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Physiochemical properties of liquid mixtures of lithium chloride and lithium carbonate
Thermodynamics of electrochemical cells consisting of Li with lithium chloride or bromide and thallium amalgam with thallium chloride or bromide in propylene carbonate
Visible absorption spectra of lithium, sodium, and potassium in molten lithium chloride-potassium chloride
Electrochemical reduction of chlorine on pyrolytic carbon in molten lithium chloride-potassium chloride
Anolyte studies of magnesium electrode in molten mixtures of lithium chloride, potassium chloride, and magnesium chloride
A study was made of the relative magnitude of the effects of various factors on the ductility of single crystals of sodium chloride (NaCl), lithium fluoride (LiF), and magnesium oxide (MgO). Specimen treatments included water-polishing, varying cleavage rate, annealing, quenching, X-irradiation, surface coating, aging, and combinations of some of these treatments. The mechanical behavior of the crystals was studied in flexure and in compression, the latter study being performed at both constant strain rate and constant load. Etch-pit studies were carried out to provide some pertinent information on the results of pretreatment on the dislocation concentration and distribution in the vicinity of the surface. The load deformation curves for these ionic single crystals show an initial region of very low slope which proved to be due to anelastic deformation. The extent of initial anelastic deformation is modified by specimen pretreatment in a way that suggests that this deformation is the result of expansion of cleaved-in dislocation loops, which can contract on the removal of the stress. The effects of the various pretreatments on the load and deflection at fracture are in accord with the prediction one might make with regard to their effect on the nucleation of fatal surface cracks. For NaCl, increases in ductility are always accompanied by increases in strength. The creep constants for NaCl are a function of treatments which affect the bulk structure but are not a function of treatments which only affect the surface.
Co-deposition electrochemical cells are a simple means to examine novel nuclear reactions. In this study, palladium and deuterium atoms were co-deposited on a cathode at stoichiometric densities, forming dendritic morphologies. Bubble detector neutron dosimeters were used to measure equivalent dose levels during electrolytic deposition. Standard configuration cells expected to produce excess neutrons were denoted as experimental cells and contained an electrolyte consisting of palladium(II) chloride, lithium chloride, and heavy water. The control cells used copper(II) chloride, lithium chloride, and heavy water electrolyte. Experimental and control cells were supplied current, increasing from 0.1 to 100.0 mA over a period of 20 days. For test days 9 through 20, the standard configuration experimental cells exhibited significantly higher average neutron radiation than the controls at a 99% confidence level. Alternative configurations involving more increasing current over a shortened time scale, substitutions of water in place of heavy water or potassium chloride for lithium chloride, as well as inclusion of depleted uranium near the cell cathodes all resulted in inconclusive evidence for promoting neutron production.
Continuous and discontinuous lithium fluoride fibers embedded in a sodium chloride matrix were produced in space and on Earth, respectively. The production of continuous fibers in a eutectic mixture was attributed to the absence of convective current in the liquid during solidification in space. Image transmission and optical transmittance measurements of transverse sections of the space-grown and Earth-grown ingots were made with a light microscope and a spectrometer. It was found that better optical properties were obtained from samples grown in space. This was attributed to a better alignment of lithium fluoride fibers along the growth direction.
Ionic conductivities of solid mixtures of lithium fluoride-lithium chloride, lithium chloride- potassium chloride, lithium fluoride-sodium chloride, and sodium chloride-potassium chloride
Visible absorption bands of alkali metals in molten alkali chlorides
An active thionyl chloride high rate battery is under development for spacecraft operations. It is a 540kC (150 Ah) battery capable of pulses up to 75A. This paper describes the design and initial test data on a 'state-of-the-art' cell that has been selected to be the baseline for the prototype cell for that battery. Initial data indicate that the specification can be met with fresh cells. Data for stored cells and additional environmental test data are in the process of being developed.
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.
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.
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.
Vapor phase chromatographic analysis of dimethyl formamide, and physical properties of electrolytes containing lithium chloride and/or aluminum chloride
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.
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.
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.