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Materials with skutterudite structure have been known for a long time. Some of them are semiconductors. A typical skutterudite is CoSb(sub 3) and its thermoelectric properties were partially studied in the 1960's. Recently, it has been discovered that many skutterudite compounds are thermoelectrics with promising future.
The preparation and characterization of the binary arsenopyrite compounds CoSb2 and IrSb2 and IrxCo1-xSb2 alloys is reported. Single crystals of CoSb2 were grown by the vertical gradient freeze technique from solution rich in antimony. Polycrystalline samples of IrSb2 and IrxCo1-xSb2 alloys were prepared by hot-pressing of prereacted elemental powders. Samples were investigated by X-ray diffractometry, microprobe analysis and density measurements. It was found that a range of solid solution exist in the system IrxCo1-xSb2 for 0.1<x<0.8. Samples were also characterized by high temperature electrical resistivity, Seebeck coefficient and thermal conductivity measurements. All materials have p-type conductivity and are semiconductors. A band gap of about 0.98 eV was calculated for IrSb2. Preliminary measurements of the thermoelectric properties of these materials showed that their potential for thermoelectric applications is limited.
Thermoelectric materials based on the skutterudite crystal structure have demonstrated enhanced performance (ZT greater than 1), along with good thermal stability and favorable mechanical properties. Binary skutterudites, with single and multiple fillers, have been intensively studied in recent years. Compared to binary skutterudites, the ternary systems have received less attention, e.g. Ni4Sb8Sn4. Ternary skutterudites are isoelectronic variants of binary skutterudites; cation substitutions appear to be isostructural to their binary analogues. In general, ternary skutterudites exhibit lower thermal conductivity. Ternary systems of Ni4Bi8Ge4, Ni4Sb8Ge4, and Ni4Sb8Sn4 were investigated using combined solidification and sintering steps. Skutterudite formation was not achieved in the Ni4Bi8Ge4 and Ni4Sb8Ge4 systems; skutterudite formation occurred in Ni4Sb8Sn4 system. P-type material was achieved by Co substitution for Ni. Thermoelectric properties were measured from 298 K to 673 K for Ni4Sb8Sn4, Ni4 Sb7Sn5 and Co2Ni2Sb7Sn5. N-type Ni4Sb8Sn4 exhibit the highest figure of merit of 0.1 at 523 K.
To achieve high thermal-to-electric energy conversion efficiency, it is desirable to operate thermoelectric geneteor devices over large temperature gradients and also to maximize the thermoelectric performance of the materials used to build the devices.
The development of new, more efficient, materials and devices is the key to expand the range of appplications of thermoelectric generators. New potential terrestrial applications have been recently described in the literature. There exists a wide range of heat source temperatures for these applications. Recent results on novel materials have demonstrated that ZT values significantly larger that 1.0 could be obtained in the 475 to 975K temperature range. These materials are excellent candidates to be used in terrestrial thermoelectric power generators using waste heat or liquid fuels.
The integration of new more efficient thermoelectric materials developed at the Jet Propulsion Laboratory into a new high-performance segmented thermoelectric generator has been reported earlier.
Modular thermoelectric cells are easily packaged in various arrays to form power supplies and have desirable voltage and current output characteristics. The cells employ two pairs of thermoelectric elements, each pair being connected in parallel between two sets of aluminum plates. They can be used as solar energy conversion devices.
Thermoelectric and mechanical performance of silicon-germanium solar thermoelectric generator
A parametric analysis of a radioisotope-thermoelectric power generator is presented. A cylindrical heat-source geometry was assumed with either lead telluride or silicon-germanium thermoelectric elements located around the lateral surface of the fuel block. Generator performance, rather than overall power-system performance, was analyzed; that is, such mission dependent considerations as nuclear shielding, reentry protection, and power conditioning were not included.
Radioisotope thermoelectric generator concepts for Voyager Surface Lander, noting PbTe and GeSi thermoelectrics, reentry body shapes and integration considerations
High efficiency thermoelectric generator utilizes a high-temperature thermoelectric material in thermal series with a low-temperature material. A thermally cascaded generator increases system efficiency.
SNAP 19 TAGS thermoelectric generator life tests at high temperature in Ar, predicting long term performance including thermoelectric material and isotope fuel decay effects
Equipment was designed to receive power from a radioisotope thermoelectric generator source, condition, distribute, and control this power for the spacecraft loads. The TOPS mission, aimed at a representative tour of the outer planets, would operate for an estimated 12 year period. Unique design characteristics required for the power conditioning equipment results from the long mission time and the need for autonomous on-board operations due to large communications distances and the associated time delays of ground initiated actions. The salient features of the selected power subsystem configuration are: (1) The PCE regulates the power from the radioisotope thermoelectric generator power source at 30 vdc by means of a quad-redundant shunt regulator; (2) 30 vdc power is used by certain loads, but is more generally inverted and distributed as square-wave ac power; (3) a protected bus is used to assure that power is always available to the control computer subsystem to permit corrective action to be initiated in response to fault conditions; and (4) various levels of redundancy are employed to provide high subsystem reliability.
The research and advanced development work is reported on a ballistic-mode, outer planet spacecraft using radioisotope thermoelectric generator (RTG) power. The Thermoelectric Outer Planet Spacecraft (TOPS) project was established to provide the advanced systems technology that would allow the realistic estimates of performance, cost, reliability, and scheduling that are required for an actual flight mission. A system design of the complete RTG-powered outer planet spacecraft was made; major technical innovations of certain hardware elements were designed, developed, and tested; and reliability and quality assurance concepts were developed for long-life requirements. At the conclusion of its active phase, the TOPS Project reached its principal objectives: a development and experience base was established for project definition, and for estimating cost, performance, and reliability; an understanding of system and subsystem capabilities for successful outer planets missions was achieved. The system design answered long-life requirements with massive redundancy, controlled by on-board analysis of spacecraft performance data.
The engineering, design, fabrication, and test history of the dual-throat thermoelectric NaK development pump is summarized, along with the engineering and design status of a similar prototype pump intended for use on the 5-kwe reactor thermoelectric system. The history of dc pump development and testing on previous programs is also summarized.
Design of the 5-kwe reactor thermoelectric system was initiated in February 1972 and extended through the conceptual design phase into the preliminary design phase. Design effort was terminated in January, 1973. This report documents the system and component requirements, design approaches, and performance and design characteristics for the 5-kwe system. Included is summary information on the reactor, radiation shields, power conversion systems, thermoelectric pump, radiator/structure, liquid metal components, and the control system.
Discussion of the test results and analysis performed on data obtained from eight thermoelectric generators exhibiting a total combined operating time of about 21 years. Three (3) SNAP-19 type generators are discussed. Generator SN-20, the engineering model of the units presently operating on the Nimbus S/C, has been in operation for over 4 years and has shown drastic degradation after losing the internal cover gas. Generator SN-21, with more than four years of operating time, is operated in an air environment. The performance of this generator appears predictable and stable. For the last 2 years of operation generator degradation has been negligible. Generator SN-31, which utilizes the TAGS material for the P thermoelectric leg, is similar in design to the units to be used on the Pioneer S/C and has operated for over two years in an all-argon atmosphere.
Results of tests performed on a SNAP 19 thermoelectric generator, SN-20. The SN-20 generator was tested for approximately 37,000 hours using electrical heating to simulate the heat released by isotope decay. After 27,000 hours of operation the output power from the generator decreased to approximately 1/3 of the beginning of life value while the internal resistance increased by a factor of 5. Analysis of the test results, confirmed by preliminary metallographic examination, indicated that the output power degradation was the result of excessive sublimation of the thermoelectric material and loss of the hot junction bond due to the depletion of the internal cover gas. This also resulted in excessive junction temperatures. Comparison is made with the behavior observed from the two flight generators and a tentative conclusion is advanced as to the reason for their failure.