Simulation of Morphological Effects on Thermoelectric Power, Thermal and Electrical Conductivity in Multi‐Phase Thermoelectric Materials

Multi‐phase thermoelectric materials are mainly investigated these days due to their potential of lattice thermal conductivity reduction by scattering of phonons at interfaces of the involved phases, leading to the enhancement of expected thermoelectric efficiency. On the other hand, electronic effects of the involved phases on thermoelectric performance are not always being considered, while developing new multi‐phase thermoelectric materials. In this chapter, electronic effects resulting from controlling the phase distribution and morphology alignment in multi‐phase composite materials is carefully described using the general effective media (GEM) method and analytic approaches. It is shown that taking into account the specific thermoelectric properties of the involved phases might be utilized for estimating expected effective thermoelectric properties of such composite materials for any distribution and relative amount of the phases. An implementation of GEM method for the IV–VI (including SnTe and GeTe), bismuth telluride (Bi2Te3), higher manganese silicides (HMS) and half‐Heusler classes of thermoelectric materials is described in details

Bismuth Telluride Solubility Limit and Dopant Effects on the Electronic Properties of Lead Telluride

The demand for energy efficiency has motivated many researchers to seek for novel methods capable of enhancing the conversion of heat to electricity. Most of the recently published methods for thermoelectric (TE) efficiency enhancement discuss on the reduction of the lattice thermal conductivity, with a minor focus on improved electronic optimization. This is attributed mainly to the fact that the electronic properties are correlated and opposing each other upon increasing the carrier concentration. It has been reported that the system of PbTe-BiTe has potentially high TE performance; this chapter is focused on a detailed investigation of the co-effect of bismuth as an effective electronic dopant and at the same time, as a second phase promoter in the PbTe matrix. (PbTe)x(BiTe)1−x alloys were thermoelectrically examined and the values were analyzed analytically by the general effective media (GEM) approach

Mechanical Properties of Thermoelectric Materials for Practical Applications

Thermoelectric (TE) direct conversion of thermal energy into electricity is a novel renewable energy conversion method currently at a technological readiness level of 3–5 approaching laboratory prototypes. While approaching practical thermoelectric devices, an increase in the thermoelectric element’s efficiency is needed at the entire service temperature range. Yet, the main focus of research was concentrated on the electronic properties of the materials, while research on the mechanical properties was left behind. As it is shown in this chapter, knowing and controlling the mechanical properties of TE materials are paramount necessities for approaching practical TEGs. The material’s elastic constants, strength and fracture toughness are the most crucial parameters for designing of practical devices. The elastic constants provide understanding about the material’s stiffness, while strength provides the loading conditions in which the material will keep its original shape. Knowing the fracture toughness provides the stress envelope in which the material could operate and its susceptibility to inherent fabrication faults. The characterization methods of these properties are varied and may be physical or pure mechanical in nature. It is the authors opinion to prefer the mechanical methods, so the results obtained will describe more accurately the material’s response to mechanical loading

Reduction of Hf via Hf/Zr Substitution in Mechanically Alloyed (Hf,Ti)CoSb Half-Heusler Solid Solutions

Abstract (Hf,Zr,Ti)Co(Sb,Sn) Solid solutions were prepared by mechanical-alloying followed by hot-press method as an attempt to reduce Hf concentration and therefore the material’s cost without negatively affecting the thermoelectric performance. To this end, two different methods were applied: (a) Hf substitution with its lighter and cheaper homologue Zr; and (b) fine tuning of carrier concentration by the substitution of Sb with Sn. The isoelectronic substitution of Hf with Zr was investigated in Hf0.6-xZrxTi0.4CoSb0.8Sn0.2 solid solutions and resulted in lower power factors and ZTs. However, the low thermal conductivity of Hf0.4Zr0.2Ti0.4CoSb0.8Sn0.2 contributed in achieving a relatively good ZT~0.67 at 970 K. The effect of charge carrier concentration was investigated by preparing Hf0.4Zr0.2Ti0.4CoSb1-ySny (y = 0.15–0.25) compounds. Hf0.4Zr0.2Ti0.4CoSb0.83Sn0.17 composition prepared by six hours milling reached the highest ZT of 0.77 at 960 K.publishedVersio

Investigation of the Microstructural and Thermoelectric Properties of the (GeTe)0.95(Bi2Te3)0.05 Composition for Thermoelectric Power Generation Applications

In the frame of the current research, the p-type Bi2Te3 doped (GeTe)(0.95)(Bi2Te3)(0.05) alloy composed of hot pressed consolidated submicron structured powder was investigated. The influence of the process parameters (i.e., powder particles size and hot pressing conditions) on both reduction of the lattice thermal conductivity and electronic optimization is described in detail. Very high maximal ZT values of up to similar to 1.6 were obtained and correlated to the microstructural characteristics. Based on the various involved mechanisms, a potential route for further enhancement of the ZT values of the investigated composition is proposed.EC, FP7 PowerDriver Projec

Physical, mechanical, and structural properties of highly efficient nanostructured n-and p-silicides for practical thermoelectric applications

et al.Cost-effective highly efficient nanostructured n-type Mg2Si 1-x Sn x and p-type higher manganese silicide (HMS) compositions were prepared for the development of practical waste heat generators for automotive and marine thermoelectric applications, in the frame of the European Commission (EC)-funded PowerDriver project. The physical, mechanical, and structural properties were fully characterized as part of a database-generation exercise required for the thermoelectric converter design. A combination of high maximal ZT values of ~0.6 and ~1.1 for the HMS and Mg2Si1-x Sn x compositions, respectively, and adequate mechanical properties was obtained. © 2013 TMS.The work was supported by the EC FP7 Power-Driver Project.Peer Reviewe

PbO-SiO2 Based Glass Coating of PbI2 Doped PbTe

Thermoelectrics is one promising way of increasing the efficiency of machines and devices by reusing some of the waste heat produced. One obstacle for commercialization is the need to coat the materials to prevent sublimation and oxidation of the thermoelectric materials. Such coatings were designed for PbI2 doped PbTe using a (SiO2)0.68(PbO)0.3(B2O3)0.01(Na2O)0.01 based glass designed for operation at 500 °C. In this research various conditions of the coating process were examined. The effect of the atmosphere on the bonding and densification of the coating was studied using argon, vacuum and air. From the three air shows, the best bonding characteristics were from a better flow of glass and increased bonding between the oxidized PbTe layer and glass. This also created a PbO rich glass in the interface between the glass and the PbTe sample. The effect of 0, 3, and 6 wt. % NaCl additive to the solution was tested and showed that NaCl achieves better coverage due to high green body density, reaction of NaCl with the glass and removal of remaining CO2 from the glass in the form of decomposing Na2CO3. In addition, when testing the time and temperature, it was shown that the temperature of 520 °C was the minimum needed for high densification of the glass, but a duration shorter than 30 min did not allow for bonding of the glass to the substrate despite adequate densification. Finely, to obtain a well bonded coating with full coverage over the sample, the glass was coated with 6% NaCl in air at 520 °C for 30 min

Compatibility between Co-Metallized PbTe Thermoelectric Legs and an Ag–Cu–In Brazing Alloy

In thermoelectric (TE) generators, maximizing the efficiency of conversion of direct heat to electricity requires the reduction of any thermal and electrical contact resistances between the TE legs and the metallic contacts. This requirement is especially challenging in the development of intermediate to high-temperature TE generators. PbTe-based TE materials are known to be highly efficient up to temperatures of around 500 °C; however, only a few practical TE generators based on these materials are currently commercially available. One reason for that is the insufficient bonding techniques between the TE legs and the hot-side metallic contacts. The current research is focused on the interaction between cobalt-metallized n-type 9.104 × 10−3 mol % PbI2-doped PbTe TE legs and the Ag0.32Cu0.43In0.25 brazing alloy, which is free of volatile species. Clear and fine interfaces without any noticeable formation of adverse brittle intermetallic compounds were observed following prolonged thermal treatment testing. Moreover, a reasonable electrical contact resistance of ~2.25 mΩmm2 was observed upon brazing at 600 °C, highlighting the potential of such contacts while developing practical PbTe-based TE generators

Microstructure Evolution of Ag-Alloyed PbTe-Based Compounds and Implications for Thermoelectric Performance

We investigate the microstructure evolution of Ag-alloyed PbTe compounds for thermoelectric (TE) applications with or without additions of 0.04 at. % Bi. We control the nucleation and temporal evolution of Ag2Te-precipitates in the PbTe-matrix applying designated aging heat treatments, aiming to achieve homogeneous dispersion of precipitates with high number density values, hypothesizing that they act as phonon scattering centers, thereby reducing lattice thermal conductivity. We measure the temperature dependence of the Seebeck coefficient and electrical and thermal conductivities, and correlate them with the microstructure. It is found that lattice thermal conductivity of PbTe-based compounds is reduced by controlled nucleation of Ag2Te-precipitates, exhibiting a number density value as high as 2.7 × 1020 m−3 upon 6 h aging at 380 °C. This yields a TE figure of merit value of ca. 1.4 at 450 °C, which is one on the largest values reported for n-type PbTe compounds. Subsequent aging leads to precipitate coarsening and deterioration of TE performance. Interestingly, we find that Bi-alloying improves the alloys’ thermal stability by suppressing microstructure evolution, besides the role of Bi-atoms as electron donors, thereby maintaining high TE performance that is stable at elevated service temperatures. The latter has prime technological significance for TE energy conversion