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Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple

The development of more efficient thermoelectric couple technology capable of operating with high-grade heat sources up to 1,275 K is key to improving the performance of radioisotope thermoelectric generators. Lanthanum telluride La3-xTe4 and 14-1-11 Zintls (Yb14MnSb11) have been identified as very promising materials. The fabrication of advanced high-temperature thermoelectric couples requires the joining of several dissimilar materials, typically including a number of diffusion bonding and brazing steps, to achieve a device capable of operating at elevated temperatures across a large temperature differential (up to 900 K). A thermoelectric couple typically comprises a heat collector/ exchanger, metallic interconnects on both hot and cold sides, n-type and ptype conductivity thermoelectric elements, and cold-side hardware to connect to the cold-side heat rejection and provide electrical connections. Differences in the physical, mechanical, and chemical properties of the materials that make up the thermoelectric couple, especially differences in the coefficients of thermal expansion (CTE), result in undesirable interfacial stresses that can lead to mechanical failure of the device. The problem is further complicated by the fact that the thermoelectric materials under consideration have large CTE values, are brittle, and cracks can propagate through them with minimal resistance. The inherent challenge of bonding brittle, high-thermal-expansion thermoelectric materials to a hot shoe material that is thick enough to carry the requisite electrical current was overcome. A critical advantage over prior art is that this device was constructed using all diffusion bonds and a minimum number of assembly steps. The fabrication process and the materials used are described in the following steps: (1) Applying a thin refractory metal foil to both sides of lanthanum telluride. To fabricate the n-type leg of the advanced thermoelectric couple, the pre-synthesized lanthanum telluride coupon was diffusion bonded to the metal foil using a thin adhesion layer. (2) Repeating a similar process for the 14-1-11 Zintl p-type leg of the advanced thermoelectric couple. (3) Bonding thick CTE-matched metal plates on the metallized lanthanum telluride and Yb14MnSb11 to form the hot and cold sides of the thermoelectric couple. The calculated conversion efficiency of such an advanced couple would be about 10.5 percent, about 35 percent better than heritage radioisotope thermoelectric technology that relies on Si-Ge alloys. In addition, unlike Si-Ge alloys, these materials can be combined with many other thermoelectric materials optimized for operation at lower temperatures to achieve conversion efficiency in excess of 15 percent (a factor of 2 increase over heritage technology).

Ravi, Vilupanur A.

High efficiency thermoelectric power generation using Zintl-type materials

The invention disclosed herein relates to thermoelectrically-active p-type Zintl phase materials as well as devices utilizing such compounds. Such thermoelectric materials and devices may be used to convert thermal energy into electrical energy, or use electrical energy to produce heat or refrigeration. Embodiments of the invention relate to p-type thermoelectric materials related to the compound Yb.sub.14MnSb.sub.11.

Snyder, G. Jeffrey

Zintl Phases for Thermoelectric Applications

The inventors demonstrate herein that various Zintl compounds can be useful as thermoelectric materials for a variety of applications. Specifically, the utility of Ca3AlSb3, Ca5Al2Sb6, Ca5In2Sb6, Ca5Ga2Sb6, is described herein. Carrier concentration control via doping has also been demonstrated, resulting in considerably improved thermoelectric performance in the various systems described herein.

Snyder, G. Jeffrey

Alumina Paste Sublimation Suppression Barrier for Thermoelectric Device

Alumina as a sublimation suppression barrier for a Zintl thermoelectric material in a thermoelectric power generation device operating at high temperature, e.g. at or above 1000K, is disclosed. The Zintl thermoelectric material may comprise Yb.sub.14MnSb.sub.11. The alumina may be applied as an adhesive paste dried and cured on a substantially oxide free surface of the Zintl thermoelectric material and polished to a final thickness. The sublimation suppression barrier may be finalized by baking out the alumina layer on the Zintl thermoelectric material until it becomes substantially clogged with ytterbia.

Paik, Jong-Ah

Expansion Compression Contacts for Thermoelectric Legs

In a proposed alternative to previous approaches to making hot-shoe contacts to the legs of thermoelectric devices, one relies on differential thermal expansion to increase contact pressures for the purpose of reducing the electrical resistances of contacts as temperatures increase. The proposed approach is particularly applicable to thermoelectric devices containing p-type (positive-charge-carrier) legs made of a Zintl compound (specifically, Yb14MnSb11) and n-type (negative charge-carrier) legs made of SiGe. This combination of thermoelectric materials has been selected for further development, primarily on the basis of projected thermoelectric performance. However, it is problematic to integrate, into a practical thermoelectric device, legs made of these materials along with a metal or semiconductor hot shoe that is required to be in thermal and electrical contact with the legs. This is partly because of the thermal-expansion mismatch of these materials: The coefficient of thermal expansion (CTE) of SiGe is 4.5 x 10(exp -6) C (exp -1), while the CTE of Yb14MnSb11 is 20 x 10(exp -6) C(exp -1). Simply joining a Yb14MnSb11 and a SiGe leg to a common hot shoe could be expected to result in significant thermal stresses in either or both legs during operation. Heretofore, such thermal stresses have been regarded as disadvantageous. In the proposed approach, stresses resulting from the CTE mismatch would be turned to advantage.

Sakamoto, Jeffrey

Yb14MnSb11 as a High-Efficiency Thermoelectric Material

Yb14MnSb11 has been found to be wellsuited for use as a p-type thermoelectric material in applications that involve hotside temperatures in the approximate range of 1,200 to 1,300 K. The figure of merit that characterizes the thermal-to-electric power-conversion efficiency is greater for this material than for SiGe, which, until now, has been regarded as the state-of-the art high-temperature ptype thermoelectric material. Moreover, relative to SiGe, Yb14MnSb11 is better suited to incorporation into a segmented thermoelectric leg that includes the moderate-temperature p-type thermoelectric material CeFe4Sb12 and possibly other, lower-temperature p-type thermoelectric materials. Interest in Yb14MnSb11 as a candidate high-temperature thermoelectric material was prompted in part by its unique electronic properties and complex crystalline structure, which place it in a class somewhere between (1) a class of semiconducting valence compounds known in the art as Zintl compounds and (2) the class of intermetallic compounds. From the perspective of chemistry, this classification of Yb14MnSb11 provides a first indication of a potentially rich library of compounds, the thermoelectric properties of which can be easily optimized. The concepts of the thermoelectric figure of merit and the thermoelectric compatibility factor are discussed in Compatibility of Segments of Thermo - electric Generators (NPO-30798), which appears on page 55. The traditional thermoelectric figure of merit, Z, is defined by the equation Z = alpha sup 2/rho K, where alpha is the Seebeck coefficient, rho is the electrical resistivity, and k is the thermal conductivity.

Snyder, G. Jeffrey

NASA Tech Briefs, November 2010

Topics covered include: Portable Handheld Optical Window Inspection Device; Salience Assignment for Multiple-Instance Data and Its Application to Crop Yield Prediction; Speech Acquisition and Automatic Speech Recognition for Integrated Spacesuit Audio Systems ; Predicting Long-Range Traversability from Short-Range Stereo-Derived Geometry; Browser-Based Application for Telemetry Monitoring of Robotic Assets; Miniature Low-Noise G-Band I-Q Receiver; Methods of Using a Magnetic Field Response Sensor Within Closed, Electrically Conductive Containers; Differential Resonant Ring YIG Tuned Oscillator; Microfabricated Segmented-Involute-Foil Regenerator for Stirling Engines; Reducing Seal Adhesion in Low Impact Docking Systems; Optimal Flow Control Design; Corrosion-Resistant Container for Molten-Material Processing; Reusable Hot-Wire Cable Cutter; Deployment of a Curved Truss; High-Volume Airborne Fluids Handling Technologies to Fight Wildfires; Modeling of Alkane Oxidation Using Constituents and Species; Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple; A Computer Model for Analyzing Volatile Removal Assembly; Analysis of Nozzle Jet Plume Effects on Sonic Boom Signature; Optical Sidebands Multiplier; Single Spatial-Mode Room-Temperature-Operated 3.0 to 3.4 micrometer Diode Lasers; Self-Nulling Beam Combiner Using No External Phase Inverter; Portable Dew Point Mass Spectrometry System for Real-Time Gas and Moisture Analysis; Maximum Likelihood Time-of-Arrival Estimation of Optical Pulses via Photon-Counting Photodetectors; Handheld White Light Interferometer for Measuring Defect Depth in Windows; Decomposition Algorithm for Global Reachability on a Time-Varying Graph; Autonomous GN and C for Spacecraft Exploration of Comets and Asteroids; Efficient Web Services Policy Combination; Using CTX Image Features to Predict HiRISE-Equivalent Rock Density; Isolation of the Paenibacillus phoenicis, a Spore-Forming Bacterium; Monolithically Integrated, Mechanically Resilient Carbon-Based Probes for Scanning Probe Microscopy; Cell Radiation Experiment System; Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite; Inversion Method for Early Detection of ARES-1 Case Breach Failure; Use of ILTV Control Laws for LaNCETS Flight Research;and Evaluating Descent and Ascent Trajectories Near Non-Spherical Bodies.

Source record

Nickel-Graphite Composite Compliant Interface and/or Hot Shoe Material

Next-generation high-temperature thermoelectric-power-generating devices will employ segmented architectures and will have to reliably withstand thermally induced mechanical stresses produced during component fabrication, device assembly, and operation. Thermoelectric materials have typically poor mechanical strength, exhibit brittle behavior, and possess a wide range of coefficient of thermal expansion (CTE) values. As a result, the direct bonding at elevated temperatures of these materials to each other to produce segmented leg components is difficult, and often results in localized microcracking at interfaces and mec hanical failure due to the stresses that arise from the CTE mismatch between the various materials. Even in the absence of full mechanical failure, degraded interfaces can lead to increased electrical and thermal resistances, which adversely impact conversion efficiency and power output. The proposed solution is the insertion of a mechanically compliant layer, with high electrical and thermal conductivity, between the low- and high-temperature segments to relieve thermomechanical stresses during device fabrication and operation. This composite material can be used as a stress-relieving layer between the thermoelectric segments and/or between a thermoelectric segment and a hot- or cold-side interconnect material. The material also can be used as a compliant hot shoe. Nickel-coated graphite powders were hot-pressed to form a nickel-graphite composite material. A freestanding thermoelectric segmented leg was fabricated by brazing the compliant pad layer between the high-temperature p- Zintl and low-temperature p-SKD TE segments using Cu-Ag braze foils. The segmented leg stack was heated in vacuum under a compressive load to achieve bonding. The novelty of the innovation is the use of composite material that re duces the thermomechanical stresses en - countered in the construction of high-efficiency, high-temperature therm - o-electric devices. The compliant pad enables the bonding of dissimilar thermoelectric materials while maintaining the desired electrical and thermal properties essential for efficient device operation. The modulus, CTE, electrical, and thermal conductances of the composite can be controlled by varying the ratio of nickel to graphite.

Firdosy, Samad A.

Compliant Interfacial Layers in Thermoelectric Devices

A thermoelectric power generation device is disclosed using one or more mechanically compliant and thermally and electrically conductive layers at the thermoelectric material interfaces to accommodate high temperature differentials and stresses induced thereby. The compliant material may be metal foam or metal graphite composite (e.g. using nickel) and is particularly beneficial in high temperature thermoelectric generators employing Zintl thermoelectric materials. The compliant material may be disposed between the thermoelectric segments of the device or between a thermoelectric segment and the hot or cold side interconnect of the device.

Firdosy, Samad A.

Solar Power System and Radioisotope Thermoelectric Generation Technologies at Jupiter-Saturn-Uranus Environments: New Insights and Paradigms

Power system selection for outer planet destinations, such as Jupiter, Saturn, and Uranus and beyond, is complex, involving and dependent on many interdisciplinary factors such as power system mass, specific power, cost, mechanical and electrical integration, and natural radiation environment. Low solar irradiance at Jupiter, Saturn, and Uranus systems (i.e., 50, 15, and 4 W/m2 , respectively) makes solar power systems challenging in mechanical / electrical integration and accommodating radiation environments. More costly radioisotope thermoelectric generator (RTG) systems can help proposed missions overcome radiation environment and spacecraft control challenges at Jupiter, Saturn, and Uranus. NASA’s Jet Propulsion Laboratory (JPL) has recently made significant strides in demonstrating high-efficiency, radiation-hard solar cell technologies for low-irradiance, low-temperature (LILT) applications, and high-efficiency thermoelectric (TE) materials and modules for higher-specific-power RTGs. Stateof-art multi-junction solar cells now routinely demonstrate high efficiencies of 30-34% at LILT (9.5AU and -165°C), making solar arrays a viable option for many near-term Saturn mission concepts. Emerging technologies like LILToptimized solar cells have recently demonstrated even higher efficiencies of 37% at 9.5AU and -165°C and 30% lower mass than the state-of-art, offering the prospect of ~3W/kg array-level, end-of-life specific powers under Saturn conditions. Having already demonstrated the tremendous utility of RTGs on Mars and in deep-space missions (e.g., Galileo at Jupiter, New Horizons at Pluto), NASA is now developing and demonstrating new TE materials and modules (e.g., skutterudites, La3-x Te4, and Zintls) for increasing RTG specific power (up to >8.5 W/kg), which strongly impacts an RTG’s mass, fuel utilization, and modularity in the power system trade domain. New accomplishments in both areas highlight the renewed requisite for updated comparisons and trade-offs in power output, specific power and mass, cost, mechanical and electrical integration, new technology timelines, and natural radiation impacts between new LILT-optimized photovoltaic technologies and next-generation RTG technologies. This work discusses and demonstrates how new LILT-based technologies are now allowing one to consider and design solar power systems for Saturn orbit and beyond, and are changing the potential cost-mass trade-offs between emerging solar power technologies and newly-envisioned RTG technologies. Key updated system mass and cost trade-offs between high-performance LILT solar technologies and new RTG technologies are presented, reinforcing and refining power selection criteria supporting possible future NASA deep-space science and exploration missions to Mars, the Jupiter system (Europa, Ganymede), the Saturn system (Titan, Enceladus), Uranus, and beyond. Key trade-offs in other above-mentioned interdisciplinary factors between these two power technologies are also discussed.

Bairstow, Brian K.

A Novel High-Performance Mission-Enabling Multi-Purpose Radioisotope Heat Source

Recent studies indicate science mission concepts targeting access to the sub-surface oceans of icy moons require ice-penetrating cryobots powered by advanced Radioisotope Power Systems (RPS). These systems would deliver waste heat for ice-melting in the range of 10 kW. Minimizing the transit time through the kilometers-thick ice shells to just a few years requires these RPS to utilize heat sources having a higher thermal energy volumetric density than the existing flight-qualified General-Purpose Heat Source (GPHS). A Compact Heat Source (CPHS)has been conceptualized in which the graphite impact shells(GIS) of the existing GPHS are rearranged in a hexagonal aeroshell containing seven GIS per module, as opposed to the standard two per module; offering a thermal energy density of 0.57 W/cm3versus 0.29 W/cm3 offered by the GPHS simply from the repackaging of Technology Readiness Level (TRL)9 subassemblies. Preliminary thermal modeling of the CPHS integrated into a notional radioisotope thermoelectric generator(RTG) structure further suggests that centerline temperatures are well within allowable limits during nominal operation. Given the need for the CPHS for a subset of missions, it is worth exploring the applicability of the CPHS for more general RTG purposes. We discuss herein how the CPHS may be implemented with either heritage or in-development thermoelectric converter technologies into a Next-Generation RTG concept. Due to a higher energy density, the legacy heat rejection fin arrangement must be modified to permit a sufficiently low cold-side temperature. Preliminary finite element analysis suggests fin-root temperatures can be kept as low as 520 K while allowing the generator to fit within the usable dimensions of currently available United States Department of Energy shipping containers. Such temperatures would certainly be compatible with the use of high temperature thermoelectric converter technologies.. A prime candidate is the heritage silicon-germanium (SiGe) unicouple, whose design could be adapted by approximately halving the leg-length, but without changes in hot and cold junction interfaces, which are features critical to the proven performance and reliability of these devices. The estimated Beginning of Life power for a SiGe-based CPHS-RTG using 12 CPHS for a thermal inventory of 10.5 kW is greater than 600 W under deep space operating conditions. Using higher performance segmented couples currently in development that are based on skutterudite,La3−xTe4and 14-1-11 Zintl thermoelectric materials in lieu of the SiGe unicouples would increase the power level to more than1 kW. The high specific power (We/kg) attribute of CPHS-RTGs found in this study could potentially enable Radioisotope Electric Propulsion (REP) mission concepts. Past NASA REP mission concept studies identified specific power needs in excess of 6to 8 We/kg. Based on a GPHS-RTG-like system configuration, we show that at fin root temperatures between 530 K and 570K (deep space environment), specific powers exceeding 10 We/kg are achievable using high performance segmented thermoelectric converters. The compact sizing and power density of the CPHS-RTG would constitute a significant step upgrade in specific power when compared to heritage GPHS-RTG (approximately5.1 We/kg) and off-the-shelf Multi-Mission RTG (approximately 2.6 We/kg).

Nesmith, Bill J.

Development Status and Plans of the Advanced Thermoelectric Converter (ATEC) Project

Advances in thermoelectric materials with high ZT in mid-90's, revived interest in advanced thermoelectric materials at DOE, DOD and NASA NASA. JPL, in collaboration with Universities, identified promising high temperature thermoelectric materials for potential use in next generation RTGs nder DOD and NASA funding (1995 to 2005). Based on these advances the ATEC project was initiated in January 2006 to develop an advanced converter by 2010 (10-12% couple efficiency). ATEC is a technology maturation project with an off-ramp to a proposed Advanced RTG (ARTG) providing 6-8 W/kg and 8-10% system efficiency to support potential future SMD missions as early as 2017. In addition, work is continuing on advancing the TE materials technology to support development of an RTG with 12-14 W/kg and 15 to 20% efficiency by 2020.

zintl metallization

Thermal Expansion Studies of Selected High Temperature Thermoelectric Materials

Radioisotope thermoelectric generators (RTGs) generate electrical power by converting the heat released from the nuclear decay of radioactive isotopes (typically plutonium-238) into electricity using a thermoelectric converter. RTGs have been successfully used to power a number of space missions and have demonstrated their reliability over an extended period of time (tens of years) and are compact, rugged, radiation resistant, scalable, and produce no noise, vibration or torque during operation. System conversion efficiency for state-of-practice RTGs is about 6% and specific power less than or equal to 5.1 W/kg. Higher specific power would result in more on-board power for the same RTG mass, or less RTG mass for the same on-board power. The Jet Propulsion Laboratory has been leading, under the advanced thermoelectric converter (ATEC) project, the development of new high-temperature thermoelectric materials and components for integration into advanced, more efficient RTGs. Thermoelectric materials investigated to date include skutterudites, the Yb14MnSb11 compound, and SiGe alloys. The development of long-lived thermoelectric couples based on some of these materials has been initiated and is assisted by a thermo-mechanical stress analysis to ensure that all stresses under both fabrication and operation conditions will be within yield limits for those materials. Several physical parameters are needed as input to this analysis. Among those parameters, the coefficient of thermal expansion (CTE) is critically important. Thermal expansion coefficient measurements of several thermoelectric materials under consideration for ATEC are described in this paper. The stress response at the interfaces in material stacks subjected to changes in temperature is discussed, drawing on work from the literature and project-specific tools developed here. The degree of CTE mismatch and the associated effect on the formation of stress is highlighted.

silicon germanium