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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Structural and spectroscopic characterization of a Tb(IV) polyoxometalate

There has been a renaissance in high valent lanthanide chemistry, which has resulted in the first examples of tetravalent praseodymium (Pr) and terbium (Tb) in molecular systems. These feats have been achieved with tailored ligands that facilitate tetravalent lanthanide stability in non-aqueous conditions. The next step in realizing the potential of high valent lanthanide chemistry is moving towards complexes that are stable in ambient and aqueous conditions. In this investigation, we advance this paradigm by obtaining definitive evidence of Tb(IV) in a molecular system under aqueous conditions utilizing the lacunary Wells-Dawson polyoxometalate, K 10 P 2 W 17 O 61 •20H 2 O. Herein we present the single crystal structure of K 16 Tb(IV)(P 2 W 17 O 61 ) 2 •39.85H 2 O (Tb(IV)W 34 ) as well as extensive spectroscopic evidence obtained via UV–Vis-NIR, X-ray absorption near edge spectroscopy, continuous wave X-band electron paramagnetic resonance spectroscopy and SQUID magnetometry measurements to confirm the oxidation state of Tb in W 34 complexes as +4.

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

Li + (ionophore) nanoclusters engineered aqueous/non-aqueous biphasic electrolyte solutions for high-potential lithium-based batteries

The use of aqueous/non-aqueous biphasic electrolyte solutions in Li-based battery systems circumvents the limitations of poor reductive stability of aqueous electrolyte solutions, broadening their electrochemical stability window. However, aqueous/non-aqueous electrolytes suffer from biphasic mixing and high impedance when Li ions cross the biphasic interface. Here we propose the use of 12-crown-4 (12C4) and tetraglyme (G4) as lithium ionophores to form Li + (ionophore) nanoclusters in both non-aqueous and aqueous phases to overcome the interface challenges in biphasic electrolytes. The Li + (ionophore) nanoclusters have the H 2 O-excluding inner Li + solvation structure in non-polar 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), allowing fast charge transport across the biphasic interface without solvent mixing or water shuttling. Further, a tailored electrolyte formulation comprising the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, 12C4, TTE and H 2 O solvents (labelled LiTFSI-12C4@TTE/H 2 O) demonstrates low impedance (2.7 Ω cm -2 ) at the TTE/H 2 O interface and enabling 2,000 cycles of prelithiated graphite||LiFePO 4 coin cells at 850 mA g -1 with an average Coulombic efficiency of 99.8%. Single-layer 22.5 mAh Li||LiMn 2 O 4 pouch cells using LiTFSI-12C4@TTE/H 2 O electrolyte with G4 delivered a stable discharge capacity of about 1.3 mAh cm -2 for 80 cycles at 0.5 mA cm -2 .

25 ENERGY STORAGE↗
DOE OSTI2023

Reducing delamination of an electron-transporting polymer from a metal oxide for electrochemical applications

Delamination of the electron-transporting polymer N2200 from indium tin oxide (ITO) in aqueous electrolytes is mitigated by modifying ITO with an azide-functionalized phosphonic acid (PA) which, upon UV irradiation, reacts with the polymer. Here, the optical, electrochemical, and spectroelectrochemical properties of N2200 thin films are retained in aqueous and non-aqueous media.

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

Insights into the mechanism of electrochemical chloride oxidation in ethanol from X-ray photoelectron spectroscopy, quiescent solution voltammetry, and rotating ring-disk electrodes

The wide availability of bio-derived alcohols provides the impetus to develop processes that convert them to valuable chemicals. The chloride ion is a redox mediator for electrocatalytic ethanol oxidation to 1,1-diethoxyethane (1,1-DEE) through an ethyl hypochlorite (EtOCl) intermediate, and this paper describes the chloride oxidation reaction (COR) to EtOCl on a glassy carbon (GC) electrode. Voltammetry measurements on a GC electrode in inert acetonitrile solvent combined with ex situ X-ray photoelectron spectroscopy (XPS) establish a Volmer step, where chloride ion from solution chemisorbs and is oxidized. In reactive ethanol solvent, ethanol adsorbs, and analyzing the current response in an LSV experiment supports a two-electron-transfer to form EtOCl, with chemisorption of the regenerated chloride. Koutecký–Levich (K–L) analysis on a rotating ring disk electrode (RRDE) shows that the kinetic rate constant of the COR in ethanol is on the order of 10 −8 cm s −1 , which is five orders of magnitude faster than the direct alcohol oxidation reaction in a kinetically limited regime. This hydrodynamic approach in understanding the electrochemistry of this non-aqueous system extends the possibilities for mediated electrocatalysis in neat alcohol solvents.

Van Daele, Ryan D. [University of Michigan, Ann Ar↗
DOE OSTI2024

Reactive capture and electrochemical conversion of CO 2 with ionic liquids and deep eutectic solvents

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO 2 due to their wide electrochemical stability window, low volatility, and high CO 2 solubility. There is environmental and economic interest in the direct utilization of the captured CO 2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO 2 , eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO 2 with aqueous electrolytes presents limited CO 2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO 2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO 2 , often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO 2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Interlayer pillaring influences the octahedral tilting and electrochemical capacity of tungsten oxides

One strategy to tune the electrochemical properties of layered inorganic materials for energy storage and conversion is to introduce molecular organic pillars. We investigated how pillaring tungsten oxides with alkylammonium cations influences their physical and electrochemical properties relative to the non-pillared host. While the presence of alkylammonium increased the interlayer spacing, we found that the electrochemical capacity of the materials decreased in non-aqueous electrolytes. In aqueous acidic electrolytes, replacement of the interlayer alkylammonium pillars with water molecules led to the recovery of the electrochemical capacity. We rationalize these results based on the influence of interlayer pillars on the degree of octahedral tilting within the inorganic tungsten oxide layers. The presence of alkylammonium in the interlayer leads to an increase in octahedral tilting relative to interlayer water. In turn, this leads to an increase in the band gap and corresponding decrease in the electrochemical capacity. Our findings emphasize the correlation between the chemical nature of the interlayer molecular pillars and the electronic structure, which in turn affects the electrochemical capacity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Comparative Study of Degradation Behaviors of LiFePO 4 , LiMn 2 O 4 , and LiNi 0.8 Mn 0.1 Co 0.1 O 2 in Different Aqueous Electrolytes

Aqueous Li-ion batteries (ALIBs) are an important class of battery chemistries owing to the intrinsic non-flammability of aqueous electrolytes. However, water is detrimental to most cathode materials and could result in rapid cell failure. Identifying the degradation mechanisms and evaluating the pros and cons of different cathode materials are crucial to guide the materials selection and maximize their electrochemical performance in ALIBs. Here, in this study, we investigate the stability of LiFePO 4 (LFP), LiMn 2 O 4 (LMO) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC) cathodes, without protective coating, in three different aqueous electrolytes, i.e., salt-in-water, water-in-salt, and molecular crowding electrolytes. The latter two are the widely reported "water-deficient electrolytes." LFP cycled in the molecular crowding electrolyte exhibits the best cycle life in both symmetric and full cells owing to the stable crystal structure. Mn dissolution and surface reduction accelerate the capacity decay of LMO in water-rich electrolyte. On the other hand, the bulk structural collapse leads to the degradation of NMC cathodes. LMO demonstrates better full-cell performance than NMC in water-deficient aqueous electrolytes. LFP is shown to be more promising than LMO and NMC for long-cycle-life ALIB full cells, especially in the molecular crowding electrolyte. However, none of the aqueous electrolytes studied here provide enough battery performance that can compete with conventional non-aqueous electrolytes. This work reveals the degradation mechanisms of olivine, spinel, and layered cathodes in different aqueous electrolytes and yields insights into improving electrode materials and electrolytes for ALIBs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthesis of Alkoxy-TEMPO Aminoxyl Radicals and Electrochemical Characterization in Acetonitrile for Energy Storage Applications

In this paper, we describe the synthesis and characterization of alkoxylated TEMPO, (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, radicals with potential application in organic non-aqueous redox flow batteries. The behavior of a series of TEMPO derivatives with varying lengths of alkoxy chain is analyzed in acetonitrile solutions using electrochemistry techniques, electron paramagnetic resonance (EPR) spectroscopy, and measurements of permeability through three different membranes. Electrochemical redox potentials are only weakly dependent on the substituent, but, in contrast, exchange current densities derived from the data do depend on the substitution. EPR lends further insight into these properties via the determination of hyperfine splitting constant and rotational correlation time. There is a negligible effect of the substituents on those parameters among the modified TEMPO radicals. Finally, permeation rates of modified TEMPO derivatives through membranes depend significantly on both the membrane and the substitution of TEMPO, providing insights into capacity fade measurements in the literature.

25 ENERGY STORAGE↗
DOE OSTI2025

Ascorbic Acid Stability and pH Testing to Support RWM-018 Pilot Scale Wellhead Treatment System Feasibility Determination

A multitude of groundwater remediation techniques for chlorinated volatile organic compounds (cVOCs) have been conducted at the A/M-Areas of the Savannah River Site (SRS). Historical in-situ chemical oxidation (ISCO) injections of potassium permanganate and sodium persulfate conducted in 2018 and 2020, have left residual oxidant concentrations in the A/M-Area groundwater system. ISCO events targeted dense non-aqueous phase liquids (DNAPLs) through the injection of strong oxidants within plume zones upgradient of current groundwater recovery wells RWM-008 and RWM-018. These residual oxidants could significantly impede the operation of the mercury removal system needed to meet National Pollutant Discharge Elimination System (NPDES) permit requirements for the ongoing pump-and-treat system that hydraulically controls potions of the A/M-Area plume. Effluent treated groundwater from this system is discharged to surface water at the receiving outfall of the M-1 Air Stripper. To prevent interference of the M-1 Air Stripper system by residual oxidants, groundwater recovery has been ceased at well RWM-018. Modeling of oxidant transport in A/M-Area from ISCO estimated that the potential oxidant load contributed by RWM-018 could be as high as 120 mg/L. It is also possible that oxidants may be contributed via pumping at well RWM-008 in the near future as residual oxidants within the aquifer migrate toward its zone of influence. Savannah River National Laboratory (SRNL) has conducted research to investigate potential pre-treatment chemicals to neutralize these residual oxidants, before reaching the M-1 Air Stripper, to allow for resumed groundwater recovery at RWM-018 and continued pumping at RWM-008. Deployment of ascorbic acid for neutralization of residual oxidants at RWM-018 (and possibly RWM-008) is recommended based on results from previous reductant testing (SRNL, 2021). For a maximum estimated oxidant load at RWM-0018, a well-head treatment system would need to dose about 400 gallons of ascorbic acid each month to ensure complete neutralization. A second system with additional reagent should also be considered for deployment at RWM-008.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Carbon Capture Plant Front-End Engineering Design Study for Cement Manufacturing

The objective of this project was to conduct a Front-End Engineering Design (FEED) study for capturing carbon dioxide (CO₂) from cement plant flue gas using non-aqueous solvents (NAS) with a 95% capture efficiency. The study aimed to develop AACE (Association for the Advancement of Cost Engineering) Class 3 cost estimates for a commercial-scale CO₂ capture system with a capacity of 2.4 million tonnes of CO₂ per year (t-CO₂/yr). The results will provide Cemex and the U.S. Department of Energy with reliable data to support investment decisions, evaluate economic feasibility, and guide future project development and implementation.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2026

Carbon Capture Pilot at Vicksburg Containerboard Mill (Final Technical Report)

This is the final technical report for the DOE-OCED project DE-CD0000051. The report provides the progress at the close of the project. The objective of the project is to design and build a large pilot plant for carbon dioxide (CO 2 ) capture from a pulp and paper (P&P) mill using RTI’s non-aqueous solvent (NAS) technology at a capacity of 120,000 t-CO 2 /year, with >90% CO 2 captured. The pilot plant will be used for testing and evaluating the NAS capture process using real flue gas from the P&P mill’s power boiler for a minimum of 1 year of parametric testing and a minimum of 2,000 hours of continuous long-term testing. The testing will provide data for process optimization and scale-up for the P&P industry, provide information on interaction of flue gas contaminants on solvent performance and degradation, and inform strategies for emission control. At the end of the project, the pilot plant will be managed by International Paper (IP), the host site owner, which will continue to capture CO 2 , sequester the captured CO 2 , and be eligible for the 45Q credit.

42 ENGINEERING↗
DOE OSTI2024

Molten Salt Electrodeposition: Review

Molten salt electrodeposition is the process of producing impressively dense deposits of refractory metals using the electrolysis of molten salts. However, predicting which electrochemical parameters and setup will best control different kinds of deposition (density, homogeneity, etc.) is an ongoing challenge, due to our limited understanding of the properties and mechanisms that drive molten salt electrodeposition. Because these advancements have been made rapidly and in different arenas, it is worth taking the time to stop and assess the progress of the field as a whole. These advancements have increasing relevance for the energy sector, the development of space materials and engineering applications. In this review, we assess four critical facets of this field: (1) how the current understanding of process variables enhances the electrodeposition of various molten salts and the quality of the resulting product; (2) how the electrochemical setup and the process parameters (e.g., cell reactions) are known to impact the electrodeposition of different metal coatings and refractory-metal coatings; (3) the benefits and drawbacks of non-aqueous molten salt electrodeposition, and (4) promising future avenues of research. The aim of this work is to enhance our understanding of the many procedures and variables that have been developed to date. The expectation is that this review will act as a stimulant, motivating scientists to delve further into the investigation of refractory-metal alloys by utilizing molten salt electrodeposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Semi-solid electrodes having high rate capability

Embodiments described herein relate generally to electrochemical cells having high rate capability, and more particularly to devices, systems and methods of producing high capacity and high rate capability batteries having relatively thick semi-solid electrodes. In some embodiments, an electrochemical cells includes an anode and a semi-solid cathode. The semi-solid cathode includes a suspension of an active material of about 35% to about 75% by volume of an active material and about 0.5% to about 8% by volume of a conductive material in a non-aqueous liquid electrolyte. An ion-permeable membrane is disposed between the anode and the semi-solid cathode. The semi-solid cathode has a thickness of about 250 μm to about 2,000 μm, and the electrochemical cell has an area specific capacity of at least about 7 mAh/cm 2 at a C-rate of C/4. In some embodiments, the semi-solid cathode slurry has a mixing index of at least about 0.9.

Chiang, Yet-Ming↗
DOE OSTI2024

Electrochemical Manipulation and Radiolytic Evaluation of Organic Phase Neptunium

Post for LDRD Annual Poster Session Under envisioned used nuclear fuel reprocessing conditions, neptunium (Np) is present in a mixture of extractable Np(IV)/Np(VI) and inextractable Np(V) species, the distribution of which is dependent on several factors that lead to the unintentional partitioning of Np into various phases and product streams, reducing process and cost efficiency. With this in mind, we tested an innovative approach to precisely control the oxidation state distribution of Np using novel, high surface area, optically transparent, ligand modified tin-doped indium oxide electrodes (LMEs). These proof-of-concept experiments employed a variety of radiation and electrochemistry (echem) techniques to determine: electrode radiation stability; aqueous echem behavior of Np at nITO|P3 electrode surfaces; radiation-induced Np-extractant reaction kinetics; and non-aqueous echem of Np in diethylhexyl butyramide (DEHBA) solutions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

CONVENTIONAL SUPERCAPACITOR ELECTROLYTES: AQUEOUS, ORGANIC, AND IONIC

This chapter thoroughly covers the most recent developments of aqueous and non-aqueous electrolytes for electrochemical supercapacitors (ESs). In more detail, the overview of different types of electrolytes and their featured properties are initially introduced. Thereafter, the conventional aqueous electrolyte was first discussed, summarized, and opened the perspectives of some new salts that can be used to enhance the ionic conductivity and the performance of supercapacitor. The organic electrolytes, including the organic solvents/salt, ionic liquids, and deep eutectic, are the main parts to explore different trends and cutting-edge advances in optimizing electrolyte formulations customized for different electrode materials. Furthermore, the discussion on the current obstacles and prospects of these electrolytes is also underlined.

electrochemical capacitors, aqueous electrolyte, o↗
DOE OSTI2024

Metal fluoride passivation coatings prepared by atomic layer deposition for Li-ion batteries

The fabrication of robust interfaces between transition metal oxides and non-aqueous electrolytes is one of the great challenges of lithium ion batteries. Atomic layer deposition (ALD) of aluminum tungsten fluoride (AlWxFy) improves the electrochemical stability of LiCoO 2 . AlWxFy thin films were deposited by combining trimethylaluminum and tungsten hexafluoride. in-situ quartz crystal microbalance and transmission electron microscopy studies show that the films grow in a layer-by-layer fashion and are amorphous nature. Ultrathin AlWxFy coatings (<10 Å) on LiCoO 2 significantly enhance stability relative to bare LiCoO 2 when cycled to 4.4 V. The coated LiCoO 2 exhibited superior rate capability (up to 400 mA/g) and discharge capacities at a current of 400 mA/g were 51% and 92% of the first cycle capacities for the bare and AlWxFy coated materials. These results open new possibilities for designing ultrathin and electrochemically robust coatings of metal fluorides via ALD to enhance the stability of Li-ion electrodes.

Mane, Anil U.↗