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At least 163 records · Page 9

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DOE OSTI2022

Three-Electrode Study of Electrochemical Ionomer Degradation Relevant to Anion-Exchange-Membrane Water Electrolyzers

Among existing water electrolysis (WE) technologies, anion-exchange-membrane water electrolyzers (AEMWEs) show promise for low-cost operation enabled by the basic solid-polymer electrolyte used to conduct hydroxide ions. The basic environment within the electrolyzer, in principle, allows the use of non-platinum-group metal catalysts and less-expensive cell components compared to acidic-membrane systems. Nevertheless, AEMWEs are still underdeveloped, and the degradation and failure modes are not well understood. To improve performance and durability, supporting electrolytes such as KOH and K 2 CO 3 are often added to the water feed. The effect of the anion interactions with the ionomer membrane (particularly other than OH – ), however, remains poorly understood. We studied three commercial anion-exchange ionomers (Aemion, Sustainion, and PiperION) during oxygen evolution (OER) at oxidizing potentials in several supporting electrolytes and characterized their chemical stability with surface-sensitive techniques. We analyzed factors including the ionomer conductivity, redox potential, and pH tolerance to determine what governs ionomer stability during OER. Specifically, we discovered that the oxidation of Aemion at the electrode surface is favored in the presence of CO 3 2– /HCO 3 – anions perhaps due to the poor conductivity of that ionomer in the carbonate/bicarbonate form. Sustainion tends to lose its charge-carrying groups as a result of electrochemical degradation favored in basic electrolytes. PiperION seems to be similarly negatively affected by a pH drop and low carbonate/bicarbonate conductivity under the applied oxidizing potential. Furthermore, the insight into the interactions of the supporting electrolyte anions with the ionomer/membrane helps shed light on some of the degradation pathways possible inside of the AEMWE and enables the informed design of materials for water electrolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Morphology and Transport of Multivalent Cation-Exchanged Ionomer Membranes Using Perfluorosulfonic Acid–Ce Z+ as a Model System

Perfluorosulfonic acids (PFSAs) are commonly used as solid polymer electrolyte membranes (PEMs) in electrochemical energy devices, where they are vulnerable to attack by radical species during operation. A popular strategy to combat this problem is to introduce radical scavengers like cerium (Ce) ions that neutralize these species before they attack the PFSA. Such cation doping creates a multi-ion system, in which understanding the mechanisms of cation solvation and transport becomes important for the effective design and utilization of PFSA–cation systems. Ce ions also provide a representative model system for multication-exchanged ionomers in electrochemical systems. In this study, hydration and conductivity measurements, along with X-ray fluorescence and scattering, are employed to elucidate how Ce ion exchange alters PFSA’s ionic solvation, as well as nano- and mesoscale morphologies, which ultimately control its ion transport properties. A molecular transport model is used to deconvolute the impact of Ce ions on the local solvation structure of water in the membrane from mesoscale changes of the transport pathways. The combined experimental and theoretical analysis reveals a nonlinear decrease in conductivity driven by cation solvation at the molecular level and morphological changes at longer length scales. Migration–diffusion coupling, its nonlinear dependence on ion exchange and hydration, and its overall implications for ionomer performance are also discussed. Finally, these findings have the potential to be translated into other mixed cation–ionomer systems for a wide range of energy and environmental devices.

36 MATERIALS SCIENCE↗

DOE OSTI2020

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↗

DOE OSTI2024

Effect of Zwitterionic Additives on Solvation and Transport of Sodium and Potassium Cations in (Ethylene Oxide)10: A Molecular Dynamics Simulation Study

Sodium- (Na + ) and potassium- (K + ) ion batteries are cost-effective alternatives to lithium-ion (Li + ) batteries due to the abundant sodium and potassium resources. Solid polymer electrolytes (SPEs) are essential for safer and more efficient Na + and K + batteries because they often exhibit low ionic conductivity at room temperature. While zwitterionic (ZW) materials enhance Li+ battery conductivity, their potential for Na + and K + transport in batteries remains unexplored. In this study, we investigated the effect of three ZW molecules (ChoPO4, i.e., 2-methacryloyloxyethyl phosphorylcholine, ImSO3, i.e., sulfobetaine ethylimidazole, and ImCO2, i.e., carboxybetaine ethylimidazole) on the dissociation of Na + and K + coordination with ethylene oxide (EO) chains in EO-based electrolytes through molecular dynamics simulations. Our results showed that ChoPO4 possessed the highest cation–EO10 dissociation ability, while ImSO3 exhibited the lowest. Such dissociation ability correlated with the cation–ZW molecule coordination strength: ChoPO4 and ImSO3 showed the strongest and the weakest coordination with cations. However, the cation–ZW molecule coordination could slow the cationic diffusion. The competition of these effects resulted in accelerating or decelerating cationic diffusion. Our simulated results showed that ImCO2 enhanced Na + diffusion by 20%, while ChoPO4 and ImSO3 led to a 10% reduction. For K + , ChoPO4 reduced its diffusion by 40%, while ImCO2 and ImSO3 caused a similar decrease of 15%. These findings suggest that the ZW structure and the cationic size play an important role in the ionic dissociation effect of ZW materials.

25 ENERGY STORAGE↗

NASA NTRS1971

Fuel cell technology program

The results of a solid polymer electrolyte fuel cell development program are summarized. A base line design was defined, and materials and components of the base line configuration were fabricated and tested. Concepts representing base line capability extensions in the areas of life, power, specific weight and volume, versatility of operation, field maintenance, and thermal control were identified and evaluated. Liaison and coordination with space shuttle contractors resulted in the exchange of engineering data.

Source record↗

NASA NTRS1973

Cost analysis of oxygen recovery systems

Report is made of the cost analysis of four leading oxygen recovery subsystems which include two carbon dioxide reduction subsystems and two water electrolysis subsystems, namely, the solid polymer electrolyte and the circulating KOH electrolyte. The four oxygen recovery systems were quantitatively evaluated. System characteristics, including process flows, performance, and physical characteristics were also analyzed. Additionally, the status of development of each of the systems considered and the required advance technology efforts required to bring conceptual and/or pre-prototype hardware to an operational prototype status were defined. Intimate knowledge of the operations, development status, and capabilities of the systems to meet space mission requirements were found to be essential in establishing the cost estimating relationships for advanced life support systems.

Yakut, M. M.↗

NASA NTRS1973

Cost analysis of oxygen recovery systems

The design and development of equipment for flight use in earth-orbital programs, when optimally approached cost effectively, proceed through the following logical progression: (1) bench testing of breadboard designs, (2) the fabrication and evaluation of prototype equipment, (3) redesign to meet flight-imposed requirements, and (4) qualification and testing of a flight-ready system. Each of these steps is intended to produce the basic design information necessary to progress to the next step. The cost of each step is normally substantially less than that of the following step. An evaluation of the cost elements involved in each of the steps and their impact on total program cost are presented. Cost analyses of four leading oxygen recovery subsystems which include two carbon dioxide reduction subsystem, Sabatier and Bosch, and two water electrolysis subsystems, the solid polymer electrolyte and the circulating KOH electrolyte are described.

Yakut, M. M.↗

NASA NTRS1972

Fuel cell ion-exchange membrane investigation

The present deficiencies in the fluorocarbon sulfonic acid membrane used as the solid polymer electrolyte in the H2/O2 fuel cell are studied. Considered are: Adhesives selection, elastomeric formulations, scavenger exploration, and membrane characterization. The significant data are interpreted and recommendations are given for both short and long range further investigations in two of the four major areas: membrane adhesives and membrane stabilization.

Toy, M. S.↗

NASA NTRS1973

Atmosphere revitalization for manned spacecraft - An assessment of technology readiness

The level of proficiency attained by the most effective physical and chemical regenerative processes capable of providing a habitable atmospheric environment in a spacecraft is assessed. It is shown that both the Sabatier and Bosh reactions are in a mature stage of technological readiness and can effectively reduce the carbon dioxide in a spacecraft. An electrochemical method for concentrating CO2 from an air environment offers promise to approach low levels of pCO2 control. Technological advances in the fields of solid polymer electrolytes and oxygen evolution electrocatalysts have led to a water electrolysis system that can maintain efficient performance for several years. Nitrogen supply and control of the composition of the spacecraft atmosphere is effectively provided by the circulating electrolyte technique.

Samonski, F. H., Jr.↗

NASA NTRS1975

Design and test status for life support applications of SPE oxygen generation systems

An advanced six-man rated oxygen generation system has been fabricated and tested as part of a NASA/JSC technology development program for a long lived, manned spacecraft life support system. Details of the design and tests results are presented. The system is based on the Solid Polymer Electrolyte (SPE) water electrolysis technology and its nominal operating conditions are 2760 kN/sq m (400 psia) and 355 K (180 F) with an electrolysis module current density capability up to 350 mA/sq cm (326 ASF). The system is centered on a 13-cell SPE water electrolysis module having a single cell active area of 214 sq cm (33 sq in) and it incorporates instrumentation and controls for single pushbutton automatic startup/shutdown, component fault detection and isolation, and self-contained sensors and controls for automatic safe emergency shutdown. The system has been tested in both the orbital cyclic and continuous mode of operation. Various parametric tests have been completed to define the system capability for potential application in spacecraft environmental systems.

Titterington, W. A.↗

NASA NTRS1975

Electrochemical oxygen concentrator as an oxygen compressor

A solid polymer electrolyte (SPE) oxygen compressor is described which generates pressures of 3000 psi. The SPE is a cation exchange membrane with chemical compatibility, and has the capability of withstanding 5000 psi. Other features of the compressor described include: gasketless sealing, porus plate cell supports, and conductive cooling. Results are presented of a computer program which defines the power of the system as a function of density, temperature, pressure, membrane thickness, and water content.

Source record↗

NASA NTRS1977

The 100 kW space station

Solar array power systems for the space construction base are discussed. Nickel cadmium and nickel hydrogen batteries are equally attractive relative to regenerative fuel cell systems at 5 years life. Further evaluation of energy storage system life (low orbit conditions) is required. Shuttle and solid polymer electrolyte fuel cell technology appears adequate; large units (approximately four times shuttle) are most appropriate and should be studied for a 100 KWe SCB system. A conservative NiH2 battery DOD (18.6%) was elected due to lack of test data and offers considerable improvement potential. Multiorbit load averaging and reserve capacity requirements limit nominal DOD to 30% to 50% maximum, independent of life considerations.

Mckhann, G.↗

NASA NTRS1983

Advanced Vehicle system concepts

Various nonpetroleum vehicle system concepts for passenger vehicles in the 1990's are being considered as part of the Advanced Vehicle (AV) Assessment at the Jet Propulsion Laboratory. The vehicle system and subsystem performance requirements, the projected characteristics of mature subsystem candidates, and promising systems are presented. The system candidates include electric and hybrid vehicles powered by electricity with or without a nonpetroleum power source. The subsystem candidates include batteries (aqueous-mobile, flow, high-temperature, and metal-air), fuel cells (phosphoric acid, advanced acids, and solid polymer electrolyte), nonpetroleum heat engines, advanced dc and ac propulsion components, power-peaking devices, and transmissions.

Hardy, K. S.↗

NASA NTRS1987

Status of commercial fuel cell powerplant system development

The primary focus is on the development of commercial Phosphoric Acid Fuel Cell (PAFC) powerplant systems because the PAFC, which has undergone extensive development, is currently the closest fuel cell system to commercialization. Shorter discussions are included on the high temperature fuel cell systems which are not as mature in their development, such as the Molten Carbonate Fuel Cell (MCFC) and the Solid Oxide Fuel Cell (SOFC). The alkaline and the Solid Polymer Electrolyte (SPE) fuel cell systems, are also included, but their discussions are limited to their prospects for commercial development. Currently, although the alkaline fuel cell continues to be used for important space applications there are no commercial development programs of significant size in the USA and only small efforts outside. The market place for fuel cells and the status of fuel cell programs in the USA receive extensive treatment. The fuel cell efforts outside the USA, especially the large Japanese programs, are also discussed.

Warshay, Marvin↗

NASA NTRS1987

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

Savinell, Robert F.↗

NASA NTRS1987

Status of commercial fuel cell powerplant system development

Warshay, Marvin↗

NASA NTRS1987

Performance evaluation of SPE electrolyzer for Space Station life support

An static water-vapor feed electrolyzer has been developed as a candidate for Space Station life-support oxygen generation. The five-cell electrolysis module has eliminated the need for phase separation devices, pumps, and deionizers by transporting only water vapor to the solid polymer electrolyte cells. The introduction of an innovative electrochemical hydrogen pump allows the use of low-pressure reclaimed water to generate gas pressures of up to 230 psia. The electrolyzer has been tested in a computer-controlled test stand featuring continuous, cyclic, and standby operation (including automatic shutdown with fault detection).

Erickson, A. C.↗

NASA NTRS1988

Hydrogen-bromine fuel cell advance component development

Advanced cell component development is performed by NASA Lewis to achieve improved performance and longer life for the hydrogen-bromine fuel cells system. The state-of-the-art hydrogen-bromine system utilizes the solid polymer electrolyte (SPE) technology, similar to the SPE technology developed for the hydrogen-oxygen fuel cell system. These studies are directed at exploring the potential for this system by assessing and evaluating various types of materials for cell parts and electrode materials for Bromine-hydrogen bromine environment and fabricating experimental membrane/electrode-catalysts by chemical deposition.

Charleston, Joann↗