Search NASA⌕ Search

SEARCH · Search NASA

Results for “EUTECTICS”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,135 records · Page 63

Stabilizing Cathode–Electrolyte Interphase of Nickel-Rich Single-Crystal Cathodes for Lithium-Ion Batteries

Nickel-rich single-crystal (SC) layered oxides are promising cathode candidates for next-generation lithium-ion batteries (LIBs) owing to their high energy density and structural robustness against intergranular cracking. However, their intrinsic surface reactivity with liquid electrolytes accelerates parasitic reactions at the cathode–electrolyte interphase (CEI), leading to transition-metal dissolution, gas generation, and impedance buildup. In this work, we synthesized SC-Li x Ni 0.9 Mn 0.05 Co 0.05 O 2 (NMC9055, 1 ≤ x ≤ 1.2) using a eutectic-assisted method and investigated interface stabilization strategies. A nickel-deficient Li x Ni 0.6 Mn 0.2 Co 0.2 O 2 (NMC622, 1 ≤ x ≤ 1.2) coating was applied via evaporation-based deposition to suppress CEI degradation pathways. Structural and compositional analyses confirmed uniform shell formation and preserved particle integrity. Half-cell electrochemical testing against lithium metal revealed ∼10% higher capacity retention and improved reversibility compared with pristine SC NMC9055, particularly under high-voltage operation. In conclusion, these results highlight the critical role of controlled surface chemistry in mitigating CEI instability in nickel-rich SC cathodes, offering a pathway toward enabling durable high-energy LIBs.

Coating processes↗

Dramatic effect of oxide on measured liquid metal rheology

Liquid metals have traditionally been treated as Newtonian liquids, but several researchers have recently suggested that some metals may shear thin. While apparent shear thinning can be caused by surface oxidation, the reports of shear-thinning metals were investigated using cup and bob type rheometers, which are expected to only be weakly impacted by the surface contamination effects. We show here that even small amounts of oxide on the surface of liquid metals can cause dramatic changes to the measured viscosity of the sample. Using a Searle-type rotational rheometer, we measured the viscosity of eutectic gallium indium and tin in a low-oxygen environment. When either metal is slightly oxidized, the measured viscosity increases by orders of magnitude and the liquid displays erroneous shear-thinning behavior. When the oxide is removed via an active flux, the measured viscosity is Newtonian. The findings outlined here provide insight into the difficulties of measuring the viscosity of easily oxidized liquids and confirm that liquid metals are likely best described as Newtonian liquids at all measured shear rates.

36 MATERIALS SCIENCE↗

Solid electrolyte interphases for high-energy aqueous aluminum electrochemical cells

Electrochemical cells based on aluminum (Al) are of long-standing interest because Al is earth abundant, low cost, and chemically inert. The trivalent Al 3+ ions also offer among the highest volume-specific charge storage capacities (8040 mAh cm -3 ), approximately four times larger than achievable for Li metal anodes. Rapid and irreversible formation of a high-electrical bandgap passivating Al 2 O 3 oxide film on Al have, to date, frustrated all efforts to create aqueous Al-based electrochemical cells with high reversibility. Here, we investigate the interphases formed on metallic Al in contact with ionic liquid (IL)–eutectic electrolytes and find that artificial solid electrolyte interphases (ASEIs) formed spontaneously on the metal permanently transform its interfacial chemistry. The resultant IL-ASEIs are further shown to enable aqueous Al electrochemical cells with unprecedented reversibility. As an illustration of the potential benefits of these interphases, we create simple Al||MnO 2 aqueous cells and report that they provide high specific energy (approximately 500 Wh/kg, based on MnO 2 mass in the cathode) and intrinsic safety features required for applications.

Science & Technology - Other Topics↗

Fatigue-resistant high-performance elastocaloric materials made by additive manufacturing

Elastocaloric cooling, a solid-state cooling technology, displays the latent heat released and absorbed by stress-induced phase transformations. Hysteresis associated with transformation, however, is detrimental to efficient energy conversion and functional durability. Here, we have created thermodynamically efficient, low-hysteresis elastocaloric cooling materials by means of additive manufacturing of nickel-titanium. The utilization of a localized molten environment and near-eutectic mixing of elemental powders has led to the formation of nanocomposite microstructures composed of a nickel-rich intermetallic compound interspersed among a binary alloy matrix. The microstructure allowed extremely small hysteresis in quasi-linear stress-strain behaviors—enhancing the materials efficiency by a factor of four to seven—and repeatable elastocaloric performance over 1 million cycles. Implementing additive manufacturing to elastocaloric cooling materials enables distinct microstructure control of high-performance metallic refrigerants with long fatigue life.

36 MATERIALS SCIENCE↗

On a neutron detector based on TlInSe{sub 2} crystals intercalated with a lithium isotope

The possibility of increasing the sensitivity of a neutron detector based on a TlInSe{sub 2} crystal by introducing the {sup 6}Li isotope into this crystal is investigated. Introduction of the isotope is conducted by the method of electrochemical intercalation from aqueous and nonaqueous solutions of LiCl and also from the melt of the LiCl–KCl eutectic. It is shown that intercalation by the electrochemical method from a LiCl solution in propylene carbonate, performed along the “c” axis of the crystal (along strong bond chains) is efficient. The attained concentration of introduced lithium amounts to (1–1.2) × 10{sup 21} cm{sup –3}, which increased the sensitivity of the detector by approximately four times. Good agreement between the calculated and experimental values of the detector sensitivity is demonstrated.

36 MATERIALS SCIENCE↗

Corrosion of Commercial Mg–Al Alloys: AZ31B, AM60, and AZ91D

Aqueous corrosion, atmospheric corrosion, and ionic liquid dissolution studies were performed on commercial alloys AZ31B, AM60, and AZ91D and compared with previously reported results for single-phase binary Mg–Al alloys containing similar Al concentrations (αMg-2 at% Al, αMg-5 at% Al, and Mg-8 at% Al). Polarization studies in 0.6 M NaCl were used to characterize the aqueous free corrosion behavior during 20-h free immersion. Accelerated corrosion testing was performed using a rotating-disk electrode which revealed the evolution of an Al-rich mud-cracking and platelet morphology. Atmospheric droplet testing showed rapid pH increases that depended on the Al concentration in the alloy. Time-dependent contact angle measurements showed that the degree of droplet wetting increased during free corrosion by ~50° over 20 h in 0.6 M NaCl. Ionic liquid dissolution studies in 1:2 M choline chloride:urea deep eutectic solvent were performed in order to examine the current-voltage behavior of these alloys in the absence of water and hydrogen reduction. The results of these studies revealed the formation of nanowire corrosion morphologies within a honeycomb lattice structure which we attribute to selective dissolution of Mg via a two-dimensional stepflow process

25 ENERGY STORAGE↗

Perspective—Hydrogen Bonded Concentrated Electrolytes for Redox Flow Batteries: Limitations and Prospects

This perspective provides a brief overview of the recent work on electrolytes with hydrogen (H)-bonding network, specifically the deep eutectic solvents (DESs), and outlines important factors to consider when adapting these electrolytes in redox flow batteries (RFBs). The redox behavior, solubility, and stability of several redox molecules of relevance to RFBs in DESs are presented, including some of our work within the Breakthrough Electrolytes for Energy Storage (BEES)—an Energy Frontier Research Center of the United States Department of Energy. Particularly, the challenges and opportunities for further development of DESs for energy storage are discussed.

25 ENERGY STORAGE↗

Determination of Kinetic Properties of Ni(II) Ions in Molten LiF-NaF-KF via Voltammetry

Kinetic properties of Ni(II) in eutectic LiF-NaF-KF (FLiNaK) molten salt were determined at T = 748–823 K using cyclic voltammetry (CV), square wave voltammetry (SWV), and chronoamperometry (CA) measurements using a glassy C working electrode, Ni(II)/Ni reference electrode, and Ni counter electrode. Reduction of Ni(II) to Ni(s) was determined to be a single step, two-electron transfer process. Diffusivity values were calculated using the Berzins and Delahay equation and semi-integral electroanalysis from the CV measurements as well as using the Cottrell equation from the CA measurements. Diffusivity of Ni(II) in molten FLiNaK at T = 748–823 K was determined to be 3.27 × 10 –7 –3.04 × 10 –6 cm 2 s –1 with an activation energy of 62–104 kJ mol –1 . The estimated kinetic properties varied appreciably among methodologies possibly due to inherent assumptions in theory regarding reversibility and unit activity during Ni metal deposition on the working electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Methods—Meso-Scale Electrodes for Characterizing Diffusion-Reaction Properties of Redox-Active Organics in Viscous Electrolytes

Deep Eutectic Solvents (DESs) have recently gained interest as flow battery electrolytes. Their advantages include a wider electrochemical stability window compared to aqueous electrolytes, higher solubility for redox-active species, and negligible volatility. However, DESs are often highly viscous, and suffer from low ionic conductivities. This can make assessing redox kinetics difficult when attempting to determine their viability for energy storage. In classical voltammetric measurements, low ionic conductivity manifests as high solution resistance, thereby requiring "live" compensation of the electrolyte ohmic drop when performing fast-scan voltammetry. An uncompensated or inadequately-compensated ohmic drop leads to misinterpretation of the voltammetric behavior, e.g., assessing reversibility vs. irreversibility of a redox reaction. Here, we present micro-fabricated electrodes as facile "meso-scale" electrodes, which overcome these issues by nearly eliminating the ohmic drop while retaining uniformity of the current distribution over the electrode surface. Their use in precise transport-kinetics measurements is demonstrated using a redox-active organic, i.e., 4-Hydroxy-TEMPO in an aqueous medium and in ethaline, which is a viscous DES. This study provides a methodical approach to design and to implement voltammetry experiments using meso-scale electrodes leading to reliable measurements of diffusion-reaction properties of 4-Hydroxy-TEMPO.

25 ENERGY STORAGE↗

The Effect of Sulfuric Acid Anodization on the Electrochemical Properties of Aluminum Alloy AlSi 10 Mg Prepared by Selective Laser Melting

Aluminum alloy, AlSi 10 Mg, prepared by selective laser melt (SLM) fabrication was anodized in 9.8% sulfuric acid (Type II) at 15 V for a total of 23 min. Experiments were performed to study the potentiostatic anodization process and its effects on the oxide coating morphology, thickness, and electrochemical properties of the alloy. Prior to anodization, the alloy microstructure is composed of aluminum cells encapsulated in a silicon network. Anodizing the abraded and polished AlSi 10 Mg surface produced a porous oxide layer with a thickness of 5μm. The oxide coating weight was 698 ± 29 mg/ft 2 . The oxide coating forms in the aluminum cells that are isolated from one another by the silicon eutectic phase. In electrochemical tests, the anodic and cathodic potentiodynamic polarization currents were suppressed by factors of 15× and 215×, respectively, as compared to the unanodized controls. The data indicate the anodic oxide coating suppresses the cathodic more than the anodic reaction rate. Linear polarization resistance (R p ) values increased by 279× after anodization. The corrosion current density values (j corr ) decreased by 133× after anodization. Taken together, the electrochemical data indicate the anodic oxide coating (unsealed) increases the corrosion resistance of the SLM alloy by two orders of magnitude.

Electrochemistry↗

Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Corrosion in molten salts greatly hampers the application for renewable energy applications like molten salt reactors. To develop effective strategies for corrosion mitigation, understanding the interfacial structures and properties such as specific ion adsorption and electrical double layer capacitance are crucial. Using cyclic voltammetry and electrochemical impedance spectroscopy, we systematically studied the interfaces on various model electrodes including W (solid), Bi (liquid), and the stainless steel 316 in LiCl-KCl eutectic molten salts with the addition of corrosion species CrCl 2 and FeCl 2 . Both Cr 2+ and Fe 2+ ions increased electrical double layer capacitance, with Cr 2+ showing specific adsorption behavior and shifting the potential of zero charge, while Fe 2+ had minimal effect on point of zero charge. Two-working electrode measurements revealed increasing open-circuit potential and electrical double layer capacitance during the exposure of stainless steel 316, indicating its progressive corrosion and ion accumulation at the interface. X-ray photoelectron spectroscopy and Raman confirmed Cr enrichment at the interface. This work highlights the strong correlation between electrical double layer behavior and corrosion dynamics in molten salts and suggests electrical double layer capacitance as a sensitive, in situ indicator for corrosion monitoring.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Progress and Perspectives: Zirconium Electrodeposition from Different Electrolytes

Zirconium (Zr) possesses outstanding properties, including exceptional chemical resistance and a high melting point, and is therefore desirable for use in a wide variety of challenging environments, such as in nuclear reactors and the chemical processing industry. To minimize the amount of Zr required for any given application, developing methods for generating metallic Zr coatings is highly advantageous. Owing to Zr’s highly negative reduction potential, electrodeposition in traditional solvents at near ambient temperatures remains challenging and thus not well understood. Due to the extreme conditions required to deposit this metal, extensive work has been conducted in molten salt electrolytes, however the broad applicability of this methodology is limited due to its corrosivity. The primary focus of this article is to present an overview of Zr’s electrochemical behavior and to consolidate the efforts of researchers in exploring electrodeposition techniques for Zr involving aqueous, organic, ionic liquid, deep eutectic, and molten salt solvents. With this information, we highlight trends across solvent systems and opportunities for future research.

42 ENGINEERING↗

Investigation Into LiCl-LiF+Li 2 O as a Low Temperature Electrolyte in Direct Electrolytic Reduction of UO 2

Direct electrolytic reduction (DER) of UO 2 in a binary LiCl-Li2O (1–3 wt%) at 650 °C has been widely reported. The process temperature can be reduced to 550 °C in theory by using a near eutectic ternary LiCl-LiF+Li 2O (∼2 wt%) electrolyte, which will result in substantial reduction in rate of salt vaporization. The feasibility of using the ternary electrolyte for the process was tested via material compatibility testing, electrochemical polarization testing, and controlled potential or current DER experiments. MgO, Pt, and 625 nickel samples were each contacted with the ternary salt for 168 h. Negligible changes to dimensions and mass of the samples were measured, and concentrations of corrosion products in the salt were 102 ppm or less. O2−oxidation was observed to occur at a lower potential than Cl-or F-on a Pt anode. DER of UO2was performed in six trials. Process variables included type of reference electrode, electrochemical control method, type of cathode basket, and electrolyte composition. UO 2conversion ranged from 28.2 to 99.9 % , and current efficiency ranged from 38 to 52%. Overall, results indicate that the use of the ternary salt is feasible for DER.

36 MATERIALS SCIENCE↗

Electrochemical Nucleation and Growth of Uranium and Plutonium from Molten Salts

This work examines the nucleation and growth behavior of uranium and plutonium from molten LiCl-KCl eutectic on inert electrodes using electrochemical techniques. Current-time transients obtained from chronoamperometric experiments were compared with theoretical models to characterize the type of nucleation (progressive or instantaneous) for deposition of U and Pu, and co-deposition of U-Pu, from molten LiCl-KCl at inert electrodes. It was established that the nucleation mode of actinides present as chlorides in molten chloride salts changes from progressive to instantaneous with an increasing concentration of the trivalent actinide ions in the salt. The effect of the material of the working electrode was investigated, and it was found that changing the material from tungsten to silver improves resolvability of the nucleation peaks and allows more accurate analysis of the experimental measurements. Using the nucleation data, diffusion coefficients were obtained for U 3+ and Pu 3+ , and were found to be in very good agreement with the values obtained from other studies. Furthermore, the density of nuclei produced during instantaneous nucleation, the rate of nucleation for progressive nucleation, and the radius of the deposited nuclei were evaluated and examined at different overpotentials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Electrochemical Recovery of Iron from Spent Pickle Liquor by Chloride-Based Molten Salt Electrolysis

Spent pickle liquor (SPL) is a waste stream generated in the steel industry that presents both a disposal challenge and a potential resource for metal recovery. This study investigates the electrochemical extraction of high-purity iron metal from SPL using chloride-based molten salt electrolysis (CMSE). Electrochemical characterization of diluted SPL confirmed Fe 2+ as the dominant species. Thermal dehydration of SPL under inert atmosphere yielded FeCl 2 -rich solids, which were directly employed as feedstock for electrolysis in LiCl–KCl eutectic melts at 500 °C. Cyclic voltammetry of FeCl 2 in this melt revealed well-defined Fe 2+ /Fe 0 redox behavior within the electrochemical stability window of the supporting electrolyte. High coulombic efficiency (>85%) electrodeposition was achieved demonstrating that iron metal can be produced from dehydrated SPL by CMSE. The electrodeposited iron exhibited >98 wt% purity, which was further enhanced to 99.9 wt% via arc melting. The resulting iron powder was ferromagnetic, and its size distribution was found to be suitable for powder metallurgy applications. This work demonstrates a scalable, energy-efficient pathway for valorizing SPL into high-purity iron metal, advancing circular economy strategies in the steel industry.

Materials science↗

Experimental demonstration of hydraulic jump control in liquid metal channel flow using Lorentz force

In this paper, hydraulic jump control using electromagnetic force in a liquid metal flow is presented. The control methods used give insight into the hydraulic jump behavior in the presence of magnetic fields and electrical currents. Flowing liquid metals is a proposed solution to heat flux challenges posed in fusion reactors, specifically the tokamak. Unfortunately, thin, fast-flowing liquid metal divertor concepts for fusion reactors are susceptible to hydraulic jumps that drastically reduce the liquid metal flow speed, leading to potential problems such as excessive evaporation, unsteady power removal, and possible plasma disruption. Highly electrically conductive flows within the magnetic fields do not exhibit traditional hydraulic jump behavior. There is very little research investigating the use of externally injected electrical currents and magnetic fields to control liquid metal hydraulic jumps. By using externally injected electrical currents and a magnetic field, a Lorentz force (also referred to as j × B force) may be generated to control the liquid metal jump behavior. In this work, a free-surface liquid metal—GaInSn eutectic or “galinstan”—flow through an electrically insulating rectangular duct was investigated. It was shown that applying a Lorentz force has a repeatable and predictable impact on the hydraulic jump, which can be used for liquid metal control within next-generation fusion reactors.

MHD↗

Detection of Off-Gassed Products From Molten Salts Using Laser-Induced Breakdown Spectroscopy

The detection of off-gassed sodium from molten sodium nitrate (NaNO 3 ) at temperatures between 330 °C and 505 °C and off-gassed calcium from molten lithium chloride–potassium chloride eutectic (LKE) mixtures at 510 °C with laser-induced breakdown spectroscopy (LIBS) was demonstrated. NaNO 3 and LKE samples were melted in a custom-built crucible that promoted the generation of off-gassed products from the molten sample. The off-gassed products were analyzed with a LIBS system designed to probe the high-temperature environment. Na D emission lines, Na(I)588.99 nm and Na(I) 589.59 nm, were detected from the NaNO 3 samples after reaching a temperature threshold, which indicated the occurrence of phase change. In LKE mixtures, the detection of Ca impurities at a concentration of 78 mg/kg was possible using the emission lines Ca(II) 393.66 nm and Ca(II) 395.85 nm. Furthermore, this work demonstrates the real-time monitoring capabilities of LIBS in high-temperature environments that simulate the conditions of molten salt reactors.

42 ENGINEERING↗

Data for "Integrated Green Biorefinery for the Production of Anthocyanins, Fermentable Sugars, and High Pure Lignin from Miscanthus × giganteus "

Miscanthus x giganteus (Mxg) is a promising perennial crop for producing natural colorants, renewable fuels, and bioproducts. However, natural recalcitrance and high pretreatment cost are major barriers to their complete conversion. In this study, a green processing method has been investigated for efficient recovery of natural pigments (anthocyanins), fermentable sugars, and pure lignin from Mxg genotypes using choline chloride-based natural deep eutectic solvents (NADES) systems. Interestingly, choline chloride: lactic acid (ChCl: LA) NADES-processed biomass resulted in 67.8 ± 2.1 μg g−1 of anthocyanins from dry biomass. A maximum of 87.4%–94.1% glucose yield was achieved after enzymatic saccharification. The effective extraction of lignin with high purity with higher β-aryl ether (βO4) bonds from advanced crops is crucial for lignin valorization. Notably, highly pure lignin (≈93.4% ± 1.4%) is achieved after low-temperature NADES pretreatment while retaining lignin’s native structure. 31P nuclear magnetic resonance demonstrated that total phenolics for ChCl: LA-lignin resulted in 1.20 mmol g−1 hydroxyls. The relative monolignol composition of syringyl (S), guaiacyl (G), and p-hydroxyphenyl (H) is 19.0, 65.7, and 14.3%, respectively, as evidenced by heteronuclear single quantum coherence analysis. This study provides a novel approach for obtaining high-purity lignin for catalytic depolymerization for oligomers and bifunctional monoaromatics production and leverages current cellulosic biorefinery technologies.

biomass analytics↗