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At least 19 records

Sodium-metal chloride battery research at JPL

Sodium - metal chloride batteries have certain distinct advantages over sodium - sulfur batteries such as increased safety, inherent overcharge capability and lower operating temperatures. Two systems, i.e., Na/FeCl2 and Na/NiCl2 were developed extensively elsewhere and evaluated for various applications including electric vehicles and space. Their performance has been very encouraging and prompted a detailed fundamental study on these cathodes here at the Jet Propulsion Laboratory. A brief review of our studies on these new cathode materials is presented here. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization." Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics and identifying the rate-limiting processes in the reduction of metal chloride cathodes. Nickel chloride emerged from these studies as the most promising candidate material and was taken up for further detailed study on its passivation - a rate limiting process - under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have higher energy density, has been assessed. Based on the criteria established from the voltametric response of FeCl2, NiCl2 and CuCI2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt chlorides appear promising.

B V Ratnakumar↗

Alternate cathodes for sodium-metal chloride batteries

Various metal chlorides were tested as possible cathode materials for sodium-metal batteries (in addition to Fe and Ni chlorides, which have been already developed to a stage of commercialization), using an electrochemical cell consisting of a pyrex tube, heated to 250 C, with the metal wire as working electrode, concentric Ni foil as counterelectrode, and high-purity Al as reference electrode. In particular, the aim of this study was to identify metal chlorides insoluble even in neutral melts, possible at the interface during overcharge, in order to eliminate the failure mode of the cell through a cationic exchange of the dissolved metal ions with sodium beta-double-prime alumina solid electrolyte. Results indicate that Mo and Co are likely alternatives to FeCl2 and NiCl2 cathodes in sodium batteries. The open circuit voltages of Na/CoCl(x) and Na/MoCl(x) cells at 250 C would be 2.55 V and 2.64 V, respectively.

Ratnakumar, B. V.↗

Sodium-metal chloride batteries

It was concluded that rapid development in the technology of sodium metal chloride batteries has been achieved in the last decade mainly due to the: expertise available with sodium sulfur system; safety; and flexibility in design and fabrication. Long cycle lives of over 1000 and high energy densities of approx. 100 Wh/kg have been demonstrated in both Na/FeCl2 and Na/NiCl2 cells. Optimization of porous cathode and solid electrolyte geometries are essential for further enhancing the battery performance. Fundamental studies confirm the capabilities of these systems. Nickel dichloride emerges as the candidate cathode material for high power density applications such as electric vehicle and space.

Ratnakumar, B. V.↗

Progress and recent developments in sodium-metal chloride batteries

Significant strides have been made in the development of high-temperature rechargeable sodium batteries utilizing transition metal chloride cathodes in the last decade, mainly due to the expertise available on Na/S batteries. These systems have already performed attractively in the various feasibility studies and have an excellent safety record. Despite the encouraging figures obtained for specific energies, certain design changes such as modifying the geometry of the beta alumina electrolyte and optimization of the porous cathodes for enhanced electrolyte flow need to be made to achieve high power densities required in applications such as electric vehicles and space. The chemistry of MCl2 cathodes, electrode fabrication, and design options are discussed, and performance data are examined.

Ratnakumar, B. V.↗

A Review of Sodium-Metal Chloride Battery Activity At JPL

Following the disclosures by Coetzer et al. on the use of transition metal chlorides in chloroaluminates as alternate cathodes to sulfur in rechargeable sodium batteries, several laboratories, including the Jet Propulsion Laboratory, focused their attention on these systems. These systems have certain distinct advantages over sodium-sulfur batteries such as increased safety, inherent overcharge capability, and lower operating temperatures. Two systems, i.e., Na/FeCl2 and NaNiCl2, were developed extensively and evaluated in various applications including electric vehicles and space. Their performance has been very encouraging and warrants a detailed fundamental study on these cathodes. At the Jet Propulsion Laboratory a program was initiated two years back to understand the electrochemical behavior of FeCl2 and NiCl2, and to identify and evaluate other transition metal chlorides of promise. The initial efforts focused on the methods of fabrication of the electrodes and their electrochemical characterization. Subsequent studies were aimed at establishing the reaction mechanism, determining the kinetics, and identifying the rate-limiting processes in te reduction of metal chloride cathodes. Nickel chloride emerged form these studies as the most promising candidate material and was taken up for further detailed study on its passivation- a rate limiting process-under different experimental conditions. Also, the feasibility of using copper chloride, which is expected to have a higher energy density, has been assessed. On the basis of the criteria established from the voltammetric response of FeCl2, NiCl2, and CuCl2, several other transition metal chlorides were screened. Of these, molybdenum and cobalt appear promising.

Ratnakumar, B. V.↗

Sodium D-line emission in Comet West /1975n/ and the sodium source in comets

A spectrum of the sodium D-line emission from Comet West (1975n) taken at heliocentric distance 1.4 AU is analyzed by comparing the D-line brightness to that in the underlying continuum. Using the observations of this comet by Ney and Merrill, it is found that the dust grains which dominate the visible and infrared continua are too cool to provide the observed sodium atoms through evaporation of sodium metal or a sodium compound from grain surfaces. Though sodium metal may evaporate from a small-grain component, it is suggested that molecules embedded in the volatile nuclear matrix are a more plausible source of sodium. The relationship between this source and the interstellar sodium abundance is discussed.

Oppenheimer, M.↗

Aerospace applications of sodium batteries using novel cathode materials

Preliminary fundamental investigations aimed at evaluating sodium metal chloride systems for future aerospace applications are described. Since the sodium metal chloride systems are relatively new, the approach has been to characterize their fundamental properties in order to understand their limitations. To this end, a series of fundamental electrochemical investigations have been carried out, the results of which are reported here. The metal chloride cathodes show high exchange current densities which corroborate their good reversibility in a battery application. The reduction mechanisms appear to be complex and involve multielectron transfer steps and intermediates. Such intermediates in the reaction mechanism have already been identified in the case of FeCl2. Similar mechanisms may be operative in the case of NiCl2. CuCl2, however, exhibits a second relaxation loop in the impedance plot at low frequencies and also a sloping discharge curve, unlike FeCl2 and NiCl2, which may indicate the existence of monovalent copper in the reduction mechanism.

Ratnakumar, B. V.↗

Separation of traces of metal ions from sodium matrices

Method for isolating metal ion traces from sodium matrices consists of two extractions and an ion exchange step. Extraction is accomplished by using 2-thenoyltrifluoracetone and dithizone followed by cation exchange.

Korkisch, J.↗

Liquid metal micro heat pipes for space radiator applications

Micromachining is a chemical means of etching three-dimensional structures, typically in single-crystalline silicon. These techniques are leading toward what is coming to be referred to as MEMS (micro electro mechanical systems), where in addition to the ordinary two dimensional (planar) microelectronics, it is possible to build three-dimensional micromotors, electrically-actuated microvalves, hydraulic systems, and much more on the same microchip. These techniques become possible because of differential etching rates of various crystallographic planes and materials used for semiconductor microfabrication. The University of Cincinnati group in collaboration with NASA Lewis formed micro heat pipes in silicon by the above techniques. Work is ongoing at a modest level, but several essential bonding and packaging techniques have been recently developed. Currently, we have constructed and filled water/silicon micro heat pipes. Preliminary thermal tests of arrays of 125 micro heat pipes etched in a 1 inch x 1 inch x 250 micron silicon wafer have been completed. These pipes are instrumented with extremely small P-N junctions to measure their effective conductivity and their maximum operating power. A relatively simple one-dimensional model has been developed in order to predict micro heat pipes' operating characteristics. This information can be used to optimize micro heat pipe design with respect to length, hydraulic diameter, and number of pipes. Work is progressing on the fabrication of liquid-metal micro heat pipes. In order to be compatible with liquid metal (sodium or potassium), the inside of the micro heat pipes will be coated with a refractory metal (such as tungsten, molybdenum, or titanium).

Gerner, F. M.↗

Calculation of Internal Pressures in the Fuel Tube of a Nuclear Reactor

General procedures for computing internal pressures in fuel tubes of nuclear reactors are described and the effects on the pressure of varying neutron flux, fissioning material, and operating temperatures are discussed. A general proof is given that during pile operation each fission product is monotonically increasing and therefore a maximum amount of all elements is present at the time of shit down. The post-shutdown build-up of elements that are held in check during pile operation because of their inordinately high capture cross sections is calculated quantitatively. An account of chemical interactions between the many fission-product elements and the resulting effect on the total pressure completes the discussion. The general methods are illustrated by calculations applied to a system consisting of 90 percent enriched U235 in the form of UO2 packed into a hollow metal cylinder or "pin", operating at a flux of 8 x 10(exp 14) at 2000 F. Calculations of the pressure inside a pin are made with and without a sodium metal heat-transfer additive. The bulk of the pressure is shown to depend on the four elements, xenon, krypton, rubidium, and cesium; the amount of free oxygen, however, was also significant. For a shutdown time of 10(exp 6) seconds, the pressure was about 100 atmospheres.

Rosenbaum, B. M.↗

Performance of low-pressure thermionic converters is evaluated

Experiments, evaluating the performance of low-pressure thermionic converters, were conducted with cesium, potassium, and sodium-metal vapors. The results of the investigation are useful in the selection of favorable conditions for the design of thermionic reactor fuel elements, including RF output for special applications.

Richards, H. K.↗

Single crystal tubes of beta alumina

Edge-defined, film-fed growth process allows both tubular shapes and single crystallinity to be achieved. Beta alumina in single crystal form makes possible membranes with improved conductivities. Single crystal membranes also eliminate problems associated with electrical short circuiting of membrane due to possible sodium metal diffusion.

Stormont, R. W.↗

Novel duplex vapor-electrochemical method for silicon solar cells

Silicon was produced by alternate pulse feeding of the reactants SiF4 gas and liquid sodium. The average temperature in the reactor could be controlled, by regulating the amount of reactant in each pulse. Silicon tetrafluoride gas was analyzed by mass spectrometry to determine the nature and amount of contained volatile impurities which included silicon oxyfluorides, sulfur oxyfluorides, and sulfur dioxide. Sodium metal was analyzed by emission spectrography, and it was found to contain only calcium and copper as impurities.

Kapur, V. K.↗