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At least 37 records · Page 2

A Molten Salt Electrochemical Process for the Preparation of Cost-Effective p-Block (Coating) Materials

Solar energy applications rely heavily on p-block elements and transition metals. Silicon is, by far, the most commonly used material in photovoltaic cells and accounts for about 85% of modules sold presently. Of late, thin film photovoltaic cells have gained momentum because of their higher efficiencies. Most of these thin film devices are made out of just five elements, namely, cadmium, tellurium, selenium, indium, gallium and copper. The present manuscript describes an elegant and inexpensive molten salt-based electrolytic process for fabricating a tellurium-coated metallic substrate. A three-electrode set up was employed to coat iridium with tellurium from a molten bath containing lithium chloride, lithium oxide and tellurium tetrachloride (LiCl-Li 2 O-TeCl 4 ) at 650 °C for a duration ranging from 30 to 120 min under a galvanostatic mode. The tellurium coating was observed to be thick, uniform, smooth and homogeneous. Additionally, the deposited tellurium did not chemically react with the iridium substrate to form intermetallic compounds, which is a good feature from the standpoint of the device’s performance characteristics. The present process, being generic in nature, shows the potential for the manufacture of both the coated substates and high-purity elements not just for tellurium but also for other p-block elements.

36 MATERIALS SCIENCE↗

Removal and Deactivation of Bond Sodium from Fast Reactor Blanket Materials

The disposition of sodium-bonded spent nuclear fuel and blanket materials in a repository is complicated by the presence of sodium metal that is used as a thermal bond between the uranium metal fuel and blanket slugs and their cladding. The concern is that the metallic sodium could react with water, producing explosive hydrogen gas, or could exhibit a pyrophoric character. Thus, experimental studies were performed to investigate and demonstrate the removal and deactivation of bond sodium from blanket material in a dry environment. Specifically, bond sodium was removed from unirradiated Fermi-1 blanket elements and an assembly via a melt-drain-evaporate process using elevated temperature and reduced pressure. The effectiveness of sodium metal removal from the blanket materials and their associated cladding was =99.9998%, based on post-test quantitative analyses. The separated sodium metal was collected and subsequently deactivated by reacting it in a molten state with a controlled addition of ammonium chloride particles atop a molten salt medium. In this process sodium chloride is formed and assimilates into the salt pool. The subsequent deactivation of the bond sodium produced a solid ingot of sodium chloride, potassium chloride, lithium chloride, and cesium chloride that was devoid of sodium metal based on post-test analyses of the salt product. Both the sodium removal and deactivation operations were conducted within a dry inert atmosphere enclosure. The results of this study substantiate a path forward for the disposition of sodium-bonded blanket materials, including 34 metric tons heavy metal in irradiated Fermi-1 blanket material currently stored at Idaho National Laboratory.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesis and characterization of uranium trichloride in alkali-metal chloride media

Given a growing interest in uranium salts for pyrochemical processing of used fuel and uranium-fueled molten salt reactors, the synthesis of uranium trichloride in alkali-metal chloride media was investigated in a series of four experiments. Specifically, uranium metal powder and uranium hydride powder were prepared and separately blended with ammonium chloride and lithium chloride – potassium chloride eutectic in two runs, while the same powders were separately blended with ammonium chloride and sodium chloride in two additional runs. Each of the lithium chloride – potassium chloride containing blends was slowly heated to 923 K, while those containing sodium chloride were heated to 1123 K. During each heat up, the ammonium chloride sublimed into gaseous ammonia and hydrogen chloride, leading to the chlorination of uranium metal or uranium hydride and the formation of molten salt solutions of the respective chlorides. Experimental conditions were incorporated in the runs to promote formation of uranium trichloride over uranium tetrachloride in the respective media. Molten samples of each run product were taken and characterized via chemical analyses, diffractometry, and microscopy. The final products from each run were dark dense ingots of the respective salt systems with uranium concentrations ranging from 44 to 51 wt%. Finally, chemical analyses and diffractometry identified the predominant presence of uranium trichloride in these systems; however, a possible minor presence of uranium tetrachloride could not be conclusively dismissed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesis and characterization of uranium trichloride in alkali-metal chloride media

Given a growing interest in uranium salts for pyrochemical processing of used fuel and uranium-fueled molten salt reactors, the synthesis of uranium trichloride in alkali-metal chloride media was investigated in a series of four experiments. Specifically, uranium metal powder and uranium hydride powder were prepared and separately blended with ammonium chloride and lithium chloride – potassium chloride eutectic in two runs, while the same powders were separately blended with ammonium chloride and sodium chloride in two additional runs. Each of the lithium chloride – potassium chloride containing blends was slowly heated to 923 K, while those containing sodium chloride were heated to 1123 K. During each heat up, the ammonium chloride sublimed into gaseous ammonia and hydrogen chloride, leading to the chlorination of uranium metal or uranium hydride and the formation of molten salt solutions of the respective chlorides. Experimental conditions were incorporated in the runs to promote formation of uranium trichloride over uranium tetrachloride in the respective media. Molten samples of each run product were taken and characterized via chemical analyses, diffractometry, and microscopy. The final products from each run were dark dense ingots of the respective salt systems with uranium concentrations ranging from 44 to 51 wt%. Chemical analyses and diffractometry identified the predominant presence of uranium trichloride in these systems; however, a possible minor presence of uranium tetrachloride could not be conclusively dismissed.

D Herrmann, Steven↗

Development of lithium-thionyl chloride batteries for Centaur

Lithium thionyl chloride (LiSOCl2) primary cells and batteries have received considerable attention over the last several years because of their high theoretical specific energy and energy density. The objective was to develop a 300 wh/kg cell capable of safe operation at C/2 rate and active storage life for 5 to 10 years. This technology would replace other primary cell technologies in NASA applications mainly the silver zinc (AgZn) batteries presently in use. The LiSOCl2 system exceeds the capabilities of the AgZn in terms of specific energy of 300 wh/kg (compared with 100 wh/kg for AgZn), active storage life of 10 to 20 times the 3 to 6 months active storage and has a significantly lower projected cost.

Halpert, Gerald↗

Development of lithium-thionyl chloride batteries for Centaur

Lithium thionyl chloride (LiSOCl2) primary cells and batteries have received considerable attention over the last several years because of their high theoretical specific energy and energy density. The objective was to develop a 300 wh/kg cell capable of safe operation at C/2 rate and active storage life for 5 to 10 years. This technology would replace other primary cell technologies in NASA applications mainly the silver zinc (AgZn) batteries presently in use. The LiSOCl2 system exceeds the capabilities of the AgZn in terms of specific energy of 300 wh/kg (compared with 100 wh/kg for AgZn), active storage life of 10 to 20 times the 3 to 6 months active storage and has a significantly lower projected cost.

Halpert, Gerald↗

Low temperature safety of lithium-thionyl chloride cells

The use of lithium thionyl chloride cells for low-temperature applications is presently restricted because of their unsafe behavior. An attempt is made in the present investigation to identify the safe/unsafe low temperature operating conditions and to understand the low temperature cell chemistry responsible for the unsafe behavior. Cells subjected to extended reversal at low rate and -40 C were found to explode upon warm-up. Lithium was found to deposit on the carbon cathodes during reversal. Warming up to room temperature may be accelerating the lithium corrosion in the electrolyte. This may be one of the reasons for the cell thermal runaway.

Subbarao, S.↗

Lithium-thionyl chloride battery safety

Primary lithium cells which use LiAlCl4/SOCl2 electrolyte exhibit high energy density and long life. Currently these cells pose a safety problem since they have been found to vent or explode. This paper summarizes experiments to resolve the safety problem of Li-SOCl2 cells by thermal modeling and identification of possibly hazardous intermediates formed during discharge of these cells. A thermal model and mechanism for the reduction of SOCl2 are presented, as well as a discussion of their application to Li-SOCl2 cell safety.

Carter, B.↗

Development of a 300 Amp-hr high rate lithium thionyl chloride cell

The development of a high-rate lithium thionyl chloride cylindrical cell with parallel plate electrodes is discussed. The development was divided into three phases: phase 1, a 150 Amp/hour low rate (1 mA/sq cm) design; phase 2, a 25 Amp/hour high rate (5 mA/sq cm) design; and phase 3, a 300 Amp/hour high rate (5 mA/sq cm) design. The basic design is the same for all three cells. The electrodes are perpendicular to the axis of the cylinder. Multiple electrodes are bussed up the side of the cylinder, 180 deg apart allowing excellent anode and cathode utilization. It is a lithium limited design with excess electrolyte. The cathode is Shawinigan or Gulf Acetylene black with no catalyst. The electrolyte is 1.8 Molar lithium tetrachloroaluminate (LiAlCl4) in thionyl chloride. All cell cases are 304L Stainless Steel with a BS&B burst disc.

Boyle, Gerard H.↗

Lithium thionyl chloride high rate discharge

Improvements in high rate lithium thionyl chloride power technology achieved by varying the electrolyte composition, operating temperature, cathode design, and cathode composition are discussed. Discharge capacities are plotted as a function of current density, cell voltage, and temperature.

Klinedinst, K. A.↗

Safety considerations of lithium-thionyl chloride cells

The use of spirally wound lithium-thionyl chloride (Li-SOCl2) cells is currently limited because of their hazardous behavior. Safety hazards have ranged from mild venting of toxic materials to violent explosions and fires. These incidents may be related to both user- and manufacturer-induced causes. Many explanations have been offered to explain the unsafe behavior of the cells under operating and abuse conditions. Explanations fall into two categories: (1) thermal mechanisms, and (2) chemical mechanisms. However, it is quite difficult to separate the two. Both may be responsible for cell venting or explosion. Some safety problems encountered with these cells also may be due to design deficiencies and ineffective quality control during cell fabrication. A well-coordinated basic and applied research program is needed to develop safe Li-SOCl2 cells. Recommendations include: (1) learnig more about Li-SOL2 cell chemistry; (2) modeling cell and battery behavior; (3) optimizing cell design for safety and performance, (4) implementing quality control procedures; and (5) educating users.

Subbarao, Surampudi↗

Hazards of lithium thionyl chloride batteries

Two different topics which only relate in that they are pertinent to lithium thionyl chloride battery safety are discussed. The first topic is a hazards analysis of a system (risk assessment), a formal approach that is used in nuclear engineering, predicting oil spills, etc. It is a formalized approach for obtaining assessment of the degree of risk associated with the use of any particular system. The second topic is a small piece of chemistry related to the explosions that can occur with lithium thionyl chloride systems. After the two topics are presented, a discussion is generated among the Workshop participants.

Parry, J. M.↗

Electrical, thermal and abusive tests on lithium thionyl chloride cells

Electrical characterizations, thermal characterizations, and outer limits tests of lithium thionyl chloride cells are discussed. Graphs of energy density vs power density and heat rate vs time are presented along with results of forced reversal and high rate discharge tests.

Frank, H. A.↗

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

In this article, the structural dynamics, chemical reactivity, anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly four times greater viscosity when compared to the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly reduced chemical reactivity with respect to lithium cations coordinating with the methyl thiocyanate when compared to the lithium halide salts.

2D IR↗

A high power lithium thionyl chloride battery for space applications

A high power, 28 V, 330 A h, active lithium thionyl chloride battery has been developed for use as main and payload power sources on an expendable launch vehicle. Nine prismatic cells, along with the required electrical components and a built-in heater system, are efficiently packaged resulting in significant weight savings over presently used silver-zinc batteries. The high rate capability is achieved by designing the cells with a large electrochemical surface area and impregnating an electrocatalyst, polymeric phthalocyanine, into the carbon cathodes. Passivation effects are reduced with the addition of sulfur dioxide into the thionyl chloride electrolyte solution. The results of conducting a detailed thermal analysis are utilized to establish the heater design parameters and the thermal insulation requirements of the battery. An analysis of cell internal pressure and vent characteristics clearly illustrates the margins of safety under different operating conditions. Performance of fresh cells is discussed using polarization scan and discharge data at different rates and temperatures. Self-discharge rate is estimated based upon test results on cells after storage. Results of testing a complete prototype battery are described.

Shah, Pinakin M.↗

Investigation of an Aberrant Cell Voltage During the Filling of a Large Lithium Thionyl Chloride Cell

The investigation of an aberrant cell voltage during the filling of a large lithium thionyl chloride cell summary is at: an aberrant voltage trace was noted during the review of cell filling data; incident was traced to an interruption during filling; experimentation suggested oxidizable sites within the carbon electrode were responsible for the drop in voltage; the voltage anomaly could be reproduced by interrupting the filling of similar cells; and anomalous voltage dip was not due to a short.

Thaller, Lawrence H.↗

Evaluation of high-energy lithium thionyl chloride primary cells

An advanced commercial primary lithium cell (LiSoCl2) was evaluated in order to establish baseline data for improved lithium batteries for aerospace applications. The cell tested had nominal capacity of 6 Ah. Maximum energy density at low rates (less than C/30, where C is the cell capacity in amp-hrs and 30 corresponds to a 30 hr discharge time) was found to be near 300 Wh/kg. An equation which predicts the operating voltage of these cells as a function of current and state of charge is presented. Heat generation rates of these cells were determined as a function of current in a calorimeter. It was found that heat rates could be theoretically predicted with some degree of accuracy at currents less than 1 amp or the C/6 rate. No explosions were observed in the cells during the condition of overdischarge or reversal nor during high rate discharge. It was found, however, that the cells can vent when overdischarge currents are greater than C/30 and when discharge rates are greater than 1.5C.

Frank, H. A.↗