Seebeck effect and electrical conductivity of stannic oxide as a function of temperature and ambient pressure Interim report
Seebeck effect and electrical conductivity of stannic oxide as function of temperature and ambient pressure
PRESSURE EFFECT↗
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Compensation of voltage drops in solid-state switches used with thermoelectric generators
Seebeck effect solid state switch was developed eliminating thermoelectric generator switch voltage drops. Semiconductor switches were fabricated from materials with large Seebeck coefficients, arranged such that Seebeck potential is generated with such polarity that current flow is aided.
Shimada, K.↗
Crystal Lattice Controlled SiGe Thermoelectric Materials with High Figure of Merit
Direct energy conversion between thermal and electrical energy, based on thermoelectric (TE) effect, has the potential to recover waste heat and convert it to provide clean electric power. The energy conversion efficiency is related to the thermoelectric figure of merit ZT expressed as ZT=S(exp 2)(sigma)T/Kappa, T is temperature, S is the Seebeck coefficient, sigma is conductance and Kappa is thermal conductivity. For a lower thermal conductivity Kappa and high power factor (S(exp 2)(sigma)), our current strategy is the development of rhombohedrally strained single crystalline SiGe materials that are highly [111]-oriented twinned. The development of a SiGe "twin lattice structure (TLS)" plays a key role in phonon scattering. The TLS increases the electrical conductivity and decreases thermal conductivity due to phonon scattering at stacking faults generated from the 60 X rotated primary twin structure. To develop high performance materials, the substrate temperature, chamber working pressure, and DC sputtering power are controlled for the aligned growth production of SiGe layer and TLS on a c-plane sapphire. Additionally, a new elevated temperature thermoelectric characterization system, that measures the thermal diffusivity and Seebeck effect nondestructively, was developed. The material properties were characterized at various temperatures and optimized process conditions were experimentally determined. The present paper encompasses the technical discussions toward the development of thermoelectric materials and the measurement techniques.
Kim, Hyun-Jung↗
Thermoelectric metal comparator determines composition of alloys and metals
Emf comparing device nondestructively inspects metals and alloys for conformance to a chemical specification. It uses the Seebeck effect to measure the difference in emf produced by the junction of a hot probe and the junction of a cold contact on the surface of an unknown metal.
Stone, C. C.↗
Global lunar crust - Electrical conductivity and thermoelectric origin of remanent magnetism
An upper limit is placed on the average crustal conductivity from an investigation of toroidal (V x B) induction in the moon, using ten-minute data intervals of simultaneous lunar orbiting and surface magnetometer data. Crustal conductivity is determined as a function of crust thickness. For an average global crust thickness of about 80 km, the crust surface electrical conductivity is of the order of 1 hundred millionth mho/m. The toroidal-induction results lower the surface-conductivity limit obtained from poloidal-induction results by approximately four orders of magnitude. In addition, a thermoelectric (Seebeck effect) generator model is presented as a magnetic-field source for thermoremanent magnetization of the lunar crust during its solidification and cooling. Magnetic fields from 1000 to 10,000 gammas are calculated for various crater and crustal geometries. Solidified crustal material cooling through the iron Curie temperature in the presence of such ancient lunar fields could have received thermoremanent magnetization consistent with that measured in most returned lunar samples.
Dyal, P.↗
Extended Analytic Device Optimization Employing Asymptotic Expansion
Analytic optimization of a thermoelectric junction often introduces several simplifying assumptionsincluding constant material properties, fixed known hot and cold shoe temperatures, and thermallyinsulated leg sides. In fact all of these simplifications will have an effect on device performance,ranging from negligible to significant depending on conditions. Numerical methods, such as FiniteElement Analysis or iterative techniques, are often used to perform more detailed analysis andaccount for these simplifications. While numerical methods may stand as a suitable solution scheme,they are weak in gaining physical understanding and only serve to optimize through iterativesearching techniques. Analytic and asymptotic expansion techniques can be used to solve thegoverning system of thermoelectric differential equations with fewer or less severe assumptionsthan the classic case. Analytic methods can provide meaningful closed form solutions and generatebetter physical understanding of the conditions for when simplifying assumptions may be valid.In obtaining the analytic solutions a set of dimensionless parameters, which characterize allthermoelectric couples, is formulated and provide the limiting cases for validating assumptions.Presentation includes optimization of both classic rectangular couples as well as practically andtheoretically interesting cylindrical couples using optimization parameters physically meaningful toa cylindrical couple. Solutions incorporate the physical behavior for i) thermal resistance of hot andcold shoes, ii) variable material properties with temperature, and iii) lateral heat transfer through legsides.
Thermoelectric Generators↗
Analytic Couple Modeling Introducing Device Design Factor, Fin Factor, Thermal Diffusivity Factor, and Inductance Factor
A set of convenient thermoelectric device solutions have been derived in order to capture a number of factors which are previously only resolved with numerical techniques. The concise conversion efficiency equations derived from governing equations provide intuitive and straight-forward design guidelines. These guidelines allow for better device design without requiring detailed numerical modeling. The analytical modeling accounts for factors such as i) variable temperature boundary conditions, ii) lateral heat transfer, iii) temperature variable material properties, and iv) transient operation. New dimensionless parameters, similar to the figure of merit, are introduced including the device design factor, fin factor, thermal diffusivity factor, and inductance factor. These new device factors allow for the straight-forward description of phenomenon generally only captured with numerical work otherwise. As an example a device design factor of 0.38, which accounts for thermal resistance of the hot and cold shoes, can be used to calculate a conversion efficiency of 2.28 while the ideal conversion efficiency based on figure of merit alone would be 6.15. Likewise an ideal couple with efficiency of 6.15 will be reduced to 5.33 when lateral heat is accounted for with a fin factor of 1.0.
Seebeck effect↗
Thermoelectric properties of Co(x)Ni(4-x)Sb(12-y)Sn(y) ternary skutterudites
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.
Seebeck Effect↗
Co(x)Ni(4-x)Sb(12-y)Sn(y) Ternary Skutterudites: Processing and Thermoelectric Properties
Skutterudites have proven to be a useful thermoelectric system as a result of their high figure of merit, favorable mechanical properties, and good thermal stability. Binary skutterudites have received the majority of interest in recent years, as a result of successful double and triple filling schemes. Ternary skutterudites, such as Ni4Sb7Sn5, also demonstrate good thermoelectric performance, with high power factor and low thermal conductivity. Ternary skutterudites, as contrasted to binary systems, provide more possibility for tuning electronic structure as substitutions can be studied on three elements. The Co(x)Ni(4-x)Sb(12-y)Sn(y) system has been investigated as both a p- and n-type thermoelectric material, stable up to 200 C. The system is processed through a combination of solidification, mechanical alloying, and hot pressing steps. Rietveld structure refinement has revealed an interesting occupancy of Sn on both the 24g Wyckoff position with Sb as well as the 2a position as a rattler. In addition to thermoelectric properties, detailed processing routes have been investigated on the system.
Seebeck effect↗
WSi2 in Si(1-x)Ge(x) Composites: Processing and Thermoelectric Properties
Traditional SiGe thermoelectrics have potential for enhanced figure of merit (ZT) via nano-structuring with a silicide phase, such as WSi2. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples were prepared using powder metallurgy techniques; including mechano-chemical alloying, via ball milling, and spark plasma sintering for densification. Processing, micro-structural development, and thermoelectric properties will be discussed. Additionally, couple and device level characterization will be introduced.
Thermoelectric Power Generation↗
Analytic Thermoelectric Couple Modeling: Variable Material Properties and Transient Operation
To gain a deeper understanding of the operation of a thermoelectric couple a set of analytic solutions have been derived for a variable material property couple and a transient couple. Using an analytic approach, as opposed to commonly used numerical techniques, results in a set of useful design guidelines. These guidelines can serve as useful starting conditions for further numerical studies, or can serve as design rules for lab built couples. The analytic modeling considers two cases and accounts for 1) material properties which vary with temperature and 2) transient operation of a couple. The variable material property case was handled by means of an asymptotic expansion, which allows for insight into the influence of temperature dependence on different material properties. The variable property work demonstrated the important fact that materials with identical average Figure of Merits can lead to different conversion efficiencies due to temperature dependence of the properties. The transient couple was investigated through a Greens function approach; several transient boundary conditions were investigated. The transient work introduces several new design considerations which are not captured by the classic steady state analysis. The work helps to assist in designing couples for optimal performance, and also helps assist in material selection.
Seebeck Effect↗
Filled Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) Skutterudites: Processing and Thermoelectric Properties
Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3 or CoAs3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) system has been investigated as both a p- and n-type thermoelectric material, and is stable up to 200 degrees Centigrade. Yb, Ce, and Dy fillers have been introduced into the skutterudite to study the influence of both the type and the quantity of fillers on processing conditions and thermoelectric properties. The system was processed through a multi-step technique that includes solidification, mechano-chemical alloying, and hot pressing which will be discussed along with thermoelectric transport properties.
Thermoelectricity↗
Thermomagnetic phenomena in the mixed state of high temperature superconductors
Galvano- and thermomagnetic-phenomena in high temperature superconductors, based on kinetic coefficients, are discussed, along with a connection between the electric field and the heat flow in superconductor mixed state. The relationship that determines the transport coefficients of high temperature superconductors in the mixed state based on Seebeck and Nernst effects is developed. It is shown that this relationship is true for a whole transition region of the resistive mixed state of a superconductor. Peltier, Ettingshausen and Righi-Leduc effects associated with heat conductivity as related to high temperature superconductors are also addressed.
Meilikhov, E. Z.↗
Synthesis and Optimization of Thermoelectric Properties of Zn(x)Sb3
High-performance thermoelectric materials are studied to investigate their abilities to optimize electrical and minimize thermal conductivities. A stoichiometric range of p-type zinc antimonide compounds was synthesized to analyze the trends in their thermoelectric properties. Zn(x)Sb3 (x=3.80, 3.85, 3.90, 3.95, 4.00, 4.05, 4.10) was reacted at 750 C and annealed at 300 C for 24 hours at each temperature. Electronic transport properties such as Seebeck and Hall Effect were measured to analyze possible trends in the set of compositions. SEM, EDS, and XRD were used to quantify both ingots and hot-pressed samples to confirm that they were single-phase and of the expected stoichiometries. Recent SEM data indicated that Zn(3.90)Sb3 and Zn(4.00)Sb3 samples were actually Zn3Sb2. In hopes of further improving the figure-of-merit (ZT) of the binary system, V, Cr, Mn, Fe, Co, In, and Sn were used to dope (Zn(0.95)M(0.05))(3.95)Sb3.
Doan-Nguyen, Vicky V.↗
Detailed Uncertainty Analysis of the ZEM-3 Measurement System
The measurement of Seebeck coefficient and electrical resistivity are critical to the investigation of all thermoelectric systems. Therefore, it stands that the measurement uncertainty must be well understood to report ZT values which are accurate and trustworthy. A detailed uncertainty analysis of the ZEM-3 measurement system has been performed. The uncertainty analysis calculates error in the electrical resistivity measurement as a result of sample geometry tolerance, probe geometry tolerance, statistical error, and multi-meter uncertainty. The uncertainty on Seebeck coefficient includes probe wire correction factors, statistical error, multi-meter uncertainty, and most importantly the cold-finger effect. The cold-finger effect plagues all potentiometric (four-probe) Seebeck measurement systems, as heat parasitically transfers through thermocouple probes. The effect leads to an asymmetric over-estimation of the Seebeck coefficient. A thermal finite element analysis allows for quantification of the phenomenon, and provides an estimate on the uncertainty of the Seebeck coefficient. The thermoelectric power factor has been found to have an uncertainty of +9-14 at high temperature and 9 near room temperature.
Seebeck effect↗
Conduction mechanism in boron carbide
Electrical conductivity, Seebeck-coefficient, and Hall-effect measurements have been made on single-phase boron carbides, B(1-x)C(x), in the compositional range from 0.1 to 0.2 X, and between room temperature and 1273 K. The results indicate that the predominant conduction mechanism is small-polaron hopping between carbon atoms at geometrically inequivalent sites.
Wood, C.↗
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↗
Uncertainty Analysis of Seebeck Coefficient and Electrical Resistivity Characterization
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.
Seebeck effect↗