were selected for evaluation. Since 10,000 hours is almost equivalent to 14 months, it was not possible to perform continuous testing with each MEA selected during Phase I of the contract. Because of the lack of time, a screening test on each MEA was performed for 400 hours under accelerated test conditions. The major criterion for an MEA pass or fail of the screening test was the gas crossover rate. If the gas crossover rate was higher than the membrane intrinsic permeability after 400 hours of testing, it was considered that the MEA had failed the test. Three types of MEAs out of the nine total membranes failed the test. The evaluation results showed that fuel cell operating conditions (current, pressure, stoichiometric flow rates) were the parameters that influenced the durability of MEAs. In addition, the durability test results indicated that the type of membrane was also an important parameter for MEA durability. At accelerated test conditions, the MEAs with casted membranes failed during the 400 hour test. However, the MEAs prepared from the casted membrane with support as well as extruded membranes, both passed the 400h durability test at accelerated operating test conditions. As a result of the MEA accelerated durability tests, four MEAs were selected for further endurance testing. These tests are being carried out with four-cell stacks under nominal fuel cell operating conditions.

Stanic, Vesna↗

High Performance Fuel Cell and Electrolyzer Membrane Electrode Assemblies (MEAs) for Space Energy Storage Systems

Regenerative fuel cells provide a pathway to energy storage system development that are game changers for NASA missions. The fuel cell/ electrolysis MEA performance requirements 0.92 V/ 1.44 V at 200 mA/cm2 can be met. Fuel Cell MEAs have been incorporated into advanced NFT stacks. Electrolyzer stack development in progress. Fuel Cell MEA performance is a strong function of membrane selection, membrane selection will be driven by durability requirements. Electrolyzer MEA performance is catalysts driven, catalyst selection will be driven by durability requirements. Round Trip Efficiency, based on a cell performance, is approximately 65%.

Plastic Encapsulated Microelectronics (PEM)↗

Mechanism of Pinhole Formation in Membrane Electrode Assemblies for PEM Fuel Cells

The pinhole formation mechanism was studied with a variety of MEAs using ex-situ and in-situ methods. The ex-situ tests included the MEA aging in oxygen and MEA heat of ignition. In-situ durability tests were performed in fuel cells at different operating conditions with hydrogen and oxygen. After the in-situ failure, MEAs were analyzed with an Olympus BX 60 optical microscope and Cambridge 120 scanning electron microscope. MEA chemical analysis was performed with an IXRF EDS microanalysis system. The MEA failure analyses showed that pinholes and tears were the MEA failure modes. The pinholes appeared in MEA areas where the membrane thickness was drastically reduced. Their location coincided with the stress concentration points, indicating that membrane creep was responsible for their formation. Some of the pinholes detected had contaminant particles precipitated within the membrane. This mechanism of pinhole formation was correlated to the polymer blistering.

Stanic, Vesna↗

Direct Air Capture of Carbon Dioxide Using Nickel Hydroxide Batteries in a Membrane Electrode Assembly

Direct air capture (DAC) is a growing field responding to the need to remove carbon dioxide from the atmosphere. Several technologies are being developed today attempting to meet this need. The technology furthest in development are temperature swing adsorption technologies which have recently moved out of the pilot plant scale.1 This presentation looks to present an electrochemical device as alternative to these technologies. The electrochemical device proposed is a pair of nickel hydroxide (Ni(OH)2) battery electrodes which produce hydroxide (OH-). The hydroxide reacts with carbon dioxide (CO2) to create carbonate (CO32-) and bicarbonate (HCO3-). These carbonates can be transported from the cathode across an anion exchange membrane to the anode where they are evolved back into CO2 due to a pH reduction at the anode. This builds on work that optimized a Hydroxide Exchange Membrane Fuel Cell (HEMFC) for CO2 capture, showing the efficacy of an electrochemically mediated pH swing carbon capture device.2,3 The benefit of the nickel hydroxide battery approach is the low energy cost associated with separation. Because a pair of nickel hydroxide batteries undergo the same electrochemical reaction, low potentials, and thus low energy cost is required. Experiments have shown device level energy requirements of less than 1 MWh ton-1CO2. Most of the energy required by the device produces the pH gradient used to capture and release CO2. The biggest hurdle for this electrochemical approach is increasing the flux of CO2 to allow for more compact devices. Strategies for managing the transient charge and discharge behavior of the battery system will be discussed. Focus will be on improving flux to reduce the overall cost of the device.

Buchen, James↗