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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

Life Testing of Yb14MnSb11 for High Performance Thermoelectric Couples

The goal of this study is to verify the long term stability of Yb14MnSb11 for high performance thermoelectric (TE) couples. Three main requirements need to be satisfied to ensure the long term stability of thermoelectric couples: 1) stable thermoelectric properties, 2) stable bonding interfaces, and 3) adequate sublimation suppression. The efficiency of the couple is primarily based on the thermoelectric properties of the materials selected for the couple. Therefore, these TE properties should exhibit minimal degradation during the operating period of the thermoelectric couples. The stability of the bonding is quantified by low contact resistances of the couple interfaces. In order to ensure high efficiency, the contact resistances of the bonding interfaces should be negligible. Sublimation suppression is important because the majority of thermoelectric materials used for power generation have peak figures of merit at temperatures where sublimation rates are high. Controlling sublimation is also essential to preserve the efficiency of the couple. During the course of this research, three different life tests were performed with Yb14MnSb11 coupons. TE properties of Yb14MnSb11 exhibited no degradation after 6 months of aging at 1273K, and the electrical contact resistance between a thin metallization layer and the Yb14MnSb11 remained negligible after 1500hr aging at 1273K. A sublimation suppression layer for Yb14MnSb11 was developed and demonstrated for more than 18 months with coupon testing at 1273K. These life test data indicate that thermoelectric elements based on Yb14MnSb11 are a promising technology for use in future high performance thermoelectric power generating couples.

thermoelectric couples

Compatibility of Segments of Thermoelectric Generators

A method of calculating (usually for the purpose of maximizing) the power-conversion efficiency of a segmented thermoelectric generator is based on equations derived from the fundamental equations of thermoelectricity. Because it is directly traceable to first principles, the method provides physical explanations in addition to predictions of phenomena involved in segmentation. In comparison with the finite-element method used heretofore to predict (without being able to explain) the behavior of a segmented thermoelectric generator, this method is much simpler to implement in practice: in particular, the efficiency of a segmented thermoelectric generator can be estimated by evaluating equations using only hand-held calculator with this method. In addition, the method provides for determination of cascading ratios. The concept of cascading is illustrated in the figure and the definition of the cascading ratio is defined in the figure caption. An important aspect of the method is its approach to the issue of compatibility among segments, in combination with introduction of the concept of compatibility within a segment. Prior approaches involved the use of only averaged material properties. Two materials in direct contact could be examined for compatibility with each other, but there was no general framework for analysis of compatibility. The present method establishes such a framework. The mathematical derivation of the method begins with the definition of reduced efficiency of a thermoelectric generator as the ratio between (1) its thermal-to-electric power-conversion efficiency and (2) its Carnot efficiency (the maximum efficiency theoretically attainable, given its hot- and cold-side temperatures). The derivation involves calculation of the reduced efficiency of a model thermoelectric generator for which the hot-side temperature is only infinitesimally greater than the cold-side temperature. The derivation includes consideration of the ratio (u) between the electric current and heat-conduction power and leads to the concept of compatibility factor (s) for a given thermoelectric material, defined as the value of u that maximizes the reduced efficiency of the aforementioned model thermoelectric generator.

Snyder, G. Jeffrey

Highly Efficient Multilayer Thermoelectric Devices

Multilayer thermoelectric devices now at the prototype stage of development exhibit a combination of desirable characteristics, including high figures of merit and high performance/cost ratios. These devices are capable of producing temperature differences of the order of 50 K in operation at or near room temperature. A solvent-free batch process for mass production of these state-of-the-art thermoelectric devices has also been developed. Like prior thermoelectric devices, the present ones have commercial potential mainly by virtue of their utility as means of controlled cooling (and/or, in some cases, heating) of sensors, integrated circuits, and temperature-critical components of scientific instruments. The advantages of thermoelectric devices for such uses include no need for circulating working fluids through or within the devices, generation of little if any noise, and high reliability. The disadvantages of prior thermoelectric devices include high power consumption and relatively low coefficients of performance. The present development program was undertaken in the hope of reducing the magnitudes of the aforementioned disadvantages and, especially, obtaining higher figures of merit for operation at and near room temperature. Accomplishments of the program thus far include development of an algorithm to estimate the heat extracted by, and the maximum temperature drop produced by, a thermoelectric device; solution of the problem of exchange of heat between a thermoelectric cooler and a water-cooled copper block; retrofitting of a vacuum chamber for depositing materials by sputtering; design of masks; and fabrication of multilayer thermoelectric devices of two different designs, denoted I and II. For both the I and II designs, the thicknesses of layers are of the order of nanometers. In devices of design I, nonconsecutive semiconductor layers are electrically connected in series. Devices of design II contain superlattices comprising alternating electron-acceptor (p)-doped and electron-donor (n)-doped, nanometer- thick semiconductor layers.

Boufelfel, Ali

Nanowire Thermoelectric Devices

Nanowire thermoelectric devices, now under development, are intended to take miniaturization a step beyond the prior state of the art to exploit the potential advantages afforded by shrinking some device features to approximately molecular dimensions (of the order of 10 nm). The development of nanowire-based thermoelectric devices could lead to novel power-generating, cooling, and sensing devices that operate at relatively low currents and high voltages. Recent work on the theory of thermoelectric devices has led to the expectation that the performance of such a device could be enhanced if the diameter of the wires could be reduced to a point where quantum confinement effects increase charge-carrier mobility (thereby increasing the Seebeck coefficient) and reduce thermal conductivity. In addition, even in the absence of these effects, the large aspect ratios (length of the order of tens of microns diameter of the order of tens of nanometers) of nanowires would be conducive to the maintenance of large temperature differences at small heat fluxes. The predicted net effect of reducing diameters to the order of tens of nanometers would be to increase its efficiency by a factor of .3. Nanowires made of thermoelectric materials and devices that comprise arrays of such nanowires can be fabricated by electrochemical growth of the thermoelectric materials in templates that contain suitably dimensioned pores (10 to 100 nm in diameter and 1 to 100 microns long). The nanowires can then be contacted in bundles to form devices that look similar to conventional thermoelectric devices, except that a production version may contain nearly a billion elements (wires) per square centimeter, instead of fewer than a hundred as in a conventional bulk thermoelectric device or fewer than 100,000 as in a microdevice. It is not yet possible to form contacts with individual nanowires. Therefore, in fabricating a nanowire thermoelectric device, one forms contacts on nanowires in bundles of the order of 10-microns wide. The fill factor for the cross-section of a typical bundle is about 1/2. Nanowires have been grown in alumina templates with pore diameters of 100 and 40 nm.

Borshchevsky, Alexander

Thermoelectric Behavior of Structurally Disordered Lanthanide and Actinide Silicides

Lanthanide and actinide intermetallic materials exhibit intriguing electronic, structural, and magnetic properties arising from their partially filled f orbitals. Strong f-electron correlations can significantly modify the electronic density of states, carrier scattering, and transport behavior, making these systems promising candidates for unconventional thermoelectric materials. In previous studies, single crystals of A1.33T4Al8Si2 (A = Ce, Th, U, Np; T = Co, Ni) were synthesized. This structure consists of ordered TAl2 corrugated double layers separated by disordered An–Si monolayers. The inherent disorder within the An–Si layers has been linked to unusual magnetic behavior, such as spin-glass phenomena, and is expected to strongly influence phonon scattering and charge-carrier transport relevant to thermoelectric performance. However, the thermoelectric properties of this material family have not previously been explored. In this work, DFT calculations were performed to evaluate the electronic density of states, band structures, and thermoelectric properties, including the effects of doping. To validate these predictions, Ce1.33Co4Al8Si2 single crystals were grown and experimentally characterized. Additionally, a new Yb1.33Co4Al8Si2 phase was synthesized and characterized using single-crystal XRD, SEM-EDS, magnetization measurements, and thermoelectric measurements. These results provide insight into structure–property relationships governing thermoelectric behavior in f-electron intermetallics and offer guidance for future thermoelectric materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C

A New High Efficiency Segmented Thermoelectric Unicouple

To achieve high thermal-to-electric energy conversion efficiency, it is desirable to operate thermoelectric generator devices over large temperature gradients and also to maximize the thermoelectric performance of the materials used to build the devices. However, no single thermoelectric material is suitable for use over a very wide range of temperatures (approx. 300 - 1000 K). It is therefore necessary to use different materials in each temperature range where they possess optimum performance. This can be achieved in two ways: 1) multistage thermoelectric generators where each stage operates over a fixed temperature difference and is electrically insulated but thermally in contact with the other stages and 2) segmented generators where the p- and n-legs are formed of different segments joined in series. The concept of integrating new thermoelectric materials developed at the Jet Propulsion Laboratory (JPL) into a segmented thermoelectric generator has been presented in detail in earlier publications . This new generator is expected to operate over a 300-973 K temperature difference and will use novel segmented legs based on a combination of state-of-the-art thermoelectric materials and novel p-type Zn4Sb3, p-type CeFe4Sb12-based alloys and n-type CoSb3-based alloys. An increase in the conversion efficiency of about 60% is expected compared to conventional Bi2Te3- and PbTe-based generators. We present in this paper the latest experimental results from the bonding studies between the different segments of the p-legs, n-legs, and p-leg to n-leg interconnect. Evaluation of the bond quality was done by measuring the contact resistance across the joints as well as by detailed microstructure investigations to reveal any potential interdiffusion. Among the materials investigated as inter-layers between the different segments of the legs, Pd-Ag joining alloys have been found to provide mechanically stable and low electrical resistance bonds.

Caillat, T.

A Model for Predicting Thermoelectric Properties of Bi2Te3

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.

Lee, Seungwon

Method of Suppressing Sublimation in Advanced Thermoelectric Devices

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.

Sakamoto, Jeffrey S.

Aerogels for Thermal Insulation of Thermoelectric Devices

Silica aerogels have been shown to be attractive for use as thermal-insulation materials for thermoelectric devices. It is desirable to thermally insulate the legs of thermoelectric devices to suppress lateral heat leaks that degrade thermal efficiency. Aerogels offer not only high thermal- insulation effectiveness, but also a combination of other properties that are especially advantageous in thermoelectric- device applications. Aerogels are synthesized by means of sol-gel chemistry, which is ideal for casting insulation into place. As the scale of the devices to be insulated decreases, the castability from liquid solutions becomes increasingly advantageous: By virtue of castability, aerogel insulation can be made to encapsulate devices having any size from macroscopic down to nanoscopic and possibly having complex, three-dimensional shapes. Castable aerogels can permeate voids having characteristic dimensions as small as nanometers. Hence, practically all the void space surrounding the legs of thermoelectric devices could be filled with aerogel insulation, making the insulation highly effective. Because aerogels have the lowest densities of any known solid materials, they would add very little mass to the encapsulated devices. The thermal-conductivity values of aerogels are among the lowest reported for any material, even after taking account of the contributions of convection and radiation (in addition to true thermal conduction) to overall effective thermal conductivities. Even in ambient air, the contribution of convection to effective overall thermal conductivity of an aerogel is extremely low because of the highly tortuous nature of the flow paths through the porous aerogel structure. For applications that involve operating temperatures high enough to give rise to significant amounts of infrared radiation, opacifiers could be added to aerogels to reduce the radiative contributions to overall effective thermal conductivities. One example of an opacifier is carbon black, which absorbs infrared radiation. Another example of an opacifier is micron- sized metal flakes, which reflect infrared radiation. Encapsulation in cast aerogel insulation also can help prolong the operational lifetimes of thermoelectric devices that must operate in vacuum and that contain SiGe or such advanced skutterudite thermoelectric materials as CoSb3 and CeFe3.5Co0.5Sb12. The primary cause of deterioration of most thermoelectric materials is thermal decomposition or sublimation (e.g., sublimation of Sb from CoSb3) at typical high operating temperatures. Aerogel present near the surface of CoSb3 can impede the outward transport of Sb vapor by establishing a highly localized, equilibrium Sb vapor atmosphere at the surface of the CoSb3.

Sakamoto, Jeffrey

Current Pulses Momentarily Enhance Thermoelectric Cooling

The rates of cooling afforded by thermoelectric (Peltier) devices can be increased for short times by applying pulses of electric current greater than the currents that yield maximum steady-state cooling. It has been proposed to utilize such momentary enhancements of cooling in applications in which diode lasers and other semiconductor devices are required to operate for times of the order of milliseconds at temperatures too low to be easily obtainable in the steady state. In a typical contemplated application, a semiconductor device would be in contact with the final (coldest) somewhat taller stage of a multistage thermoelectric cooler. Steady current would be applied to the stages to produce steady cooling. Pulsed current would then be applied, enhancing the cooling of the top stage momentarily. The principles of operation are straightforward: In a thermoelectric device, the cooling occurs only at a junction at one end of the thermoelectric legs, at a rate proportional to the applied current. However, Joule heating occurs throughout the device at a rate proportional to the current squared. Hence, in the steady state, the steady temperature difference that the device can sustain increases with current only to the point beyond which the Joule heating dominates. If a pulse of current greater than the optimum current (the current for maximum steady cooling) is applied, then the junction becomes momentarily cooled below its lowest steady temperature until thermal conduction brings the resulting pulse of Joule heat to the junction and thereby heats the junction above its lowest steady temperature. A theoretical and experimental study of such transient thermoelectric cooling followed by transient Joule heating in response to current pulses has been performed. The figure presents results from one of the experiments. The study established the essential parameters that characterize the pulse cooling effect, including the minimum temperature achieved, the maximum temperature overshoot, the time to reach minimum temperature, the time while cooled, and the time between pulses. It was found that at large pulse amplitude, the amount of pulse supercooling is about a fourth of the maximum steady-state temperature difference. For the particular thermoelectric device used in one set of the experiments, the practical optimum pulse amplitude was found to be about 3 times the optimum steady-state current. In a further experiment, a pulse cooler was integrated into a small commercial thermoelectric threestage cooler and found to provide several degrees of additional cooling for a time long enough to operate a semiconductor laser in a gas sensor.

Snyder, G. Jeffrey

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

Transient Thermoelectric Solution Employing Green's Functions

The study works to formulate convenient solutions to the problem of a thermoelectric couple operating under a time varying condition. Transient operation of a thermoelectric will become increasingly common as thermoelectric technology permits applications in an increasing number of uses. A number of terrestrial applications, in contrast to steady-state space applications, can subject devices to time varying conditions. For instance thermoelectrics can be exposed to transient conditions in the automotive industry depending on engine system dynamics along with factors like driving style. In an effort to generalize the thermoelectric solution a Greens function method is used, so that arbitrary time varying boundary and initial conditions may be applied to the system without reformulation. The solution demonstrates that in thermoelectric applications of a transient nature additional factors must be taken into account and optimized. For instance, the materials specific heat and density become critical parameters in addition to the thermal mass of a heat sink or the details of the thermal profile, such as oscillating frequency. The calculations can yield the optimum operating conditions to maximize power output andor efficiency for a given type of device.

thermoelectric power generation

Advanced thermoelectric materials with enhanced crystal lattice structure and methods of preparation

New skutterudite phases including Ru.sub.0.5 Pd.sub.0.5 Sb.sub.3, RuSb.sub.2 Te, and FeSb.sub.2 Te, have been prepared having desirable thermoelectric properties. In addition, a novel thermoelectric device has been prepared using skutterudite phase Fe.sub.0.5 Ni.sub.0.5 Sb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor compounds and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor materials having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using powder metallurgy techniques. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities and good Seebeck coefficients. These materials have low thermal conductivity and relatively low electrical resistivity, and are good candidates for low temperature thermoelectric applications.

Fleurial, Jean-Pierre

New Technology for Microfabrication and Testing of a Thermoelectric Device for Generating Mobile Electrical Power

Thermoelectric (TE) power generation is an increasingly important power generation technology. Major advantages include: no moving parts, low-weight, modularity, covertness/silence, high power density, low amortized cost, and long service life with minimum or no required maintenance. Despite low efficiency of power generation, there are many specialized needs for electrical power that TE technologies can uniquely and successfully address. Recent advances in thermoelectric materials technology have rekindled acute interest in thermoelectric power generation. We have developed single crystalline n- and p- type PbTe crystals and are also, developing PbTe bulk nanocomposites using PbTe nano powders and emerging filed assisted sintering technology (FAST). We will discuss the materials requirements for efficient thermoelectric power generation using waste heat at intermediate temperature range (6500 to 8500 K). We will present our recent results on production of n- and p- type PbTe crystals and their thermoelectric characterization. Relative characteristics and performance of PbTe bulk single crystals and nano composites for thermoelectric power generation will be discussed.

Prasad, Narasimha S.

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.

Large language model-driven database for thermoelectric materials

Thermoelectric materials have the ability to convert waste heat into electricity, offering a valuable solution for energy harvesting. However, their widespread use is hindered by low conversion efficiency, the reliance on expensive rare earth elements, and the environmental and regulatory concerns associated with lead-based materials. A fast and cost-effective way to identify highly efficient thermoelectric materials is through data-driven methods. These approaches rely on robust and comprehensive datasets to train models. Although there are several databases on thermoelectric materials, there is still a need to collect and integrate experimental data from peer-reviewed research articles to capture diverse compositions and properties of materials. Here, in this work, we developed a comprehensive database of 7,123 thermoelectric compounds, containing key information such as chemical composition, structural detail, seebeck coefficient, electrical and thermal conductivity, power factor, and figure of merit (ZT). We used the GPTArticleExtractor workflow, powered by large language models (LLM), to extract and curate data automatically from the scientific literature published in Elsevier journals. This process enabled the creation of a structured database that addresses the challenges of manual data collection. The open access database could stimulate data-driven research and advance thermoelectric material analysis and discovery.

Database

Fast-airflow tumble clothes dryer with small thermoelectric heat pump: Experimental evaluation

Residential clothes drying accounts for about 5% of the total residential-sector energy consumption in the United States. Most dryers use electric resistance heaters to dry clothes and have low efficiencies. Higher-efficiency dryers that use vapor compression heat pumps are expensive and complex and have not gained a large market share in the United States. A novel tumble clothes dryer using a small thermoelectric heat pump with faster airflow than typical dryers is presented in this work. The benchtop performance of the thermoelectric heat pump and high-speed blower are presented, and the development of the prototype dryer is described. The dryer was tested for efficiency and dry time for a range of airflow rates and applied currents to the thermoelectric heat pump. The combined efficiency factor was 5.09–6.29 lb BDW /kWh (specific moisture extraction rate of 1.23–1.53 kg w /kWh) with 100–138 min dry times for these tests. The measured efficiency was 36 %–68 % greater than the minimum efficiency standard in the United States, and compared with vapor compression heat pump–based clothes dryers, the prototype dryer had less expensive, less complex components and did not use refrigerants. Finally, the performance of this small thermoelectric heat pump clothes dryer is also compared with previous iterations of the thermoelectric tumble clothes dryer described in the literature.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI