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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Degradation of Anion Exchange Membranes by Cation Elimination: Impact on Water Uptake, Nanostructure, and Ionic Mobility

Anion exchange membranes (AEMs) are an attractive platform for fuel cell and electrolysis technologies since they enable the use of cheaper, nonplatinum group metal electrodes and components. However, the widespread adoption of AEM-based devices is limited by chemical degradation of the AEM in the highly alkaline medium of operation. Experimental studies report three major pathways of degradation, including substitution (S N 2), elimination (E2), and backbone cleavage. The decline in membrane performance is likely due to a cumulative effect of several pathways, which has proven to be difficult to disentangle through experiments. Here we use coarse-grained molecular simulations to isolate the impact of E2 degradation, where cationic sites are replaced by an alkene group, on AEM water uptake, nanoscale morphology, structure of the ion-conducting channels, water mobility, and ionic conductivity. Our studies focus on the well-studied model AEM polyphenylene oxide with tetraalkylammonium cationic sites (PPO-TMA). We find that about half of the hydrophobic groups resulting from the degradation retract into the hydrophobic domains of the membrane. The reduction in ion exchange capacity (IEC) and the hydrophobicity of the alkene groups decrease both the equilibrium water uptake (%WU) and the number of water molecules per cation (λ) of the membrane. Interestingly, the evolution of λ with the IEC seems to follow that of undegraded PPO-TMA membranes. Additionally, we ascribe this to the similarity between the structure of the degraded monomer and the neutral one in the polymer. We conclude that most of the performance losses originate in the lower hydration of the degraded membrane.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Quaternary Ammonium-Functionalized Poly(Arylene Ether Sulfone) Random Copolymers for Direct Air Capture

Direct air capture (DAC) is a promising tool for reducing CO 2 concentrations in the atmosphere and fighting climate change. We synthesized a series of quaternary ammonium (QA) functionalized poly(arylene ether sulfone) copolymers with varying mole fractions of charge content and demonstrated their potential as sorbents for DAC. Molecular weight analysis determined high monomer conversion was achieved in <6 h and relatively high molecular weights for all copolymer compositions. Thermal analysis revealed all polymers had degradation temperatures >240 °C and a single glass transition temperature (T g ); the T g decreased with an increase in ion exchange capacity (IEC). Fractional free volume and water uptake percentage increased and water contact angle decreased with the number of QA sites when compared to a neutral, commercially available polysulfone (Udel® P-1700 PSU). Next, the novel series of ammonium-functionalized copolymers exhibited a moisture-mediated capture and release of atmospheric CO 2 . When exposed to air containing 30% relative humidity the polymers captured CO 2 and the capacity increased with the IEC. When the relative humidity was increased to 95% the samples released the CO 2 . This study demonstrates a promising CO 2 DAC sorbent and highlights the possibility for continuous DAC with purpose-built free-standing membranes.

42 ENGINEERING↗
DOE OSTI2023

Morphology–Diffusivity Relationships in Fluorine-Free Random Terpolymers for Proton-Exchange Membranes

Here, using atomistic molecular dynamics simulations, we investigate the morphology and transport properties of a new family of fluorine-free terpolymers designed as proton-exchange membranes. Simulated random terpolymers consist of three monomers with a 5-carbon backbone with a phenylsulfonate, phenyl, or no pendant group and have ion exchange capacities (IECs) ranging from 1.06–4.14 mmol/g. At a hydration level of 9, cluster analysis reveals macrophase separation between water and terpolymers with IEC < 2.1 mmol/g and continuous, percolated hydrophilic and hydrophobic nanoscale domains at higher IECs. Channel width distribution analysis of the percolated morphologies revealed that more hydrophobic units produce less uniform channels. Decreasing the surface area per sulfonate group and increasing the fractal dimension of the hydrophilic domains correlate with increased water diffusivity, due to a more acidic interface and more isotropic water channels. Relative to the previously studied phenylsulfonate homopolymer, these terpolymers with lower IECs have only modestly lower water diffusion, and we anticipate other advantages related to processability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Water-Fed Hydroxide Exchange Membrane Electrolyzer Enabled by a Fluoride-Incorporated Nickel–Iron Oxyhydroxide Oxygen Evolution Electrode

Here, we have developed a dissolved oxygen and galvanic corrosion method to synthesize vertically aligned fluoride-incorporated nickel–iron oxyhydroxide nanosheet arrays on a compressed Ni foam as an efficient self-supported oxygen evolution electrode. It is integrated with poly(aryl piperidinium) hydroxide exchange membrane and ionomers with high ion exchange capacity into a hydroxide exchange membrane electrolyzer fed with pure water, which achieves a performance of 1020 mA cm –2 at 1.8 V and prevents the detachment of catalysts during continuous operation (>160 h at 200 mA cm –2 ). Furthermore, this work provides a potential pathway for massively producing low-cost hydrogen using intermittent renewable energy sources.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Effect of Sulfonation Level on the Percolated Morphology and Proton Conductivity of Hydrated Fluorine-Free Copolymers: Experiments and Simulations

Using all-atom molecular dynamics simulations and a variety of experimental methods, we previously reported on a linear polyethylene with pendant phenyl sulfonated groups precisely on every fifth carbon along the backbone. With increasing relative humidity this fluorine-free polymer self-assembled to form nanoscale water channels and exhibited exceptional proton conductivity. Expanding upon those findings, here we explore partially sulfonated random copolymers, referred to as p 5PhSH-Y. Using either acetyl sulfate or sulfuric acid, a wide range of sulfonation levels were prepared ( Y = 34−98%) corresponding to ion-exchange capacities (IEC) of 2.0−4.4 mmol/g. Combining experimental techniques and all-atom molecular dynamics simulations, we study the effect of Y on water uptake, nanoscale morphology, and the proton/water transport properties of p5PhSH- Y . The proton conductivity of p 5PhSH- Y increases with relative humidity and with Y and achieves values in excess of 0.1 S/cm. These high conductivities are attributed to high IEC and welldeveloped nanoscale percolated hydrophilic domains made possible by the flexible backbone. We quantitatively describe the nature of the water channels using the characteristic distance, channel width distribution, the area per sulfonate group at the hydrophilic/ hydrophobic interface, and the fractal dimension. Notably, the channel widths and the areas per sulfonate group are nominally independent of the level of sulfonation, while depending significantly on the level of hydration. The fractal dimension of the water channels correlates strongly with the water diffusion coefficients calculated from the molecular dynamics (MD) simulations. These findings demonstrate that the p 5PhSH- Y hydrocarbon copolymers can be modified to tune properties, particularly proton conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exploring CO 2 reduction and crossover in membrane electrode assemblies

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Crosslinked metallo-polyelectrolytes with enhanced flexibility and dimensional stability for anion-exchange membranes

High-performing anion-exchange membranes (AEMs) have attracted tremendous interest for applications in emerging energy storage and conversion devices. In this work, we present a strategy for the synthesis of crosslinked metallo-polyelectrolytes as mechanically flexible, dimensionally stable and ionically conductive AEMs. The water uptake and swelling ratio are suppressed remarkably by introducing a crosslinked polymeric network. The as-prepared membranes also exhibit excellent thermal stability. The phase-separated morphology allows rapid ion-transport with low water uptake at various temperatures. Specifically, a conductivity of 53.3 mS cm -1 at 80 °C was achieved with an ion exchange capacity of 1.07 mmol g -1 and a low swelling ratio of 13%.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Poly(norbornene) anion conductive membranes: homopolymer, block copolymer and random copolymer properties and performance

It has previously been shown that phase-separated block copolymers with non-ion conducting (hydrophobic) blocks and ion conducting (hydrophilic) blocks can form efficient ion conducting channels with high ionic mobility and conductivity. Block copolymers can provide a means for phase segregation and ion channel formation while homopolymers and random copolymers have been shown to have lower ion mobility. In this study, the properties of poly(norbornene) based anion exchange membranes (AEMs) comprising homopolymers, block copolymers, and random copolymers with high ion-exchange capacity (IEC) (3.48–4.55 meq. g -1 ) have been investigated and compared. The polymers were cross-linked with N,N,N',N'-tetramethyl-1,6-hexanediamine before casting the membranes to avoid excessive water swelling due to high water uptake. It was shown that high ionic conductivity can be achieved in both random copolymers and homopolymers even in the absence of microphase-separated structures. For example, the conductivity of a random copolymer was 194 mS cm -1 at 80 °C, which was comparable to the block copolymer, 201 mS cm -1 at 80 °C. The H 2 /O 2 fuel cell performance of random copolymer composite membranes showed a peak power density of 3.05 W cm -2 and peak current density of 7.85 A cm -2 at 80 °C compared to block copolymer membranes (peak power density of 3.21 W cm -2 and peak current density of 8.27 A cm -2 at 80 °C). It is more critical that high water transport be achieved in AEMs than achieving a phase-segregated morphology. Finally, the homopolymer, block copolymer, and random copolymer membranes showed <1.35% degradation after aging in 1 M NaOH at 80 °C for 1000 h.

08 HYDROGEN↗
DOE OSTI2022

Experimental Studies of Graphene-Coated Polymer Electrolyte Membranes for Direct Methanol Fuel Cells

The two main technical limitations of direct methanol fuel cells (DMFCs) are the slow kinetic reactions of the methanol oxidation reaction (MOR) in the anode and the crossing over of unreacted methanol through the proton exchange membrane (PEM). It is a common practice to use Nafion membranes as PEMs, which have high ion exchange capacity. However, Nafion-based membranes also have high fuel permeability, decreasing fuel utilization, and reducing the potential power density. This article focuses on using graphene-coated (Gr-coated) PEMs to reduce fuel crossover. Protons can permeate across graphene, and thus, it can be employed in various devices as a proton conductive membrane. Here, we report the efficiency of Gr-coated Nafions. We tested performance and crossover at three different temperatures with four different fuel concentrations and compared it to a Nafion PEM that underwent the same test conditions. We found that the adhesion of Gr on to PEMs is insufficient for prolonging fuel cell operation, resulting in Gr delamination at high temperatures and higher fuel crossover values compared to lower temperature testing. Furthermore, the results for 7.5M methanol fuel show a reduction of up to 25% in methanol crossover, translating to a peak power density that increases from 3.9 to 9.5 mW/cm 2 when using a Gr-coated PEM compared to a Nafion PEM at 30 °C.

25 ENERGY STORAGE↗
DOE OSTI2021

Editors’ Choice—Examining Performance and Durability of Anion Exchange Membrane Fuel Cells with Novel Spirocyclic Anion Exchange Membranes

A series of spirocyclic copolymer membranes with varying ion exchange capacities (IECs) were investigated to probe the impact of polymer properties on in situ fuel cell performance and stability. In-situ electrochemical tests and post-mortem electron microscopy analysis of cross-sectioned membrane electrode assemblies (MEAs) have been combined with voltage loss breakdown analysis to evaluate the performance and degradation of different MEAs, and to probe the catalyst morphology and electrode structure at different stages of operation. Voltage loss breakdown results show that membrane degradation and kinetic losses played only a minor role in observed performance degradation and that performance losses were primarily related to increasing mass transport losses. From microscopy studies, carbon corrosion and Pt nanoparticle growth were identified at both the cathode and anode although more pronounced on the cathode resulting in significant structural changes. The membrane with the lowest IEC (1.3 mmolg −1 ) demonstrated the lowest peak power density ~ 1.16 W cm −2 , however, it showed the most stable performance (constant 0.6 A cm −2 hold) with ~ 5% degradation over 540 h. Isolation of performance losses and microscopic analysis of electrodes for anion exchange membrane fuel cells has not been reported previously, and these results help identify critical performance degradation concerns.

25 ENERGY STORAGE↗
DOE OSTI2022

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↗
DOE OSTI2020

Removal of High Specific Activity Fission Products from Uranyl Sulfate Waste Solutions

The Savannah River National Laboratory (SRNL) is currently providing support to SHINE Medical Technologies (SHINE) which plans to deploy a low energy, accelerator-based neutron source to fission low enriched U in a uranyl sulfate target solution for 99 Mo production. The 99 Mo is initially separated from the fission products and target solution by an extraction column. Subsequent washing of the column will generate waste solutions containing residual U and fission product activity. A small number of high specific activity fission products (e.g., 90 Sr, 137 Cs, and 144 Ce) in these streams will likely control the classification of the low level waste (LLW). If a sufficient amount of the high specific activity isotopes are separated from the SHINE waste streams and concentrated into a waste form, it would be possible to treat a majority of the wash solutions from the column operations as a lower class of LLW (Class A versus Class B or C or Class B versus Class C). The high specific activity fission product elements could then be dispositioned as a much smaller volume of waste rather than requiring the disposal of the entire waste stream at the higher waste classification. The Savannah River Site (SRS) has experience with using monosodium titanate (MST) and crystalline silicotitanate (CST) to remove Cs and Sr from high salt content waste solutions generated during the reprocessing of nuclear fuels and targets. Both of these materials have worked very well for their intended purposes at the SRS where the fission product elements are removed from highly alkaline waste. On the other hand, SHINE waste streams from the extraction column contain H 2 SO 4 which makes the solution acidic. Additionally, the SRS waste streams do not contain other fission product elements such as transition metals or lanthanides because they precipitate upon neutralization of the SRS waste and are not present in the supernate which is dispositioned as LLW following treatment. As such, there are inherent differences between SHINE and SRS waste treatment strategies. Savannah River National Laboratory was tasked with performing scoping studies to see if MST and CST would remove Sr, Cs, and Ce from an acidic mixed metal simulant solution. Batch contact experiments were performed using MST and two CST type materials. The MST material is a 15 wt % powder in 0.15 M NaOH slurry. The MST showed low adsorption for elements of interest from acidic solution. Furthermore, the powder size makes MST non-ideal for column operations. A CST IE-911 ion exchange material had high Cs adsorption, moderate Sr, and marginal Ce adsorption. Based on adsorption of all species, the ion exchange capacity was found to be 0.032 meq/mL. A bench-top column experiment to measure elemental breakthrough curves was performed using CST IE-911 where chromatographic separations of the mixed simulant were expected to occur. While most elements behaved as expected, the lanthanide series, containing Ce, broke though the column earlier than expected. The second CST material, CST R9120, displayed high adsorption for all elements in the acidic mixed simulant solutions in a batch contact study, and had a calculated loading capacity of 0.091 meq/mL. Future studies to develop a waste treatment flowsheet should focus on CST R9120 to treat SHINE waste solutions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Assessing the Oxidative Stability of Anion Exchange Membranes in Oxygen Saturated Aqueous Alkaline Solutions

While anion exchange membrane water electrolyzers show promise as a source of green hydrogen using low-temperatures and non-platinum group metal catalysts, many concerns must be addressed. A primary challenge for the development of high-performance anion exchange membrane water electrolyzers is the fabrication of a stable membrane that will be able to survive long-term stability test while maintaining high anion conductivity, which is a necessity for a durable water electrolyzer. This method will present a standardized protocol that can be used by researchers to assess the quality of their AEM materials and be able to provide insight into how materials may be degrading and how to improve the quality of AEMs. Using Mohr or Volhard titration to measure ion-exchange capacity, EIS to determine the ionic conductivity, NMR and FTIR to understand the extent of membrane degradation over time, and mechanical analyzers to determine the strength of their AEMs, this standardized protocol will guide researchers to determining and improving upon the long-term durability and performance of their AEM materials.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Stabilization of porous glass reverse-osmosis membranes

Application of porous glass in form of capillary tubes for low capacity ion exchange in hyperfiltration experiments is discussed. Efficiency of desalination by process of reverse osmosis is described. Stabilization of porous glass membrane by presence of aluminum chloride is analyzed.

Ballou, E. V.↗
NASA NTRS1973

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Coplen, T. B.↗
NASA NTRS1980

Advances in membrane technology for the NASA redox energy storage system

Anion exchange membranes used in the system serve as a charge transferring medium as well as a reactant separator and are the key enabling component in this storage technology. Each membrane formulation undergoes a series of screening tests for area-resistivity, static (non-flow) diffusion rate determination, and performance in Redox systems. The CDIL series of membranes has, by virtue of its chemical stability and high ion exchange capacity, demonstrated superior properties in the redox environment. Additional resistivity results at several acid and iron solution concentrations, iron diffusion rates, and time dependent iron fouling of the various membrane formulations are presented in comparison to past standard formulations.

Ling, J. S.↗
NASA NTRS1994

A new material for removing heavy metals from water

The NASA Lewis Research Center developed and is patenting a new high capacity ion exchange material (IEM) that removes toxic metals from contaminated water in laboratory tests. The IEM can be made into many forms, such as thin films, coatings, pellets, and fibers. As a result, it can be adapted to many applications to purify contaminated water wherever it is found, be it in waste water treatment systems, lakes, ponds, industrial plants, or in homes. Laboratory tests have been conducted on aqueous solutions containing only one of the following metal cations: lead, copper, mercury, cadmium, silver, chromium (III), nickel, zinc, and yttrium. Tests were also conducted with: (1) calcium present to determine its effects on the uptake of cadmium and copper, and (2) uranium and lanthanides which are stand-ins for other radioactive elements, (3) drinking water for the removal of copper and lead, and (3) others compositions. The results revealed that the IEM removes all these cations, even in the presence of the calcium. Of particular interest are the results of the tests with the drinking water: the lead concentration was reduced from 142 ppb down to 2.8 ppb (well below the accepted EPA standard).

Philipp, Warren H., Jr.↗