Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

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.

Abstract not provided.

Abstract not provided.

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.

Abstract not provided.

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.

A literature survey and technical evaluation was carried out of past and present battery technologies with the goal of identifying appropriate candidates for use in geothermai borehole and, to a lesser extend, oil/gas boreholes. The various constraints that are posed by such an environment are discussed. The promise as well as the limitations of various candidate technologies are presented. Data for limited testing of a number of candidate systems are presented and the areas for additional future work are detailed. The use of low-temperature molten salts shows the most promise for such applications and includes those that are liquid at room temperature. The greatest challenges are to develop an appropriate electrochemical couple that is kinetically stable with the most promising electrolytes-both organic as well as inorganic- over the wide operating window that spans both borehole environments. © 2000 by the American Institute of Aeronautics and Astronautics, Inc. All rights reserved.

Conventional electroactive stack components in thermal batteries are constructed from pressed-powder parts. These include the anode, separator, and cathode pellets (discs). Pressing parts that are less than 0.010 inch thick is difficult. The use of plasma spray to deposit thin CoS{sub 2} cathode films onto a stainless steel substrate was examined as an alternative to pressed-powder cathodes. The plasma-sprayed electrodes were tested in single cells under isothermal conditions and constant-current discharge over a temperature range of 400 C to 550 C using standard LiSi anodes and separators based on the LiCl-KCl eutectic. Similar tests were conducted with cells built with conventional pressed-powder cathodes, which were tested under the same conditions for comparative purposes. This paper presents the results of those tests.

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.

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.

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.

The effects on electrochemical performance of the nitrogen content of disordered carbons derived from polymethacryonitrile (PMAN)-divinylbenzene (DVB) copolymers were examined in galvanostatic cycling tests between 2 V and 0.01 V vs. Li/Li+ in lM LiPF₆/ethylene carbonate (EC)-dimethyl carbonate (DMC). The first-cycle reversible capacities and coulombic efficiencies increased with increase in the level of nitrogen for samples prepared at 700°C. However, the degree of fade also increased. Similar tests were performed on materials that were additionally heated at 1,000° and 1,300°C for five hours. Loss of nitrogen, oxygen, and hydrogen occurred under these conditions, with none remaining at the highest temperature in all cases but one. The pyrolysis temperature dominated the electrochemical performance for these samples, with lower reversible and irreversible capacities for the first intercalation cycle as the pyrolysis temperature was increased. Fade was reduced and coulombic efficiencies also improved with increase in temperate. The large irreversible capacities and high fade of these materials makes them unsuitable for use in Li-ion cells.

Thermal batteries are normally constructed using pressed-powder anode, separator, and cathode pellets (discs). However, parts less than 0.010" thick are difficult to press from the starting powders. The use of plasma spraying to deposit thin pyrite films onto a stainless steel substrate was examined as an alternative to pressed-powder cathodes. The electrodes were tested under isothermal conditions and constant-current discharge over a temperature range of 400°C to 550°C using a standard LiSi anode and a separator based on the LiCIKCI eutectic. The plasma-sprayed cathodes were also evaluated in similar 5-cell thermal batteries. Cells and batteries using pressed-powder cathodes were tested under the same conditions for comparative purposes.

Thermally activated batteries use electrodes that are typically fabricated by cold pressing of powder. In the LiSi/FeS2 system, natural (mineral) pyrite is used for the cathode. In an effort to increase the energy density and specific energy of these batteries, flame and plasma spraying to form thin films of pyrite cathodes were evaluated. The films were deposited on a 304 stainless steel substrate (current collector) and were characterized by scanning electron microscopy and x-ray dlfllaction. The films were electrochemically tested in single cells at 5000C and the petiormance compared to that of standard cells made with cold-pressed powders. The best results were obtained with material deposited by de-arc plasma spraying with a proprietq additive to suppress thermal decomposion of the pyrite.

The ignition processes that take place during activation of a 16 cell, center hole fired thermal battery were examined by monitoring the voltage of each cell during activation. The average rise time of each cell to a voltage of 1.125 V was determined for the LiSi/LiCl-LiBr-LiF/FeS{sub 2} electrochemical system. The effects of heat pellet composition, center hole diameter, and the load on the activation parameters were examined for three different igniters. A large variability in individual cell performance was evident along with cell reversal, depending on the location of the cell in the stack. It was not possible to draw detailed statistical information of the relative ignition sequence due to the intrinsic large scatter in the data.

The power requirements for an inverter application were specified to be 500 V at 360 A, or 180 kW per each of six 1-s pulses delivered over a period of 10 minutes. Conventional high-power sources (e.g., flywheels) could not meet these requirements and the use of a thermal battery was considered. The final design involved four, 125-cell, 50-kW modules connected in series. A module using the LiSi/CoS{sub 2} couple and all-Li (LiCI-LiBr-LiF minimum-melting) electrolyte was successfully developed and tested. A power level of over 40 kW was delivered during a 0.5-s pulse. This translates into a specific power level of over 9 kW/kg or 19.2 kW/L delivered from a module. The module was still able to deliver over 30 kW during a 1-s pulse after 10 minutes.

The effect of temperature on the reversible and irreversible capacities of disordered carbons derived from polymethacryonitrile (PMAN) and divinylbenzene (DVB) copolymers was studied in 1 M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) (1:1 v/v) solution by galvanostatic cycling. The kinetics of passive film formation were examined by complex-impedance spectroscopy. Temperatures of 5, 21, and 35 C were used in the study.

A study was undertaken to examine the use of a number of solution additives in 1M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) solutions to improve the performance of carbon anodes derived from polymethylacrylonitrile (PMAN)-divinylbenzene (DVB) copolymers. The study goals were to improve the cycle life and reduce the formation of the passivation layer during the first reduction, thereby minimizing the irreversible-capacity losses. Additives studied were 12-crown-4 (12-Cr-4) ether, decalin, and dilithium phthalocyanine (Li{sub 2}Pc). The carbon performance was characterized by galvanostatic cycling, cyclic voltammetry, and complex-impedance spectroscopy. Limited success was obtained with 12-Cr-4 ether at 0.25 M and decalin at 1 v/o. Poor results were noted with Li{sub 2}Pc at 0.025 M and 0.5 M.

A study was undertaken to examine the effects of partial oxidation on the electrochemical performance of carbons derived from poly(methylacrylonitrile) (PMAN)-divinylbenzene (DVB) co-polymers. Mild oxidation was examined as a possible technique to increase the reversible capacity, improve cycleability, and reduce the amount of irreversible capacity associated with the formation of the passivation layer during the first reduction. Oxidizing conditions involved treatment of the PMAN carbon prepared at 700 C with dry CO{sub 2} or with steam at 600 C for one hour. The effects on the performance in 1M LiPF{sub 6}/ethylene carbonate (EC)-dimethyl carbonate (DMC) solutions were evaluated by galvanostatic cycling tests, complex-impedance spectroscopy, and, to a more limited extent, cyclic voltammetry. Partial oxidation of PMAN carbon showed little or no overall beneficial effects in performance relative to the control.