Improving mechanical properties of thermoelectric materials to increase roubustness of couple assemblies
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The field of thermoelectric energy conversion is reviewed from both a theoretical and an experimental standpoint. The basic theory is introduced and the thermodynamic and solid state views are compared. An overview of the development of thermoelectric materials is presented with particular emphasis being placed on the most recent developments in high-temperature semiconductors. A number of possible device applications are discussed and the successful use and suitability of these devices for space power is manifest.
The efficient use of silicon germanium thermoelectric material for radioisotope thermoelectric generators (RTG) is achieved by operation at relatively high temperatures. The insulation technique which is most appropriate for this application uses multiple layers of molybdenum foil and astroquartz. Even so, the long term operation of these materials at elevated temperatures can cause material interaction to occur within the system. To investigate these material interactions, the Jet Propulsion Laboratory is currently testing a number of thermoelectric modules which use four silicon germanium thermoelectric couples in conjunction with the multifoil thermal insulation. The paper discusses the results of the ongoing four-couple module test program and correlates test results with those of a basic material test program.
The present invention provides a composite thermoelectric material. The composite thermoelectric material can include a semiconductor material comprising a rare earth metal. The atomic percent of the rare earth metal in the semiconductor material can be at least about 20%. The composite thermoelectric material can further include a metal forming metallic inclusions distributed throughout the semiconductor material. The present invention also provides a method of forming this composite thermoelectric material.
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.
Magnesium antimonide and magnesium bismuthide evaluated as thermocouple material for thermoelectric power generation
A method of applying a physical barrier to suppress thermal decomposition near a surface of a thermoelectric material including applying a continuous metal foil to a predetermined portion of the surface of the thermoelectric material, physically binding the continuous metal foil to the surface of the thermoelectric material using a binding member, and heating in a predetermined atmosphere the applied and physically bound continuous metal foil and the thermoelectric material to a sufficient temperature in order to promote bonding between the continuous metal foil and the surface of the thermoelectric material. The continuous metal foil forms a physical barrier to enclose a predetermined portion of the surface. Thermal decomposition is suppressed at the surface of the thermoelectric material enclosed by the physical barrier when the thermoelectric element is in operation.
Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.
Theoretical work of two decades ago adequately explained the transport behavior and effectively guided the development of thermoelectric materials of high conversion efficiencies of conventional semiconductors (e.g., SiGe alloys). The more significant contributions involved the estimaiation of optimum doping concentrations, the reduction of thermal conductivity by solid solution doping and the development of a variety of materials with ZT approx. 1 in the temperature range 300 K to 1200 K. ZT approx. 1 is not a theoretical limitation although, experimentally, values in excess of one were not achieved. Work has continued with emphasis on higher temperature energy conversion. A number of promising materials have been discovered in which it appears that ZT 1 is realizable. These materials are divided into two classes: (1) the rare-earth chalcogenides which behave as itinerant highly-degenerate n-type semiconductors at room-temperature, and (2) the boron-rich borides, which exhibit p-type small-polaronic hopping conductivity.
JPL has been leading a concentrated effort to develop improved thermoelectric materials for space applications. Thermoelectric generators are an attractive source of electrical energy for space power because of lack of moving parts and slow degradation of performance. Thermoelectric material is characterized by: Seebeck coefficient, electrical resistivity and thermal conductivity. To measure the high temperature thermal conductivity is experimentally very difficult. However, it can be calculated from the specific heat and thermal diffusivity which are easier to measure at high temperatures, especially using the flash method. Data acquisition and analysis for this experiment were automated at JPL using inexpensive microcomputer equipment. This approach is superior to tedious and less accurate manual analysis of data. It is also preferred to previously developed systems utilizing expensive minicomputers or mainframes.
In order to provide a complete description of a materials thermoelectric power factor, in addition to the measured nominal value, an uncertainty interval is required. The uncertainty may contain sources of measurement error including systematic bias error and precision error of a statistical nature. The work focuses specifically on the popular ZEM-3 (Ulvac Technologies) measurement system, but the methods apply to any measurement system. The analysis accounts for sources of systematic error including sample preparation tolerance, measurement probe placement, thermocouple cold-finger effect, and measurement parameters; in addition to including uncertainty of a statistical nature. Complete uncertainty analysis of a measurement system allows for more reliable comparison of measurement data between laboratories.
A parameterized orthogonal tight-binding mathematical model of the quantum electronic structure of the bismuth telluride molecule has been devised for use in conjunction with a semiclassical transport model in predicting the thermoelectric properties of doped bismuth telluride. This model is expected to be useful in designing and analyzing Bi2Te3 thermoelectric devices, including ones that contain such nano - structures as quantum wells and wires. In addition, the understanding gained in the use of this model can be expected to lead to the development of better models that could be useful for developing other thermoelectric materials and devices having enhanced thermoelectric properties. Bi2Te3 is one of the best bulk thermoelectric materials and is widely used in commercial thermoelectric devices. Most prior theoretical studies of the thermoelectric properties of Bi2Te3 have involved either continuum models or ab-initio models. Continuum models are computationally very efficient, but do not account for atomic-level effects. Ab-initio models are atomistic by definition, but do not scale well in that computation times increase excessively with increasing numbers of atoms. The present tight-binding model bridges the gap between the well-scalable but non-atomistic continuum models and the atomistic but poorly scalable ab-initio models: The present tight-binding model is atomistic, yet also computationally efficient because of the reduced (relative to an ab-initio model) number of basis orbitals and flexible parameterization of the Hamiltonian.
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.
Of the six types of radioisotope thermoelectric generators NASA has flown in space, only the Multi-Mission Radioisotope Thermoelectric Generator (MMRTG) is currently available for spaceflight, and it relies on technology first used for RTGs in the 1970s. The MMRTG is a rugged power system capable of delivering 110W at launch. NASA is considering future missions with higher power demands however, and sponsored a study to identify concepts and plans to address those needs. The Director of NASA’s Planetary Sciences Division was briefed on a potential enhancement to the MMRTG in late-2012, just a couple of days after the landing of the Mars Science Laboratory rover, Curiosity, on Mars. NASA subsequently funded system-level engineering and technology maturation tasks for a proposed enhanced MMRTG, or eMMRTG, in fiscal year 2013. There was no plan to build a complete generator, rather the engineering of one, and the transfer of technology from laboratories at the Jet Propulsion Laboratory to industry were begun. NASA has now formed a Project to take the eMMRTG from technology to a qualification unit. This would form the first of a new generation of RTGs in 50 years. NASA has also formed a Project for a Next-Generation RTG concept based upon a study led by this author and a large team. NASA’s Radioisotope Power Systems (RPS) Program set the objective for the study to explore what possible options NASA has for Next-Generation-RTGs. The scope and breadth of the study included many possible destinations within the solar system, and traded a variety of RTG conceptual designs, and risk rated a variety of thermoelectric materials and couple configurations. Requirements were defined for the RTG concepts, a variety of thermoelectric materials were evaluated to find the most mature candidates, and performance was estimated for each RTG concept that could use the most mature of these new thermoelectric materials. The study relied upon mission concepts outlined in the latest Planetary Science Decadal Survey (2011), other more recent mission studies completed throughout the agency, and recent analyses of potential missions to ocean worlds to identify requirements that were not applied to previous RTGs but might prove valuable to these NG-RTGs. RTG concepts with maximal potential utility were identified as being modular and ranging in power output from 50 to 500W. A variety of RTG design concepts with several distinguishing characteristics were formulated. The plans and concepts for a new generation of RTGs (the eMMRTG and NG-RTG) will be discussed.
Figures of merit almost double current state-of-art thermoelectric materials. IrSb3 is semiconductor found to exhibit exceptional thermoelectric properties. CoSb3 and RhSb3 have same skutterudite crystallographic structure as IrSb3, and exhibit exceptional transport properties expected to contribute to high thermoelectric performance. These three compounds form solid solutions. Combination of properties offers potential for development of new high-performance thermoelectric materials for more efficient thermoelectric power generators, coolers, and detectors.
Planar two-dimensional arrays of thermopiles intended for use as thermal-imaging detectors are to be fabricated by a process that includes surface micromachining. These thermopile arrays are designed to perform better than do prior two-dimensional thermopile arrays. The lower performance of prior two-dimensional thermopile arrays is attributed to the following causes: The thermopiles are made from low-performance thermoelectric materials. The devices contain dielectric supporting structures, the thermal conductances of which give rise to parasitic losses of heat from detectors to substrates. The bulk-micromachining processes sometimes used to remove substrate material under the pixels, making it difficult to incorporate low-noise readout electronic circuitry. The thermoelectric lines are on the same level as the infrared absorbers, thereby reducing fill factor. The improved pixel design of a thermopile array of the type under development is expected to afford enhanced performance by virtue of the following combination of features: Surface-micromachined detectors are thermally isolated through suspension above readout circuitry. The thermopiles are made of such high-performance thermoelectric materials as Bi-Te and Bi-Sb-Te alloys. Pixel structures are supported only by the thermoelectric materials: there are no supporting dielectric structures that could leak heat by conduction to the substrate.
Compositions related to skutterudite-based thermoelectric materials are disclosed. Such compositions can result in materials that have enhanced ZT values relative to one or more bulk materials from which the compositions are derived. Thermoelectric materials such as n-type and p-type skutterudites with high thermoelectric figures-of-merit can include materials with filler atoms and/or materials formed by compacting particles (e.g., nanoparticles) into a material with a plurality of grains each having a portion having a skutterudite-based structure. Methods of forming thermoelectric skutterudites, which can include the use of hot press processes to consolidate particles, are also disclosed. The particles to be consolidated can be derived from (e.g., grinded from), skutterudite-based bulk materials, elemental materials, other non-Skutterudite-based materials, or combinations of such materials.
Team Spacering will design SpaceRing, a cooling and waste heat recycling system that addresses NASA’s interest for a cooling and power-generating unit in its prototype deep space habitat[1]. The merits of this system are as follows: - Controllable cooling is critical in maintaining a habitable environment and in the functionality of life support systems, powering electronics and other devices in a spacecraft. - Power is expensive to produce in a space environment. Converting wasted thermal energy into electricity will save energy and money for the space station. Space habitation is a highly complex endeavor. Consequently, the SpaceRing must adhere to additional constraints, which include: - Lack of natural fluid or gas convection due to micro-gravity environment - Limited range for heat source and cold sink temperature - Subject to high fluctuations of incoming thermal energy - Minimal weight due to the high cost of transporting items into space After consulting with NASA and experts in thermal studies, several design objectives were identified and are listed below in order of importance: - High cooling capacity - Reliable safety control and alert system - Maximization of energy generation from wasted heat - Optimization of cooling capability and power generation - Long operational life and minimization of maintenance In space, conventional cooling systems utilize passive heat pipe systems for small-scale heat rejection and pumped pipes with heat exchangers for large-scale heat rejection. Thermal power generation in space is mainly achieved by using thermoelectric material that produces electric energy from temperature differentials. We propose a design that combines cooling and thermoelectric power generation. Using a hot pipe connected to a heat source, a cold pipe connected to a radiator, a heat exchanger in contact with both pipes, and a pump in each pipe to move the fluid, we make an active cooling system. The thermoelectric material is inserted in the heat exchanger between the hot and cold pipes to extract energy from the maximum temperature difference coming from the two pipes. It also provides controllable cooling capacity through the use of the thermoelectric material as cooling modules. We have tested our system under target heat source and sink conditions and measured the temperatures and flow rates. Our preliminary results are promising, demonstrating the output of 25 Watts of power on average. We are in the process of running control tests to compare the heat transfer performance without the thermoelectric generators, which is vital in determining whether or not the generators introduce an unacceptable amount of thermal resistance. While some control tests have been run already, the results have been noisy. We have modified our testing environment and data acquisition methods to allow for simple comparison between the control test results and thermoelectric performance results. Lastly, we have modified the heat exchanger design slightly to include acrylic baffles. This will allow the heat to flow through the heat exchanger more efficiently. We have presented our preliminary results to NASA and will deliver the final product by the end of May 2014.