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.     

Transport Properties of Bulk Thermoelectrics: An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat, and Thermal Conductivity

For bulk thermoelectrics, improvement of the figure of merit ZT to above 2 from the current values of 1.0 to 1.5 would enhance their competitiveness with alternative technologies. In recent years, the most significant improvements in ZT have mainly been due to successful reduction of thermal conductivity. However, thermal conductivity is difficult to measure directly at high temperatures. Combined measurements of thermal diffusivity, specific heat, and mass density are a widely used alternative to direct measurement of thermal conductivity. In this work, thermal conductivity is shown to be the factor in the calculation of ZT with the greatest measurement uncertainty. The International Energy Agency (IEA) group, under the implementing agreement for Advanced Materials for Transportation (AMT), has conducted two international round-robins since 2009. This paper, part II of our report on the international round-robin testing of transport properties of bulk bismuth telluride, focuses on thermal diffusivity, specific heat, and thermal conductivity measurements.     

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.     

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.     

Effect of Suppression of Grain Growth of Hot Extruded (Bi0.2Sb0.8)2Te3 Thermoelectric Alloys by MoS2 Nanoparticles

Nanostructured bulk materials are regarded as a means of enhancing the performance of thermoelectric (TE) materials and devices. Powder metallurgy has the distinct advantage over conventional synthesis that it can start directly from nanosized particles. However, further processing, for example extrusion, usually requires elevated temperatures, which lead to grain growth. We have found that introduction of semiconductor nanoparticles of molybdenum disulfide (MoS₂), a well-known solid lubricant, suppresses grain growth in bismuth telluride-based alloys, thus improving the extrusion process. Scanning electron microscope images show that adding MoS₂ particles at concentrations of 0.2, 0.4, and 0.8 wt% to p-type (Bi_0.2Sb_0.8)₂Te₃, under otherwise identical extrusion conditions, reduces average grain size by a factor of four. Scherer’s formula applied to x-ray diffraction data indicates that average crystallite sizes (～17 nm) of powders are not significantly different from those of alloys extruded with MoS₂ (～18 nm), which is in stark contrast with those for conventional alloy (Bi_0.2Sb_0.8)₂Te₃ extruded under the same conditions (～80 nm). Harman measurements of TE properties reveal a decrease of the thermal conductivity accompanied by reduction of the room-temperature figure of merit (ZT) from 0.9 to 0.7, because of a lower power factor. Above 370 K, however, the performance of alloys containing MoS₂ surpasses that of (Bi_0.2Sb_0.8)₂Te₃, with reduction of the thermal conductivity which is more significant at temperatures above the cross point of the ZT values.     

Thermoelectric Properties of Nanostructured Bismuth-Doped Lead Telluride Bi x (PbTe)1−x Prepared by Co-Ball-Milling

In this work we present a simple method to synthesize nanostructured, bismuth-doped lead telluride by co-ball-milling. The obtained nanopowders were compacted via either a cold pressing/annealing approach or by hot pressing. The two compacting methods were compared regarding sample density. Series with bismuth content up to 6 at.% were characterized by measuring the thermoelectric transport properties over a wide temperature range between 123 K and 773 K using two different techniques for the Seebeck coefficient and electrical conductivity. A decreasing thermal conductivity and increasing electrical conductivity were found with increasing doping level. The best results were obtained for samples with 5 at.% and 6 at.% bismuth, showing a maximum ZT value of 1.1 at 773 K. Transmission electron microscopy study was performed to analyze the microstructure of the nanopowders, suggesting that, in addition to n-type doping of the lead telluride matrix, segregation effects occur and the samples consist of multiple phases.     

Thermal Conductivity and ZT in Disordered Organic Thermoelectrics

For decades, continuous attempts have been made to improve the figure of merit (ZT) of thermoelectrics. The theory behind the Seebeck effect itself is well researched, but the problem with ZT is related to materials properties that offset one another. This work analyzed the link between the site energy distributions and thermal conductivity of oxidized poly(3,4-ethylenedioxythiophene-tosylate) (PEDOT:Tos), which was reported to be a good organic thermoelectric. To understand how heat flow was affected by “disorder” in PEDOT:Tos and the associated electron–phonon interactions, we computed the values of the thermal conductivity κ and ZT using materials parameters extracted from the open literature. By varying the values of the parameters separately, we were able to identify their individual influence on κ and ZT. Our results suggest that ZT is most sensitive to changes in σ, the bandwidth of the density of states (DOS) of the transport sites, and less so to changes in n _eff, the effective carrier density. Our simulations also suggested that ZT could become exceptionally large (approaching a value of ~20) if σ were lowered to 1 meV to 2 meV. This would be a tremendous approach to increase ZT in oxidized PEDOT:Tos.     

Cost-Efficient Preparation and Enhanced Thermoelectric Performance of Bi0.48Sb1.52Te3 Bulk Materials with Micro- and Nanostructures

A cost-efficient method has been developed based on the combination of hydrothermal exfoliation and spark plasma sintering (SPS) to fabricate Bi_0.48Sb_1.52Te₃ bulk material with multiscale microstructures composed of micro- and nanosized microstructures. The thermoelectric (TE) transport properties of the bulk material with multiscale microstructures were measured along the directions parallel (||) and perpendicular (⊥) to the SPS pressing direction. It is confirmed that the anisotropy of the electrical conductivity (σ) and thermal conductivity (κ) was decreased by the transformation of the microstructure from a single microscale structure to multiscale microstructures. As compared with Bi_0.48Sb_1.52Te₃ bulk material with single microscale microstructures, the κ value of the Bi_0.48Sb_1.52Te₃ bulk material with multiscale microstructures was significantly reduced, the σ value was slightly decreased, while the α value was slightly increased. Thus, a maximum ZT value of 1.1 was achieved at 350 K along the direction perpendicular to the pressing direction, increased by 20%. The enhanced ZT value was mainly attributed to the significant decrease in κ induced by the multiscale microstructures. This work offers a new approach to improve TE performance by multiscale microstructural engineering.     

Inorganic Colloidal Solution-Based Approach to Nanocrystal Synthesis of (Bi,Sb)2Te3

There is an interest in higher-ZT thermoelectric materials for high-watt-density cooling of electronics. Reducing thermal conductivity through increased phonon scattering in nanomaterials has been shown to be effective and is being investigated by many groups. Solution-based synthesis is a method for making thermoelectric nanomaterials that can provide particle sizes <20?nm and can be scaled to production quantities of materials. We are exploring an approach that proceeds through formation of an ??ink?? that contains inorganic colloidal nanocrystals of thermoelectric materials. This approach has the advantage that, by adjustments within the basic synthesis process, the size, shape, and composition of the nanocrystals can be tightly controlled to study changes in the transport properties. Currently we are making materials from inks that contain Bi₂Te₃ nanocrystals with Sb₂Te₃ ligands, suspended in a solvent. Powders formed by curing the inks are made into solid pellets by hot pressing, and the pellets are used for characterization and transport property measurements. The best result from our thermoelectric property measurements is ZT?=?0.9 with power factor of 27???W/cm?K², which to our knowledge is the best value for solution-based synthesis.     

Inversion of the impurity conductivity sign in As2Se3:Bi films deposited by two different methods

It is demonstrated that As₂Se₃:Bi _x films deposited by thermal evaporation have p-type impurity conductivity, whereas films of the same composition, produced by ion-plasma cosputtering in vacuum exhibit n-type impurity conductivity. On the basis of these results, a new method is suggested for the fabrication of p-n homojunctions in film structures made of chalcogenide glassy semiconductors doped with bismuth in various ways.     

Grain-Size-Dependent Thermoelectric Properties of SrTiO3 3D Superlattice Ceramics

The thermoelectric (TE) performance of SrTiO₃ (STO) 3D superlattice ceramics with 2D electron gas grain boundaries (GBs) was theoretically investigated. The grain size dependence of the power factor, lattice thermal conductivity, and ZT value were calculated by using Boltzmann transport equations. It was found that nanostructured STO ceramics with smaller grain size have larger ZT value. This is because the quantum confinement effect, energy filtering effect, and interfacial phonon scattering at GBs all become stronger with decreasing grain size, resulting in higher power factor and lower lattice thermal conductivity. These findings will aid the design of nanostructured oxide ceramics with high TE performance.     

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.     

Neodymium-Strontium Titanate: A New Ceramic for an Old Problem

High density ceramics based on neodymium-calcium titanate (RE_0.6II_0.1TiO₃) where RE = Nd, Pr, Sm and II = Ca, Sr, were prepared by the mixed oxide route. All products exhibited low thermal conductivity due to the presence of A-site vacancies assisting strong phonon scattering. The moderate electrical conductivity and high Seebeck coefficient resulted in the highest thermoelectric figure of merit (ZT) in neodymium-strontium titanate (NT-ST) ceramic with a value of 0.03 at 900 K. The temperature stable ZT behavior of NT-ST is promising for device applications.     

Enhancement of the Thermoelectric Performance of Bi0.4Sb1.6Te3 Alloys by In and Ga Doping

We report an enhancement of the thermoelectric figure of merit in polycrystalline In- and Ga-doped Bi_0.4Sb_1.6Te₃ compounds. Via the controlled doping of In or Ga, the lattice thermal conductivity was effectively reduced by strong point-defect phonon scattering while the power factor was not significantly changed due to the similarity of the density of states near the valence-band maximum between undoped and In- or Ga-doped compositions. An enhanced ZT of 1.2 at 320 K was obtained in 0.5 at.% In-doped Bi_0.4Sb_1.6Te₃ compound by these synergetic effects.     

Theoretical and experimental investigations of the thermoelectric properties of Al-, Bi- and Sn-doped ZnO

In this paper, the thermoelectric properties of ZnO doped with Al, Bi and Sn were investigated by combining experimental and theoretical methods. The average Seebeck coefficient of Bi doped ZnO over the measured temperature range is improved from −90 to −497 μV/K. However, segregation of Bi₂O₃ in ZnO:Bi sample, confirmed by FESEM, lead to enormous grain growth and low electrical conductivity, which makes Bi is not a good dopant to improve ZT value of ZnO. As a 4+ valence cation, Sn doping actually show an increase in carrier concentration to 10²⁰ cm⁻³, further enhancing the electrical conductivity. Unfortunately, the Seebeck coefficient of ZnO:Sn samples is even lower than pure ZnO sample, which lead to a low ZT value. As for ZnO:Al sample, with nearly no change in lattice thermal conductivity, electrical conductivity and Seebeck coefficient were both enhanced. Threefold enhancement in ZT value has been achieved in ZnO:Al sample at 760 °C compared with pure ZnO.     

Fabrication of Bismuth Telluride Thermoelectric Films Containing Conductive Polymers Using a Printing Method

We prepared a mixture of thermoelectric bismuth telluride particles, a conductive polymer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)], poly(acrylic acid) (PAA), and several organic additives to fabricate thermoelectric films using printing or coating techniques. In the mixture, the organic components (PEDOT:PSS, PAA, and an additive) act as a binder to connect bismuth telluride particles mechanically and electrically. Among the organic additives used, glycerol significantly enhanced the electrical conductivity and bismuth telluride particle dispersibility in the mixture. Bi_0.4Te_3.0Sb_1.6 films fabricated by spin-coating the mixture showed a thermoelectric figure of merit (ZT) of 0.2 at 300 K when the Bi_0.4Te₃Sb_1.6 particle diameter was 2.8 μm and its concentration in the elastic films was 95 wt.%.     

Highly efficient n-(Bi, Sb)2Te3 thermoelectric materials for temperatures below 200 K

The possibility of using an n-type Bi_2?x Sb_xTe₃ solid solution in thermoelectric refrigerators at T<200 K is considered. It is shown that, if the material under consideration is optimized for the above temperature region, the temperature dependence of the Seebeck coefficient α becomes less pronounced, and the crystal-lattice thermal conductivity κ_L decreases as compared to what is observed in a conventional n-Bi₂Te_3?y Se_y solid solution. These factors and a high mobility of charge carriers μ₀ bring about an increase in the parameter β ～ ZT, where Z is the thermoelectric efficiency.     

Effect of Nano-ZrW2O8 on the Thermoelectric Properties of Bi85Sb15/ZrW2O8 Composites

In this study, Bi₈₅Sb₁₅/x wt.% ZrW₂O₈ (x?=?0, 0.1, 0.5, 1) thermoelectric nanocomposites were prepared successfully by ball milling and spark plasma sintering. The effect of ZrW₂O₈ nanoparticles on the thermoelectric properties of the Bi₈₅Sb₁₅/ZrW₂O₈ composite was investigated. Thermal conductivity, Seebeck coefficient, and electrical conductivity were measured between 77?K and 300?K. x-Ray diffraction and scanning electron microscopy were adopted for microstructure characterization of the composites. The electrical transport properties are mainly discussed with regard to the microstructures. The results show that nanoinclusions did not grow during sintering. It is found that the thermal conductivity decreases with the addition of a small amount of ZrW₂O₈ nanoparticles, which serve as additional phonon-scattering centers. The obtained thermal conductivity is 0.5?W/m?K for the Bi₈₅Sb₁₅/1?wt.% ZrW₂O₈ composite at 80?K, which is just half of the value for the Bi₈₅Sb₁₅ matrix. However, the electrical transport properties are degraded with increasing content of ZrW₂O₈. The calculated ZT is also degraded due to the poor electrical properties.     

p-Type Bismuth Telluride-Based Composite Thermoelectric Materials Produced by Mechanical Alloying and Hot Extrusion

We produced six different composites of p-type bismuth antimony telluride alloys and studied their structure and thermoelectric properties. The components of the composites were obtained in powder form by mechanical alloying. Mixed powders of two different compositions were consolidated by hot extrusion to obtain each bulk composite. The minimum grain size of bulk composites as revealed by scanning electron microscopy shows a 50% reduction compared with the conventional (Bi_0.2Sb_0.8)₂Te₃. X-ray diffraction (XRD) analysis only shows peak broadening with no clear indication of separate phases, and indicates a systematic decrease of crystallite size in the composite materials. Scattering mechanisms of charge carriers were evaluated by Hall-effect measurements. The thermoelectric properties were investigated via the Harman method from 300 K up to 460 K. The composites show no significant degradation of the power factor and high peak ZT values ranging from 0.86 to 1.04. The thermal conductivity of the composites slightly increases with respect to the conventional alloy. This unexpected behavior can be attributed to two factors: (1) the composites do not yet contain a significant number of grains whose sizes are sufficiently small to increase phonon scattering, and (2) each of the combined components of the composites corresponds to a phase with thermal conductivity higher than the minimum value corresponding to the (Bi_0.2Sb_0.8)₂Te₃ alloy.     

Thermoelectric Properties of the Bi2Te3 Compound Prepared by an Aqueous Chemical Method Followed by Hot Pressing

Bi₂Te₃ powders were synthesized at 453 K from Bi(NO₃)₃·5H₂O and Te by an aqueous chemical method, then bulk material was fabricated by hot pressing at 673 K. To investigate the effect of microstructure on the transport properties of electrons and phonons, the thermoelectric performance of the hot-pressed sample and a zone-melted crystal with similar chemical composition was measured and compared. Strong grain-boundary scattering caused a significant decrease of the thermal conductivity; however, the maximum ZT value of the hot-pressed sample was 0.28, which was lower than that of the zone-melted crystal. Further improvement could be obtained through optimization of both chemical composition and microstructure.