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Ten commercial MgO powders were evaluated for their suitability to act as a binder in the separator of thermal batteries to immobilize the electrolyte when it is molten. One brand in particular, Maglite S from Calgon, outperformed all the others. This report describes the results of a characterization study of this MgO as well as similar materials from other commercial vendors. The study objective was to define the critical properties of Maglite S MgO that are responsible for its superior performance in thermal-battery separators. Separator mixes were prepared with the various MgO powders and the resulting powders and pellets were characterized, to correlate key physical properties of these materials to select physical and chemical properties of the MgO powders used in their preparation. The MgO pore-size distribution was the only parameter that could be related to the deformation and electrolyte-leakage behavior of separator pellets. A potential replacement for the Maglite S is currently being qualified, since Maglite S MgO is no longer available.

Fe/KClO{sub 4} pyrotechnic mixtures are used in thermal batteries to provide the heat necessary to bring the battery stack to operating temperatures of 550 to 600 C. This heat source is normally used as discs pressed from bulk powder. To evaluate the consequences associated with unexpected ignition of large amounts of heat powder, combustion of 84% Fe/16% KClO{sub 4} heat powders was conducted for various scenarios under controlled conditions and the response documented. Increasing amounts of heat powder--up to 8 lbs--were ignited in both unconfined and confined (sealed) containers in a remote area. The containers were thermocoupled and the resulting burning filmed with a standard video camera, high-speed (1,000 frames/s) film and video cameras, and an infrared video camera. A 20- minute video of the burning under the various conditions is presented.

The thermal response under geothermal-borehole conditions of a conventional thermal battery was evaluated for various designs by numerical simulations using a finite-element thermal model. This technology, which is based on molten salts, may be suitable as a power source for geothermal borehole applications for data logging. Several promising candidate electrolytes were identified for further study.

Over 100 candidates were examined, including commercial materials and many that were synthesized in house. The mixed oxides were based on Ti, V, Nb, Cr, Mo, W, Mn, Fe, Co, Ni, and Cu doped with other transition metals. A number of individual (single-metal) oxides were included for comparison. The candidates were tested in single cells with Li(Si) anodes and separators based on LiCl-KCl eutectic. Screening was done under constant-current conditions at current densities of 125 me/cm{sup 2} and, to a lesser extent, 50 me/cm{sup 2} at 500 C. Relative performance and limitations of the oxide cathodes are discussed.

Carbons derived from polymethylacrylonitrile (PMAN) have been studied for use as intercalation anodes in Li-ion cells. The effect of Si doping upon the electrochemical performance of PMAN carbons was studied using tetravinylsilane (TVS) and tetramethysilane (TMS) as sources of Si during the formation of the PMAN precursors. The carbons were characterized by galvanostatic cycling, cyclic voltammetry, and complex impedance. The presence of 9 to 11 w/o Si in the PMAN lattice greatly increased the irreversible capacity of these materials.

The separator pellet in a thermal battery consists of electrolyte immobilized by a binder (typically, MgO powder). The melting point of the electrolyte determines the effective operating window for its use in a thermal battery. The development of a two-hour thermal battery required the use of a molten salt that had a lower melting point and larger liquidus range than the LiCl-KCl eutectic which melts at 352 C. Several candidate eutectic electrolyte systems were evaluated for their suitability for this application. One was the LiCl-LiBr-KBr eutectic used at Argonne National Laboratories for high-temperature rechargeable batteries for electric-vehicle applications. Using a custom-designed high-temperature conductivity cell, the authors were able to readily determine the liquidus region for the various compositions studied around the original eutectic for the LiBr-KBr-LiF system. The actual eutectic composition was found to be 60.0 m/o LiBr-37.5 m/o KBr-2.5 m/o LiF with a melting point of 324 {+-} 0.5 C.

Intercalation anodes of graphite or disordered carbon in rechargeable Li-ion batteries (based on aprotic organic solvents) develop a passivating film during the first intercalation of Li{sup +}. The formation of this film reduces the cycling efficiency and results in excessive consumption of Li{sup +}. The exact nature of this film is not well defined, although there are many similarities in properties to the films that form on Li anodes under similar cycling conditions. In this study we report on characterization studies of films formed during galvanostatic cycling of disordered carbons derived from polymethylacryolintrile (PMAN) in a 1M LiPF{sub 6} solution in ethylene carbonateldimethyl carbonate solution (1:1 by vol.). Complementary tests were also conducted with glass carbon, where intercalation cannot occur. Complex-impedance spectroscopy was the primary measurement technique, supplemented by cyclic voltammetry.

The thermal conductivities of a variety of insulating materials used in thermal batteries were measured in atmospheres of argon and helium using several techniques. (Helium was used to simulate the hydrogen atmosphere that results when a Li(Si)/FeS{sub 2} thermal battery ages.) The guarded-hot-plate method was used with the Min-K insulation because of its extremely low thermal conductivity. For comparison purposes, the thermal conductivity of the Min-K insulating board was also measured using the hot-probe method. The thermal-comparator method was used for the rigid Fiberfrax board and Fiberfrax paper. The thermal conductivity of the paper was measured under several levels of compression to simulate the conditions of the insulating wrap used on the stack in a thermal battery. The results of preliminary thermal-characterization tests with several silica aerogel materials are also presented.

Thermally activated batteries use an epoxy for encapsulation of the electrical feedthroughs in the header of the battery. When the thermal battery is thermally abused, the encapsulant can pyrolyze and generate large internal pressures. This causes the battery to vent in extreme cases. The nature of these gases has never been adequately documented. Therefore, a study was undertaken to address this deficiency. The pyrolysis of various encapsulants that have been used, or are being considered for use, in thermally activated batteries was studied over a temperature range of 155 to 455 C. The composition of the pyrolysis decomposition products was determined by gas chromatography/mass spectrometry (GS/MS). This determination is helpful in assessing the potential environmental and health effect for personnel exposed to such gases. In addition, the thermal stability of the various epoxies was measured by thermogravimetric analysis (TGA).

Thermally activated (``thermal``) batteries have been used for ordnance applications (e.g., proximity fuzes) since World War II and, subsequent to that, in nuclear weapons. This technology was developed by the Germans as a power source for their V2 rockets. It was obtained by the Allies by interrogation of captured German scientists after the war. The technology developed rapidly from the initial primitive systems used by the Germans to one based on Ca/CaCrO{sub 4}. This system was used very successfully into the late 1970s, when it was replaced by the Li-alloy/FeS{sub 2} electrochemical system. This paper describes the predominant electrochemical couples that have been used in thermal batteries over the years. Major emphasis is placed on the chemistry and electrochemistry of the Ca/CaCrO{sub 4} and Li-alloy/FeS{sub 2} systems. The reason for this is to give the reader a better appreciation for the advances in thermal-battery technology for which these two systems are directly responsible. Improvements to date in the current Li-alloy/FeS{sub 2} and related systems are discussed and areas for possible future research and development involving anodes, cathodes, electrolytes, and insulations are outlined. New areas where thermal-battery technology has potential applications are also examined.

The deformation characteristics of pellets of electrolyte-binder (EB) mixes based on MgO were measured under simulated, thermal-battery conditions. Measurements (using a statistically designed experimental strategy) were made as a function of applied pressure, temperature, and percentage of theoretical density for four molten-salt electrolytes at two levels of MgO. The EB mixes are used as separators in Li-alloy thermal batteries. The electrolytes included LiCl-KCI eutectic, LiCl-LiBr-KBr eutectic, LiBr-KBr-LiF eutectic, and a LiCl-LiBr-LiF electrolyte with a minimum-melting composition. The melting points ranged from 313 C to 436 C. The experimental data were used to develop statistical models that approximate the deformation behavior of pellets of the various EB mixes over the range of experimental conditions we examined. This report, discusses the importance of the deformation response surfaces to thermal-battery design.

A tester was developed to evaluate prototype thermal cells and batteries--especially high-voltage units--under a wide range of constant-current and constant-resistance discharge conditions. Programming of the steady-state and pulsing conditions was by software control or by hardware control via an external pulse generator. The tester was assembled from primarily Hewlett-Packard (H-P) instrumentation and was operated under H-P`s Rocky Mountain Basic (RMB). Constant-current electronic loads rated up to 4 kW (400 V at up to 100 A) were successfully used with the setup. For testing under constant-resistance conditions, power metal-oxide field-effect transistors (MOSFETs) controlled by a programmable pulse generator were used to switch between steady-state and pulse loads. The pulses were digitized at up to a 50 kHz rate (20 {mu} s/pt) using high-speed DVMs; steady-state voltages were monitored with standard DVMs. This paper describes several of the test configurations used and discusses the limitations of each. Representative data are presented for a number of the test conditions.

The purification of pyrite (FeS{sub 2}) used in Li-alloy/FeS{sub 2} thermal batteries by the physical process of flotation was evaluated for reduction of the quartz impurity. The process was compared to the standard process of leaching with concentrated hydrofluoric acid. Flotation was an attractive alternative because it avoided many of the safety and environmental concerns posed by the use of concentrated HF. The effects of particle size and initial purity of the pyrite feed material upon the final purity and yield of the product concentrate were examined for batch sizes from 3.5 kg to 921 kg. Feed materials as coarse as 8 mm and as fine as -325 mesh were treated; the coarse pyrite was ground wet in a rod mill or dry in a vibratory mill to -230 mesh prior to flotation. Both the HF-leached and the flotation-treated pyrite were leached with HCI (1:1 v/v) to remove acid-soluble impurities. The flotation-purified pyrite concentrates were formulated into catholytes; their electrochemical performance was evaluated in both single cells and 5-cell batteries for comparison to data generated under the same discharge conditions for catholytes formulated with HF/HCI-purified pyrite.

Diethyltoluenediamine (DETDA) (Ethyl Corp.`s Ethacure 100) was evaluated as a curing agent to replace methylenedianiline (MDA) (Shell`s Agent Z), which is a suspected carcinogen. Shell Z and Ethacure 100 are used to cure Epon 828 epoxy resin for encapsulation of headers for thermal batteries at Sandia. The physical properties of the alumina-filled epoxies cured with Shell Z and Ethacure 100 were characterized to determine if the material strengths were comparable. The study also included epoxies that were aged at 130{degrees}C for one month, to simulate storage at 40{degrees}C for 25 years. Properties that were measured included tensile strength, elastic modulus, shear strength, butt tensile strength, and elongation. The. specific heats of the alumina-filled epoxies were measured for use in thermal-modeling programs for thermal batteries. Batteries built with the Ethacure 100-cured epoxy encapsulation were aged for up to one year at 74{degrees}C and were subjected to severe (1,800 g/50 ms) lateral shock to test the adhesion to the stainless steel header.

A number of metal oxides were evaluated for their ability to immobilize molten LiCl-KCl eutectic in electrolyte-binder (EB) mixes used in thermally activated batteries. These metal oxides included fumed silicas, alumina, and a titania (all prepared by steam hydrolysis of the halides), floated silicas, MgO, and an alumina molecular sieve. The characteristics of the EB powders that were used as metrics were flow properties, homogeneity, BET surface area, particle-size distribution, and moisture content. The characteristics of EB pellets used as metrics were deformation at 530{degrees}C under an applied pressure and tendency for electrolyte leakage at 400{degrees}C. Many of the same characterization techniques used for EB powders were applied to the LiCl-KCl eutectic, its component halides, and the metal oxides as well. The reproducibility of the properties of several of the standard Sandia EB mixes was evaluated for materials prepared at a number of thermal-battery manufacturing facilities following the same processing procedures. 13 refs., 14 figs., 18 tabs.

The establishment of a database for the materials that are used in production Li(Si)/FeS{sub 2} thermal batteries designed at Sandia National Laboratories is described. The database is a Hewlett-Packard (HP) network type (IMAGE) designed to run on an HP3000 computer. Heavy emphasis is placed on the use of screen forms for entry, editing, and retrieval of data. Custom screen forms were used for the various materials in the battery. For the purposes of the materials database, each battery is composed of four mixes: cathode, separator, anode, and heat (pyrotechnic) powders. A consistent lot-numbering system was adopted for both the mixes and the discrete components that make up the mixes. Each serial number of a particular battery is linked to the lot numbers of the four mixes used in the battery. Each mix, in turn, is linked to the lot numbers of the discrete components that are contained within the mix. This allows traceability of each of the components used in any given serial number of a particular battery. The materials database provides the necessary traceability, as required by the Department of Energy, for the lifetime of the program associated with the battery. 3 refs., 23 figs.