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Proton-Exchange-Membrane Fuel Cell Powerplants Developed and Tested for Exploration Missions

Proton-exchange-membrane fuel cell (PEMFC) technology has received major attention for terrestrial applications, such as the automotive and residential markets, for the past 20 years. This attention has significantly advanced the maturity of the technology, resulting in ever more compact, efficient, reliable, and inexpensive PEMFC designs. In comparison to the terrestrial operating environment, the space operating environment is much more demanding. Microgravity to high-gravity loads and the need to use pure oxygen (rather than air) as the fuel cell oxidizer place more stringent demands on PEMFC technology. NASA and its partners from industry are leveraging terrestrial PEMFC advancements by conducting parallel space technology development for future exploration missions. A team from the NASA Glenn Research Center, NASA Johnson Space Center, and NASA Kennedy Space Center recently completed the first phase of a PEMFC powerplant development effort for exploration missions. The industry partners for this phase of the development effort were ElectroChem, Inc., and Teledyne Energy Systems, Inc. Under contract to Glenn, both of these industry partners successfully designed, fabricated, and tested a breadboard PEMFC powerplant in the 1- to 5-kW power range. These powerplants were based on existing company-proprietary fuel cell stack designs, combined with off-the-shelf components, which formed the balance of the powerplant design. Subsequent to the contractor development efforts, both powerplants were independently tested at Johnson to verify operational and performance characteristics, and to determine suitability for further technology development in the second phase of the NASA-led effort. Following the independent NASA testing, Teledyne Energy Systems, Inc., was selected to develop an engineering model PEMFC powerplant. This effort was initiated by the 2nd Generation Reusable Launch Vehicle (RLV) Program Office in 2001; it transitioned to the Next Generation Launch Technologies (NGLT) Program Office in 2003. The effort is now being funded by the Exploration Program Office. We plan to summarize the results from the ongoing engineering model PEMFC powerplant development in a future Research & Technology article.

Hoberecht, Mark A.↗

Bridging interfacial properties and cell performance: A multiscale model for proton-exchange-membrane fuel cells

Here, to elucidate the impact of local interfaces on mass-transport resistance and overall cell performance of low-loaded proton-exchange-membrane fuel cells (PEMFCs), we present a multiscale modeling framework incorporating a novel modified agglomerate model. The model considers three distinct Pt-electrolyte interfaces: Pt on the carbon surface covered by either ionomer or water film and Pt inside carbon nanopores. Detailed mass-transport voltage-loss breakdowns reveal that coupled agglomerate-interface-scale mass transport dominates the mass-transport loss. The ionomer poisons the exterior-Pt surface through suppressing O 2 adsorption and intrinsic ORR activity, leading to low current-density performance. Conversely, interior-Pt interface enhances the kinetic performance but limits high current-density performance due to its low interfacial permeability. The exterior-Pt/water interface demonstrates superior kinetic performance and mass transport, though its practical implementation requires ensuring proton transport. By coupling the multiscale CL properties with ink parameters, the model identifies an optimal I to C ratio of approximately 0.5, a moderate value where the ionomer content is sufficient to guarantee proton transport without fully covering the Pt surface and forming large agglomeration, thus allowing the utilization of the Pt-water interface and avoiding high mass-transport loss. Overall, the model helps unravel limiting phenomena across different operating regimes and provides routes for optimizing performance.

Cell diagnostic↗

Proton exchange membrane fuel cells

Disclosed embodiments concern a membrane electrode assembly or a proton exchange membrane fuel cell comprising a phosphoric acid-doped polymeric membrane comprising a cationic functional group, such as an assembly or fuel cell having an ion exchange capacity of 0.8 to 3 mmol/gram and an operating temperature range of from 80° C. to 220° C. The cationic functional group can be any suitable functional group, such as ammonium, imidazolium, guanidinium, phosphazenium, sulfonium, oxonium, and phosphonium, with working embodiments typically using quaternary ammonium cationic functional groups tethered to the polymeric core. The polymeric material may be any suitable polymeric material, such as a material selected from polyaryl polymers, polyarylamides, polyimides, polystyrenes, polysulfones, polyethers, polyether sulfones, polyketones, polyetherketones, polyarylethers, polyolefins, and polynitriles. The membrane electrode assembly or a proton exchange membrane fuel cell can be used in any application now known or hereafter developed, such as a vehicle or a stationary power device.

30 DIRECT ENERGY CONVERSION↗

A novel unitized regenerative proton exchange membrane fuel cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed in work performed at Lynntech. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel unitized regenerative fuel cell and results obtained on testing it will be presented.

Murphy, O. J.↗

A Novel Unitized Regenerative Proton Exchange Membrane Fuel Cell

A difficulty encountered in designing a unitized regenerative proton exchange membrane (PEM) fuel cell lies in the incompatibility of electrode structures and electrocatalyst materials optimized for either of the two functions (fuel cell or electrolyzer) with the needs of the other function. This difficulty is compounded in previous regenerative fuel cell designs by the fact that water, which is needed for proton conduction in the PEM during both modes of operation, is the reactant supplied to the anode in the electrolyzer mode of operation and the product formed at the cathode in the fuel cell mode. Drawbacks associated with existing regenerative fuel cells have been addressed. In a first innovation, electrodes function either as oxidation electrodes (hydrogen ionization or oxygen evolution) or as reduction electrodes (oxygen reduction or hydrogen evolution) in the fuel cell and electrolyzer modes, respectively. Control of liquid water within the regenerative fuel cell has been brought about by a second innovation. A novel PEM has been developed with internal channels that permit the direct access of water along the length of the membrane. Lateral diffusion of water along the polymer chains of the PEM provides the water needed at electrode/PEM interfaces. Fabrication of the novel single cell unitized regenerative fuel cell and results obtained on testing it are presented.

Murphy, O. J.↗

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↗

Ion-Pair Proton Exchange Membrane Fuel Cells for Heavy-duty Transportation

The purpose of this project is to build a fuel cell prototype that demonstrates high temperature proton exchange membrane fuel cell technology (HT PEMFC) commercial readiness. It advances from a technology baseline established in a prior CRADA in which these same Parties collaborated during the years 2020-2024. These efforts are aligned with the intentions of the DOE Hydrogen Fuel Cell Technology Office (HFTO) L’Innovator Pilot Program. Participant observes that its US-based competitive advantage may be improved by further optimizing Laboratory inventions. This CRADA is intended to further improve National Laboratory compositions and to develop commercial HT PEMFC membrane electrode assemblies (MEAs) that perform over a range of operating temperatures and relative humidity, that generate power from both low grade and pure hydrogen, and that are resistant to air impurities. Participant’s goal is to advance the commercial competitiveness of National Laboratory technologies in fuel cell products for heavy-duty truck integrators, for stationary power generation, marine applications, and for emerging interest from commercial aviation. The Parties will collaborate on producing a HT PEMFC MEA that integrates LANL ion pair technology and Brookhaven catalyst technology. The Laboratories plan to research and develop compositions for testing and evaluation. The participant will manufacture multiple MEAs based on the Laboratory compositions and will enable selected customers to validate performance characteristics. The Laboratories will convey to Participant the methods of making the National Laboratory compositions such that Participant may reproduce and then scale Laboratory methods into commercial production. Throughout the project, the Laboratories and Participant will iteratively test and optimize the compositions of materials of the MEAs, intending to optimize characteristics such as power density and lifecycle durability. Participant’s intended customers include fuel cells for large trucks, aviation, power back up, marine, and portable power.

99 GENERAL AND MISCELLANEOUS↗

Nonhumidified High-Temperature Membranes Developed for Proton Exchange Membrane Fuel Cells

Fuel cells are being considered for a wide variety of aerospace applications. One of the most versatile types of fuel cells is the proton-exchange-membrane (PEM) fuel cell. PEM fuel cells can be easily scaled to meet the power and space requirements of a specific application. For example, small 100-W PEM fuel cells are being considered for personal power for extravehicular activity suit applications, whereas larger PEM fuel cells are being designed for primary power in airplanes and in uninhabited air vehicles. Typically, PEM fuel cells operate at temperatures up to 80 C. To increase the efficiency and power density of the fuel cell system, researchers are pursuing methods to extend the operating temperature of the PEM fuel cell to 180 C. The most widely used membranes in PEM fuel cells are Nafion 112 and Nafion 117--sulfonated perfluorinated polyethers that were developed by DuPont. In addition to their relatively high cost, the properties of these membranes limit their use in a PEM fuel cell to around 80 C. The proton conductivity of Nafion membranes significantly decreases above 80 C because the membrane dehydrates. The useful operating range of Nafion-based PEM fuel cells can be extended to over 100 C if ancillary equipment, such as compressors and humidifiers, is added to maintain moisture levels within the membrane. However, the addition of these components reduces the power density and increases the complexity of the fuel cell system.

Kinder, James D.↗

Proton exchange membrane fuel cells for space and electric vehicle applications: From basic research to technology development

The proton exchange membrane fuel cell (PEMFC) is one of the most promising electrochemical power sources for space and electric vehicle applications. The wide spectrum of R&D activities on PEMFC's, carried out in our Center from 1988 to date, is as follows (1) Electrode Kinetic and Electrocatalysis of Oxygen Reduction; (2) Optimization of Structures of Electrodes and of Membrane and Electrode Assemblies; (3) Selection and Evaluation of Advanced Proton Conducting Membranes and of Operating Conditions to Attain High Energy Efficiency; (4) Modeling Analysis of Fuel Cell Performance and of Thermal and Water Management; and (5) Engineering Design and Development of Multicell Stacks. The accomplishments on these tasks may be summarized as follows: (1) A microelectrode technique was developed to determine the electrode kinetic parameters for the fuel cell reactions and mass transport parameters for the H2 and O2 reactants in the proton conducting membrane. (2) High energy efficiencies and high power densities were demonstrated in PEMFCs with low platinum loading electrodes (0.4 mg/cm(exp 2) or less), advanced membranes and optimized structures of membrane and electrode assemblies, as well as operating conditions. (3) The modeling analyses revealed methods to minimize mass transport limitations, particularly with air as the cathodic reactant; and for efficient thermal and water management. (4) Work is in progress to develop multi-kilowatt stacks with the electrodes containing low platinum loadings.

Srinivasan, Supramaniam↗

Water Dynamics of Superacid Aromatic Proton Exchange Membranes for Fuel Cell Applications

Proton exchange membranes (PEMs) with high conductivity are of critical importance for the development of fuel cells, electrolyzers, and other electrochemical technologies. In this research, poly(1,1,2,2-tetrafluoro-2-phenoxyethane-1-sulfonic acid) (PTPS) with an aromatic polymer main chain and a perfluorinated superacidic polymer side chain was synthesized. The water dynamics of PTPS were characterized across various length scales using a combination of Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR) and compared with Nafion, a standard perfluorinated PEM, and sulfonated poly(ether sulfone) (SPES 40), an aromatic PEM without perfluorinated superacid side chains. The T 1 and T 2 relaxation times of water in the samples probed by NMR increase from SPES 40 to PTPS to Nafion, indicating that the local motion of the water molecules becomes faster. This trend corresponds well with the relative fraction of bulk-like water determined using FTIR. At larger length scales, the diffusion coefficient of water was characterized using pulsed-field gradient NMR (PFG-NMR). At a longer diffusion time (Δ = 100 ms), PTPS has a smaller diffusion coefficient compared with both Nafion and SPES 40, due to restricted diffusion, and this effect is also evident in the proton conductivity of the hydrated membranes. From this comparison, it is apparent that the aromatic backbone and side chain type greatly influence the water dynamics in PEMs at various length scales and the water dynamics significantly impact the bulk proton conductivity. These insights will lead to new designs for aromatic PEMs and help to identify bottlenecks in current materials.

25 ENERGY STORAGE↗

Durable hybrid electrocatalysts for proton exchange membrane fuel cells

The low durability of carbon-based non-precious metal electrocatalysts hinders their practical applications in proton exchange membrane fuel cells (PEMFCs). In this study, we rationally design a hybrid Pt-Fe-N-C electrocatalyst with unprecedented durability. It consists of abundant Pt and Fe single atoms homogeneously dispersed on the nitrogen-doped carbon support and a small amount of Pt-Fe alloy nanoparticles. A PEMFC with Pt-Fe-N-C as the cathode shows a larger peak power density (0.75 W cm -2 ) than that with Fe-N-C as the cathode (0.50 W cm -2 ). The remarkable durability of Pt-Fe-N-C is reflected from no noticeable drop in the half-wave potential after 70000 potential cycles between 0.6 and 1.0 V in the liquid cell, and 80% current retention after 85 h of potential hold at 0.4 V in the fuel cell. This work demonstrates the feasibility of improving the durability of Fe-N-C material via ultra-low Pt doping and makes non-precious metal electrocatalysts be close to achieving commercial metrics.

25 ENERGY STORAGE↗

Recent advances in integrating platinum group metal-free catalysts in proton exchange membrane fuel cells

Platinum group metal (PGM)-free catalysts are promising low-cost materials for the oxygen reduction reaction in proton exchange membrane fuel cells (PEMFCs). A variety of chemical precursors and synthesis methods have been proposed to increase their catalytic activity. In comparison, significantly less attention has been dedicated to the integration of these PGM-free catalysts into operating electrodes by investigating the role of the membrane electrode assembly (MEA) fabrication on the PEMFC performance. Here, we discuss here some remarkable performance improvements recently achieved by tuning catalyst loading, ionomer content, and ink solvent composition, and call for further explorations of the ink processing and MEA fabrication to improve performance.

25 ENERGY STORAGE↗

Effect of Reactant Purity on Proton Exchange Membrane Fuel Cell Performance

NASA has set a goal to return to the Moon and to establish a sustained lunar presence. Many applicable lander and upperstage vehicle concepts utilize cryogenic H2 and O2 propellants. This propellant selection enables appealing potential mission concepts wherein electricity is generated by operating a fuel cell on residual H2 and O2 propellants. This concept depends on the capability of the fuel cell to utilize dry, propellant-grade reactants with concentrations of up to 30 percent He present. This study consists of the evaluation of a 12-cell non-flow-through proton exchange membrane fuel cell stack of 50 sq. cm active area with passive water removal. This stack was supplied with three levels of reactant purity: >99.999, 99.1, and 70 mol%, with the remainder made up of He. The reactant humidity and flow-through rate were also assessed as performance factors, and the fuel stack repeatedly supported a load profile with current densities up to 500 mA/sq. cm (25 A). The fuel cell performed consistently over the course of testing, with cell voltages decreasing approximately 50 mV at the maximum current density when supplied with reactants with 30 percent He present.

electrochemistry↗

Proton Exchange Membrane Fuel Cell Engineering Model Powerplant. Test Report: Benchmark Tests in Three Spatial Orientations

Proton exchange membrane (PEM) fuel cell technology is the leading candidate to replace the aging alkaline fuel cell technology, currently used on the Shuttle, for future space missions. This test effort marks the final phase of a 5-yr development program that began under the Second Generation Reusable Launch Vehicle (RLV) Program, transitioned into the Next Generation Launch Technologies (NGLT) Program, and continued under Constellation Systems in the Exploration Technology Development Program. Initially, the engineering model (EM) powerplant was evaluated with respect to its performance as compared to acceptance tests carried out at the manufacturer. This was to determine the sensitivity of the powerplant performance to changes in test environment. In addition, a series of tests were performed with the powerplant in the original standard orientation. This report details the continuing EM benchmark test results in three spatial orientations as well as extended duration testing in the mission profile test. The results from these tests verify the applicability of PEM fuel cells for future NASA missions. The specifics of these different tests are described in the following sections.

Loyselle, Patricia↗

Studying the Durability of Molybdenum Carbide Aerogel as an Electrocatalyst Support for Proton Exchange Membrane Fuel Cells

Carbon-supported platinum nanoparticles (Pt/C) are currently the state-of-the-art catalyst in proton exchange membrane fuel cells (PEMFCs). Unfortunately, the carbon support lacks the ability to stabilize the metal catalyst, as platinum tends to dissolve and agglomerate, significantly compromising the durability. Herein, we synthesized a ceramic material, molybdenum carbide aerogel (MCAG), and utilized it as a Pt support for PEMFCs, as an alternative for conventional carbon supports. N 2 adsorption and XRD analysis showed that the MCAG possesses a combination of high porosity and a well-defined ceramic crystalline structure. The Pt/MCAG system was studied for its electrocatalytic activity toward ORR in a half-cell and demonstrated satisfactory reaction kinetics and electrochemical active surface area, comparable to the commercial Pt/C. For durability examination, an accelerated stress test (AST) in a single cell was conducted with the Pt/MCAG catalyst at the cathode, following the U.S. DOE electrocatalyst AST protocol. Intermediate polarization curves and cyclic voltammograms were recorded over the course of the AST to monitor the aging process. The results indicated that the MCAG support exhibited superior durability in long-term fuel cell operation compared to a carbon support. The Pt/MCAG system demonstrated stable behavior during the progressive stages of the AST, retaining more than 50% of its initial performance by the end of the test, whereas carbon-supported Pt preserved only 30%.

25 ENERGY STORAGE↗

Prediction of Performance Variation Caused by Manufacturing Tolerances and Defects in Gas Diffusion Electrodes of Phosphoric Acid (PA)–Doped Polybenzimidazole (PBI)-Based High-Temperature Proton Exchange Membrane Fuel Cells

The automated process of coating catalyst layers on gas diffusion electrodes (GDEs) for high-temperature proton exchange membrane fuel cells results inherently into a number of defects. These defects consist of agglomerates in which the platinum sites cannot be accessed by phosphoric acid and which are the consequence of an inconsistent coating, uncoated regions, scratches, knots, blemishes, folds, or attached fine particles—all ranging from μm to mm size. These electrochemically inactive spots cause a reduction of the effective catalyst area per unit volume (cm2/cm3) and determine a drop in fuel cell performance. A computational fluid dynamics (CFD) model is presented that predicts performance variation caused by manufacturing tolerances and defects of the GDE and which enables the creation of a six-sigma product specification for Advent phosphoric acid (PA)-doped polybenzimidazole (PBI)-based membrane electrode assemblies (MEAs). The model was used to predict the total volume of defects that would cause a 10% drop in performance. It was found that a 10% performance drop at the nominal operating regime would be caused by uniformly distributed defects totaling 39% of the catalyst layer volume (~0.5 defects/μm2). The study provides an upper bound for the estimation of the impact of the defect location on performance drop. It was found that the impact on the local current density is higher when the defect is located closer to the interface with the membrane. The local current density decays less than 2% in the presence of an isolated defect, regardless of its location along the active area of the catalyst layer.

Gurau, Vladimir (ORCID:0000000327429061)↗

Advanced Nanocarbons for Enhanced Performance and Durability of Platinum Catalysts in Proton Exchange Membrane Fuel Cells

Insufficient stability of current carbon supported Pt and Pt alloy catalysts is a significant barrier for proton-exchange membrane fuel cells (PEMFCs). As a primary degradation cause to trigger Pt nanoparticle migration, dissolution, and aggregation, carbon corrosion remains a significant challenge. Compared with enhancing Pt and PtM alloy particle stability, improving support stability is rather challenging due to carbon's thermodynamic instability under fuel cell operation. In recent years, significant efforts have been made to develop highly durable carbon-based supports concerning innovative nanostructure design and synthesis along with mechanistic understanding. Here, this review critically discusses recent progress in developing carbon-based materials for Pt catalysts and provides synthesis–structure–performance correlations to elucidate underlying stability enhancement mechanisms. The mechanisms and impacts of carbon support degradation on Pt catalyst performance are first discussed. The general strategies are summarized to tailor the carbon structures and strengthen the metal–support interactions, followed by discussions on how these designs lead to enhanced support stability. Based on current experimental and theoretical studies, the critical features of carbon supports are analyzed concerning their impacts on the performance and durability of Pt catalysts in fuel cells. Finally, the perspectives are shared on future directions to develop advanced carbon materials with favorable morphologies and nanostructures to increase Pt utilization, strengthen metal-support interactions, facilitate mass/charge transfer, and enhance corrosion resistance.

25 ENERGY STORAGE↗