Topological insulators for thermoelectrics: A perspective from beneath the surface
Not Available
Engineering topics
Publications and source records attributed to Snyder, G. Jeffrey.
Not Available
The first exploration of the impact of Yb 11 Sb 10 and Yb 10 MnSb 9 secondary phases in Yb 14 MnSb 11 , explaining years of confusing thermoelectric data.
Polyhedral coordination in disordered Ca10MSb9 (M = Al and Cd). The new Zintl phases are intrinsic semiconductors showing ultralow thermal conductivity and candidates for the optimization of their thermoelectric performance.
The present invention discloses heavily doped PbSe with high thermoelectric performance. Thermoelectric property measurements disclosed herein indicated that PbSe is high zT material for mid-to-high temperature thermoelectric applications. At 850 K a peak zT (is) greater than 1.3 was observed when n(sub H) approximately 1.0 X 10(exp 20) cm(exp -3). The present invention also discloses that a number of strategies used to improve zT of PbTe, such as alloying with other elements, nanostructuring and band modification may also be used to further improve zT in PbSe.
A high temperature Seebeck coefficient measurement apparatus and method with various features to minimize typical sources of errors is described. Common sources of temperature and voltage measurement errors which may impact accurate measurement are identified and reduced. Applying the identified principles, a high temperature Seebeck measurement apparatus and method employing a uniaxial, four-point geometry is described to operate from room temperature up to 1300K. These techniques for non-destructive Seebeck coefficient measurements are simple to operate, and are suitable for bulk samples with a broad range of physical types and shapes.
The present invention teaches an effective mechanism for enhancing thermoelectric performance through additional conductive bands. Using heavily doped p-PbTe materials as an example, a quantitative explanation is disclosed, as to why and how these additional bands affect the figure of merit. A high zT of approaching 2 at high temperatures makes these simple, likely more stable (than nanostructured materials) and Tl-free materials excellent for thermoelectric applications.
The present invention demonstrates that weak scattering of carriers leads to a high mobility and therefore helps achieve low electric resistivity with high Seebeck coefficient for a thermoelectric material. The inventors demonstrate this effect by obtaining a thermoelectric figure of merit, zT, higher than 1.3 at high temperatures in n-type PbSe, because of the weak scattering of carriers in the conduction band as compared with that in the valence band. The invention further demonstrates favorable thermoelectric transport properties of n-type PbTe.sub.1-xI.sub.x with carrier concentrations ranging from 5.8.times.10.sup.18-1.4.times.10.sup.20 cm.sup.-3.
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.
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.
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.
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.
Compounds having compositions of Mo(3)Sb(7-x)Te(x) (where x = 1.5 or 1.6) have been investigated as candidate thermoelectric materials. These compounds are members of a class of semiconductors that includes previously known thermoelectric materials. All of these compounds have complex crystalline and electronic structures. Through selection of chemical compositions and processing conditions, it may be possible to alter the structures to enhance or optimize thermoelectric properties.
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.
The present invention relates to a castable, aerogel-based, ultra-low thermal conductivity opacified insulation to suppress sublimation. More specifically, the present invention relates to an aerogel opacified with various opacifying or reflecting constituents to suppress sublimation and provide thermal insulation in thermoelectric modules. The opacifying constituent can be graded within the aerogel for increased sublimation suppression, and the density of the aerogel can similarly be graded to achieve optimal thermal insulation and sublimation suppression.
Degra (now in version 3) is a computer program that simulates the performance of a radioisotope thermoelectric generator (RTG) over its lifetime. Degra is provided with a graphical user interface that is used to edit input parameters that describe the initial state of the RTG and the time-varying loads and environment to which it will be exposed. Performance is computed by modeling the flows of heat from the radioactive source and through the thermocouples, also allowing for losses, to determine the temperature drop across the thermocouples. This temperature drop is used to determine the open-circuit voltage, electrical resistance, and thermal conductance of the thermocouples. Output power can then be computed by relating the open-circuit voltage and the electrical resistance of the thermocouples to a specified time-varying load voltage. Degra accounts for the gradual deterioration of performance attributable primarily to decay of the radioactive source and secondarily to gradual deterioration of the thermoelectric material. To provide guidance to an RTG designer, given a minimum of input, Degra computes the dimensions, masses, and thermal conductances of important internal structures as well as the overall external dimensions and total mass.
A method of fabricating Bi(2-x)Sb(x)Te3-based thermoelectric microdevices involves a combination of (1) techniques used previously in the fabrication of integrated circuits and of microelectromechanical systems (MEMS) and (2) a relatively inexpensive MEMS-oriented electrochemical-deposition (ECD) technique. The present method overcomes the limitations of prior MEMS fabrication techniques and makes it possible to satisfy requirements.
A technique for suppressing sublimation of key elements from skutterudite compounds in advanced thermoelectric devices has been demonstrated. The essence of the technique is to cover what would otherwise be the exposed skutterudite surface of such a device with a thin, continuous film of a chemically and physically compatible metal. Although similar to other sublimation-suppression techniques, this technique has been specifically tailored for application to skutterudite antimonides. The primary cause of deterioration of most thermoelectric materials is thermal decomposition or sublimation - one or more elements sublime from the hot side of a thermoelectric couple, changing the stoichiometry of the device. Examples of elements that sublime from their respective thermoelectric materials are Ge from SiGe, Te from Pb/Te, and now Sb from skutterudite antimonides. The skutterudite antimonides of primary interest are CoSb3 [electron-donor (n) type] and CeFe(3-x)Co(x)Sb12 [electron-acceptor (p) type]. When these compounds are subjected to typical operating conditions [temperature of 700 C and pressure <10(exp -5) torr (0.0013 Pa)], Sb sublimes from their surfaces, with the result that Sb depletion layers form and advance toward their interiors. As the depletion layer advances in a given device, the change in stoichiometry diminishes the thermal-to-electric conversion efficiency of the device. The problem, then, is to prevent sublimation, or at least reduce it to an acceptably low level. In preparation for an experiment on suppression of sublimation, a specimen of CoSb3 was tightly wrapped in a foil of niobium, which was selected for its chemical stability. In the experiment, the wrapped specimen was heated to a temperature of 700 C in a vacuum of residual pressure <10(exp -5) torr (0.0013 Pa), then cooled and sectioned. Examination of the sectioned specimen revealed that no depletion layer had formed, indicating the niobium foil prevented sublimation of antimony at 700 C. This was a considerable improvement, considering that uncoated CoSb3 had been found to decompose to form the lowest antimonide at the surface at only 600 C. Evidently, because the mean free path of Sb at the given temperature and pressure was of the order of tens of centimeters, any barrier closer than tens of centimeters (as was the niobium foil) would have suppressed transport of Sb vapor, thereby suppressing sublimation of Sb
A document presents a study of why materials of composition (Ag1 ySbTe2)0.05 (PbTe)0.95 [0< or = y < or = 1] were previously reported to have values of the thermoelectric figure of merit [ZT (where Z = alpha(sup 2)/rk, alpha is the Seebeck coefficient, r is electrical resistivity, k is thermal conductivity, and T is absolute temperature)] ranging from <1 to >2. In the study, samples of (AgSbTe2)0.05(PbTe)0.95, (Ag0.67SbTe2)0.05 (PbTe)0.95, and (Ag0.55SbTe2)0.05(PbTe)0.95 were prepared by melting followed, variously, by slow or rapid cooling. Analyses of these samples by x-ray diffraction, electron microscopy, and scanning-microprobe measurements of the Seebeck coefficient led to the conclusion that these materials have a multiphase character on a scale of the order of millimeters, even though they appear homogeneous in x-ray diffraction and electron microscopy. The Seebeck measurements showed significant variations, including both n-type and p-type behavior in the same sample. These variations were found to be consistent with observed variations of ZT. The rapidly quenched samples were found to be less inhomogeneous than were the furnace-cooled ones; hence, rapid quenching was suggested as a basis of research on synthesizing more nearly uniform high-ZT samples.