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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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Mechanism of Lithium Ion Exchange Into Spinel Manganese Oxide

Lithium manganese oxide (LMO) is an effective absorbent for lithium recovery from brines, characterized by its high adsorption capacity, excellent regeneration performance, and selectivity. Here, this study investigates the mechanisms of material degradation during lithium loading and unloading in LMO, employing a combination of time‐resolved Raman spectroscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy. Key findings reveal that the A 1g vibrational mode wavenumber shifts from 635 cm −1 at the onset of lithium ion exchange to 656 cm −1 after 12 min, indicating local symmetry loss and manganese (Mn) loss during lithium intercalation. The proposed lithium exchange mechanism involves initial occupation of tetrahedral interstitial voids, followed by migration into interstitial sites between Mn octahedral sites. Computational modeling suggests that the loss of symmetry in MnO cubane‐like groups occurs as lithium migrates, significantly affecting the Raman spectra. Importantly, the study demonstrates that after 100 cycles of lithium/hydrogen loading, a 24% loss in Mn is observed, which correlates with decreased structural stability; however, the structural integrity of LMO is enhanced when subjected to multiple cycles without complete loading. Here, these insights contribute to the understanding of LMO's performance in lithium recovery applications and highlight potential strategies to optimize its use in future technologies.

15 GEOTHERMAL ENERGY↗
DOE OSTI2020

Computational modeling predicts the stability of both Pd + and Pd2 + ion-exchanged into H-CHA

Passive NO x adsorbers (PNA) using Pd/zeolites have emerged as a promising solution for the reduction of cold-start emissions from vehicle exhaust. However, the nature of the active sites and the mechanisms underlying NO x adsorption in Pd/zeolites remain a subject of ongoing investigation. In this study, we employ quantum chemical simulations to investigate the structure of Pd species in cation-exchange sites at isolated Al and Al pairs in the 6-ring and 8-ring of the CHA framework before the introduction of NO x . Our calculations show that the speciation of Pd in these exchange sites strongly depends on the precise Al arrangement within the framework, as well as the operating conditions. Ionically dispersed Pd is found to be the most favorable species over a wide range of oxidizing and reducing conditions. Small oligomers of PdO and metallic Pd do not appear to be competitive at either isolated Al or Al pairs. Notably, our calculations show that ion exchange sites other than next–next–nearest neighbor Al pairs in the 6-ring will be preferentially occupied by Pd + instead of Pd 2+ . The stability of Pd + in the zeolite environment is an interesting contrast with its rareness in molecular Pd compounds. Nonetheless, a detailed analysis of the electronic structure shows that predicted Pd oxidation states are consistent with chemical intuition for all complexes investigated in this study. We also discuss the potential ambiguity in Pd characterization provided by typical experimental techniques such as XANES, EXAFS and UV-Vis, and highlight the need for additional EPR spectroscopy studies to further elucidate the initial Pd speciation in zeolites for PNA applications.

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

Adsorption Equilibrium, Kinetics, and Column Breakthrough Data for Aqueous Solutions of Binary-Acid and Ternary-Acid Mixtures of Acetic Acid, Butyric Acid, and Lactic Acid on IRN-78 Ion-Exchange Resin at Initial pH Levels of ∼3–7 and at 25–55 °C

This work is part of an effort to develop thermophysical property data and models supporting adsorptive process development for organic acid separation from a dilute aqueous solution of fermentation broth. It presents systematic experimental measurements for aqueous-phase adsorption equilibrium, kinetics, and column breakthrough for three binary-acid aqueous mixtures (acetic acid + lactic acid, butyric acid + lactic acid, and acetic acid + butyric acid) and one ternary-acid aqueous mixture (acetic acid + butyric acid + lactic acid) on Amberlite IRN-78 ion-exchange resin. The equilibrium measurements covered broad ranges of the initial acid concentration (100–400 mmol/L), initial pH (∼3–7), and temperature (25–55 °C). The equilibrium data for the binary-acid and ternary-acid aqueous mixtures indicate selective adsorption of lactic acid at initial pH levels of ∼3 and 4, while acetic acid and butyric acid are selectively adsorbed at initial pH levels of 5, 6, and 7. The subsequent kinetics and column breakthrough experiments were performed at 200 mmol/L with equimolar ratios, an initial pH of 6, and 25 °C. In conclusion, the measurements provide essential data sets for rigorous thermodynamic modeling and process simulation of adsorptive separation processes for organic acid separation from fermentation broth.

Adsorption↗
DOE OSTI2020

NaGaS 2 : An Elusive Layered Compound with Dynamic Water Absorption and Wide‐Ranging Ion‐Exchange Properties

Abstract Most ternary sulfides belonging to the MGaS 2 structure‐type have been known for many years and are well‐characterized. Surprisingly, there have been no reports of the NaGaS 2 composition, which contains Na, a monovalent cation slightly larger in size than Li, found in LiGaS 2 , a compound known for its non‐linear optical properties. Now it is demonstrated for the first time that the unique reversible water absorption in NaGaS 2 has resulted in its absence from previous reports owing to difficulties encountered when characterizing this compound by SC XRD. The layered structure of this compound coupled with uniquely easy migration of water molecules between the layers allows for ion exchange with 3d and 5f metal cations. Some cations, for example, Ni 2+ , facilitate exfoliation of the layers, providing a facile synthetic route to a new class of 2D chalcogenide materials and furthermore demonstrating that NaGaS 2 can readily uptake uranyl species from aqueous solutions.

Klepov, Vladislav V.↗
DOE OSTI2025

Ion-Exchange Membrane-Centric Durability Testing and Degradation Characterization for Industry-Relevant CO 2 Reduction

Electrochemical CO 2 reduction is a promising conversion process for producing value-added fuels and chemicals from electricity and CO 2 as a sustainable carbon feedstock to domestically produce fuels and chemicals from industrial waste. Having reached industrially viable performance metrics with small-scale CO 2 electrolysis cells, the field must now increasingly focus on extending the device durability of large stacks to achieve equivalent metrics for 35,000+ hours to decrease maintenance and capital costs. Reported device lifetimes have increased in recent years, with the longest stability studies for CO, ethylene, and formic acid production being published in 2024–2025 with operation times of 4500, 1000, and 5200 h, respectively. Unfortunately, significant extension of the device durability is still required. Here, we provide an overview of ion-exchange membranes (IEMs) and provide insight into the variety of degradation mechanisms that must be overcome to enable the community to meet durability targets. In an effort to accelerate the extension of device lifetimes, we propose a general approach for characterizing CO 2 electrolysis cell degradation before and after durability testing to better elucidate the mechanisms and failure modes of IEMs in zero-gap cells. Furthermore, we encourage the adoption of operando characterizations in tandem with accelerated stress and durability tests, postulating that their combined applications will be increasingly valuable. We hope that this perspective motivates future durability studies to evaluate degradation across the entire electrolysis cell.

09 BIOMASS FUELS↗
DOE OSTI2021

Ion Exchange Processing of AP-105 Hanford Tank Waste through Crystalline Silicotitanate in a Staged 2- then 3-Column System

The U.S. Department of Energy (DOE) is working to expedite processing of Hanford tank waste supernate at the Hanford Waste Treatment and Immobilization Plant (WTP). To support this goal, Washington River Protection Solutions, LLC (WRPS, Richland, WA) is designing a system for suspended solids and cesium (Cs/ 137 Cs) removal from Hanford tank waste supernate. The effluent will then be sent to the WTP Low-Activity Waste (LAW) Facility for vitrification. The Cs removal is critical for eliminating the high dose rate associated with 137 Cs and facilitating a contact maintenance philosophy for the LAW Facility. The maximum 137 Cs concentration in the LAW sent to the WTP is targeted to be below the 3.18E-5 Ci 137 Cs/mole of Na waste acceptance criteria (WAC) limit. The filtration and ion exchange systems will be placed near the Hanford tanks and are collectively termed the Tank Side Cesium Removal (TSCR) system.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Critical role of polymer-ceramic ion exchange for high conductivity composite electrolytes

Polymer-ceramic composites offer a path to enhance the transport and mechanical properties of solid electrolytes. However, an in-depth understanding of the extent and role of ion transport along and across polymer-ceramic interfaces in these systems is lacking. We have recently shown that Li-conducting Li 0.11 Na 0.24 K 0.02 La 0.43 TiO 2.82 (LMTO) nanorods can be prepared by a molten flux method, and the addition of 30–50 weight (wt.)% LMTO to a bis[(trifluoromethyl)sulfonyl]imide-vinyl ethylene carbonate-based single-ion conducting (SIC) polymer electrolyte leads to a two-fold enhancement in Li-ion conductivity, from 1.4 to 3.0 × 10 −5 S/cm at 30 °C. In the present study, we use NMR methods to identify the Li-ion transport pathways and determine the timescale of chemical exchange between the SIC polymer and LMTO ceramic components. Tracer exchange NMR indicates preferential transport through the polymer or polymer-interfacial regions, and exchange spectroscopy (EXSY) and a new isotope exchange method reveal negligible Li exchange between the SIC polymer and LMTO ceramic up to several days. Here, LMTO nanorods act as a passive filler. Our results further highlight that significant (e.g., 10- or 100-fold) conductivity enhancements in composite electrolytes can only be achieved 1) with ionically-conductive fillers, and 2) when both the ceramic and polymer components actively participate in long-range transport. For this, fast interfacial ion exchange is needed. In conclusion, this leads us to introduce a critical interfacial ion exchange time to evaluate whether a filler actively contributes to conduction in a composite electrolyte, and screen for promising polymer-ceramic pairings to accelerate the development of high conductivity solid electrolytes.

Battery, Solid electrolyte↗
DOE OSTI2025

PFAS Removal by Ion Exchange Resins: Background and Knowledge Gaps with Respect to the Hanford Site

Per- and polyfluoroalkyl substances (PFAS) have been a rising concern for the past two decades, with the United States Department of Defense and Environmental Protection Agency investing millions of dollars in research into remediation and clean-up technologies. Due to the environmental persistence, toxicity, biological uptake, and ongoing changes in both federal and state regulatory space, understanding the fate and transport of PFAS compounds has been of growing concern to the US Department of Energy (DOE). The DOE’s Hanford Site is investigating historical use of PFAS and will be doing site characterization for PFAS. Thus, PFAS have not yet been identified as a contaminant concern in regulatory documents. Based on historical records that mention the discharge of aqueous film-forming foam containing PFAS and having on-site fire stations (a risk factor for PFAS contamination), it seems likely that environmental releases of PFAS may have occurred. Pump and treat (P&T) remediation is the selected remedy for multiple groundwater contaminant plumes at Hanford. These P&T systems use ion exchange (IX) as a component of aboveground treatment, with the specific resins depending on the target contaminants. There is potential that these IX resins may be able to remove PFAS from groundwater, but investigation is needed to understand affinity/selectivity and removal capacity given the groundwater composition and the operating conditions. This report provides background on PFAS uses and chemistry, then provides a review of IX resin applications for PFAS, identifying knowledge gaps. Recommendations are provided regarding research needed to address knowledge gaps and acquire information needed to propose IX as a future PFAS remediation technology at the Hanford Site, as well as other U.S. Department of Energy sites. Generally, PFAS compounds are fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon – with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS. These chemical compounds are characterized as non-biodegradable, non-reactive, non-photolytic, and hydrolysis resistant. This makes them highly recalcitrant within the environment, however polyfluoroalkyl materials are less recalcitrant as the carbon chains contain C–H bonds which are more easily broken than carbon – fluorine (C–F) bonds. The backbone carbon structures are commonly punctuated with a head group, the most well-known of them are perfluorooctanesulfonic acid and perfluorooctanoic acid, which possess a sulfonate and a carboxylate group, respectively. IX resins are marketed for the removal of PFAS from water systems and industrial water, however, the mechanism of removal is not as well understood as for anion or cation removal. A better understanding of the mechanism of removal would enable the development of IX resins that have improved specificity for PFAS removal. Four knowledge gaps were identified: 1) the effect of dissolved ions on the IX resin PFAS removal effectiveness, 2) the effect of additional primary contaminants of concern (PCOCs) or secondary contaminants of concern (SCOCs) on the effectiveness of PFAS via IX resin, 3) the mechanisms of PFAS removal from water, and 4) practical solutions to IX resin regeneration and waste disposal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Small to Full Height Scale Comparisons of Cesium Ion Exchange Performance with Crystalline Silicotitanate

The U.S. Department of Energy’s (DOE) Hanford Site houses 56 million gallons of high-level radioactive waste generated from plutonium production from 1944 to 1988. The supernatant waste, currently stored in underground tanks, is intended to be vitrified following filtration and 137 Cs removal at the Hanford Waste Treatment and Immobilization Plant (WTP) Low-Activity Waste (LAW) Vitrification Facility. The WTP Pretreatment Facility will not be operational for several years. The Tank Side Cesium Removal (TSCR) system is a technology demonstration that will remove cesium from tank waste supernate to support directly feeding LAW to the vitrification facility. The 137 Cs removal is important to meet the WTP LAW contract specification and ultimately for creating a contact-handled waste form. The waste acceptance criteria (WAC) limit for the WTP LAW Facility is <3.18E-5 Ci 137 Cs per mole Na. The TSCR system is skid mounted and employs two key technologies: dead end filtration for solids removal and ion exchange (IX) for cesium removal. Filtration is necessary to protect the functionality of the IX columns. The IX process utilizes sodium form crystalline silicotitanate (CST) IX media produced by UOP Honeywell, LLC (Des Plaines, IL) under the product name IONSIV R9140-B, 18 x 50 mesh, in a lead-lag-polish column configuration. Each column contains a CST bed height of 92 inches and a volume of approximately 157 gallons of CST IX media. The full-scale TSCR operation will run at a residence time of 1.9 bed volumes (BV)/h, which results in a superficial velocity of 7.3 cm/min and a flowrate of ~5 gal/min. Column testing at small (2.5% of the full bed height), medium (12% of the full bed height), and full-height scales has been previously conducted to evaluate process variables and scale up performance of Cs exchange onto the CST. Cesium load performances from various sieve cuts at the small scale indicated that a 30-mesh sieve cut be tested to determine if it better reflects the 12% and full-height column performances at the small scale. Two process flowrates were tested in the small-column configuration with <30-mesh CST and simulant solutions. These tests were compared to full-height column tests at the same residence times to assess CST particle size effect on column scaling. Table S.1 summarizes the observed column performance determined for the two flowrates juxtaposed to the previous work with 5.6 M Na simulant at higher scales (used as benchmarks). The WAC breakthroughs between the small and full-height tests at 1.3 BV/h differed by ~59 BVs. The WAC breakthroughs for small, medium, and full-height tests at 1.8 BV/h were consistent at 240 BVs. The 50% Cs breakthroughs were nominally equivalent for all column tests. The common transition zones and onsets of Cs breakthrough at the 1.8 BV/h tests indicated that the Cs mass transfers were equivalent and thus the <30-mesh CST Cs load performance at the small scale successfully modeled that of the full-height system. It is recommended that the <30-mesh CST be used in subsequent 10-mL CST bed tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Polyamide-Based Ion Exchange Membranes: Cation-Selective Transport through Water Purification Membranes

Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO 2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes–those that typically find application in reverse osmosis and nanofiltration desalination–as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na + transference numbers compared to Nafion 117 in Na 2 SO 4 and NaHCO 3 -containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ion Exchange of Selected Group II Metals and Lead by Crystalline Silicotitanate and Competition for Cs Exchange Sites

A series of batch contact tests were conducted to evaluate the exchange behavior of Ba, Ca, Pb, and Sr onto crystalline silicotitanate (CST) in support of an expedited Cs removal and pretreatment system at the Hanford site. Binary Na/M 2+ and ternary Na/Cs/M 2+ isotherms were generated to understand selectivity, capacity, and competitive impact of each analyte on Cs uptake from a simple 1 M NaOH/4.6 M NaNO 3 simulant. Analyte loading from a 0.1 M NaOH/5.5 M NaNO 3 simulant was assessed to determine the effect of hydroxide concentration on binary Na/M 2+ isotherms. Finally, results from binary and ternary isotherms indicated that group II metals, and Pb do not impact CST performance toward CST at concentrations expected in Hanford tank waste supernate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗