High-Efficiency Thermoelectric Module Based on High-Performance Bi0.42Sb1.58Te3 Materials

Bismuth-telluride-based alloy is the sole thermoelectric candidate for commercial thermoelectric application in low-grade waste heat harvest near room temperature, but the sharp drop of thermoelectric properties at higher temperature and weak mechanical strength in zone-melted material are the main obstacles to its wide development for power generation. Herein, an effective approach is reported to improve the thermoelectric performance of p-type Bi_0.42Sb_1.58Te₃ hot-pressed sample by incorporating Ag₅SbSe₄. A peak ZT of 1.40 at 375 K and a high average ZT of 1.25 between 300 and 500 K are achieved. Such outstanding thermoelectric performance originates from the synergistic effects of improved density-of-states effective mass, reduced bipolar thermal conductivity by the boosted carrier concentration, and suppressed lattice thermal conductivity by the induced phonon scattering centers including substitute point defects, dislocations, stress–strain clusters, and grain boundaries. Comprised of the p-type Bi_0.42Sb_1.58Te₃ + 0.10 wt% Ag₅SbSe₄ and zone-melted n-type Bi₂Te_2.7Se_0.3, the thermoelectric module exhibits a high conversion efficiency of 6.5% at a temperature gradient of 200 K, indicating promising applications for low-grade heat harvest near room temperature.     

Lorenz Function of Bi2Te3/Sb2Te3 Superlattices

Combining first-principles density functional theory and semiclassical Boltzmann transport, the anisotropic Lorenz function was studied for thermoelectric Bi₂Te₃/Sb₂Te₃ superlattices and their bulk constituents. It was found that, already for the bulk materials Bi₂Te₃ and Sb₂Te₃, the Lorenz function is not a clear function of charge carrier concentration and temperature. For electron-doped Bi₂Te₃/Sb₂Te₃ superlattices, large oscillatory deviations of the Lorenz function from the metallic limit were found even at high charge carrier concentrations. The latter can be referred to quantum well effects, which occur at distinct superlattice periods.     

High‐Performance N‐type Mg3Sb2 towards Thermoelectric Application near Room Temperature

Se‐doped Mg_3.2Sb_1.5Bi_0.5‐based thermoelectric materials are revisited in this study. An increased ZT value ≈ 1.4 at about 723 K is obtained in Mg_3.2Sb_1.5Bi_0.49Se_0.01 with optimized carrier concentration ≈ 1.9 × 10¹⁹ cm^?3. Based on this composition, Co and Mn are incorporated for the manipulation of the carrier scattering mechanism, which are beneficial to the dramatically enhanced electrical conductivity and power factor around room temperature range. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Se&Mn‐codoped sample, a highest room temperature ZT value ≈ 0.63 and a peak ZT value ≈ 1.70 at 623 K are achieved for Mg_3.15Mn_0.05Sb_1.5Bi_0.49Se_0.01, leading to a high average ZT ≈ 1.33 from 323 to 673 K. In particular, a remarkable average ZT ≈ 1.18 between the temperature of 323 and 523 K is achieved, suggesting the competitive substitution for the commercialized n‐type Bi₂Te₃‐based thermoelectric materials.     

Synthesis of Bi0.5Sb1.5Te3 Thermoelectric Powder Using an Oxide-Reduction Process

The present study focused on synthesis of Bi_0.5Sb_1.5Te₃ thermoelectric powder using an oxide-reduction process. The phase structure and particle size of the synthesized powders were analyzed using x-ray diffractometry and scanning electron microscopy. The synthesized powder was sintered using the spark plasma sintering method. The thermoelectric properties of the sintered body were evaluated by measuring the Seebeck coefficient, electrical resistivity, and thermal conductivity. Bi_0.5Sb_1.5Te₃ powder was synthesized using a combination of mechanical milling, calcination, and reduction processes, using a mixture of Bi₂O₃, Sb₂O₃, and TeO₂ powders. The sintered body of the oxide-reduction-synthesized Bi_0.5Sb_1.5Te₃ powder showed p-type thermoelectric characteristics. The thermoelectric properties of the sintered bodies depended on the reduction time. After being reduced for 2 h at 663 K, the sintered body of the Bi_0.5Sb_1.5Te₃ powder showed a figure of merit of approximately 1.0 at room temperature.     

High-Density Frenkel Defects as Origin of N-Type Thermoelectric Performance and Low Thermal Conductivity in Mg3Sb2-Based Materials

Mg₃Sb₂-based intermetallic compounds with exceptionally high thermoelectric performance exhibit unconventional n-type dopability and anomalously low thermal conductivity, attracting much attention to the underlying mechanisms. To date, investigations have been limited to first-principle calculations and thermodynamic analysis of defect formation, and detailed experimental analysis on crystal structure and phonon modes has not been achieved. Here, a synchrotron X-ray diffraction study clarifies that, against a previous view of a simple crystal structure with a small unit cell, Mg₃Sb₂ is inherently a heavily disordered material with Frenkel defects, charge-neutral defect complexes of cation vacancies and interstitials. Ionic charge neutrality preserved in Mg₃Sb₂ is responsible for exotic n-type dopability, which is unachievable for other Zintl phase materials. The thermal conductivity of Mg₃Sb₂ exhibits deviation from the standard T⁻¹ temperature dependency with strongly limited phonon transport due to a strain field. Inelastic X-ray scattering measurement reveals enhanced phonon scattering induced by disorder. The results will draw renewed attention to crystal defects and disorder as means to explore new high-performance thermoelectric materials.     

Nanostructure, Excitations, and Thermoelectric Properties of Bi2Te3-Based Nanomaterials

The effect of dimensionality and nanostructure on thermoelectric properties in Bi₂Te₃-based nanomaterials is summarized. Stoichiometric, single-crystalline Bi₂Te₃ nanowires were prepared by potential-pulsed electrochemical deposition in a nanostructured Al₂O₃ matrix, yielding transport in the basal plane. Polycrystalline, textured Sb₂Te₃ and Bi₂Te₃ thin films were grown at room temperature using molecular beam epitaxy and subsequently annealed at 250°C. Sb₂Te₃ films revealed low charge carrier density of 2.6?×?10¹⁹?cm^?3, large thermopower of 130???V?K^?1, and large charge carrier mobility of 402?cm²?V^?1?s^?1. Bi₂(Te_0.91Se_0.09)₃ and (Bi_0.26Sb_0.74)₂Te₃ nanostructured bulk samples were prepared from as-cast materials by ball milling and subsequent spark plasma sintering, yielding grain sizes of 50?nm and thermal diffusivities reduced by 60%. Structure, chemical composition, as well as electronic and phononic excitations were investigated by x-ray and electron diffraction, nuclear resonance scattering, and analytical energy-filtered transmission electron microscopy. Ab?initio calculations yielded point defect energies, excitation spectra, and band structure. Mechanisms limiting the thermoelectric figure of merit ZT for Bi₂Te₃ nanomaterials are discussed.     

Improvement of Thermoelectric Properties in (Bi0.5Sb0.5)2Te3 Films of Nanolayered Pillar Arrays

In this work, it is found that unique pillar arrays with nanolayered structure can favorably influence the carrier and phonon transport properties of films. p-(Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) orientation was successfully achieved by a simple ion-beam-assisted technique at deposition temperature of 400°C, owing to the enhanced mobility of deposited atoms for more sufficient growth along the in-plane direction. The pillar diameter was about 250 nm, and the layered nanostructure was clear, with each layer in the pillar array being <30 nm. The properties of the oriented (Bi_0.5Sb_0.5)₂Te₃ pillar array were greatly enhanced in comparison with those of ordinary polycrystalline films synthesized at deposition temperature of 350°C and 250°C. The (Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) preferred orientation exhibited a thermoelectric dimensionless figure of merit of ZT = 1.25 at room temperature. The unique pillar array with nanolayered structure is the main reason for the observed improvement in the properties of the (Bi_0.5Sb_0.5)₂Te₃ film.     

Tailoring Interfacial Charge Transfer for Optimizing Thermoelectric Performances of MnTe-Sb2Te3 Superlattice-Like Films

Interfacial charge transfer has a vital role in tailoring the thermoelectric performance of superlattices (SLs), which, however, is rarely clarified by experiments. Herein, based on epitaxially grown p-type (MnTe)_x(Sb₂Te₃)_y superlattice-like films, synergistically optimized thermoelectric parameters of carrier density, carrier mobility, and Seebeck coefficient are achieved by introducing interfacial charge transfer, in which effects of hole injection, modulation doping, and energy filtering are involved. Carrier transport measurements and angle-resolved photoemission spectroscopy (ARPES) characterizations reveal a strong hole injection from the MnTe layer to the Sb₂Te₃ layer in the SLs, originating from the work function difference between MnTe and Sb₂Te₃. By reducing the thickness of MnTe less than one monolayer, all electronic transport parameters are synergistically optimized in the quantum-dots (MnTe)_x(Sb₂Te₃)₁₂ superlattice-like films, leading to much improved thermoelectric power factors (PFs). The (MnTe)_0.1(Sb₂Te₃)₁₂ obtains the highest room-temperature PF of 2.50 mWm⁻¹K⁻², while the (MnTe)_0.25(Sb₂Te₃)₁₂ possesses the highest PF of 2.79 mWm⁻¹K⁻² at 381 K, remarkably superior to the values acquired in binary MnTe and Sb₂Te₃ films. This research provides valuable guidance on understanding and rationally tailoring the interfacial charge transfer of thermoelectric SLs to further enhance thermoelectric performances.     

Enhancement of Thermoelectric Figure of Merit for Bi0.5Sb1.5Te3 by Metal Nanoparticle Decoration

Introducing nanoinclusions in thermoelectric (TE) materials is expected to lower the lattice thermal conductivity by intensifying the phonon scattering effect, thus enhancing their TE figure of merit ZT. We report a novel method of fabricating Bi_0.5Sb_1.5Te₃ nanocomposite with nanoscale metal particles by using metal acetate precursor, which is low cost and facile to scale up for mass production. Ag and Cu particles of ??40?nm were successfully near-monodispersed at grain boundaries of Bi_0.5Sb_1.5Te₃ matrix. The well-dispersed metal nanoparticles reduce the lattice thermal conductivity extensively, while enhancing the power factor. Consequently, ZT was enhanced by more than 25% near room temperature and by more than 300% at 520?K compared with a Bi_0.5Sb_1.5Te₃ reference sample. The peak ZT of 1.35 was achieved at 400?K for 0.1?wt.% Cu-decorated Bi_0.5Sb_1.5Te₃.     

Preparation and Characterization of Bi0.4Sb1.6Te3 Bulk Thermoelectric Materials

This work focused on the preparation of p-type Bi_0.4Sb_1.6Te₃ bulk materials by combining mechanical alloying (MA) and hot extrusion, with emphasis on grain refinement and preferred grain orientation. Pure Bi, Sb, and Te powders were mechanically alloyed then hot extruded in the temperature range 360–450°C. Bi_0.4Sb_1.6Te₃ bulk materials were successfully prepared by MA and hot extrusion. All the samples had sound appearance, with single phases and high densities. The hot-extruded samples had small grain sizes, and the lower the extrusion temperature, the smaller the grain sizes. The results indicated that the extrudates had preferred orientation. The basal plane was predominantly oriented parallel to the direction of extrusion. Similar Seebeck coefficients were obtained when extrusion temperature was in the range 380–420°C. Electrical resistivity decreased with increasing extrusion temperature. Thermal conductivity was relatively low, even if the extrusion temperature was 450°C. As a result, a ZT value of 1.2 was obtained at room temperature for the sample extruded at 400°C. Therefore, combination of MA and hot extrusion results in significant improvement of both the thermoelectric and mechanical performance of Bi_0.4Sb_1.6Te₃ bulk materials.     

Enhancing the Thermoelectric Properties of p-Type Bulk Bi-Sb-Te Nanocomposites via Solution-Based Metal Nanoparticle Decoration

Embedding nanosized particles in bulk thermoelectric materials is expected to lower the lattice thermal conductivity by enhancing the degree of interface phonon scattering, thus improving their thermoelectric figure of merit ZT. We have developed a wet chemical process to fabricate Bi_0.5Sb_1.5Te₃-based thermoelectric nanocomposites which include nanometer-sized metal particles. By simple solution mixing of metal acetate precursors and Bi_0.5Sb_1.5Te₃ powders in ethyl acetate as a medium for homogeneous incorporation, it is possible to apply various types of metal nanoparticles onto the surfaces of the thermoelectric powders. Next, bulk Bi_0.5Sb_1.5Te₃ nanocomposites with homogeneously dispersed metal nanoparticles were fabricated using a spark plasma sintering technique. The lattice thermal conductivities were reduced by increasing the long-wavelength phonon scattering in the presence of metal nanoparticles, while the Seebeck coefficients increased for a few selected metal-decorated nanocomposites, possibly due to the carrier-energy-filtering effect. Finally, the figure of merit ZT was enhanced to 1.4 near room temperature. This approach highlights the feasibility of incorporating various types of nanoparticles into an alloy matrix starting by wet chemical routes, which is an effective means of improving the thermoelectric performance of Bi-Te-based alloys.     

Thermoelectric Performance Enhancement in BiSbTe Alloy by Microstructure Modulation via Cyclic Spark Plasma Sintering with Liquid Phase

The widespread application of thermoelectric (TE) technology demands high-performance materials, which has stimulated unceasing efforts devoted to the performance enhancement of Bi₂Te₃-based commercialized thermoelectric materials. This study highlights the importance of the synthesis process for high-performance achievement and demonstrates that the enhancement of the thermoelectric performance of (Bi,Sb)₂Te₃ can be achieved by applying cyclic spark plasma sintering to Bi_xSb_2–xTe₃-Te above its eutectic temperature. This facile process results in a unique microstructure characterized by the growth of grains and plentiful nanostructures. The enlarged grains lead to high charge carrier mobility that boosts the power factor. The abundant dislocations originating from the plastic deformation during cyclic liquid phase sintering and the pinning effect by the Sb-rich nano-precipitates result in low lattice thermal conductivity. Therefore, a high ZT value of over 1.46 is achieved, which is 50% higher than conventionally spark-plasma-sintered (Bi,Sb)₂Te₃. The proposed cyclic spark plasma liquid phase sintering process for TE performance enhancement is validated by the representative (Bi,Sb)₂Te₃ thermoelectric alloy and is applicable for other telluride-based materials.     

Effect of NiTe Nanoinclusions on Thermoelectric Properties of Bi2Te3

Metal nanoinclusions in bulk thermoelectric matrix create metal?Csemiconductor interfaces, which can result in improvement in the thermoelectric power factor due to low-energy electron filtering and a simultaneous reduction in lattice thermal conductivity due to increased phonon scattering at grain boundaries. The combined effect results in enhancement of the thermoelectric figure of merit. We report the effect of NiTe nanoinclusions in a Bi₂Te₃ matrix. The Bi₂Te₃/NiTe nanocomposite was synthesized by planetary ball milling. Different volume fractions of NiTe nanoinclusions were incorporated into the bulk (Bi₂Te₃) matrix and uniaxially hot pressed at 100?MPa and 500°C. The presence of nanoinclusions was confirmed by x-ray diffraction and transmission electron microscopy. The Seebeck coefficient, electrical conductivity, and thermal diffusivity were measured from room temperature to 150°C. The carrier concentration of the matrix (Bi₂Te₃) and the nanocomposites (NiTe/Bi₂Te₃) at room temperature were deduced from Hall-effect measurements. Addition of NiTe decreased the carrier concentration, and the power factor increased in the 1?vol.% NiTe/Bi₂Te₃ compared with inclusion-free Bi₂Te₃ matrix due to an increase in mobility.     

High Performance BiSbTe Alloy for Superior Thermoelectric Cooling

At present, the weak thermoelectric and mechanical performance of zone-melting bismuth telluride alloys cannot support the further improvement of cooling and processing performance of semiconductor refrigeration devices. Here, MnO₂ is added into high-strength Bi_0.4Sb_1.6Te₃ prepared by ball milling method to optimize its thermoelectric transport properties. Via in situ reaction, Sb₂O₃ nano-precipitates are formed in the matrix, which also leads to the surplus of Te element. As results, the donor-like effect is suppressed, thereby increasing carrier concentration and power factor. Besides, volatilization of Te-rich phases during sintering leaves plentiful nanopores, which together with Sb₂O₃ nano-precipitates significantly decrease the lattice thermal conductivity. Eventually, the maximum ZT reaches 1.43 at 75 °C for the Bi_0.4Sb_1.6Te₃+0.01MnO₂ sample. On this basis, a 31-pairs module made of the material and commercial n-type BiTeSe produces large temperature differences (ΔT) of 70.1, 80.8, and 89.4 K at the hot-side temperature (T_h) of 300, 325, and 350 K respectively, which are highly competitive. The maximum coefficient of performance of 8.6 and cooling capacity of 7 W are achieved when T_h is set as 325 K. This excellent progress will promote the further development of bismuth telluride refrigeration modules.     

Nb-Mediated Grain Growth and Grain-Boundary Engineering in Mg3Sb2-Based Thermoelectric Materials

The poor carrier mobility of polycrystalline Mg₃Sb₂ at low temperatures strongly degrades the thermoelectric performance. Ionized impurities are initially thought to dominate charge carrier scattering at low temperatures. Accordingly, the increased electrical conductivity by replacing Mg with metals such as Nb is also attributed to reduced ionized impurity scattering. Recent experimental and theoretical studies challenge this view and favor the grain boundary (GB) scattering mechanism. A reduction of GB scattering improves the low-temperature performance of Mg₃(Sb, Bi)₂ alloys. However, it is still elusive how these metal additions reduce the GB resistivity. In this study, Nb-free and Nb-added Mg₃Sb₂ are studied through diffraction, X-ray absorption spectroscopy, solid-state nuclear magnetic resonance spectroscopy, and atom probe tomography. It is shown that Nb does not enter the Mg₃Sb₂ matrix and remains in the metallic state. Besides, Nb diffuses along the GB forming a wetting layer, which modifies the interfacial energy and accelerates grain growth. The GB resistivity appears to be reduced by Nb-enrichment, as evidenced by modeling the electrical transport properties. This study not only confirms the GB scattering in Mg₃Sb₂ but also reveals the hitherto hidden role of metallic additives on enhancing grain growth and reducing the GB resistivity.     

In-situ monitoring of the growth of Bi2 Te2 and Sb2 Te3 films and Bi2 Te3-Sb2 Te3 superlattice using spectroscopic ellipsometry

In this work, we present in-situ monitoring of the growth of bismuth telluride (Bi₂Te₃) and antimony telluride (Sb₂Te₃) thin films as well as Bi₂ Te₃-Sb₂Te₃ superlattice using a spectroscopic ellipsometer (SE). Bi₂Te₃ and Sb₂ Te₃ films were grown by metalorganic chemical vapor deposition (MOCVD) at 350 C. A44-wavelength ellipsometer with spectral range from 404 nm to 740 nm was used in this work. The optical constants of Bi₂ Te₃ and Sb₂Te₃ at growth temperature were determined by fitting a model to the extracted in-situ SE data of optically thick Bi₂ Te₃ and Sb₂ Te₃ films. Compared to the optical constants of Bi₂ Te₃ and Sb₂ Te₃ at room temperature, significant temperature dependence was observed. Using their optical constants at growth temperature, the in-situ growth of Bi₂ Te₃ and Sb₂ Te₃ thin films were modeled and excellent fit between the experimental data and data generated from the best-fit model was obtained. In-situ growth of different Bi₂ Te₃-Sb₂ Te₃ superlattices was also monitored and modeled. The growth of Bi₂ Te₃ and Sb₂ Te₃ layers can be seen clearly in in-situ SE data. Modeling of in-situ superlattice growth shows perfect superlattice growth with an abrupt interface between the two constituent films.     

Thermoelectric properties of the (Bi,Sb)2Te3-based material obtained by spark plasma sintering

The dependence of the thermoelectric properties of the nanostructured bulk (Bi,Sb)₂Te₃ material on the composition and the spark plasma-sintering (SPS) temperature T _SPS has been studied. It has been revealed that the Bi_0.4Sb_1.6Te₃ solid solution sintered at a temperature of 450–500°C has a thermoelectric figure of merit ZT = 1.25–1.28. The dependence of thermoelectric properties on the sintering temperature T _SPS above 400°C is correlated to the transformation of the fine structure of the material due to the rearrangement of point vacancy-donor defects in the process of repeated recrystallization. It has been established that point structural defects make a considerable contribution to the formation of the thermoelectric properties of nanostructured material.     

Effects of annealing on the thermoelectric and microstructural properties of deformed n-type Bi2Te3-based compounds

We studied the effects of deformation and annealing of n-type 90Bi₂Te₃-5Sb₂Te₃-5Sb₂Se₃ thermoelectric compound. Hot-extrusion was conducted to prepare the deformed compound and then this compound was annealed at 400°C for 1–24 hr. When the undoped cast-ingot was extruded, the compound was changed from p-type to n-type due to the electrons generated during the extrusion process. For the compound extruded with SbI₃-doped powders, the thermoelectric properties were also varied for the extrusion process. After annealing at 400°C more than 9 hr, the powder-extruded compound was recrystallized. This caused a decrease in carrier concentration and crystallographic anisotropy. In case of the compound extruded at the ratio of 10:1, the Seebeck coefficient α and the electrical resistivity ρ increased due to recrystallization. However, thermal conductivity κ of the compound decreased. This resulted in an increase in the figure-of-merit from 1.23 × 10⁻³ to 1.63 × 10⁻³ K⁻¹.     

A Resistance Ratio Analysis for CoSb3-Based Thermoelectric Unicouples

In the search for desirable materials for use in thermoelectric generators, CoSb₃-based skutterudites have stimulated much scientific interest due to their high performance capabilities even at high temperatures. In this work, we tested the electrical power-generation characteristics of CoSb₃-based unicouples. We manufactured power-generation unicouples using n-type In_0.25Co_3.95Ni_0.05Sb₁₂ and p-type In_0.25Co_3.0Fe_1.0Sb₁₂ legs. The dimensions of the thermoelectric legs were 10?mm in diameter and 10?mm in height, with Cu sheets and Cu/Mo alloy as the electrode materials. For our unicouples, we evaluated the resistance ratio m?? (=R _o/R), which represents the ratio of the load resistance to the internal resistance of the unicouple. From this analysis of the resistance ratio m??, we obtained a considerable amount of information about the loss factors that caused the difference between the measured power output and the theoretical value. Through these analyses of two types of loss factors, we sought to improve the open-circuit voltage and internal resistance of a unicouple with CoSb₃/Ti/electrode interfaces. In addition, a long-term durability test of the unicouple at high temperature was performed to test the stability of the thermoelectric materials and of the interface between the electrodes and the thermoelectric legs at the same time.