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At least 19 records

Hot filament technique for measuring the thermal conductivity of molten lithium fluoride

Molten salts, such as lithium fluoride, are attractive candidates for thermal energy storage in solar dynamic space power systems because of their high latent heat of fusion. However, these same salts have poor thermal conductivities which inhibit the transfer of heat into the solid phase and out of the liquid phase. One concept for improving the thermal conductivity of the thermal energy storage system is to add a conductive filler material to the molten salt. High thermal conductivity pitch-based graphite fibers are being considered for this application. Although there is some information available on the thermal conductivity of lithium fluoride solid, there is very little information on lithium fluoride liquid, and no information on molten salt graphite fiber composites. This paper describes a hot filament technique for determining the thermal conductivity of molten salts. The hot filament technique was used to find the thermal conductivity of molten lithium fluoride at 930 C, and the thermal conductivity values ranged from 1.2 to 1.6 W/mK. These values are comparable to the slightly larger value of 5.0 W/mK for lithium fluoride solid. In addition, two molten salt graphite fiber composites were characterized with the hot filament technique and these results are also presented.

Jaworske, Donald A.↗

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↗

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↗

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↗

High-Energy Two-Stage Pulsed Plasma Thruster

A high-energy (28 kJ per pulse) two-stage pulsed plasma thruster (MSFC PPT-1) has been constructed and tested. The motivation of this project is to develop a high power (approximately 500 kW), high specific impulse (approximately 10000 s), highly efficient (greater than 50%) thruster for use as primary propulsion in a high power nuclear electric propulsion system. PPT-1 was designed to overcome four negative characteristics which have detracted from the utility of pulsed plasma thrusters: poor electrical efficiency, poor propellant utilization efficiency, electrode erosion, and reliability issues associated with the use of high speed gas valves and high current switches. Traditional PPTs have been plagued with poor efficiency because they have not been operated in a plasma regime that fully exploits the potential benefits of pulsed plasma acceleration by electromagnetic forces. PPTs have generally been used to accelerate low-density plasmas with long current pulses. Operation of thrusters in this plasma regime allows for the development of certain undesirable particle-kinetic effects, such as Hall effect-induced current sheet canting. PPT-1 was designed to propel a highly collisional, dense plasma that has more fluid-like properties and, hence, is more effectively pushed by a magnetic field. The high-density plasma loading into the second stage of the accelerator is achieved through the use of a dense plasma injector (first stage). The injector produces a thermal plasma, derived from a molten lithium propellant feed system, which is subsequently accelerated by the second stage using mega-amp level currents, which eject the plasma at a speed on the order of 100 kilometers per second. Traditional PPTs also suffer from dynamic efficiency losses associated with snowplow loading of distributed neutral propellant. The twostage scheme used in PPT-I allows the propellant to be loaded in a manner which more closely approximates the optimal slug loading. Lithium propellant was chosen to test whether or not the reduced electrode erosion found in the Lithium Lorentz Force Accelerator (LiLFA) could also be realized in a pulsed plasma thruster. The use of the molten lithium dense plasma injector also eliminates the need for a gas valve and electrical switch; the injector design fulfills both roles, and uses no moving parts to provide, in principle, a highly reliable propellant feed and electrical switching system. Experimental results reported in this paper include: second-stage current traces, high-speed photographic and holographic imaging of the thruster exit plume, and internal mapping of the discharge chamber magnetic field from B-dot probe data. The magnetic field data is used to create a two-dimensional description of the evolution of the current sheet inside the thruster.

Markusic, Tom↗

A survey of advanced battery systems for space applications

The results of a survey on advanced secondary battery systems for space applications are presented. The objectives were: to identify advanced battery systems capable of meeting the requirements of various types of space missions, with significant advantages over currently available batteries, to obtain an accurate estimate of the anticipated improvements of these advanced systems, and to obtain a consensus for the selection of systems most likely to yield the desired improvements. Few advanced systems are likely to exceed a specific energy of 150 Wh/kg and meet the additional requirements of safety and reliability within the next 15 years. The few that have this potential are: (1) regenerative fuel cells, both alkaline and solid polymer electrolyte (SPE) types for large power systems; (2) lithium-intercalatable cathodes, particularly the metal ozides intercalatable cathodes (MnO2 or CoO2), with applications limited to small spacecrafts requiring limited cycle life and low power levels; (3) lithium molten salt systems (e.g., LiAl-FeS2); and (4) Na/beta Alumina/Sulfur or metal chlorides cells. Likely technological advances that would enhance the performance of all the above systems are also identified, in particular: improved bifunctional oxygen electrodes; improved manufacturing technology for thin film lithium electrodes in combination with polymeric electrolytes; improved seals for the lithium molten salt cells; and improved ceramics for sodium/solid electrolyte cells.

Attia, Alan I.↗

Evaluation of T-111 forced-convection loop tested with lithium at 1370 C

A T-111 alloy (Ta-8% W-2% Hf) forced-convection loop containing molten lithium was operated 3000 hr at a maximum temperature of 1370 C. Flow velocities up to 6.3 m/sec were used, and the results of this forced-convection loop are very similar to those observed in lower velocity thermal-convection loops of T-111 containing lithium. Weight changes were determined at 93 positions around the loop. The maximum dissolution rate occurred at the maximum wall temperature of the loop and was less than 1.3 microns/year. Mass transfer of hafnium, nitrogen, and, to a lesser extent, carbon occurred from the hotter to cooler regions. Exposed surfaces in the highest temperature region were found to be depleted in hafnium to a depth of 60 microns with no detectable change in tungsten content. There was some loss in room-temperature tensile strength for specimens exposed to lithium at 1370 C, attributable to depletion of hafnium and nitrogen and to attendant grain growth.

Devan, J. H.↗

The Au Cathode in the System Li2CO3-CO2-CO at 800 to 900 C

Gold is one of several metals being evaluated at NASA Lewis Research Center as positive electrode catalysts for an alkali metal/molten alkali metal carbonate/carbon dioxide electrochemical cell. Such a cell is proposed for CO2-rich planetary atmospheres such as those of Mars and Venus. Its application could be as a primary power supply, as a secondary power supply recharged either 'chemically' by replenishment of the alkali metal or electrochemically from a central station power source, or as a converter of carbon dioxide to oxygen via a complete electrochemical cycle. For the work being reported, lithium was assumed to be the alkali metal of choice for the negative electrode of the cell, and therefore molten lithium carbonate was the electrolyte used in the Au electrode experiments. Cathodic linear sweep voltammetry (LSV) was the primary analytical technique for evaluating the performance of the Au cathode. interest comprised the cell temperature and the total pressure and composition of the reactant gas. In the absence of operational difficulties, the effect of bubbling the reactant gas through the melt was also determined. On the basis of the variation of electrode performance with changes in these parameters, inferences have been made concerning the electrochemical and chemical processes at and near the electrode. The results of post-test micrographic analyses of the Au cathode are also presented. An attempt is then made to project from the experimental results to some relevant conclusions pertaining to a gold cathode in a practical alkali metal - carbon dioxide cell.

Hagedorn, Norman H.↗

Control of internal and external short circuits in lithium batteries using a composite thermal switch

A composite material has been developed, consisting of a blend of metal and fluorocarbon particles, which behaves as an electronic conductor at room temperature and which abruptly becomes an insulator at a predetermined temperature. This switching behavior results from the difference in thermal expansion coefficients between the conductive and non-conductive portions of the composite. This material was applied as a thin film between the carbon cathode in Li/SOCl2 cells, and the metallic cathode current collector. Using test articles incorporating this feature it was shown that lithium cells externally heated or internally heated during a short circuit lost rate capability and the ability to overheat well below the melting point of lithium (180 C). Thus, during an internal or external cell short circuit, the potential for thermal runaway involving reactions of molten lithium is avoided.

Mcdonald, Robert C.↗

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↗

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↗

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↗

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↗

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↗

Compatibility of molten salts with advanced solar dynamic receiver materials

Metal-coated graphite fibers are being considered as a thermal conductivity enhancement filler material for molten salts in solar dynamic thermal energy storage systems. The successful metal coating chosen for this application must exhibit acceptable wettability and must be compatible with the molten salt environment. Contact angle values between molten lithium fluoride and several metal, metal fluoride, and metal oxide substrates have been determined at 892 C using a modification of the Wilhelmy plate technique. Reproducible contact angles with repeated exposure to the molten LiF indicated compatibility.

Jaworske, D. A.↗