Thermoelectric Properties of Nano/microstructured p-Type Bi0.4Sb1.6Te3 Powders Fabricated by Mechanical Alloying and Vacuum Hot Pressing

Two kinds of Bi_0.4Sb_1.6Te₃ powder with different particle and grain sizes were fabricated by high-energy ball milling. Powder mixtures with varied weight ratios were consolidated by vacuum hot pressing (HP) to produce nano/ microstructured composites of identical chemical composition. From measurements of the Seebeck coefficient, electrical resistivity, and thermal conductivity of these composites, a figure of merit (ZT) value of up to 1.19 was achieved at 373 K for the sample containing 40% nanograin powder. This ZT value is higher than that of monolithic nanostructured Bi_0.4Sb_1.6Te₃. It is further noted that the ZT value of this sample in the temperature range of 450 K to 575 K is in the range of 0.7 to 1.1. Such ZT characteristics are suitable for power generation applications as no other material with a similar high ZT value in this temperature range has been observed until now. The achieved high ZT value can probably be attributed to the unique nano/microstructure, in which the dispersed nanograin powder increases the number of phonon scattering sites, which in turn results in a decrease of the thermal conductivity while simultaneously increasing the electrical conductivity, owing to the existence of the microsized powder that can provide a fast carrier transportation network. These results indicate that the nano/microstructured Bi_0.4Sb_1.6Te₃ alloy can serve as a high-performance material for application in thermoelectric devices.     

Thermoelectric Properties of Higher Manganese Silicides Prepared by Mechanical Alloying and Hot Pressing

Higher manganese silicides (HMS), MnSi_1.75–δ , were synthesized by mechanical alloying and consolidated by hot pressing. The optimum condition of mechanical alloying was ball milling at 400 rpm for 6 h, and sound sintered compacts could be obtained by hot pressing at temperature higher than 1073 K. The phase fraction of HMS showed no significant difference with compositional (δ) variation, but the MnSi_1.75 specimen had the lowest fraction of MnSi of approximately 3%. The lattice constants of HMS with compositional variation were similar to values reported in the literature. All specimens showed Nowotny phase with tetragonal structure, and exhibited i-type conduction at measuring temperatures between 323 K and 823 K. HMS behaved as degenerate semiconductors in that the absolute values of the Seebeck coefficient increased and the electrical conductivity slightly decreased with increasing temperature. MnSi_1.73 showed the highest figure of merit of 0.28 at 823 K.     

Interface Microstructure and Performance of Sb Contacts in Bismuth Telluride-Based Thermoelectric Elements

A thermoelectric joint composed of p-type Bi_0.5Sb_1.5Te₃ (BiSbTe) material and an antimony (Sb) interlayer was fabricated by spark plasma sintering. The reliability of the thermoelectric joints was investigated using electron probe microanalysis for samples with different accelerated isothermal aging time. After aging for 30 days at 300°C in vacuum, the thickness of the diffusion layer at the BiSbTe/Sb interface was about 30 μm, and Sb₂Te₃ was identified to be the major interfacial compound by element analysis. The contact resistivity was 3 × 10^?6 ohm cm² before aging and increased to 8.5 × 10^?6 ohm cm² after aging for 30 days at 300°C, an increase associated with the thickness of the interfacial compound. This contact resistivity is very small compared with that of samples with solder alloys as the interlayer. In addition, we have also investigated the interface behavior of Sb layers integrated with n-type Bi₂Se_0.3Te_2.7 (BiSeTe) material, and obtained similar results as for the p-type semiconductor. The present study suggests that Sb may be useful as a new interlayer material for bismuth telluride-based power generation devices.     

Thermoelectric Properties of Sn-S Bulk Materials Prepared by Mechanical Alloying and Spark Plasma Sintering

To study the possibility of SnS as an earth-abundant and environmentally friendly thermoelectric material, the electrical and thermal transport properties of bulk materials prepared by combining mechanical alloying and spark plasma sintering were investigated. It was revealed that SnS has potential as a good thermoelectric material, benefiting from its intrinsically low thermal conductivity below 1.0 W/m/K above 400 K and its high Seebeck coefficient over 500 μV/K. Although the highest ZT value was 0.16 at 823 K in the pristine sample, further enhancement can be expected through chemical doping to increase the electrical conductivity. It was also revealed that changing the stoichiometric ratio and sintering temperature had less apparent influence on the microstructure and thermoelectric properties of SnS because redundant S in the powders decomposed during the sintering process.     

Effect of Processing Route on the Microstructure and Thermoelectric Properties of Bismuth Telluride-Based Alloys

Considerable work has been done to engineer materials with high efficiencies of thermoelectric heat-to-electricity conversion and the mechanical strength necessary to withstand the demands of practical applications. In particular, in the bismuth telluride system, extrusion pressing has been found to be effective for improving the mechanical strength of alloys via grain refinement. We review some of the literature relating to processing approaches for the bismuth telluride system. We also present preliminary data for a series of samples obtained by incorporating C₆₀ via ball milling and spark plasma sintering into a matrix consisting of a (Bi,Sb)₂Te₃ alloy, with a focus on the texture of the composites and its relation to thermoelectric transport properties, in comparison to the parent material. The viability of improving the thermoelectric performance of bismuth telluride alloys by the insertion of nanoparticles into a composite is also considered.     

Improved Thermoelectric Properties of p-Type Bismuth Antimony-Based Alloys Prepared by Spark Plasma Sintering

Bi₈₅Sb_15?x Pb _x (x = 0, 0.5, 1, 2, 3) alloys have been prepared by the mechanical alloying–spark plasma sintering (MA-SPS) method. X-ray diffraction and scanning electron microscopy were used to characterize the microstructure of the alloys. The effect of Pb content on the thermoelectric properties was investigated in the temperature range 77–300 K. The results showed that the electrical transport properties of the Bi–Sb alloys changed from n-type to p-type with substitution of Sb by Pb. The maximum power factor reached 1.6 × 10^?3 W/mK² at 190 K, a significant improvement on values reported elsewhere. This study demonstrated that high-performance p-type thermoelectric Bi–Sb materials can be obtained by spark plasma sintering.     

Fabrication of Bismuth Telluride-Based Alloy Thin Film Thermoelectric Devices Grown by Metal Organic Chemical Vapor Deposition

Bismuth–antimony–telluride based thin film materials were grown by metal organic vapor phase deposition (MOCVD). A planar-type thermoelectric device was fabricated with p-type Bi_0.4Sb_1.6Te₃ and n-type Bi₂Te₃ thin films. The generator consisted of 20 pairs of p-type and n-type legs. We demonstrated complex structures of different conduction types of thermoelectric elements on the same substrate using two separate deposition runs of p-type and n-type thermoelectric materials. To demonstrate power generation, we heated one side of the sample with a heating block and measured the voltage output. An estimated power of 1.3 μW was obtained for the temperature difference of 45 K. We provide a promising procedure for fabricating thin film thermoelectric generators by using MOCVD grown thermoelectric materials that may have a nanostructure with high thermoelectric properties.     

Thermoelectric Properties of Nanocrystalline PbTe Synthesized by Mechanical Alloying

In this work, nanocrystalline lead telluride powder was synthesized from high-purity elements by mechanical alloying by means of a planetary ball-milling procedure. The milling medium was tungsten carbide, and the diameter of the balls was varied in order to investigate the effect on the structural features of the material. Phase transformations and crystallite evolution during ball-milling were followed by powder x-ray diffraction (PXRD). The broadened PXRD peaks were analyzed with Voigt functions, revealing small crystalline size and stress introduced during the mechanical alloying process. Transmission electron microscopy (TEM) studies confirmed the material’s nanostructure, as well as the effect of ball diameter on the size of the crystals. Thermoelectric properties are discussed in terms of the Seebeck coefficient and the nominal carrier concentration, as determined by Hall-effect measurements. The enhancement of the Seebeck coefficient is reported to be higher compared with other PbTe-based nanocomposites.     

Synthesis of Thermoelectric Manganese Silicide by Mechanical Alloying and Pulse Discharge Sintering

Manganese silicide is a candidate for low-cost thermoelectric materials with low-environmental load. MnSi_1.73 compound was studied as a thermoelectric material available for thermoelectric power generation using waste heat. Manganese and silicon powders were mechanically alloyed under three different conditions (at 200 r.p.m. for 36 ks, at 400 r.p.m. for 3.6 ks and at 400 r.p.m. for 36 ks) with planetary ball milling equipment. Then, the mechanically alloyed powder was consolidated by a pulse discharge sintering process. Phases of MnSi_1.73 (primary phase) and MnSi were synthesized by mechanical alloying and pulse discharge sintering. Thermoelectric properties were dependent on the mechanical alloying condition. The sample mechanically alloyed at 400 r.p.m. for 3.6 ks gave the best thermoelectric performance. The maximum dimensionless figure of merit ZT of 0.47 was achieved at 873 K.     

Thermoelectric Properties of Indium-Selenium Nanocomposites Prepared by Mechanical Alloying and Spark Plasma Sintering

Indium-selenium-based compounds have received much attention as thermoelectric materials since a high thermoelectric figure of merit of 1.48 at 705?K was observed in In₄Se_2.35. In this study, four different compositions of indium-selenium compounds, In₂Se₃, InSe, In₄Se₃, and In₄Se_2.35, were prepared by mechanical alloying followed by spark plasma sintering. Their thermoelectric properties such as electrical resistivity, Seebeck coefficient, and thermal conductivity were measured in the temperature range of 300?K to 673?K. All the In-Se compounds comprised nanoscaled structures and exhibited n-type conductivity with Seebeck coefficients ranging from ?159???V?K^?1 to ?568???V?K^?1 at room temperature.     

Generation of Nanosized Particles during Mechanical Alloying and Their Evolution through the Hot Extrusion Process in Bismuth-Telluride-Based Alloys

Our extensive studies of extruded alloys have shown that mechanically strong polycrystalline alloys also deliver surprisingly high thermoelectric performance with ZT > 1 for p-type material in the temperature range from 25°C to 90°C, which was traditionally attributed to the strong texture generated by the extrusion process. Optical and low-resolution scanning electron microscopy observations of the powder produced by mechanical alloying show a particle size distribution in the micrometric range. However, high-resolution transmission electron microscopy (HRTEM) observations of the powders obtained after milling clearly show nanosized crystal grains. The larger microparticles appear to be agglomerations of grains whose size goes down to 5 nm to 20 nm. Examination of bulk n-type and p-type materials using x-ray diffraction (XRD) combined with HRTEM shows that nanosized subgrains can also be found in materials after hot extrusion. In this article we present experimental evidence of the generation and evolution of nanocrystalline particles through the mechanical alloying and hot extrusion processes used to produce the thermoelectric alloys. We also discuss the possible influence of nanocrystalline inclusions on the thermoelectric performance of the produced material. The optimization of the hot extrusion process, in order to maximize the influence of the nanostructures, offers new opportunities to increase the thermoelectric performance of bulk materials.     

Nanostructure Characterization of Bismuth Telluride-Based Powders and Extruded Alloys by Various Experimental Methods

High-resolution transmission electron microscopy (HRTEM) observations of mechanically alloyed powders and bulk extruded alloys give experimental evidence of nanosized grains in bismuth telluride-based materials. In this study we combine HRTEM observations and x-ray diffraction (XRD) measurements, of both mechanically alloyed powders and extruded samples, with mechanical spectroscopy (MS) of extruded rods. Both HRTEM and XRD show that nanostructures with an average grain size near 25 nm can be achieved within 2 h of mechanical alloying from pure elements in an attritor-type milling machine. Residual strain orthogonal to the c-axis of powder nanoparticles has been evaluated at about 1.2% by XRD peak broadening. In contrast, XRD has been found unreliable for evaluation of grain size in highly textured extruded materials for which diffraction conditions are similar to those of single crystals, while MS appears promising for study of bulk extruded samples. Nanostructured extruded alloys at room temperature exhibit an internal friction (IF) background that is one order of magnitude higher than that of conventional zone-melted material with a grain size of several millimeters. IF as a function of sample temperature gives activation energies that are also different between bulk materials having nano- and millimeter-size grains, a result that is attributed to different creep mechanisms. Nanograin size, as well as orientation and volumetric proportion, provide valuable information for optimization of technological parameters of thermoelectric alloys and should be carefully cross-examined by various independent methods.     

Thermoelectric Modules Based on Half-Heusler Materials Produced in Large Quantities

Half-Heusler (HH) compounds are some of the most promising candidates among the medium-temperature thermoelectric materials being investigated for automotive and industrial waste heat recovery applications. For n- as well as p-type material, peak ZT values larger than one have been published recently, and first modules have been built. The next step to facilitate the industrialization of thermoelectric module production is upscaling of material synthesis. In this paper, the latest results of the thermoelectric properties of HH compounds produced in kg batches are presented and compared with values published in the literature. The performance of modules built from these materials is analyzed with respect to power output and long-term stability of the material and electrical contacts.     

Mechanical Alloying and Spark Plasma Sintering of Higher Manganese Silicides for Thermoelectric Applications

The present challenges in the energy crisis require finding new ways to reduce consumption of fossil fuels. Thermoelectrics can help reduce fuel consumption by producing electricity from waste heat. The higher manganese silicides (HMS) have shown promise in this field as inexpensive, nontoxic, and highly stable p-type thermoelectric materials. One of the production techniques for HMS is mechanical alloying by ball milling. In this research the effect of the ball-milling duration and speed on the phases produced was studied. Mn and Si powders were milled at speeds of 200 RPM to 800 RPM for 1 h to 7 h. X-ray diffraction (XRD) results of the samples prepared using mechanical alloying show deterioration into the MnSi phase. The sample that underwent 5 h of milling at 800 RPM showed the greatest amount of HMS phase and was subsequently spark plasma sintered. The sample showed insufficient thermoelectric properties (ZT ≈ 0.1 at 450°C), compared with either solid-state reaction samples showing ZT ≈ 0.4 or cast samples showing ZT ≈ 0.63 at 450°C. The reduced ZT values of the mechanically alloyed and spark-plasma-sintered samples were attributed to the high relative amount of MnSi phase. The correlation between the relative amount of MnSi and the transport properties is described in detail.     

Thermoelectric Properties of Sintered n-Type and p-Type Tellurides

Characterization of powder-metallurgically manufactured (Bi _x Sb_1?x )₂(Te _y Se_1?y )₃ thermoelectric materials is presented. The manufacturing methods were spark plasma sintering (SPS) and hot isostatic pressing (HIP). x-Ray diffraction (XRD) and density measurements as well as transport characterization and scanning electron microscopy were performed on the materials. It is shown that both sintering techniques yield reasonable thermoelectric characteristics for p-type (x = 0.2, y = 1) as well as n-type (x = 0.95, y = 0.95) materials. Insight into the underlying reasons such as the scattering processes limiting the characteristics is gained by fitting experimental transport data using a theoretical model. The limitations and further optimization issues of our approach in thermoelectric material preparation are discussed.     

Preparation and Thermoelectric Properties of p-Type Yb-Filled Skutterudites

p-Type Yb _z Fe_4?x Co _x Sb₁₂ skutterudites were prepared by encapsulated melting and hot pressing, and the filling and doping (charge compensation) effects on the transport and thermoelectric properties were examined. The electrical conductivity of all specimens decreased slightly with increasing temperature, indicating that they were in a degenerate state due to high carrier concentrations of 10²⁰ cm^?3 to 10²¹ cm^?3. The Hall and Seebeck coefficients exhibited positive signs, indicating that the majority carriers are holes (p-type). The Seebeck coefficient increased with increasing temperature to maximum values of 100 μV/K to 150 μV/K at 823 K. The electrical and thermal conductivities were reduced by substitution of Co for Fe, which was responsible for the decreased carrier concentration. Overall, the Yb-filled Fe-rich skutterudites showed better thermoelectric performance than the Yb-filled Co-rich skutterudites.     

Effects of Excess Sb on Thermoelectric Properties of Barium and Indium Double-Filled Iron-Based p-Type Skutterudite Materials

A series of Ba and In double-filled iron-based p-type skutterudite thermoelectric (TE) materials with nominal composition BaInFe_3.7Co_0.3Sb_12+m (0.72????m????2.4) have been prepared by melting, quenching, annealing, and spark plasma sintering (SPS) methods. The effects of excess Sb on the phase composition, microstructure, and TE transport properties of these materials were investigated in this work. All the SPS bulk materials are composed of the main skutterudite phase and trace InSb and FeSb₂. The content of FeSb₂ in the SPS bulk materials gradually decreased and that of InSb remained nearly invariable with increasing m. The impurities InSb and metallic Sb are found at grain boundaries. The amount of metallic Sb at grain boundaries gradually increased with increasing m. The excess Sb had no effect on the growth of grains. The dependence of the TE properties on m indicates that preventing the formation of FeSb₂ by adjusting the excess Sb value may significantly improve the TE properties of Ba and In double-filled iron-based p-type skutterudite materials. The significant increases in the carrier concentration and electrical conductivity as well as the remarkable reduction in the lattice thermal conductivity of the sample with m?=?0.96 are due to the significant reduction in the FeSb₂ content induced by the excess Sb. The gradual increase in ZT with increasing m from 0.72 to 1.44 is attributed to the gradual decrease of the FeSb₂ content, and the gradual decrease in ZT in the m range of 1.44 to 2.4 is due to the gradual increase of the Sb content in the Sb-In alloy impurity occurring at grain boundaries. The lowest lattice thermal conductivity of 0.31?W?m^?1?K^?1 and the highest ZT value of 0.63 were obtained at 800?K for the sample with m?=?1.44.     

High-Temperature Mechanical and Thermoelectric Properties of p-Type Bi0.5Sb1.5Te3 Commercial Zone Melting Ingots

Bismuth telluride-based compounds have been extensively utilized for commercial application. However, thermoelectric materials must suffer numerous mechanical vibrations and thermal stresses while in service, making it equally important to discuss the mechanical properties, especially at high temperature. In this study, the compressive and bending strengths of Bi_0.5Sb_1.5Te₃ commercial zone melting (ZM) ingots were investigated at 25, 100, and 200 °C, respectively. Due to the obvious anisotropy of materials prepared by ZM method, the effect of anisotropy on the strengths was also explored. Two-parameter Weibull distribution was employed to fit a series of values acquired by a universal testing machine. And digital speckle photography was applied to record the strain field evolution, providing visual observation of surface strain. The compressive and bending strengths along ZM direction were approximately three times as large as those perpendicular to the ZM direction independent of the temperature, indicating a weak van der Waals bond along the c axis.     

Synthesis and Electronic Properties of Thermoelectric and Magnetic Nanoparticle Composite Materials

Application of a magnetic field greatly enhances the thermoelectric efficiency of bismuth-antimony (Bi-Sb) alloys. We synthesized a hybrid of Bi-Sb alloy and magnetic nanoparticles, expecting improvement of the thermoelectric performance due to the magnetic field generated by the nanoparticles. Powder x-ray diffraction and magnetic measurements of the synthesized hybrid Bi_0.88Sb_0.12(FeSb)_0.05 sample indicated that the ferromagnetic FeSb nanoparticles, with a size of about 30 nm, were distributed in the main phase of the Bi-Sb alloy. The FeSb nanoparticles act as soft ferromagnets in the diamagnetic host Bi-Sb alloy. The electrical resistivity ρ of the host Bi_0.88Sb_0.12 sample decreased concomitantly with decreasing temperature, showing a shoulder at 80 K. In contrast, ρ for the hybrid sample was enhanced below 100 K because of carrier scattering by the nanoparticles. The temperature dependence of the Seebeck coefficient S was also altered by the nanoparticle addition. In contrast, the addition of magnetic nanoparticles only slightly influenced the thermal conductivity κ. These results indicate that the addition of magnetic nanoparticles to thermoelectric materials modulates the electronic structures but does not influence the lattice system.