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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

Corrosion of 316 L stainless steel under the natural circulation of molten NaCl-MgCl 2 salt

The corrosion behavior of 316 L stainless steel (SS) was studied via the natural circulation of molten eutectic NaCl-MgCl 2 salt through a microloop. The post-corrosion tested 316 L SS microloop sections were characterized with microscopy techniques to determine the microstructural and microchemical changes that occurred at the alloy/salt interface. It was found that 316 L SS showed heterogeneous dissolution at the hot-leg, whereas deposition of corrosion products occurred at the cold-leg. For the first time, experimentally obtained molten salt flow-induced corrosion of 316 L SS results were combined with computational thermodynamic-kinetic models to validate the dissolution and deposition in terms of elemental compositional changes at the alloy/salt interface. The thermodynamic-kinetic modeling predicted that the heterogeneous dissolution of Cr and Fe from the hot-leg section of 316 L SS persisted throughout the salt circulation. The model also estimated that, despite Cr deposition starting earlier than Fe, the total redeposition of Fe is expected to be significantly greater than that of Cr over the circulation of salt. Furthermore, the modeling accurately predicted the subsurface enrichment of Mo which is attributed to the reduced Cr activity and the relatively higher diffusion rate of Mo within the alloy matrix. Here, the agreement between modeling and experimental results confirms that Fe chlorides dissolve at the hot-leg and subsequently deposit at the cold-leg due to activity changes driven by the thermal gradient. By contrast, Cr was not detected in the cold-leg deposits, which is attributed to its weaker temperature dependence on activity, limiting its redeposition under these conditions.

36 - MATERIALS SCIENCE↗
DOE OSTI2021

Environmental degradation of electroplated nickel and copper coated SS316H in molten FLiNaK salt

Corrosion of nickel and copper electroplated coatings on SS316H in molten FLiNaK salt was studied. 500- and 1000-hour static corrosion tests were performed in molten FLiNaK at 700 degrees Celsius. Characterization of the coatings following corrosion indicated that they did not degrade in the molten salt during the corrosion experiment and fully protected the underlying SS316H from chromium dissolution. Interdiffusion between the copper coating and SS316H was extremely limited, interdiffusion between the nickel coating and SS316H. Diffusion modelling revealed that the nickel coatings still significantly reduced chromium dissolution over 60 years despite the interdiffusion.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hydrogenous Content in Residues from Aqueous Chloride Pu and Am Recovery Operations

Byproduct residues generated from Aqueous Chloride Pu and Am recovery operations at Los Alamos National Laboratory have been investigated and determined to contain high weight % chloride salts and minimal hydrogen content. Hydrogen content is the result of limited surface area adsorption of ambient moisture. The assumption used in technical analysis NCS-TECH-19-029 to model potentially hydrogenous items as mixtures of polyethylene is shown to be overly conservative. Our results and literature precedent indicate that water adsorption of 1-3 % by weight is expected for hydroxide cakes and Pu oxides, and a conservative bounding assumption for these materials is 5% water by weight. LOH results for a dissolution heel stored long term showed 6.25% weight loss, which was conservatively assumed to be water. A conservative bounding assumption for dissolution heels is 8 wt.% water content. This equates to 0.55 % hydrogen by weight for hydroxide cakes, and 0.88% hydrogen by weight for dissolution heels. The bulk composition of dissolution heels reflects the composition of the original byproduct feed material, chloride salts of potassium, sodium, magnesium and calcium. The bulk composition of calcined hydroxide precipitation residues is composed of potassium chloride as a result of potassium hydroxide neutralization of hydrochloric acid solutions. Metal hydroxides generated during the hydroxide precipitation process are decomposed under the conditions of calcination to metal oxide forms.

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

Protonation Stimulates the Layered to Rock Salt Phase Transition of Ni‐Rich Sodium Cathodes

Abstract Protonation of oxide cathodes triggers surface transition metal dissolution and accelerates the performance degradation of Li‐ion batteries. While strategies are developed to improve cathode material surface stability, little is known about the effects of protonation on bulk phase transitions in these cathode materials or their sodium‐ion battery counterparts. Here, using NaNiO 2 in electrolytes with different proton‐generating levels as model systems, a holistic picture of the effect of incorporated protons is presented. Protonation of lattice oxygens stimulate transition metal migration to the alkaline layer and accelerates layered‐rock‐salt phase transition, which leads to bulk structure disintegration and anisotropic surface reconstruction layers formation. A cathode that undergoes severe protonation reactions attains a porous architecture corresponding to its multifold performance fade. This work reveals that interactions between electrolyte and cathode that result in protonation can dominate the structural reversibility/stability of bulk cathodes, and the insight sheds light for the development of future batteries.

25 ENERGY STORAGE↗
DOE OSTI2026

Rapid Analytical Methodology for Chloride Molten Salt Reactor Safeguards and Process Monitoring

Technologies that enable near real-time isotopic analysis of advanced molten salt reactor (MSR) fuels are critically needed to safeguard these reactors, increase their operational efficiency, and enable their widespread deployment with confidence. We present a systematic approach to developing near real-time dissolution and chemical isolation of U, Pu, and major fission products from highly radioactive chloride molten salt samples. Chemical yields greater than 95% were observed for both uranium and the lanthanides. Interference reduction enabled the detection and quantification of key diagnostic isotopes (including 112Ag, 147Nd, and 153Sm) that were previously undetectable in the original sample. The results from this initial scoping study lay the foundation for the development of future automated systems that can enable cost-efficient, near-real time chemical separation and analysis of extremely highly radioactive molten salt samples.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2020

Removal of Na + and Ca2 + with Prussian blue analogue electrodes for brackish water desalination

Desalination of brackish water sources is critical to addressing the growing global freshwater demand. One promising approach is electrically driven desalination using intercalation electrodes. While intercalation electrodes have been widely researched for energy storage applications, only a small subset of those materials is suitable for desalination. In this work, we report the synthesis, characterization, and in-device testing of three Prussian blue analogue intercalation compounds: copper, manganese, and zinc hexacyanoferrate with formulas K x M[Fe(CN) 6 ] z ·nH 2 O (M = Cu, Mn, Zn). The desalination performance for each of these materials against carbon electrodes is reported for Na + intercalation and for Ca 2+ intercalation using 1000 ppm NaCl and 1000 ppm CaCl 2 feed solutions, respectively. While the copper and manganese analogs showed promising performance for Na + and Ca 2+ intercalation, the zinc compound was unstable and underwent rapid dissolution. Manganese hexacyanoferrate showed the best desalination performance in terms of salt removal capacities and salt removal rates with NaCl while copper hexacyanoferrate performed the best with CaCl 2 . The manganese analog proved to be the most stable intercalation material, retaining 83% and 72% of its salt removal capacity after 280 cycles in NaCl and CaCl 2 feed solutions respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1969

Self-discharge in bimetallic cells containing alkali metal

Theoretical analysis of thermally regenerative bimetallic cells with alkali metal anodes shows a relation between the current drawn and the rate of discharge under open-circuit conditions. The self-discharge rate of the cell is due to the dissolution and ionization of alkali metal atoms in the fused-salt electrolyte

Foster, M. S.↗
DOE OSTI2025

Hot corrosion behavior of 304 & P91 graded composite transition joint under molten sulfate salts

A novel graded composite transition joint (GCTJ) between AISI 304 stainless steel and ASTM A335 P91 steel, has been demonstrated remarkablely superior creep performance compared to the conventional dissimilar metal weldment (DMW) under equivalent conditions. However, this advance is challenged by hot corrosion under salt deposition at elevated temperatures. Here, this study investigates the hot corrosion behavior of 304&P91 GCTJ exposed to sulfate salts at 700°C. Compared to the 304 steel, corrosion attacks initiate in the P91 triangle, where the dual-phase microstructure of ferrite and tempered martensite significantly influences pitting initiation. Anodic dissolution mainly occurs within the tempered martensite due to more vulnerable sites within the tempered martensite. With prolonged exposure, corrosion propagates across both phases, and the corrosion depth within the P91 triangle is related to the exposed surface area ratio between 304 and P91. Electrochemical analysis reveals the occurrence of galvanic corrosion between the 304 and P91, with a positive linear relationship between anodic dissolution current density (I a ) and the exposed surface area ratio between 304 and P91 in molten salts, further emphasizing the critical impact of this ratio on the corrosion severity in the P91 triangle. These findings underscore the importance of transition zone design optimization in mitigating localized corrosion.

Galvanic corrosion↗
DOE OSTI2021

Achieving Stable Molybdenum Oxide Cathodes for Aqueous Zinc-Ion Batteries in Water-in-Salt Electrolyte

A layered MoO 3 material with large interlayer spacing represents a promising cathode for aqueous rechargeable Zn-ion batteries (ARZIBs), but the implementation of this material is limited due to the intrinsically low conductivity and poor structural stability. A 30 m ZnCl 2 water-in-salt electrolyte (WISE) was introduced to a MoO 3 nanobelt cathode for the first time, significantly increasing the stability of MoO 3 cathodes compared to those in 3 M ZnSO 4 and 3 M ZnCl2 electrolyte. The Zn/MoO 3 cell in WISE unambiguously demonstrated significantly improved rate performance delivering 349, 253, and 222 mAh/g at 100, 500, and 1000 mA/g, denoting a 2×, and 12× capacity increase of those achieved in 3 M electrolytes at 500 and 1000 mA/g, respectively. A capacity retention rate of 73% was achieved after (dis)charging at 100 mA/g for 100 cycles, and no obvious capacity fading was observed at higher current densities of 500 mA/g and 2A/g. A compilation of structural and morphological characterization was systematically performed to provide insight into the mechanisms of the improved performance in ZnCl 2 WISE for the MoO3 cathode materials. Specifically, our data collectively suggested that the drastic fading in 3M electrolytes can be attributed to the parasitic surface deposits on Zn originated from Mo dissolution and H 2 formation due to Zn corrosion and hydrogen evolution reaction (HER), which were significantly suppressed in the ZnCl 2 WISE. The direct visualization of these side reactions was achieved for the first time in the Zn-MoO 3 system, using an in situ optoelectrochemical measurement.

25 ENERGY STORAGE↗
DOE OSTI2021

Stability of Calcium Ion Battery Electrolytes: Predictions from Ab Initio Molecular Dynamics Simulations

Multivalent batteries, such as magnesium-ion, calcium-ion, and zinc-ion batteries, have attracted significant attention as next-generation electrochemical energy storage devices to complement conventional lithium-ion batteries (LIBs). Among them, calcium-ion batteries (CIBs) are the least explored due to the difficult reversible Ca deposition-dissolution. In this work, we examined the stability of four different Ca salts with weakly coordinating anions and three different solvents commonly employed in existing battery technologies to identify suitable candidates for CIBs. By employing Born-Oppenheimer molecular dynamics (BOMD) simulations on salt-Ca and solvent-Ca interfaces, we find that the tetraglyme solvent and carborane salt are promising candidates for CIBs. Due to the strong reducing nature of the calcium surface, the other salts and solvents readily decompose. Further, we explain the microscopic mechanisms of salt/solvent decomposition on the Ca surface using time-dependent projected density of states, time-dependent charge-transfer plots, and climbing-image nudged elastic band calculations. Collectively, this work presents the first mechanistic assessment of the dynamical stability of candidate salts and solvents on a Ca surface using BOMD simulations, and provides a predictive path toward designing stable electrolytes for CIBs.

Born-Oppenheimer molecular dynamics↗
DOE OSTI2024

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40 degrees C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55 degrees C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Azam, Saad↗
DOE OSTI2021

Core-flood Effluent and Shale Surface Chemistries in Predicting Interaction between Shale, Brine, and Reactive Fluid

We report field and laboratory observations to date indicate that the efficiency of hydraulic fracturing, as it relates to hydrocarbon recovery, depends significantly on geochemical alterations to rock surfaces that diminish accessibility by partial or total plugging of the pore and fracture networks. This is caused by mineral scale deposition such as coating of fracture surfaces with precipitates, particle migration, and/or crack closure due to dissolution under stress. In reactive flow-through experiments, mineral reactions in response to acidic fluid injection significantly reduced system porosity and core permeability. The present study focuses on changes to fluid chemistry and shale surfaces (inlet and fracture walls) resulting from shale-fluid interactions and integrating these findings for an improved estimate of transport-related consequences. The reacted shale surfaces were examined by spatially-resolved scanning electron microscopy - energy dispersive spectroscopy (SEM-EDS) analysis. Importantly, inductively coupled plasma - mass spectrometry/optical emission spectroscopy (ICP-MS/OES) was utilized to probe the chemical evolution of the core-flood effluents. The three study cores selected from the Marcellus formation represent different mineralogies and structural features. In flow-through experiments, lab-generated brine and HCl-based fracture fluid (pH=2) were injected sequentially under effective stress (up to 500 psi) at reservoir temperature (80°C). SEM-EDS results confirmed by the ICP concentration trends showed significant Fe hydroxide precipitates in clay- and pyrite-rich outcrop samples due to partial oxidation of Fe-bearing phases in the case of intrusion of low salinity water-based fluids. Porosity reduction in the MSEEL (Marcellus Shale Energy and Environmental Laboratory) carbonate-rich sample is related to compaction of cores under stress due to matrix softening with substantial dissolution, and pore-filling by hydroxides, as well as barite and salts. Despite the same fluid compositions and experimental conditions used for both MSEEL samples, barite precipitation was much more intense in the MSEEL clay-rich sample due to its greater sorption capacity and additional sulfate source as well as fissile nature with multiple lengthwise cracks. ICP tests revealed time-resolved concentration trends in produced brine and reactive fluids that in turn complemented the pre-/post-reaction SEM-EDS observations.

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

Heuristics for Molten-Salt Synthesis of Single-Crystalline Ultrahigh-Nickel Layered Oxide Cathodes

In pursuit of Li-ion batteries with higher energy density, ultrahigh-nickel layered oxides are a leading candidate for next-generation cathode materials. Single-crystalline morphology offers a neat solution to the poor stability of ultrahigh-Ni cathodes; a lower active surface area mitigates electrolyte decomposition at high voltages, and the elimination of grain boundaries improves mechanical resilience and increases volumetric energy density. However, single-crystal cathodes possess their own challenges, several of which originate from synthesis at elevated temperatures meant to induce grain growth. Molten-salt synthesis is an alternative method for obtaining single crystals, accelerating grain growth through the presence of a molten flux without the need for increased temperature. Herein, we offer heuristic guidelines for molten-salt synthesis, discussing key factors for designing reaction mixtures and the necessary exploratory research for novel molten salt/cathode systems. Here, the influence of different salts and synthesis conditions on the morphology and properties of single-crystal LiNiO 2 is presented. It is found that oxidative salts, such as Li 2 O 2 and LiNO 3 , are crucial to supplementing dissolution of gaseous oxygen into the molten phase. Through these discussions, this work aims to provide a set of overarching principles for obtaining higher-quality single-crystal layered oxide cathodes and engender more rigorous and impactful investigation into their fundamental nature and applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Comprehensive parametric study of CO 2 sequestration in deep saline aquifers

Carbon dioxide injection in deep saline aquifers is a key method for permanently sequestering anthropogenic CO 2 . Here this study employs a reactive transport model to explore mineral precipitation/dissolution and its impact on reservoir properties in deep saline aquifers. We also assess capillary pressure and relative permeability hysteresis on various CO 2 trapping mechanisms. Results from this study reveal the significant influence of initial brine composition on mineral precipitation/dissolution. The dissolution and precipitation of minerals have different effects around the wellbores compared to the overall reservoir. Additionally, salt concentration (Ca ++ and Mg ++ ) and quartz surface area affect CO 2 mineralization, while Na + impacts halite precipitation, altering flow properties. The effect of capillary pressure is significant, as including the capillary pressure in the simulation case resulted in significantly improved CO 2 trapping, achieving almost total dissolution of the injected CO 2 in around 300 years. This study offers novel insights into the interactions of reservoir minerals, brine properties, and the injected CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Effect of seawater as mixing water on the hydration behaviour of tricalcium aluminate

This study explored the mechanism of the effect of seawater on tricalcium aluminate (C{sub 3}A) hydration. The results showed that seawater retarded C{sub 3}A hydration and reduced the reaction degree of C{sub 3}A. The co-existence or ion pairing of Ca{sup 2+} and SO{sub 4}{sup 2−} onto the surface of C{sub 3}A poisoning the reactive sites is the main reason for this retardation. Besides, the precipitation of Mg(OH){sub 2} on the surface of C{sub 3}A would prolong the induction period for another 30 min and then consequently decrease the dissolution rate of C{sub 3}A hydration. Trace amounts of MgSO{sub 4}{sup 0} and Mg{sup 2+} present in the alkaline solution had little retardation effect. It was also found that Cl{sup −} would preferentially react with C{sub 3}A to form Friedel's salt, rather than forming hydroxy-AFm as that in the C{sub 3}A-deionized water paste. The direct formation of Friedel's salt resulted in an accumulation of Al{sup 3+} in solution, which would also hinder the subsequent dissolution of C{sub 3}A.

36 MATERIALS SCIENCE↗
NASA NTRS1985

Aircraft measurements of ammonia and nitric acid in the lower troposphere

The first simultaneous measurements of ammonia and nitric acid in the troposphere have been made from an aircraft using a tungsten oxide denuder system. Vertical profiles of NH3 and HNO3 taken over coastal Virginia and Maryland in March and September, 1983, at altitudes from 150 m to 3000 m, show mixing ratios that decrease with altitude. Ammonia profiles show substantial seasonal variation, while nitric acid profiles do not. Using the measured profiles and a one-dimensional photochemical model, lifetimes due to heterogeneous loss of one day for HNO3 and ten days for NH3 are calculated. In contrast, NH3 profiles up to 5300 m over the North Atlantic Ocean during August 1982 show mixing ratios that increase slightly with altitude. These data represent the first ammonia profiles measured over the ocean. It is suggested that the increase in NH3 with altitude is a result of an ammonia-rich continental air mass advected over the ocean, followed by the dissolution of NH3 in the marine boundary layer on water-covered sea salt particles.

Lebel, P. J.↗
DOE OSTI2022

Unveiling Charge Transport and Degradation Mechanisms of Aqueous Zn|α-MoO 3 Batteries in Conventional Concentration and Water-in-Salt Electrolytes: A Multi-Modal In Situ and Operando Study

Herein charge storage and transport properties are elucidated and cell degradation mechanisms of rechargeable aqueous Zn|alpha-MoO 3 batteries in three electrolyte systems (3 m ZnSO 4 , 3 m ZnCl 2 , and 30 m ZnCl 2 [12.5 m] water-in-salt (WIS)) are distinguished by a combination of in situ X-ray diffraction (XRD), in situ X-ray absorption spectroscopy (XAS), operando optoelectrochemistry, and operando energy dispersive X-ray diffraction (EDXRD). In conventional concentration 3 m electrolytes, in situ XRD and XAS, as well as ex situ scanning transmission electron microscopy data collectively support Zn 2+ as the primary charge carrier. In addition, these systems are susceptible to cathode dissolution, Zn corrosion coupled with the hydrogen evolution reaction, and the resultant formation of basic zinc salt phases. The multi-modal in situ and operando experimental analyses validate facile H+ intercalation and extraction in concentrated 30 m ZnCl 2 WIS electrolyte. Via operando EDXRD, reaction front and charge transport limitation during discharge and charge in the viscous WIS electrolyte are spatially tracked. Here this work provides new insight into the stability and degradation mechanisms of aqueous zinc batteries during static storage and upon dynamic cycling, and highlights the utility of in situ and operando techniques in understanding the superior stability of WIS electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2020

Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces

In this work, we examine the evolution of events occurring when a Li metal surface is in contact with a 2 M solution of a Li salt in a solvent or mixture of solvents, via classical molecular dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidation and electrolyte reduction along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some organics) is characterized. The analysis clearly reveals the details of these physical–chemical events as a function of time, during 20 nanoseconds. The effects of the chemistry of the electrolyte on Li oxidation and dissolution in the liquid electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF 6 and LiCF 3 SO 3 , and various solvents including ethers and carbonates and mixtures of them. The kinetics and thermodynamics of Li 6 F, the core nuclei in the LiF crystal, are studied by analysis of the MD trajectories, and via density functional theory calculations respectively. The SEI formed in this computational experiment is the “native” film that would form upon contact of the Li foil with the liquid electrolyte. As such, this work is the first in a series of computational experiments that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.

25 ENERGY STORAGE↗