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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.

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At least 109 records · Page 6

Gas Permeability Test Protocol for Ion-Exchange Membranes

The membrane-based electrolysis of water is a growing topic of interest due to the advantages of employing membranes in hydrogen production efficiency and system safety over the traditional alkaline water electrolysis. Ion-exchange membranes with low gas permeability are highly desirable for stable and safe operation of membrane-based water-splitting technologies, hence gas permeability through ion-exchange membranes needs to be properly assessed with standardized methods. We addressed three methods to measure gas permeability of ion-exchange membranes, a pressure permeation cell, chronoamperometry microelectrodes, and in situ testing of the membrane electrode assembly, and provide a guideline for choosing the appropriate method for the targeted operating conditions of the water electrolyzers.

08 HYDROGEN↗

Ionomer Optimization for Water Uptake and Swelling in Anion Exchange Membrane Electrolyzer: Oxygen Evolution Electrode

Water electrolysis using an anion conductive, solid polymer electrolyte is an attractive method for point-of-use hydrogen production. Recent advances in catalysts and anion exchange membranes (AEM) have made alkaline devices increasingly competitive with their acidic counterparts. However, less attention has been paid to the anion conductive ionomers (ACI) used in the fabrication of electrodes for AEM electrolyzers. The ACI contributes to ion conduction between the catalyst and bulk electrolyte and serves as a binder for adhering the catalyst to the gas diffusion layer and AEM. Ionic conductivity, water uptake and ionomer swelling are critical properties for electrode performance. High ion exchange capacity (IEC) in the ionomer is desired for reduced electrode resistance, however, it can lead to excess water uptake (WU) and disruptive ACI swelling. In this study, a series of poly(norbornene)-based ionomers were synthesized, characterized and used to fabricate oxygen evolving anodes for low-temperature AEM water electrolysis. The IEC of the ionomers (0 to 4.73 meq g −1 ) was adjusted by controlling the ratio of ion conducting to non-ion conducting norbornene monomers in the ACI tetrablock copolymers. Low conductivity ionomers are shown to yield the best-performing oxygen evolution electrodes, in the absence of ACI polymer cross-linking because they do not experience excessive water swelling. Light cross-linking within the anode ACI was used as a means to independently lower WU of the ionomer without compromising ionic conductivity. This control over water swelling allows higher ionic conductivity within the ACI to be used in water-fed electrolyzer applications. Other methods of water management were compared including the use of hydrophobic additives and adjustment of the ionomer concentration in the electrode. As a result, it was shown that the cell performance greatly benefits from a highly conductive ionomer in the oxygen evolution reaction electrode if the WU is managed.

08 HYDROGEN↗

Improving durability and performance of solid oxide electrolyzers by controlling surface composition on oxygen electrodes

Solid oxide electrolysis cell (SOEC) is a promising technology for high-efficiency energy conversion, enabling the production of hydrogen, syngas, synthetic fuels, and various commodity chemicals. Unlike traditional thermochemical processes, SOECs operate at elevated temperatures (600-850°C), benefiting from favorable thermodynamics and reaction kinetics. This makes them highly energy efficient compared to alkaline or polymer electrolyte membrane (PEM) electrolysis technologies. However, despite these advantages, SOECs face significant challenges related to performance degradation over time. A primary issue is the degradation of the oxygen electrode due to strontium (Sr) segregation and impurity poisoning from chromium (Cr) and sulfur (S). This is because the pathway to deposition of Cr and S include the reaction of Cr and S with the segregated SrO at the surface. Sr segregation leads to the formation of insulating compounds such as SrCrO4 and SrSO4, which block active sites, reduce oxygen exchange rates, and compromise the electrode's electrochemical stability. The degradation mechanisms involve complex interactions between the electrode material's surface chemistry, microstructure, and the operating environment. Sr segregation is particularly problematic because it facilitates the deposition of Cr and S impurities, exacerbating performance losses. Addressing these issues is critical to enhancing the durability and economic viability of SOEC technology. The primary goal of this project is to improve the durability and performance of SOECs by controlling the surface composition of the oxygen electrode. This is achieved by suppressing Sr segregation, thereby mitigating impurity poisoning pathways. The project aims to enhance the oxygen exchange rate, improve cell stability, and extend the operational lifespan of SOECs without necessitating major changes to electrode chemistry or stack components.

30 DIRECT ENERGY CONVERSION↗

Advanced fuel cell concepts for future NASA missions

Studies of primary fuel cells for advanced all electric shuttle type vehicles show an all fuel cell power system with peak power capability of 100's of kW to be potentially lighter and have lower life cycle costs than a hybrid system using advanced H2O2 APU's for peak power and fuel cells for low power on orbit. Fuel cell specific weights of 1 to 3 lb/kW, a factor of 10 improvement over the orbiter power plant, are projected for the early 1990's. For satellite applications, a study to identify high performance regenerative hydrogen oxygen fuel cell concepts for geosynchronous orbit was completed. Emphasis was placed on concepts with the potential for high energy density (Wh/lb) and passive means for water and heat management to maximize system reliability. Both alkaline electrolyte and polymer membrane fuel cells were considered.

Stedman, J. K.↗

Electrochemical energy storage using PEM systems

Results of an engineering assessment for future, long lived space power systems for extraterrestrial applications are given. Solar based, regenerative fuel cell power plants formed from either alkaline or Polymer Exchange Membrane (PEM) components are the focus. Test results on advanced PEM fuel cell stack components are presented.

Vanderborgh, N. E.↗

Recovery of high-quality calcium phosphate fertilizer products from anaerobic membrane bioreactor treated swine wastewater

The aim of this study is the sustainable recovery of phosphorus as high-quality calcium phosphate from anaerobic membrane bioreactor treated swine permeate for targeted use as fertilizer or raw material for the fertilizer industry. Phosphorus removal efficiencies from treated swine permeate were evaluated by adding various calcium/phosphorus molar ratios ranging from 1/1 to 12/1. Results showed that removal efficiencies were inconsistent in duplicate trials at the same calcium doses (maximum P removal 93% in Trial 1 and <20% removal in Trial 2). The variability in P removal was due to the high bicarbonate alkalinity of the swine permeate, which buffered the system and thereby prevented it from reaching alkaline pH conditions ideal for P removal. Total alkalinity and initial solution pH had the greatest impact on P removal and caused unintended precipitation of non-specific calcium minerals (Calcite). Further, the carbonate alkalinity from the permeate was removed using process modifications that included acid addition and aeration for removal as CO 2 . Carbonate removal resulted in 97% P removal with increased total P content (11.8% P) in the final product and better solubility. Additional COD removal was also observed during the flocculation process.

09 BIOMASS FUELS↗

La–Sr–Co oxide catalysts for oxygen evolution reaction in anion exchange membrane water electrolyzer: The role of electrode fabrication on performance and durability

Anion exchange membrane water electrolysis is an attractive technology for low-cost generation of “green” hydrogen by combining the use of noble metal-free catalysts with pure water feed. By thus addressing main drawbacks of the liquid alkaline electrolysis and proton exchange membrane water electrolysis, anion exchange membrane water electrolysis stands an excellent chance of replacing the two technologies. The development of active and stable platinum group metal (PGM)-free catalysts for oxygen evolution reaction (OER) is crucial for making anion exchange membrane water electrolyzers (AEMWEs) practical. For this work, we synthesized, characterized and tested two La–Sr–Co oxide-based OER catalysts. First, we characterized the catalysts by XRD, SEM, and N 2 physisorption and assessed their OER activity in a three-electrode cell. Next, we focused on electrode fabrication, demonstrating the importance of catalyst-ink application to the porous transport layers (PTLs) and a key role of adding a binder to the catalyst ink to prevent the catalyst detachment from the PTL in pure water. We tested three membrane electrode assemblies prepared using different formulations of the anode catalyst ink. The results show that the optimum ink formulation is essential for the performance on pure-water feed by maximizing OH - conductivity of the catalyst layer and catalyst-membrane interface.

47 OTHER INSTRUMENTATION↗

Self-Adhesive Ionomers for Alkaline Electrolysis: Optimized Hydrogen Evolution Electrode

Hydrogen produced through low-temperature water electrolysis using anion exchange membranes (AEM) combines the benefits of liquid-electrolyte alkaline electrolysis and solid-polymer proton exchange membrane electrolysis. The anion conductive ionomers in the oxygen-producing anode and hydrogen-producing cathode are a critical part of the three-dimensional electrodes. The ionomer in the hydrogen-producing cathode facilitates hydroxide ion conduction from the cathode catalyst to the anode catalyst, and water transport from the anode to the cathode catalyst through the AEM. This ionomer also binds the catalyst particles to the porous transport layer. Here in this study, the cathode durability was improved by use of a self-adhesive cathode ionomer to chemically bond the cathode catalyst particles to the porous transport layer. It was found that the cathode ionomers with high ion exchange capacity (IEC) were more effective than low IEC ionomers because of the need to transport water to the cathode catalyst and transport hydroxide away from the cathode. The cathode durability was improved by using ionomers which were soluble in the spray-coated cathode ink. Optimization of the catalyst and ionomer content within the cathode led to electrolysis cells which were both mechanically durable and operated at low voltage.

08 HYDROGEN↗

Cyclic olefin copolymer-based reinforced anion exchange membranes for water electrolyzers

Anion exchange membranes (AEMs) have emerged as a promising technology for water electrolysis in hydrogen production since they offer significant cost reduction in choices of electrocatalysts and bipolar plates. However, AEMs satisfying multiple requirements of high ionic conductivity, good chemical stability, robust mechanical properties, scalable synthesis, and low manufacturing costs are rare. Herein, we introduce quaternary ammonium functionalized cyclic olefin copolymers (COCs) as a new class of chemically stable and low-cost AEM materials. To further enhance the mechanical robustness, we prepared reinforced composite AEMs by impregnating the ionically functionalized COC into a mechanically robust matrix. The resulting reinforced composite membrane exhibits a high hydroxide conductivity of 127 mS cm −1 and excellent mechanical strength. In water electrolyzers, the MEA demonstrated outstanding performance, achieving a current density of 2.24 A cm −2 at 1.8 V, attributable to high conductivity, enhanced mechanical properties, and good alkaline stability of the composite membrane. These results indicate that the COC-based AEMs demonstrate good potential for application in AEM electrolyzers.

08 HYDROGEN↗

Reports from the Frontier: Understanding Voltage Losses in Anion Exchange Membrane Water Electrolyzers

With the growth of renewable energy sources, hydrogen is attracting significant attention worldwide as an effective medium for energy storage. “Green hydrogen” is currently produced primarily by water electrolysis in which water is split into hydrogen and oxygen using power from low-carbon energy sources such as wind, solar, and nuclear. Among the low temperature water electrolysis technologies, anion exchange membrane water electrolyzers (AEMWEs) have recently emerged as a promising competitor to traditional alkaline water electrolyzers (AWEs) and proton exchange membrane electrolyzers (PEMELs) due to their potential stack cost reduction in various cell components. In conclusion, favorable aspects of AEMWEs include the use of PGM-free electrocatalysts as well as low-cost membranes, bipolar plates (BPs), and porous transport layers while offering high voltage efficiency and durability.

08 HYDROGEN↗

Influence of Supporting Electrolyte on Hydroxide Exchange Membrane Water Electrolysis Performance: Anolyte

Hydroxide-exchange-membrane water electrolysis (HEMWE) is an emerging hydrogen-production pathway that combines many advantages of incumbent alkaline water electrolysis (AWE) and proton-exchange-membrane water electrolysis (PEMWE). Advancement in HEMWE has been accelerated with the development of stable and conductive hydroxide exchange membranes (HEMs) and a more comprehensive understanding of alkaline gas-evolving kinetics. However, performance and durability without supporting electrolytes (SELs) remain inferior to PEMWE and AWE and little is known about the role and impact of the SELs. This study investigates the effects of SELs used as anolyte solutions in HEMWEs including cation-type, anion-type, SEL conductivity and pH, presence of carbonates and increased cation/OH- ratios on cell voltage and stability. We report our findings that (i) cell potential and high-frequency resistance did not correlate with anolyte SEL conductivity, (ii) cation-type influences cell voltage at low current densities (<50 mA cm -2 ) as predicted by half-cell measurements, (iii) increased cation/OH- ratio causes increased overpotentials, and (iv) carbonates are exchanged in the HEM but removed via self-purging at high current density. Overall, this study concludes that concentrated KOH is still the best SEL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of CO 2 -Regenerative Film Properties in Enhancing C 2+ Products Selectivity While Mitigating CO 2 Crossover

Zero-gap anion-exchange membrane electrode assembly (AEMEA) electrolyzers operating in alkaline media face challenges such as CO 2 crossover and salting-out. The bipolar membrane electrode assembly (BPMEA) electrolyzer, using DI water as the electrolyte, addresses both CO 2 crossover and salting-out issues. As cations, which are crucial in stabilizing the CO 2 R intermediates, are absent in the electrolyte, cations embedded in the AEM play an important role in dictating the CO 2 R selectivity and activity in BPMEA systems. So far, no systematic study has been conducted on the influence of cations embedded in AEMs on CO 2 selectivity and activity in BPMEA systems. Moreover, BPMEA systems impose an additional challenge: low stability due to delamination of the bipolar membrane caused by CO 2 regeneration at the membrane-membrane interface. To enhance the stability of the electrolyzer, a simple yet highly reproducible strategy for coating a porous CO 2 regenerative film on smooth Nafion 117 is demonstrated in this work, along with a systematic study of four different commercially available AEMs, composed of different cations and cation densities, for use in combination with Nafion 117 and copper catalyst at the cathode. We found that the PiperION membrane delivers selectivity and activity comparable to those of alkali-metal cations, owing to the enhanced local electric field resulting from the combined effects of a high positive charge on the N atom of the piperidinium cation and the high ion-exchange capacity. Further, we studied the influence of the thickness of the PiperION porous layer over Nafion 117 on CO 2 R selectivity and found that 70 μm is the minimum thickness to achieve maximum C 2+ products selectivity, reduced the CO 2 crossover to 5% from 25% at 4 SCCM and 150 mA cm –2 , and was stable for operation beyond 100 h. The selectivity of this system, compared with AEMEA, and stability outperformed both AEMEA and BPMEA. This study helps design more effective BPMs to inhibit CO 2 crossover while enabling stable and selective electrochemical CO 2 reduction to C 2+ hydrocarbons.

Cations↗

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↗

LTE-P-22 Alkaline Stability of AEMs

A procedure for ex-situ evaluation of chemical (alkaline) stability of anion exchange membranes (AEM). The IEC and ionic conductivity of an AEM is measured before and after being heated (typically at 80C in 1 M KOH) for ~1000 hours.

AEM↗

Thermal management of advanced fuel cell power systems

It is shown that fuel cell devices are particularly attractive for the high-efficiency, high-reliability space hardware necessary to support upcoming space missions. These low-temperature hydrogen-oxygen systems necessarily operate with two-phase water. In either PEMFCs (proton exchange membrane fuel cells) or AFCs (alkaline fuel cells), engineering design must be critically focused on both stack temperature control and on the relative humidity control necessary to sustain appropriate conductivity within the ionic conductor. Water must also be removed promptly from the hardware. Present designs for AFC space hardware accomplish thermal management through two coupled cooling loops, both driven by a heat transfer fluid, and involve a recirculation fan to remove water and heat from the stack. There appears to be a certain advantage in using product water for these purposes within PEM hardware, because in that case a single fluid can serve both to control stack temperature, operating simultaneously as a heat transfer medium and through evaporation, and to provide the gas-phase moisture levels necessary to set the ionic conductor at appropriate performance levels. Moreover, the humidification cooling process automatically follows current loads. This design may remove the necessity for recirculation gas fans, thus demonstrating the long-term reliability essential for future space power hardware.

Vanderborgh, N. E.↗

Graphene-transition metal catalyst for hydrogen evolution reaction

Functionalized catalysts for use in a hydrogen evolution reaction (HER) contain nanoparticles containing a transition metal enveloped in layers of graphene, which renders the nanoparticles resistant to passivation while maintaining an optimal ratio of transition metal and transition metal oxide in the nanoparticles. The catalysts can be utilized with anionic exchange polymer membranes for hydrogen production by alkaline water electrolysis.

Mukerjee, Sanjeev↗

Quaternized polyaromatics for use in electrochemical devices

Disclosed herein in various embodiments are aryl-ether free polyaromatic polymers based on random copolymer architecture with two, three, or more aromatic ring components and methods of preparing those polymers. The polymers of the present disclosure can be used as ion exchange membranes, e.g., as anion exchange membranes, and ionomer binders in alkaline electrochemical devices.

Bae, Chulsung↗

Bipolar membrane polarization behavior with systematically varied interfacial areas in the junction region

The palette of applications for bipolar membranes (BPMs) has expanded recently beyond electrodialysis as they are now being considered for fuel cell and electrolysis applications. Their deployment in emerging electrochemical technologies arises from the need to have a membrane separator that provides disparate pH environments and to prevent species crossover. Most materials research for BPMs has focused on water dissociation catalysts and less emphasis has been given to the design of the polycation–polyanion interface for improving BPM performance. Here, soft lithography fabricated a series of micropatterned BPMs with precise control over the interfacial area in the bipolar junction. Polarization experiments showed that a 2.28× increase in interfacial area led to a 250 mV reduction in the onset potential. Additionally, the same increase in interfacial area yielded marginal improvements in current density due to the junction region being under kinetics-diffusion control. A simple physics model based on the electric field of the junction region rationalized the reduction in the overpotential for water dissociation as a function of interfacial area. Finally, the soft lithography approach was also conducive for fabricating BPMs with different chemistries ranging from perfluorinated polymer backbones to alkaline stable poly(arylene) hydrocarbon polymers. These polymer chemistries are better suited for fuel cell and electrolysis applications. The BPM featuring the alkaline stable poly(terphenyl) anion exchange membrane had an onset potential of 0.84 V, which was near the thermodynamic limit, and was about 150 mV lower than a commercially available variant.

25 ENERGY STORAGE↗