Search NASA⌕ Search

SEARCH · Search NASA

Results for “AEMFC”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 19 records

Water limiting current measurements in anion exchange membrane fuel cells (AEMFCs); part 1: Water limiting current method development

We report water management is critical in optimizing anion exchange membrane fuel cell (AEMFCs) performance and durability. The role of membranes on determining cell water balance in AEMFCs has received limited study. A more thorough understanding of membrane water transport parameters is necessary for thorough cell optimization. In this study, a novel method for probing limiting current based on water flux across an AEMFC is presented for the first time. The water limiting current has been investigated as a function of relative humidity of anode and cathode streams, cathode backpressure and cell operating temperature. From these studies, it is clearly shown that water diffusion through the membrane from the anode is the most critical mechanism for achieving high current density performance and durability. The developed method can act as a novel screening technique that focuses on the impacts of water transport parameters and helps identify promising membrane materials based on their water transport properties. A critical but underappreciated facet of AEMFC performance and durability.

30 DIRECT ENERGY CONVERSION↗

Multi-atom Pt and PtRu catalysts for high performance AEMFCs with ultra-low PGM content

To reduce the platinum group metal (PGM) loading in anion exchange membrane fuel cells (AEMFCs), it is important to transition to catalysts with very low PGM content, and eventually to catalysts that are completely PGM-free. Here, in this work, four supported low-PGM Pt and PtRu catalysts were prepared using a new, simple, scalable technique: Controlled Surface Tension (CST) method. CST allows for a high density of very small multi-atom clusters. Catalysts were physically characterized using a wide array of techniques and tested for their ORR and HOR activity both ex-situ and integrated into operating AEMFCs. The PGM loading was reduced by a factor of 14 while achieving comparable performance to commercial catalysts. AEMFCs were also assembled with ultralow PGM loading (0.05 mgPGM cm -2 ), where PtRu anodes were paired with Fe–N–C cathodes to achieve a specific power of 25 W/mg PGM (40 W/mg Pt ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Anion Exchange Membranes with Tunable Water Transport for PGM-Free AEMFCs

This project advanced the synthesis, characterization, and testing of anion exchange membranes for use in fuel cells. Our goal was to improve the water transport in anion exchange membrane fuel cells to improve their performance and durability. Through the work in this project we: 1) developed new composite anion exchange membranes through polymer synthesis and membrane casting into mechanical supports; 2) optimized electrode architecture and cell conditions to achieve; 3) demonstrated an integrated approach to achieving over 1 W/cm 2 in an operating device. While we did not achieve 1000 hours of continuous operation, we demonstrated multiple runs of more than 300 hours of device performance at steady-state.

08 HYDROGEN↗

Understanding Recoverable vs Unrecoverable Voltage Losses and Long-Term Degradation Mechanisms in Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently shown excellent progress in terms of their performance – e.g., achievable power and current density. However, very few AEMFCs have been demonstrated with the ability to operate for a long duration (>1000 h). In addition, it is unknown whether performance losses observed during operation are reversible, irreversible, or a combination of the two. In this study, a high-performance AEMFC operated continuously at 600 mA/cm 2 for 3600 h (150 days) at 80 °C with H 2 /O 2 reacting gases was demonstrated. Throughout testing, the electrochemical properties of the AEMFC were probed to provide information about performance degradation pathways and their degree of reversibility. It was found that a portion of the performance loss that occurs during AEMFC operation was due to suboptimal reaction conditions and can be recovered. At the end of the experiment, the cell was disassembled, and its structure and composition were evaluated at the nanoscale by aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. The structure and composition of the electrode were compared to cells at the beginning of their operational life. It was found that the primary mechanism for long-term AEMFC performance loss was catalyst agglomeration. During the operational time, there was no evidence of significant polymer degradation, likely due to the high hydration state of the cell. By documenting the long-term changes in high-performing AEMFCs, this work provides important information for the systematic design of cell components and demonstrates the importance of controlling cell operation, which can aid in the commercialization and widespread deployment of low-cost, long-life AEMFCs.

30 DIRECT ENERGY CONVERSION↗

Achieving High‐Performance and 2000 h Stability in Anion Exchange Membrane Fuel Cells by Manipulating Ionomer Properties and Electrode Optimization

The primary function of the ionomers that are incorporated into fuel cell electrode catalyst layers is to provide pathways for ion transport between the catalyst active sites and the electrolyte. This is influenced by many variables, including the ion-exchange capacity, water uptake, and molecular weight. In anion exchange membrane fuel cells (AEMFCs), controlling ionomer water uptake is particularly important and tailoring this property in each electrode is an important consideration when looking to maximize cell performance. In this study, three poly(norbornene) tetrablock copolymer ionomers with a range of physical properties are synthesized and incorporated into AEMFC anode and cathode electrodes. Systematic electrode engineering with these ionomers allows the peak power density to be increased by 100% (1.6 W cm -2 → 3.2 W cm -2 ) and the current density at 0.2 V to be increased by 59% (5.9 A cm -2 → 9.4 A cm -2 ). Moreover, the top-performing electrode configuration is tested in an operating AEMFC at the US Department of Energy defined current density of 600 mA cm -2 for 2000 h, showing a record-low voltage decay rate of 15.36 µV h -1 – only 3.65% –a over 2000 h. Here, this work sets a new bar for AEMFCs, reporting the best combination of performance and durability of any AEMFC to date.

08 HYDROGEN↗

High-performance ionomerless cathode anion-exchange membrane fuel cells with ultra-low-loading Ag–Pd alloy electrocatalysts

Rapid translation of catalysts from fundamental studies to high-performance devices could facilitate the process of developing and commercializing anion-exchange membrane fuel cells (AEMFCs). Traditionally, translation from material screening in three-electrode rotating disk electrode (RDE) cells to AEMFCs is complicated by differences in microenvironments, e.g. solid ionomer/membrane vs liquid electrolyte. Herein, we introduce a platform for translation to devices that utilizes ionomerless ultra-low-loading Ag-Pd alloy electrocatalyst cathodes synthesized by co-physical vapor deposition (PVD). Our ionomerless cathodes allow for systematic H 2 -O 2 AEMFC experiments while demonstrating comparable activity trends to those in three-electrode cells. Furthermore, here we show that our Ag 10 Pd 90 -based AEMFC reaches a peak power density of ~1 W cm$_{geo}^{-2}$ and ~10 W mg$_{PGM Cathode}^{-1}$ satisfying the U.S. Department of Energy’s platinum-group-metal (PGM) loading and cost targets. Our approach shows promise in facilitating the rapid translation between three-electrode studies and AEMFCs, offering a simple and effective design for decreasing PGM loadings.

25 ENERGY STORAGE↗

Asymmetric electrode ionomer for low relative humidity operation of anion exchange membrane fuel cells

The operation of fuel cells under low relative humidity (RH) conditions gives substantial cost and performance benefits. Nonetheless, it is not currently feasible to operate anion exchange membrane fuel cells (AEMFCs) at low RH conditions because current materials for membrane electrode assembly cannot provide sufficient water for the oxygen reduction reaction. In this work, we synthesized polyfluorene ionomers with different ammonium concentrations for anode and cathode to control water management. We designed several asymmetric electrodes that enable high performance under low RH conditions via not only conventional backward water diffusion (anode to cathode) but also forward diffusion (cathode to anode). The AEMFCs using optimized asymmetric electrodes exhibited high H 2 /CO 2 -free air performance (rated power density of circa 540 mW cm -2 at 90 °C under 75% (anode) and 50% RH (cathode) conditions), which is comparable to those of state-of-the-art AEMFCs under nearly water-saturated conditions. The durability of the AEMFCs is excellent, generating 0.6 A cm -2 for >900 h at 80 °C under 50% RH (cathode) conditions. This study demonstrates that high-performance and durable AEMFCs under low RH and high current generating conditions are possible.

25 ENERGY STORAGE↗

Porphyrin Aerogel Catalysts for Oxygen Reduction Reaction in Anion-Exchange Membrane Fuel Cells

Platinum group metal (PGM)-free catalysts for oxygen reduction reaction have shown high oxygen reduction reaction activity in alkaline media. In order to further increase the power density of anion-exchange membrane fuel cells (AEMFCs), PGM-free catalysts need to have a high site density to reach high current densities. In this work, synthesis, characterization, and utilization of heat-treated iron porphyrin aerogels are reported as cathode catalysts in AEMFCs. The heat treatment effect is thoroughly studied and characterized using several techniques, and the best performing aerogel is studied in AEMFC, showing excellent performance, reaching a peak power density of 580 mW cm –2 and a limiting current density of as high as 2.0 A cm –2 , which can be considered the state-of-the-art for PGM-free based AEMFCs.

25 ENERGY STORAGE↗

Understanding how single-atom site density drives the performance and durability of PGM-free Fe–N–C cathodes in anion exchange membrane fuel cells

One of the most important needs for the future of low-cost fuel cells is the development of highly active platinum group metal (PGM)-free catalysts. For the oxygen reduction reaction, Fe–N–C materials have been widely studied in both acid and alkaline media. However, reported catalysts in the literature show quite different intrinsic activity and in-cell performance, despite similar synthesis routes and precursors. Here, two types of Fe–N–C are prepared from the same precursor and procedure – the main difference is how the precursor was handled prior to use. It is shown that in one case Fe overwhelmingly existed as highly active single-metal atoms in FeN4 coordination (preferred), while in the other case large Fe particles coexisting with few single metal atoms were obtained. As a result, there were drastic differences in the catalyst structure, activity, and especially in their performance in an operating anion exchange membrane fuel cell (AEMFC). Additionally, it is shown that catalyst layers created from single-atom-dominated Fe–N–C can have excellent performance and durability in an AEMFC using H 2 /O 2 reacting gases, achieving a peak power density of 1.8 W cm -2 – comparable to similar AEMFCs with a Pt/C cathode – and being able to operate stably for more than 100 h. Finally, the Fe–N–C cathode was paired with a low-loading PtRu/C anode electrode to create AEMFCs (on H 2 /O 2 ) with a total PGM loading of only 0.135 mg cm -2 (0.090 mg Pt cm -2 ) that was able to achieve a very high specific power of 8.4 W mg PGM -1 (12.6 W mg Pt< sup>-1 ).

36 MATERIALS SCIENCE↗

Elucidating the degradation mechanisms of Pt-free anode anion-exchange membrane fuel cells after durability testing

The development of anion-exchange membrane fuel cells (AEMFCs) has recently accelerated due to synergistic improvements yielding highly conductive membranes, stable ionomers, and enhanced alkaline electrocatalysts. However, cell durability, especially under realistic conditions, still poses a major challenge. Herein, we employ low-loadings of Pt-free Pd-based catalysts in the anode of AEMFCs and elucidate potential degradation mechanisms impacting long-term performance under conditions analogous to the real-world (high current density, H 2 –air (albeit CO 2 -free), and intermittent operation). Our high-performing AEMFCs achieve impressive performance with power densities approaching 1 W cm —2 and current densities up to 3.5 A cm —2 . Over a 200 h period of continuous operation in H 2 –air at a current density of 600 mA cm —2 , our model Pd/C–CeO 2 anode cell exhibits record stability (~30 μV h —1 degradation) compared to the literature and up to 6× better stability than our Pd/C and commercial Pt/C anode cells. Following an 8 h shutdown, the Pd/C–CeO 2 anode cell was restarted and continued for an additional 300 h with a higher degradation rate of ~600 μV h —1 . Thorough in situ evaluations and post-stability analyses provide insights into potential degradation mechanisms to be expected during extended operation under more realistic conditions and provide mitigation strategies to enable the widespread development of highly durable AEMFCs.

08 HYDROGEN↗

Hydrogenated TiO 2 Carbon Support for PtRu Anode Catalyst in High‐Performance Anion‐Exchange Membrane Fuel Cells

Abstract The availability of durable, high‐performance electrocatalysts for the hydrogen oxidation reaction (HOR) is currently a constraint for anion‐exchange membrane fuel cells (AEMFCs). Herein, a rapid microwave‐assisted synthesis method is used to develop a core–shell catalyst support based on a hydrogenated TiO 2 /carbon for PtRu nanoparticles (NPs). The hydrogenated TiO 2 provides a strong metal‐support interaction with the PtRu NPs, which improves the catalyst's oxophilicity and HOR activity compared to commercial PtRu/C and enables greater size control of the catalyst NPs. The as‐synthesized PtRu/TiO 2 /C‐400 electrocatalyst exhibits respectable performance in an AEMFC operated at 80 °C, yielding the highest current density (up to 3× higher) within the catalytic region (compared at 0.80–0.90 V) and voltage efficiency (68%@ 0.5 A cm −2 ) values in the compared literature. In addition, the cell demonstrates promising short‐term voltage stability with a minor voltage decay of 1.5 mV h −1 . This “first‐of‐its‐kind in alkaline” work may open further research avenues to develop rapid synthesis methods to prepare advanced core–shell metal‐oxide/carbon supports for electrocatalysts for use in the next‐generation of AEMFCs with potential applicability to the broader electrochemical systems research community.

08 HYDROGEN↗

Effect of reacting gas flowrates and hydration on the carbonation of anion exchange membrane fuel cells in the presence of CO 2

Anion exchange membrane fuel cells (AEMFCs) have been widely touted as a low-cost alternative to existing proton exchange membrane fuel cells. However, one of the limitations of this technology has been the severe performance penalty related to the introduction of CO 2 to the cell – typically in the air cathode feed. Introduction of CO 2 into AEMFCs results in cell carbonation, which imparts thermodynamic, kinetic and Ohmic overpotentials that can add up to hundreds of millivolts. Therefore, it is important to find strategies and operational protocols for AEMFCs that minimize these overpotentials. In this paper, we reserach the impacts of the anode and cathode flowrate, as well as the cell hydration level, on the extent of cell carbonation and cell polarization. Key findings include: (1) decreasing the cathode flowrate generally decreases the total CO 2 -related voltage loss while changing the anode flowrate has a minimal effect; (2) increasing cell hydration helps to mitigate the performance loss in the presence of CO 2 ; and (3) operational combinations are found that significantly reduce the CO 2 penalty compared to the present literature.

25 ENERGY STORAGE↗

High-performing commercial Fe–N–C cathode electrocatalyst for anion-exchange membrane fuel cells

Here, to reduce the cost of fuel cell stacks and systems, it is important to create commercial catalysts that are free of platinum group metals (PGMs). To do this, such catalysts must have very high activity, but also have the correct microstructure to facilitate the transport of reactants and products. Here, we show a high-performing commercial oxygen reduction catalyst that was specifically developed for operation in alkaline media and is demonstrated in the cathode of operating anion-exchange membrane fuel cells (AEMFCs). With H 2 /O 2 reacting gases, AEMFCs made with Fe–N–C cathodes achieved a peak power density exceeding 2 W cm –2 (>1 W cm –2 with H 2 /air) and operated with very good voltage durability for more than 150 h. These AEMFCs also realized an iR-corrected current density at 0.9 V of 100 mA cm –2 . Finally, in a second configuration, Fe–N–C cathodes paired with low-loading PtRu/C anodes (0.125 mg PtRu per cm 2 , 0.08 mg Pt per cm 2 ) demonstrated a specific power of 10.4 W per mg PGM (16.25 W per mg Pt).

25 ENERGY STORAGE↗

Probing Anion Exchange Membrane Fuel Cell Cathodes by Varying Electrocatalysts and Electrode Processing

To date, several high-performing anion exchange membrane fuel cells (AEMFCs) have been demonstrated, but most these studies have focused on Pt containing cathodes with high loadings. Here, we explore and compare the performance and perform electrochemical diagnostics on three leading AEMFC cathode electrocatalysts: Pt/C, Ag/C, and Fe–N–C with electrodes that have been processed with either powder or dispersion-based ionomers using perfluorinated anion exchange polymers. Pt/C had the highest performance but also showed a strong dependence on ionomer type, with powder ionomer exhibiting much higher performance. These results were consistent with the observations for Ag/C but did not hold for the Fe–N–C catalyst where almost no change was observed between powder and dispersion-based ionomers. This is the first-time the impact of powder and dispersion ionomer with different classes of cathode electrocatalysts on the fuel cell performance have been compared, and the results have strong implications for the ability to achieve high performance at low loadings and for better understanding catalyst-ionomer interactions within AEMFCs.

30 DIRECT ENERGY CONVERSION↗

Migration and Precipitation of Platinum in Anion‐Exchange Membrane Fuel Cells

Abstract Despite the recent progress in increasing the power generation of Anion‐exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X‐ray micro‐computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X‐ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt +2 ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical “Pt line” within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo−N−C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.

Raut, Aniket↗

Migration and Precipitation of Platinum in Anion–Exchange Membrane Fuel Cells

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt+2 ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical “Pt line” within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Furthermore, diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo–N–C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

30 DIRECT ENERGY CONVERSION↗

Electronic structure and oxophilicity optimization of mono-layer Pt for efficient electrocatalysis

The slow kinetics of the anodic hydrogen oxidation reaction (HOR) in alkaline medium is one of the limitations for anion exchange membrane fuel cells (AEMFCs). Hence, accurately regulate and understand catalytic interface structure are essential to solve this bottleneck and reveal the structure-activity relationship. In this work, a novel trimetal core-shell model with mono-layer Pt-shell is employed for hydrogen electrooxidation to avoid thermodynamic driven bulk/surface composition deviation. On account of the atomic radius discrepancies of 3d-transition metals M (M = Fe, Co and Cu), the electronic structure of mono-layer Pt is regulated by the strain-engineered Pd-M core and the electrocatalytic activity for HOR is tuned accordingly. Nevertheless, step-by-step electrochemical monitoring and surface-treatment experiments indicate that the oxophilicity optimization by low-valence M(OH) x species, rather than the hydrogen binding energy (HBE) optimization caused by strain engineering, influence the activity obviously. It is mainly derived from the enhanced adsorption of OH ad and accelerated desorption of the H ad . The trimetal core-shell model breathes new life into the low-Pt catalyst design for hydrogen electrooxidation reaction.

77 NANOSCIENCE AND NANOTECHNOLOGY↗