Thermoelectric Properties of Ca-Filled CoSb<Subscript>3</Subscript>-Based Skutterudites Synthesized by Mechanical Alloying

Ca _z Co_4−x (Fe/Mn) _x Sb₁₂ skutterudites were prepared by mechanical alloying and hot pressing. The phases of mechanically alloyed powders were identified as γ-CoSb₂ and Sb, but they were transformed to δ-CoSb₃ by annealing at 873 K for 100 h. All specimens had a positive Hall coefficient and Seebeck coefficient, indicating p-type conduction by holes as majority carriers. For the binary CoSb₃, the electrical conductivity behaved like a nondegenerate semiconductor, but Ca-filled and Fe/Mn-doped CoSb₃ showed a temperature dependence of a degenerate semiconductor. While the Seebeck coefficient of intrinsic CoSb₃ increased with temperature and reached a maximum at 623 K, the Seebeck coefficient increased with increasing temperature for the Ca-filled and Fe/Mn-doped specimens. Relatively low thermal conductivity was obtained because fine particles prepared by mechanical alloying lead to phonon scattering. The thermal conductivity was reduced by Ca filling and Fe/Mn doping. The electronic thermal conductivity was increased by Fe/Mn doping, but the lattice thermal conductivity was decreased by Ca filling. Reasonable thermoelectric figure-of-merit values were obtained for Ca-filled Co-rich p-type skutterudites.     

Thermoelectric Performance Optimization in p-Type Ce y Fe3CoSb12 Skutterudites

In this study, we investigated the impact of the Ce filling fraction on the thermoelectric properties of p-type filled skutterudites Ce _y Fe₃CoSb₁₂ (y = 0.6 to 1.0). The electrical conductivity decreases gradually with increasing y, while the Seebeck coefficient displays an opposite variation tendency, consistent with the expected electron donor role of the Ce filler in this compound. The overall power factors are invariable among all the samples. Alteration of the Ce filling fraction exerts little influence on the phonon transport, but the total thermal conductivity markedly declined with increasing y due to the reduced contribution to heat transfer from carriers. As a consequence, the maximum thermoelectric figure of merit ZT reaches ～0.8 for the sample with y = 0.9, comparable to that of pure Fe-based skutterudite CeFe₄Sb₁₂; more importantly, the former possesses a much larger average ZT between 300 K and 800 K than the latter, showing superior potential for use in intermediate-temperature thermoelectric power generation applications. Further enhancement of ZT in p-type Fe₃CoSb₁₂-based skutterudites could be realized via nanostructuring or a multiple-filling approach.     

Preparation and Enhanced Thermoelectric Properties of p-Type BaFe12O19/CeFe3CoSb12 Magnetic Nanocomposite Materials

A series of p-type xBaFe₁₂O₁₉/CeFe₃CoSb₁₂ (x = 0, 0.05%, 0.10%, 0.20%, 0.40%) magnetic nanocomposite thermoelectric (TE) materials have been prepared by the combination of ultrasonic dispersion and spark plasma sintering (SPS). The effects of BaFe₁₂O₁₉ magnetic nanoparticles on the phase composition, microstructure, and TE properties of the nanocomposite materials were investigated in this work. x-Ray diffraction analysis shows that all the SPSed bulk samples are composed of main phase skutterudite besides a small amount of FeSb₂ and Sb. The TE transport measurements demonstrated that remarkable enhancements in electrical conductivity and Seebeck coefficient can be simultaneously realized by optimizing the doping content of BaFe₁₂O₁₉ magnetic nanoparticles. The lattice thermal conductivity was significantly reduced because of enhanced phonon scattering induced by BaFe₁₂O₁₉ nanoparticles. The highest ZT value reached 0.75 at 800 K for the sample with x = 0.05%, increased by 41.5% as compared with that of p-type CeFe₃CoSb₁₂ bulk material without BaFe₁₂O₁₉ magnetic nanoparticles. This work confirms that doping a small amount of BaFe₁₂O₁₉ magnetic nanoparticles can significantly improve the ZT value of p-type xBaFe₁₂O₁₉/CeFe₃CoSb₁₂ magnetic nanocomposite TE materials.     

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.     

Effect of Nanopores on the Phonon Conductivity of Crystalline CoSb3: A Molecular Dynamics Study

Molecular dynamics simulations have been performed to investigate the effect of nanometer-size pores on the phonon conductivity of single-crystal bulk CoSb₃. The cylindrical pores are uniformly distributed along two vertical principal crystallographic directions of a square lattice. Because pore diameter and porosity are two key factors that could affect the performance of the materials, they were varied individually in the ranges a ₀–6a ₀ and 0.1–5%, respectively, where a ₀ is the lattice constant of CoSb₃. The simulation results indicate that the phonon conductivity of nanoporous CoSb₃ is significantly lower than that of no-pore CoSb₃. The reduction of phonon conductivity in this simulation was consistent with the ballistic–diffusive microscopic effective medium model, demonstrating the ballistic character of phonon transport when the phonon mean-free-path is comparable with or larger than the pore size. Reducing pore diameter or increasing porosity are alternative means of effective reduction of the thermal conductivity of CoSb₃. These results are expected to provide a useful basis for the design of high-performance skutterudites.     

Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Multiple-Filled Skutterudites

Filled skutterudites are prospective intermediate temperature materials for␣thermoelectric power generation. CoSb₃-based n-type filled skutterudites have good electrical transport properties with power factor values over 40 μW/cm K² at elevated temperatures. Filling multiple fillers into the crystallographic voids of skutterudites would help scatter a broad range of lattice phonons, thus resulting in lower lattice thermal conductivity values. We report the thermoelectric properties of n-type multiple-filled skutterudites between 5 K and 800 K. The combination of different fillers inside the voids of the skutterudite structure shows enhanced phonon scattering, and consequently a strong suppression of the lattice thermal conductivity. Very good power factor values are achieved in multiple-filled skutterudite compared with single-element-filled materials. The dimensionless thermoelectric figure of merit for n-type filled skutterudites is improved through multiple-filling in a wide temperature range.     

Thermoelectric Properties of Skutterudites Co4−x Ni x Sb11.9−y Te y Se0.1

CoSb₃-based skutterudites with substitution of Ni atoms for Co, and substitution of Te and Se atoms for Sb were successfully prepared by solid-state reaction and spark plasma sintering. According to x-ray diffraction analysis the major phase of all the samples had a CoSb₃-type structure, although back-scattered electron images showed that small amounts of impurity phases were present in all the samples. The temperature-dependent transport properties were characterized over the temperature range 300–800 K for all the samples. It was found that appropriate substitution with Ni, Te, and Se effectively improved the power factor and reduced the thermal conductivity. As a result, Ni, Te, and Se-tri-doped CoSb₃ materials with enhanced thermoelectric figures of merit, ZT, were obtained. The highest ZT was greater than 1.1 at high temperature.     

Effect of Ti Substitution on Thermoelectric Properties of W-Doped Heusler Fe2VAl Alloy

Effects of element substitutions on thermoelectric properties of Heusler Fe₂VAl alloys were evaluated. By W substitution at the V site, the thermal conductivity is reduced effectively because of the enhancement of phonon scattering resulting from the introduction of W atoms, which have much greater atomic mass and volume than the constituent elements of Fe₂VAl alloy. W substitution is also effective to obtain a large negative Seebeck coefficient and high electrical conductivity through an electron injection effect. To change the conduction type from n-type to p-type, additional Ti substitution at the V site, which reduces the valence electron density, was examined. A positive Seebeck coefficient as high as that of conventional p-type Fe₂VAl alloy was obtained using a sufficient amount of Ti substitution. Electrical resistivity was reduced by the hole doping effect of the Ti substitution while maintaining low thermal conductivity. Compared with the conventional solo-Ti-substituted p-type Fe₂VAl alloy, the ZT value was improved, reaching 0.13 at 450 K.     

Lower Thermal Conductivity and Higher Thermoelectric Performance of Fe-Substituted and Ce, Yb Double-Filled p-Type Skutterudites

Substituting Fe on Co sites is an effective way to produce p-type skutterudite compounds as well as to reduce the thermal conductivity of skutterudites. In this work, we investigated thermoelectric properties of Fe-substituted and Ce + Yb double-filled Ce _x Yb _y Fe _z Co_4?z Sb₁₂ (x = y = 0.5, z = 2.0 to 3.25 nominal) skutterudite compounds by studying the Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient over a broad range of temperatures. All samples were prepared by using the traditional method of melting–annealing and spark plasma sintering. The signs of the Hall coefficient and Seebeck coefficient indicate that all samples are p-type conductors. Electrical conductivity increases with increasing Fe content. The temperature dependence of electrical conductivity indicates that a transition from the extrinsic to the intrinsic regime of conduction depends on the amount of Fe substituted for Co. The temperature dependence of mobility reflects the dominance of acoustic phonon scattering at temperatures above ambient. Except for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂, the thermal conductivity increases with increasing Fe content, reaching the maximum value of 2.23 W/m K at room temperature for Ce_0.5Yb_0.5Fe₃CoSb₁₂. A high power factor (27 μW/K² cm) combined with a rather low thermal conductivity for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂ (nominal) lead to a dimensionless figure of merit ZT = 1.0 at 750 K for this compound, one of the highest ZT values achieved in p-type skutterudite compounds prepared by the traditional method of melting–annealing and spark plasma sintering.     

Lattice Thermal Conductivity Reduction Due to In Situ-Generated Nano-Phase in Bi0.4Sb1.6Te3 Alloys by Microwave-Activated Hot Pressing

The p-type Bi_0.4Sb_1.6Te₃ alloys are prepared using a new method of mechanical alloying followed by microwave-activated hot pressing (MAHP). The effect of sintering temperature on the microstructure and thermoelectric properties of Bi_0.4Sb_1.6Te₃ alloys is investigated. Compared with other sintering techniques, the MAHP process can be used to produce relatively compact bulk materials at lower sintering temperatures owing to its unique sintering mechanism. The grain size of the MAHP specimens increases gradually with the sintering temperature and a partially oriented lamellar structure can be formed in some regions of specimens obtained. The formation of the in situ-generated nano-phase is induced by the arcing effect of the MAHP process, which enhances the phonon scattering effect and decreases the lattice thermal conductivity. A minimum lattice thermal conductivity of 0.41 W/(m·K) and a maximum figure of merit value of 1.04 are obtained at 100°C for the MAHP specimen sintered at 325°C. This technique may also be extended to other functional materials to obtain ultrafine microstructures at low sintering temperatures.     

Synthesis and Thermoelectric Properties of InzCo4?xFexSb12 Skutterudites

The thermoelectric properties of In-filled and Fe-doped CoSb₃ (In _z Co_4−x - Fe _x Sb₁₂) skutterudites prepared by encapsulated induction melting were examined. A single δ-phase was obtained successfully by subsequent annealing at 823 K for 120 h. The Hall and Seebeck coefficients of the In _z Co_4−x Fe _x Sb₁₂ samples had positive signs, indicating p-type conduction. The electrical conductivity was increased by Fe doping, and the thermal conductivity was decreased by In filling due to phonon scattering. The thermoelectric properties were improved by In filling and Fe doping, and were closely related to the optimum carrier concentration and phonon scattering.     

The Effect of High-Pressure Sintering Process on the Microstructure and Thermoelectric Properties of CoSb<Subscript>3</Subscript>

The high-pressure sintering process is studied for the fabrication of the bulk CoSb₃ thermoelectric material. The CoSb₃ powder is prepared by a solid reaction method, and then the samples are sintered under high-pressure conditions. The emphasis of the present study is on the influence of the pressure on the grain size and the electrical properties of the material. For the present study, the pressure is taken to be from 1.5 GPa to 6 GPa, and the sintering temperature is 723 K. The experimental results show that the major phase of skutterudite and traces of metal impurities of Sb and the CoSb₂ phase coexist in some of the samples, and that the grain size of all the samples increase after sintering. In the range of 3.0 GPa to 6.0 GPa, the grain size increases with increasing pressure. In the range of 1.5 GPa to 3.0 GPa, the grain size also increases, but with a diminishing growth rate. All the materials show p-type transport behaviors, and the sample sintered under 2.0 GPa shows higher electrical conductivity than the 5.7 GPa sample, which may be due to the impurities.     

Oxide Thermoelectric Materials: A Structure–Property Relationship

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity (ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure–property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron–phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.     

Fast Fabrication of High-Performance CoSb3-Based Thermoelectric Skutterudites via One-Step Yb-Promoted Peritectic Solidification

As a most promising mid-temperature thermoelectric material, CoSb₃-based bulk material exhibits an applicable figure-of-merit (ZT) of more than one. However, their fabrication is historically time-consuming due to the long-time solid-state phase transitions from CoSb₂ to CoSb₃. To overcome this challenge, here, a fast one-step process is developed to fabricate n-type Yb-doped CoSb₃ with stable ZT of 1.12 at 765 K in <5 h. Experiments confirm Yb promotes peritectic reactions of CoSb + Liquid → CoSb₂ and CoSb₂ + Liquid → CoSb₃, optimizes power factor, and suppresses thermal conductivity. Moreover, the dense grains, induced by the one-step crystallization, result in outstanding mechanical properties with a Young's modulus of 171.4 GPa and a hardness of 8.8 GPa in the Yb-doped CoSb₃. This study indicates that the fast one-step fabrication route can effectively promote the practical applications of CoSb₃-based thermoelectrics and provide guidance for thermoelectric fabrication via rational phase design.     

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.     

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.     

Search for Resonant-Like Impurity in Ag-Doped CoSb3 Skutterudite: Theoretical and Experimental Study

Korringa–Kohn–Rostoker coherent potential approximation (KKR-CPA) calculations of Ag-doped CoSb₃ point to the presence of either an extra sharp peak of s-symmetry Ag density of states near the valence-band edge when filling the void (2a) or to conventional p-type doping when substituting Sb site (24g). These results suggest a resonant-like impurity level in the former or nearly rigid-band behavior in the latter. To confirm the theoretical predictions, a series of samples with nominal composition Co₈Sb₂₄:Ag _x (x = 0, 0.1, 0.3, 0.4, 0.5) were prepared. Structural and phase composition analyses were carried out by x-ray diffraction, scanning electron microscopy, and scanning thermoelectric microprobe. Investigations of the influence of Ag impurity on the electrical conductivity and Seebeck coefficient were performed over the temperature range from 300 K to 560 K. It was found that doping CoSb₃ with Ag leads to an increase of the thermoelectric power factor α ² σ in the temperature range from 300 K to 475 K of about an order of magnitude for all doped samples. However, electron probe microanalysis revealed accumulation of Ag mainly in grain boundaries while the presence of Ag in CoSb₃ crystallites was not confirmed. This observation corroborates the results of KKR-CPA calculations concerning the formation energy of the Ag _x Co₄Sb₁₂ system, which is much lower than values calculated for A _x Co₄Sb₁₂ (A = Ca, Ba).     

The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure‐of‐merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered‐skutterudite CoSb₃. The CoSb₃ powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb₃ was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si–Ge alloys.     

Molecular Dynamics Simulation on Mechanics of Skutterudite CoSb<Subscript>3</Subscript> Nanowire

For the binary thermoelectric material CoSb₃ with a complex crystal structure, the Morse potential functional form is employed to describe its three-dimensional atomic interactions. The mechanical responses and deformation behavior of a rectangular cross-section CoSb₃ nanowire subjected to uniaxial tensile strain are simulated at constant temperature by the molecular dynamics method. The deformation is strain controlled with constant strain rate. When the strain increases, necking gradually becomes distinct near the middle of the model, and complete damage occurs at around 60% strain. The single-crystal CoSb₃ nanowire exhibits properties distinct from those of single-crystal CoSb₃ bulk previously studied. Comparison of the stress–strain curves and configuration evolutions of the CoSb₃ nanowire and bulk during tensile loading indicate that an interesting brittle–ductile transition phenomenon occurs when the single-crystal CoSb₃ varies from bulk to nanowire. Future efforts should be devoted to seeking the critical dimension at which this transition happens and the mechanism behind it.     

Modeling of Thermoelectric Properties of Magnesium Silicide (Mg2Si)

Thermoelectric (TE) materials based on alloys of magnesium (Mg) and silicon (Si) possess favorable properties such as high electrical conductivity and low thermal conductivity. Additionally, their abundance in nature and lack of toxicity make them even more attractive. To better understand the electronic transport and thermal characteristics of bulk magnesium silicide (Mg₂Si), we solve the multiband Boltzmann transport equation within the relaxation-time approximation to calculate the TE properties of n-type and p-type Mg₂Si. The dominant scattering mechanisms due to acoustic phonons and ionized impurities were accounted for in the calculations. The Debye model was used to calculate the lattice thermal conductivity. A unique set of semiempirical material parameters was obtained for both n-type and p-type materials through simulation testing. The model was optimized to fit different sets of experimental data from recently reported literature. The model shows consistent agreement with experimental characteristics for both n-type and p-type Mg₂Si versus temperature and doping concentration. A systematic study of the effect of dopant concentration on the electrical and thermal conductivity of Mg₂Si was also performed. The model predicts a maximum dimensionless figure of merit of about 0.8 when the doping concentration is increased to approximately 10²⁰?cm^?C3 for both n-type and p-type devices.