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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Garnet-Type Solid-Electrolyte-Based Molten Lithium–Molybdenum–Iron(II) Chloride Battery with Advanced Reaction Mechanism

Solid-electrolyte-based molten-metal batteries have attracted considerable attention for grid-scale energy storage. Although ZEBRA batteries are considered one of the promising candidates, they still have the potential concern of metal particle growth and ion exchange with the β”-Al 2 O 3 electrolyte. Herein, a Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 solid-electrolyte-based molten lithium–molybdenum–iron(II) chloride battery (denoted as Li–Mo–FeCl 2 ) operated at temperature of 250 °C, comprising a mixture of Fe and LiCl cathode materials, a Li anode, a garnet-type Li-ion ceramic electrolyte, and Mo additive, is designed to overcome these obstacles. Different from conventional battery reaction mechanisms, this battery revolutionarily synchronizes the reversible Fe–Mo alloying–dealloying reactions with the delithiation–lithiation processes, meaning that the porous Mo framework derived from Fe–Mo alloy simultaneously suppresses the growth of pure Fe particles. By adopting a Li anode and a Li-ion ceramic electrolyte, the corrosion problem between the cathode and the solid electrolyte is overcome. With similar battery cost ($12 kWh –1 ), the theoretical energy density of Li–Mo–FeCl 2 battery surpasses that of a Na–FeCl 2 ZEBRA battery over 25%, to 576 Wh kg –1 and 2216 Wh L –1 , respectively. Experimental results further prove this cell has excellent cycling performance (472 mAh g LiCl –1 after 300 cycles, 50 mg active material) and strong tolerance against the overcharge–overdischarge (3–1.6 V) and freezing–thawing (25–250 °C) incidents.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Corrosion characteristics of Mo and TZM alloy for plasma facing components in molten lithium at 623 K

Here, in this study, the corrosion behaviours of molybdenum (Mo) and a Mo-based alloy (TZM) were investigated using a static immersion corrosion technique. Weight loss, surface microstructure, and corrosion depth of Mo and the TZM alloy were correlated with elements. The compatibility of Mo and the TZM alloy in static liquid Li was suitable. Mo demonstrated uniform corrosion with a homogenous dissolution of free C and Mo, and TZM alloy exhibited a nonuniform corrosion behaviour with a preferential grain boundary attack caused by the selective dissolution of free C, Ti, and Zr. When the surface oxidation layer of the samples was consumed, free C from Mo and TZM diffused into molten Li to form Li 2 C 2 and then was captured by Zr, Ti, and Mo to form thermodynamically stable carbides, which resulted in the enrichment of the C layer near the sample surfaces. In addition, Ti and Zr acted as N-trappers in liquid Li; the formation of Zr and Ti nitrides resulted in the enrichment of N, Ti, and Zr elements on the surface and led to TZM corrosion increase. Thus, Zr and Ti depletion, pitting, and grain boundary corrosion were problematic for TZM under long-term exposure to liquid Li. Reducing the content of free C and nonmetallic N and increasing the amount of Ti and Zr carbides on the surface of and inside the raw TZM alloy helped improve the corrosion resistance of TZM in liquid Li.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Molten Lithium-Brass/Zinc Chloride System as High-Performance and Low-Cost Battery

Batteries with high safety, low cost, and reasonable energy density are essential for grid-scale energy storage and still remain elusive. In this paper, we report a solid electrolyte-based liquid lithium-brass/zinc chloride (SELL-brass/ZnCl 2 ) battery using garnet-type lithium-ion solid electrolyte, lithium anode, and brass/ZnCl 2 cathode. The chemistry of the cell reaction and the ability of being assembled in discharged state ensures a high safety. The use of low-cost ZnCl 2 cathode can realize a low cell material cost of $16 kWh –1 . The adoption of lithium anode guarantees a high theoretical energy density of 750 Wh kg –1 and 2,250 Wh L –1 . Moreover, by using brass powder as a Zn source in the cathode, the Zn particle growth issue is successfully solved, and a good cycling stability of the battery can be obtained. As full cell performance and scalability are also verified, our SELL-brass/ZnCl 2 battery shows a high potential for practical use in grid energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

The high-pressure lithium–palladium and lithium–palladium–hydrogen systems

Abstract The lithium–palladium and lithium–palladium–hydrogen systems are investigated at high pressures at and above room temperature. Two novel lithium–palladium compounds are found below $${18.7}\,{\mathrm{GPa}}$$ 18.7 GPa . An ambient temperature phase is tentatively assigned as $$F{\bar{4}}3m\,\hbox {Li}_{17}\hbox {Pd}_{4}$$ F 4 ¯ 3 m Li 17 Pd 4 , with $$a = 17.661(1)$$ a = 17.661 ( 1 ) Å at 8.64 GPa, isostructural with $$\hbox {Li}_{17}\hbox {Sn}_{4}$$ Li 17 Sn 4 . The other phase occurs at high-temperature and is $$I{\bar{4}}3m\, \hbox {Li}_{11}\hbox {Pd}_{2}$$ I 4 ¯ 3 m Li 11 Pd 2 , $$a = 9.218(1)$$ a = 9.218 ( 1 ) Å at 3.88 GPa and 200 $$^\circ {\mathrm{C}}$$ ∘ C , similar to $$\hbox {Li}_{11}\hbox {Pt}_{2}$$ Li 11 Pt 2 , which is also known at high pressure. The presence of hydrogen in the system results in an $$I{\bar{4}}3m$$ I 4 ¯ 3 m structure with $$a = 8.856(1)$$ a = 8.856 ( 1 ) Å at 9.74 GPa. This persists up to $${13.3}\,\mathrm{GPa}$$ 13.3 GPa , the highest pressure studied. Below $${2}\,{\mathrm{GPa}}$$ 2 GPa an fcc phase with a large unit cell, $$a = 19.324(1)$$ a = 19.324 ( 1 ) Å at 0.39 GPa, is also observed in the presence of hydrogen. On heating the hydrogen containing system at 4 GPa the $$I{\bar{4}}3m$$ I 4 ¯ 3 m phases persists to the melting point of lithium. In both systems melting the lithium results in the loss of crystalline diffraction from palladium containing phases. This is attributed to dissolution of the palladium in the molten lithium, and on cooling the palladium remains dispersed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

The high-pressure lithium-palladium and lithium-palladium-hydrogen systems

The lithium-palladium and lithium-palladium-hydrogen systems are investigated at high pressures at and above room temperature. Two novel lithium-palladium compounds are found below 18.7 GPa. An ambient temperature phase is tentatively assigned as $F\bar{4}3m$ Li 17 Pd 4 , with a = 17.661(1) Å at 8.64 GPa, isostructural with Li 17 Sn 4 . The other phase occurs at high-temperature and is $I\bar{4}3m$ Li 11 Pd 2 , a = 9.218(1) Å at 3.88 GPa and 200 °C, similar to Li 11 Pt 2 , which is also known at high pressure. The presence of hydrogen in the system results in an $I\bar{4}3m$ structure with a = 8.856(1) Å at 9.74 GPa. This persists up to 13.3 GPa, the highest pressure studied. Below 2 GPa an fcc phase with a large unit cell, a = 19.324(1) Å at 0.39 GPa, is also observed in the presence of hydrogen. On heating the hydrogen containing system at 4 GPa the $I\bar{4}3m$ phases persists to the melting point of lithium. In both systems melting the lithium results in the loss of crystalline diffraction from palladium containing phases. This is attributed to dissolution of the palladium in the molten lithium, and on cooling the palladium remains dispersed.

Frost, Mungo↗
DOE OSTI2024

Spectro-electrochemistry of vanadium ions in LiCl-KCl-VCl2,3

Owing to their relatively high thermal conductivity and corrosion resistance, and low radiation heating and embrittlement properties, vanadium (V) alloys are being considered for fusion blanket structural materials. As such, the fundamental behavior of these materials, including the speciation of their corrosion products in molten lithium salts, must be elucidated to enable quantitative lifetime prediction. Yuan et al. [REF#1] demonstrated the reduction and oxidation of vanadium ions in molten LiCl-KCl eutectic salt using a tungsten wire, indicating the possibility of metallic vanadium reduction from V3+ negative potentials

36 - MATERIALS SCIENCE↗
DOE OSTI2022

Radiation-induced reaction kinetics of Zn 2+ with e S - and Cl 2 ˙ - in Molten LiCl–KCl eutectic at 400–600 °C

We report molten chloride salts are currently under consideration as combined coolant and liquid fuel for next-generation molten salt nuclear reactors. Unlike complementary light-water reactor technologies, the radiation science underpinning molten salts is in its infancy, and thus requires a fundamental mechanistic investigation to elucidate the radiation-driven chemistry within molten salt reactors. Here we present an electron pulse radiolysis kinetics study into the behaviour of the primary radiolytic species generated in molten chloride systems, i.e., the solvated electron (e S - ) and di-chlorine radical anion (Cl 2 ˙- ). We examine the reaction of e S - with Zn 2+ from 400–600 °C (E a = 30.31 ± 0.09 kJ mol -1 ), and the kinetics and decay mechanisms of Cl 2 ˙- in molten lithium chloride-potassium chloride (LiCl–KCl) eutectic. In the absence of Zn 2+ , the lifetime of e S - was found to be dictated by residual impurities in ostensibly “pure” salts, and thus the observed decay is dependent on sample history rather than being an intrinsic property of the salt. The decay of Cl 2 ˙- is complex, owing to the competition of Cl 2 ˙- disproportionation with several other chemical pathways, one of which involves reduction by radiolytically-produced Zn + species. Overall, the reported findings demonstrate the richness and complexity of chemistry involving the interactions of ionizing radiation with molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Kinetics of Radiation-induced Cr( II ) and Cr( III ) Redox Chemistry in Molten LiCl-KCl Eutectic

Chromium (Cr) is a frequent constituent of the metal alloys proposed for molten salt nuclear reactor (MSR) applications, and is typically the least noble metal ion present. Consequently, chromium is preferentially corroded into molten salt solutions. Here, the redox poise and redox cycling of chromium ions in the salt can greatly influence its corrosivity towards structural alloys, ultimately impacting the longevity of MSR systems. Radiation-induced chemistry is expected to play a significant role in determining the chromium oxidation state distribution during MSR operations. In the present research, electron pulse radiolysis techniques were employed to characterize the reactivity of Cr(II) and Cr(III) ions with primary radiolysis products in molten lithium chloride–potassium chloride (LiCl–KCl) eutectic over a temperature range of 400–600 °C. Both chromium oxidation states were found to rapidly react with the primary products of molten chloride salt radiolysis, i.e., the solvated electron (e S - ) and the dichlorine radical anion (Cl 2 ˙ - ). For reactions with the e S - , second-order rate coefficients (k) of k = (4.1 ± 0.2) and (6.1 ± 0.3) × 10 10 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively, were determined. Temperature-dependent measurements allowed for the derivation of activation parameters for electron capture by Cr(II) and Cr(III). Both chromium ions also react with Cl 2 ˙ - , k = (7.2 ± 0.3) and (1.4 ± 0.1) × 10 9 M -1 s -1 at 400 °C for Cr(II) and Cr(III), respectively.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2021

Temperature-Dependent Properties of Molten Li 2 BeF 4 Salt Using Ab Initio Molecular Dynamics

Molten lithium tetrafluoroberyllate (Li 2 BeF 4 ) salt, also known as FLiBe, with a 2:1 mixture of LiF and BeF 2 is being proposed as a coolant and solvent in advanced nuclear reactor designs, such as the molten salt reactor or the fluoride salt cooled high-temperature reactor. We present the results on the structure and properties of FLiBe over a wide range of temperatures, 0–2000 K, from high-throughput ab initio molecular dynamics simulation using a supercell model of 504 atoms. The variations in the local structures of solid and liquid FLiBe with temperature are discussed in terms of a pair distribution function, coordination number, and bond angle distribution. The temperature-dependent electronic structure and optical and mechanical properties of FLiBe are calculated. The optical and mechanical property results are reported for the first time. The results above and below the melting temperature (~732 K) are compared with the experimental data and with data for crystalline FLiBe. The electronic structure and interatomic bonding results are discussed in correlation with the mechanical strength. A novel concept of total bond order density (TBOD), an important quantum mechanical parameter, is used to characterize the internal cohesion and strength in the simulated models. The results show a variation in the rate of change in properties in solid and liquid phases with anomalous behavior across the melting region. The observed trend is the decrease in mechanical strength, band gap, and TBOD in a nonlinear fashion as a function of temperature. The refractive index shows a surprising minimum at 850 K, among the tested temperatures, which lies above the melting point. These findings provide a new platform to understand the interplay between the temperature-dependent structures and properties of FLiBe salt.

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

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↗
DOE OSTI2022

High-pressure CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes

CO 2 permeation properties and stability of ceramic-carbonate dual-phase membranes at high pressures/temperatures are critical to their CO 2 separation and membrane reactor applications, but such data are not available in the literature. Here, this work aims to study the effect of high transmembrane pressure on CO 2 permeation flux and the stability of molten carbonate in the dual-phase samarium-doped ceria (SDC) and molten-carbonate (MC) membranes. Dead-end porous SDC tubular supports were made by a cold isostatic press (CIP)/sintering method with a low porosity (below 7%), and gas-tight SDC-MC membranes were prepared by direct infiltration of molten lithium and sodium carbonate mixture into SDC pores, with a MC volume fraction less than 7%. CO 2 permeation/separation tests were performed on the SDC-MC membranes using feed gas of equal molar CO 2 /N 2 mixture at feed pressures up to 15 atm and sweep gas of helium at 1 atm. CO 2 permeation flux for the SDC-MC membranes depends logarithmically on feed/permeate CO 2 pressure ratio in 660–810°C. The temperature dependence of CO 2 permeation shows activation energy of 30 kJ/mol. Due to the small MC volume fraction and hence low effective carbonate conductivity, CO 2 permeation of the SDC-MC membranes is dominated by the carbonate ionic conduction in the MC phase. The SDC-MC membranes remain in the same structure, morphology, and gas-tightness after CO 2 separation tests at high feed pressures and temperatures, showing high stability of SDC-MC membranes for high-temperature, high-pressure separation and chemical reaction applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Consequences of sp 2 –sp 3 boron isomerization in supercooled liquid borates

In this study, time-resolved high-energy synchrotron x-ray total scattering measurements on supercooled molten lithium metaborate (LiBO 2 ) reveal an isomerization reaction involving conversion of trigonal sp 2 boron to tetrahedral sp 3 boron during quenching and glass formation. Van't Hoff analysis yields an accurate enthalpy change, ΔH = 21(1) kJ mol –1 boron, from which we develop an analytical model for the sp 3 isomer fraction and its contribution to configurational heat capacity (C p conf ) and entropy as a function of temperature and composition. Isomerization constitutes 40% of the total calorimetric C p conf at the glass transition for LiBO 2 and directly contributes to the observed rise in liquid fragility with the lithium content.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Magnetic Bearing Pumps for Molten Salt Fusion Energy Devices

The Commonwealth Fusion Systems (CFS) ARC reactor will employ a novel liquid immersion blanket design that uses a molten lithium salt as both the tritium-breeding material and the vacuum vessel coolant. fluoride lithium beryllium (FLiBe) (a lithium fluoride–beryllium difluoride mixture) is currently the leading salt candidate. Its low-Z components provide good moderation, it has adequate heat transfer properties and low electrical conductivity, and it has good neutron multiplication properties, which further enhance tritium production.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Electrolytic recovery of metals from lithium battery cathodes in moisture-tolerant molten hydroxide salt

Lithium-ion battery recycling offers an opportunity to develop innovative technologies to close the loop on the battery materials cycle and increase the resilience of the battery supply chain. Here, in this study, we demonstrate a two-step pyroelectrochemical method for producing mixed-metals from lithium-ion cathodes in a molten hydroxide salt. Mixed metal oxides in the form of insoluble lithium-ion cathode materials of LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) and spent lithium-ion battery materials (black mass) were electrochemically reduced to a soluble form and dissolved into a molten hydroxide salt bath. Electrochemical characterization of the process salt indicated accumulation of dissolved transition metals in the salt. A separate cathode was used to produce alloys of Ni, Mn, and Co electrochemically from the dissolved lithium-ion cathode materials. Characterization by scanning electron microscopy fitted with an energy dispersive X-ray spectrometer showed transition metals present in the cathode materials were recovered at the separate cathode. This approach represents a scalable, low temperature pyroelectrochemical process that can potentially reduce the cost and close the loop of battery cathode recycling.

25 ENERGY STORAGE↗
DOE OSTI2025

Demonstration of Electroreduction Technology to Convert GNF Uranium Oxide Powder to Metal

Global Nuclear Fuel – Americas LLC (GNF) has partnered with Argonne National Laboratory to demonstrate electroreduction of uranium oxides produced by deconversion of UF 6 to uranium metal through the Gateway for Accelerated Innovation in Nuclear (GAIN) program under the U.S. Department of Energy to accelerate the domestic production of metallic advanced reactor fuels. Electroreduction of uranium oxide was first demonstrated and patented by Argonne in the early 2000s as a technology to convert used oxide nuclear fuel from light water reactors to metal for further fuel reprocessing. More recently, electroreduction has been proposed as a front-end technology for metallization of uranium oxides produced by deconversion of UF 6 and for scrap recovery of oxide materials. During the electroreduction process, UO 2 powder is contained in a stainless-steel mesh basket with a cathode lead located in the center of the UO 2 bed. The basket is immersed in lithium chloride molten salt electrolyte containing 1 wt% lithium oxide along with a platinum anode and a nickel/nickel oxide (Ni/NiO) reference electrode. Current is applied to the cell between the cathode and anode to reduce the UO 2 to metallic uranium via a solid-state reduction reaction. Oxide ions released from the UO 2 during reduction are transported through the salt to the anode where oxygen gas is evolved. Once reduction is complete, the basket containing the metallicized uranium is removed from the salt and can be processed to remove the salt and consolidate the uranium into an ingot for use in metallic fuel fabrication. This project was performed to provide evidence of the electroreduction technology readiness level for metallization of UO 2 powder, identify and retire technical risks for industrialization of electroreduction, and accelerate the path to commercialization for metallic fast reactor fuel production. To that end, five electroreduction tests were performed with UO 2 provided by GNF and the resulting product was analyzed for the extent of conversion to metal and for impurity contents of the metal product to verify that electroreduction does not introduce impurities that would prevent use of the product in metallic fuel fabrication.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic

Alternatives to the widely-used standard anodic decomposition reference electrodes in molten salts are necessary to enable more easily reproduced thermochemical and electrochemical data in molten salt electrolytes. The class of standard reference electrodes called cathodic decomposition electrodes (CDEs) are easily constructed and can be used to make thermochemical measurements in molten salts more directly compared to anodic decomposition electrodes. The lithium eutectic electrode (LEE) was chosen as a sample test case for validation and was applied to thermochemical measurements of electroactive species in molten LiCl-KCl eutectic. Transient measurements were made to measure the Li + /Li reduction potential at zero current in pure LiCl-KCl eutectic relative to a Li-alloy reference electrode to validate the reference potential of the LEE. Literature-reported electromotive force measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode and this relationship was used to evaluate measured and reported formal potential measurements for the LiCl-KCl-GdCl 3 system. This work demonstrates the general framework for defining CDEs for any molten salt system and a method for calibrating external reference electrodes against a CDE standard reference electrode, improving the ease of obtaining thermochemical and electrochemical measurements in any molten salt system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗