Pellets of Fe/KClO{sub 4} mixtures are used as a heat source for thermally activated ('thermal') batteries. They provide the energy necessary for melting the electrolyte and bringing the battery stack to operating temperature. The effects of morphology of the Fe and the heat-pellet density and composition on both the physical properties (flowability, pelletization, and pellet strength) and the pyrotechnic performance (burn rate and ignition sensitivity) were examined using several commercial sources of Fe.
The development and testing of a new technique for blending of electrolyte-binder (separator) mixes for use in thermal batteries is described. The original method of blending such materials at Sandia involved liquid Freon TF' as a medium. The ban on the use of halogenated solvents throughout much of the Department of Energy complex required the development of an alternative liquid medium as a replacement. The use of liquid nitrogen (LN) was explored and developed into a viable quality process. For comparison, a limited number of dry-blending tests were also conducted using a Turbula mixer. The characterization of pellets made from LN-blended separators involved deformation properties at 530 C and electrolyte-leakage behavior at 400 or 500 C, as well as performance in single-cells and five-cell batteries under several loads. Stack-relaxation tests were also conducted using 10-cell batteries. One objective of this work was to observe if correlations could be obtained between the mechanical properties of the separators and the performance in single cells and batteries. Separators made using three different electrolytes were examined in this study. These included the LiCl-KCl eutectic, the all-Li LiCl-LiBr-LiF electrolyte, and the low-melting LiBr-KBr-LiF eutectic. The electrochemical performance of separator pellets made with LN-blended materials was compared to that for those made with Freon T P and, in some cases, those that were dry blended. A satisfactory replacement MgO (Marinco 'OL', now manufactured by Morton) was qualified as a replacement for the standard Maglite 'S' MgO that has been used for years but is no longer commercially available. The separator compositions with the new MgO were optimized and included in the blending and electrochemical characterization tests.
The use of plasma spray to deposit thin metal-sulfide cathode films is described in this paper. Conventional electroactive stack components in thermal batteries are constructed from pressed-powder parts that are difficult to fabricate in large diameters in thicknesses <0.010. Plasma-sprayed electrodes do not steer from this difficulty, allowing greater energy densities and specific energies to be realized. Various co-spraying agents have been found suitable for improving the mechanical as well as electrochemical properties of plasma-sprayed cathodes for thermal batteries. These electrodes generally show equal or improved performance over conventional pressed-powder electrodes. A number of areas for future growth and development of plasma-spray technology is discussed.
Using an optimized thermal-spray process, coherent, dense deposits of pyrite (FeS{sub 2}) with good adhesion were formed on 304 stainless steel substrates (current collectors). After leaching with CS{sub 2} to remove residual free sulfur, these served as cathodes in Li(Si)/FeS{sub 2} thermal cells. The cells were tested over a temperature range of 450 C to 550 C under baseline loads of 125 and 250 mA/cm{sup 2}, to simulate conditions found in a thermal battery. Cells built with such cathodes outperformed standard cells made with pressed-powder parts. They showed lower interracial resistance and polarization throughout discharge, with higher capacities per mass of pyrite. Post-treatment of the cathodes with Li{sub 2}O coatings at levels of >7% by weight of the pyrite was found to eliminate the voltage transient normally observed for these materials. Results equivalent to those of standard lithiated catholytes were obtained in this manner. The use of plasma-sprayed cathodes allows the use of much thinner cells for thermal batteries since only enough material needs to be deposited as the capacity requirements of a given application demand.
The Li(Si)/FeS{sub 2} and Li(Si)/CoS{sub 2} couples were evaluated with a low-melting LiBr-KBr-LiF eutectic and all-Li LiCl-LiBr-LiF electrolyte for a battery application that required both high energy and high power for short duration. Screening studies were carried out with 1.25 inch-dia. triple cells and with 10-cell batteries. The Li(Si)/LiCl-LiBr-LiF/CoS{sub 2} couple performed the best under the power load and the Li(Si)/LiCl-LiBr-LiF/FeS{sub 2} was better under the energy load. The former system was selected as the best overall performer for the wide range of temperatures for both loads, because of the higher thermal stability of CoS{sub 2}.
In order to determined the capabilities of a thermal battery with high-voltage and high-power requirements, a detailed characterization of the candidate LiSi/LiCl-LiBr-LiF/CoS{sub 2} electrochemical couple was conducted. The rate capability of this system was investigated using 0.75 inch-dia. and 1.25 inch-dia. single and multiple cells under isothermal conditions, where the cells were regularly pulsed at increasingly higher currents. Limitations of the electronic loads and power supplies necessitated using batteries to obtain the desired maximum current densities possible for this system. Both 1.25 inch-dia. and 3 inch-dia. stacks were used with the number of cells ranging from 5 to 20. Initial tests involved 1.25 inch-dia. cells, where current densities in excess of 15 A/cm{sup 2} (>200 W/cm{sup 2}) were attained with 20-cell batteries during 1-s pulses. In subsequent follow-up tests with 3 inch-dia., 10-cell batteries, ten 400-A 1-s pulses were delivered over an operating period often minutes. These tests formed the foundation for subsequent full-sized battery tests with 125 cells with this chemistry.
We are continuing to study the suitability of modified thermal-battery technology as a potential power source for geothermal borehole applications. Previous work focused on the LiSi/FeS{sub 2} couple over a temperature range of 350 C to 400 C with the LiBr-KBr-LiF eutectic, which melts at 324.5 C. In this work, the discharge processes that take place in LiSi/CsBr-LiBr-KBr eutectic/FeS{sub 2} thermal cells were studied at temperatures between 250 C and 400 C using pelletized cells with immobilized electrolyte. The CsBr-LiBr-KBr eutectic was selected because of its lower melting point (228.5 C). Incorporation of a quasi-reference electrode allowed the determination of the relative contribution of each electrode to the overall cell polarization. The results of single-cell tests and limited battery tests are presented, along with preliminary data for battery stacks tested in a simulated geothermal borehole environment.
The performance of Li-alloy/CsBr-LiBr-KBr/Ag{sub 2}CrO{sub 4} systems was studied over a temperature range of 250 C to 300 C, for possible use as a power source for geothermal borehole applications. Single cells were discharged at current densities of 15.8 and 32.6 mA/cm{sup 2} using Li-Si and Li-Al anodes. When tested in 5-cell batteries, the Li-Si/CsBr-LiBr-KBr/Ag{sub 2}CrO{sub 4} system exhibited thermal runaway. Thermal analytical tests showed that the Ag{sub 2}CrO{sub 4} cathode reacted exothermically with the electrolyte on activation. Consequently, this system would not be practical for the envisioned geothermal borehole applications.
Fiberglass tape and borosilicate filter discs impregnated with molten LiCl-KCl eutectic were examined for potential use as separators for high-temperature LiSi/LiCl-KCl/FeS{sub 2} thermal batteries. Test discs were punched from these materials and evaluated at 400 C in single cells at a steady-state current of 63 mA/cm{sup 2}. The performance generally improved with electrolyte loading for most of the materials. Better results were obtained with the filter discs than with the tape. The best overall results were obtained with Whatman GF/A discs. Active lives for cells with these separators were about 85% of the standard cells with pressed-powder separators. More work with other materials and electrolytes over a wider temperature range is underway, along with 5-cell-battery tests.
Thin-film electrodes of a plasma-sprayed Li-Si alloy were evaluated for use as anodes in high-temperature thermally activated (thermal) batteries. These anodes were prepared using 44% Li/56% Si (w/w) material as feed material in a special plasma-spray apparatus under helium or hydrogen, to protect this air- and moisture-sensitive material during deposition. Anodes were tested in single cells using conventional pressed-powder separators and lithiated pyrite cathodes at temperatures of 400 to 550 C at several different current densities. A limited number of 5-cell battery tests were also conducted. The data for the plasma-sprayed anodes was compared to that for conventional pressed-powder anodes. The performance of the plasma-sprayed anodes was inferior to that of conventional pressed-powder anodes, in that the cell emfs were lower (due to the lack of formation of the desired alloy phases) and the small porosity of these materials severely limited their rate capability. Consequently, plasma-sprayed Li-Si anodes would not be practical for use in thermal batteries.