Synthesis and Characterization of Polythiophene/Bi2Te3 Nanocomposite Thermoelectric Material

To achieve low thermal conductivity, polythiophene (PTh)/bismuth telluride (Bi₂Te₃) nanocomposite has been prepared by spark plasma sintering using a mixture of nanosized Bi₂Te₃ and PTh powders. Bi₂Te₃ powder with spherical-shaped particles of 30 nm diameter and PTh nanosheet powder were first prepared by hydrothermal synthesis and chemical oxidation, respectively. X-ray diffraction analysis and scanning electron microscopy observations revealed that the hybrid composite consists of PTh nanosheets and spherical Bi₂Te₃. The organic PTh acts as an adhesive in the composite. Transport measurements showed that the PTh in the Bi₂Te₃ matrix can reduce its thermal conductivity significantly, but also dramatically reduces its electrical conductivity. As a result, the figure of merit of the composite is lower than that of pure Bi₂Te₃ prepared under the same conditions. The maximum value of ZT for the sample with 5% PTh (by weight) was 0.18 at 473 K, which is rather high compared with other polymer/inorganic thermoelectric material composites.     

Effects of Cooling Rate on Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>(Se<Subscript>0.4</Subscript>Te<Subscript>0.6</Subscript>)<Subscript>3</Subscript> Compounds

A series of Bi₂(Se_0.4Te_0.6)₃ compounds were synthesized by a rapid route of melt spinning (MS) combined with a subsequent spark plasma sintering (SPS) process. Measurements of the Seebeck coefficient, electrical conductivity, and thermal conductivity were performed over the temperature range from 300 K to 520 K. The measurement results showed that the cooling rate of melt spinning had a significant impact on the transport properties of electrons and phonons, effectively enhancing the thermoelectric properties of the compounds. The maximum ZT value reached 0.93 at 460 K for the sample prepared with the highest cooling rate, and infrared spectrum measurement results showed that the compound with lower tellurium content, Bi₂(Se_0.4Te_0.6)₃, possesses a larger optical forbidden gap (E _g) compared with the traditional n-type zone-melted material with formula Bi₂(Se_0.07Te_0.93)₃. Our work provides a new approach to develop low-tellurium-bearing Bi₂Te₃-based compounds with good thermoelectric performance.     

Correlation between microstructure and drastically reduced lattice thermal conductivity in bismuth telluride/bismuth nanocomposites for high thermoelectric figure of merit

The concept of nanocomposite/nanostructuring in thermoelectric materials has been proven to be an effective paradigm for optimizing the high thermoelectric performance primarily by reducing the thermal conductivity. In this work, we have studied the microstructure details of nanocomposites derived by incorporating a semi-metallic Bi nanoparticle phase in Bi₂Te₃ matrix and its correlation mainly with the reduction in the lattice thermal conductivity. Incorporating Bi inclusion in Bi₂Te₃ bulk thermoelectric material results in a substantial increase in the power factor and simultaneous reduction in the thermal conductivity. The main focus of this work is the correlation of the microstructure of the composite with the reduction in thermal conductivity. Thermal conductivity of the matrix and nanocomposites was derived from the thermal diffusivity measurements performed from room temperature to 150 °C. Interestingly, significant reduction in total thermal conductivity of the nanocomposite was achieved as compared to that of the matrix. A detailed analysis of high-resolution transmission electron microscope images reveals that this reduction in the thermal conductivity can be ascribed to the enhanced phonon scattering by distinct microstructure features such as interfaces, grain boundaries, edge dislocations with dipoles, and strain field domains.     

Three-Dimensional Bi2Te3 Nanocrystallites Embedded in 2D Bi2Te3 Films Grown by MOCVD

Two- (2D) and three-dimensional (3D) growth of nanostructured Bi₂Te₃ films was performed on 4° tilt (100) GaAs substrates using a metalorganic chemical vapor deposition system. To obtain 3D Bi₂Te₃ crystallites embedded in 2D planar film, we alternately changed the gas flow rate in the reactor. By repeating two steps, 3D Bi₂Te₃ crystallites embedded in 2D planar Bi₂Te₃ film were obtained. The thermoelectric properties in terms of the thermal conductivity, electrical conductivity, and Seebeck coefficient were investigated at room temperature. The thermal conductivities of the nanostructured Bi₂Te₃ films were from 0.63?W/(m?K) to 0.94?W/(m?K) at room temperature, which are low compared with that of film without nanostructure [1.62?W/(m?K)]. The thermal conductivity of the film was effectively decreased with the decrease of size and increase of density of 3D crystallites. The results of this study open up a new method to fabricate nanostructured thermoelectric films with high thermoelectric figure of merit.     

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.     

Effect of Chromium Doping on the Thermoelectric Properties of Bi2Te3: Cr x Bi2Te3 and Cr x Bi2−x Te3

The thermoelectric (TE) properties of Bi₂Te₃ compounds intercalated and substituted with Cr, namely Cr _x Bi₂Te₃ and Cr _x Bi_2?x Te₃, respectively, have been investigated to study the influence of chromium on the TE properties of Bi₂Te₃. The Seebeck coefficients were found to be positive for all the samples in the temperature range between 300 K and 550 K. Although no effective enhancement of the Seebeck coefficient was observed, doping with Cr by means of either substitution or intercalation clearly not only improved the electrical conductivity but also lowered the thermal conductivity of Bi₂Te₃. As a result of the improvement, the figure of merit ZT is increased up to 0.8 and 0.65 at 300 K for 1% intercalated and 1% substituted Bi₂Te₃, respectively.     

Effect of Composition on Thermoelectric Properties in PbTe-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Composites

The solidification of alloys in the Bi₂Te₃-PbTe pseudobinary system at off- and near-eutectic compositions was investigated for their microstructure and thermoelectric properties. Dendritic and lamellar structures were clearly observed due to the phase separation and the existence of a metastable ternary phase. In this system, three phases with different compositions were observed: binary Bi₂Te₃, PbTe, and metastable PbBi₂Te₄. The Seebeck coefficient, electrical resistivity, and thermal conductivity of ternary alloys as well as binary compounds were measured. The phonon thermal conductivities of Pb-Bi-Te alloys were lower than those in binary PbTe and Bi₂Te₃, which could have resulted from the increased interfacial area between phases due to the existence of the metastable ternary phase and the resultant phase separation.     

Synthesis and Thermoelectric Characterization of Bi2Te3 Nanoparticles

Here, a novel synthesis for near monodisperse, sub‐10 nm Bi₂Te₃ nanoparticles is reported. A new reduction route to bismuth nanoparticles is described, which are then applied as starting materials in the formation of rhombohedral Bi₂Te₃ nanoparticles. After ligand removal by a novel hydrazine hydrate etching procedure, the nanoparticle powder is spark plasma sintered to a pellet with preserved crystal grain sizes. Unlike previous works on the properties of Bi₂Te₃ nanoparticles, the full thermoelectric characterization of such sintered pellets shows a highly reduced thermal conductivity and the same electric conductivity as bulk n‐type Bi₂Te₃.     

Electrodeposition of Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films from DMSO Solution

The electrochemical behavior of nonaqueous dimethyl sulfoxide solutions of Bi^III, Te^IV, and Sb^III was investigated using cyclic voltammetry. On this basis, Bi _x Sb_2−x Te _y thermoelectric films were prepared by the potentiodynamic electrodeposition technique in nonaqueous dimethyl sulfoxide solution, and the composition, structure, morphology, and thermoelectric properties of the films were analyzed. Bi _x Sb_2−x Te _y thermoelectric films prepared under different potential ranges all possessed a smooth morphology. After annealing treatment at 200°C under N₂ protection for 4 h, all deposited films showed p-type semiconductor properties, and their resistances all decreased to 0.04 Ω to 0.05 Ω. The Bi_0.49Sb_1.53Te_2.98 thermoelectric film, which most closely approaches the stoichiometry of Bi_0.5Sb_1.5Te₃, possessed the highest Seebeck coefficient (85 μV/K) and can be obtained under potentials of −200 mV to −400 mV.     

Effects of Different Morphologies of Bi2Te3 Nanopowders on Thermoelectric Properties

Thermoelectric Bi₂Te₃ alloy nanopowders with different morphologies were synthesized by hydrothermal processes with different surfactants. The nanopowders were hot-pressed into pellets, and their thermoelectric properties were investigated. The results show that the morphologies of the nanopowders have remarkable effects on the thermoelectric properties of the hot-pressed bulk pellets. A suitable microstructure of the bulk pellet prepared from flower-like nanosheets was found, having a lower electrical resistivity, larger Seebeck coefficient, and lower thermal conductivity, resulting in a high figure of merit ZT ≈ 1.16. The effects of the nanopowders with different morphologies on the microstructure and thermoelectric properties of hot-pressed bulk pellets are discussed.     

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.     

Thermoelectric Properties of Ag-Doped n-Type (Bi2?xAgxTe3)0.96?(Bi2Se3)0.04 Pseudobinary Alloys

n-Type thermoelectric powders of (Bi_2−x Ag _x Te₃)_0.96−(Bi₂Se₃)_0.04 (0 ≤ x ≤ 0.05) have been synthesized by mechanical alloying and then consolidated by spark plasma sintering. The analysis results show that the grain size of pure Bi, Te, Ag, and Se powders is decreased to about 1 μm to 0.5 μm after they are mechanically alloyed for 2 h. The power factor of bulk material increases with increasing Ag-doping content, while the trend for the lattice thermal conductivity is the opposite. Bulk (Bi_0.99Ag_0.04)₂(Te_0.96Se_0.04)₃ after milling for 12 h exhibits a higher power factor, lower thermal conductivity, and thus a higher ZT of 0.74 at 373 K.     

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.     

Effects of Bi2Se3 Nanoparticle Inclusions on the Microstructure and Thermoelectric Properties of Bi2Te3-Based Nanocomposites

A series of thermoelectric nanocomposite samples were prepared by integrating Bi₂Se₃ nanoparticles into a bulk Bi₂Te₃ matrix. Primarily, spherical Bi₂Se₃ nanoparticles with diameter of ～30 nm were synthesized by combining bismuth acetate with elemental Te in oleic acid solution. Bi₂Te₃-based nanocomposite samples were prepared by consolidating the appropriate quantity of Bi₂Se₃ nanoparticles with the starting elements (Bi and Te) using typical solid-state synthetic reactions. The microstructure and composition of the Bi₂Te₃-based nanocomposites, as well as the effects of the Bi₂Se₃ nanoparticles on their thermoelectric properties, are investigated. Transmission electron microscopy observation of the Bi₂Te₃-based nanocomposites reveals two types of interface between the constituent materials, i.e., coherent and incoherent, depending on the Bi₂Se₃ concentration. The Bi₂Se₃ nanoparticles in the Bi₂Te₃ matrix act as scattering centers for a wider range of phonon frequencies, thereby reducing the thermal conductivity. As a result, the maximum ZT value of 0.75 is obtained for the Bi₂Te₃ nanocomposite with 10 wt.% Bi₂Se₃ nanoparticles at room temperature. It is clear that the reduction in the thermal conductivity plays a central role in the enhancement of the ZT value.     

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.     

Multi-Functional and Stretchable Thermoelectric Bi2Te3 Fabric for Strain,Pressure, and Temperature-Sensing

Fiber-based electronics are essential components for human-friendly wearable devices due to their flexibility, stretchability, and wearing comfort. Many thermoelectric (TE) fabrics are investigated with diverse materials and manufacturing methods to meet these potential demands. Despite such advancements, applying inorganic TE materials to stretchable platforms remains challenging, constraining their broad adoption in wearable electronics. Herein, a multi-functional and stretchable bismuth telluride (Bi₂Te₃) TE fabric is fabricated by in situ reduction to optimize the formation of Bi₂Te₃ nanoparticles (NPs) inside and outside of cotton fabric. Due to the high durability of Bi₂Te₃ NP networks, the Bi₂Te₃ TE fabric exhibits excellent electrical reliability under 10,000 cycles of both stretching and compression. Interestingly, intrinsic negative piezoresistance of Bi₂Te₃ NPs under lateral strain is found, which is caused by the band gap change. Furthermore, the TE unit achieves a power factor of 25.77 µWm⁻¹K⁻² with electrical conductivity of 36.7 Scm⁻¹ and a Seebeck coefficient of −83.79 µVK⁻¹ at room temperature. The Bi₂Te₃ TE fabric is applied to a system that can detect both normal pressure and temperature difference. Balance weight and a finger put on top of the 3 × 3 Bi₂Te₃ fabric assembly are differentiated through the sensing system in real time.     

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.     

Improvement of Thermoelectric Power Factor of Hydrothermally Prepared Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> Compared with its Solvothermally Prepared Counterpart

We report on the successful hydrothermal synthesis of Bi_0.5Sb_1.5Te₃, using water as the solvent. The products of the hydrothermally prepared Bi_0.5 Sb_1.5Te₃ were hexagonal platelets with edges of 200–1500 nm and thicknesses of 30–50 nm. Both the Seebeck coefficient and electrical conductivity of the hydrothermally prepared Bi_0.5Sb_1.5Te₃ were larger than those of the solvothermally prepared counterpart. Hall measurements of Bi_0.5Sb_1.5Te₃ at room temperature indicated that the charge carrier was p-type, with a carrier concentration of 9.47 × 10¹⁸ cm⁻³ and 1.42 × 10¹⁹ cm⁻³ for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively. The thermoelectric power factor at 290 K was 10.4 μW/cm K² and 2.9 μW/cm K² for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively.     

Thermoelectric figure of merit of a p-n junction

The thermoelectric figure of merit of a semiconductor p-n junction is calculated in terms of the diode theory taking account of the bipolar thermal conductivity. The thermoelectric figure of merit of a Bi₂Te₃ diode is estimated and it is shown that the Ioffe criterion may be at the same level as the best modern thermoelectric materials but cannot exceed unity.