Enhanced thermoelectric performance via randomly arranged nanopores: Excellent transport properties of YbZn2Sb2 nanoporous materials

Fabricating nanoporous bulk thermoelectric (TE) materials with periodically arranged nanopores is highly challenging and expensive, although TE materials exhibit high power factors (α²σ) and low thermal conductivities (κ). Enhanced TE performance via randomly arranged nanopores is demonstrated with a YbZn₂Sb₂ nanoporous material (nPM) fabricated by a combination of melt quenching and two stage spark plasma sintering in less than 10 h. Measurement of the electrical conductivity, Hall mobility, Seebeck coefficient, and thermal conductivity show that simultaneously enhancing α²σ and reducing κ can realize in the YbZn₂Sb₂ nPM with randomly arranged nanopores about 50-200 nm in diameter. Compared with YbZn₂Sb₂ dense bulk materials (dBM) fabricated by a conventional method taking more than 180 h, α²σ at 300 K increases by 122%, κ at 300 K decreases by 29%, and the maximum ZT value at 775 K reaches 0.67, increasing by 46% for the nPM725 sample. This work shows that a periodic arrangement of nanopores is not essential for the fabrication of attractive TE materials, which offers a wider approach to nanostructure engineering to improve TE performance.     

Sintering behaviors, magnetic and electric properties of Bi-Zn co-doped Co2Y ferrites

The Bi and Zn substitution effects on the sintering behaviors, magnetic and electric properties of hexagonal ferrites with a composition of 2(Ba_1−xBi_xO)·2(Zn_yCo_0.8−yCu_0.2O)·6(Fe_2−x/3Zn_x/3O₃) were investigated. The results showed that the addition of Bi and Zn can significantly promote Co₂Y densification. The Y phase may be triggered to decompose into M and spinel phases at high sintering temperatures (above 1050 °C) for samples with excess Bi (x = 0.2) substitution, which resulted in densification and magnetic properties degradation. Co₂Y ferrites with x = 0.1 and y = 0.4 sintered at 1050 °C show a relative density of 94%, a high initial permeability of 4.5, a quality factor (Q) of 50.     

High temperature thermoelectric properties and energy transfer devices of Ca3Co4−xAgxO9 and Ca1−ySmyMnO3

The high temperature oxide thermoelectric materials of p-type Ca₃Co_4−xAg_xO₉ (denoted as p-Co349/Ag_x) and n-type Ca_1−ySm_yMnO₃ (denoted as n-Mn113/Sm_y) were prepared by the self-ignition method combined with a sintering technique. The influence of doping Ag and Sm on the thermoelectric properties of the corresponding materials was evaluated. The figures of merit, ZT, for the p-Co349/Ag_0.2 and n-Mn113/Sm_0.02 materials reached maxima of 0.20 and 0.15 at 973 K, respectively. The performances of thermoelectric devices constructed with the p- and n-type pairs were evaluated in terms of the maximum output power (P_max) and manufacturing factor. The P_max and volume power density for the four-leg devices reached 36.8 mW and 81.9 mW cm⁻³ at ΔT of 523 K, respectively.     

Thermoelectric properties of indium-filled InxRh4Sb12 skutterudites

This study reports the synthesis and characterization of polycrystalline indium-filled In_xRh₄Sb₁₂ (0 ≤ x ≤ 0.2) skutterudites. The structural response to indium filling was monitored by whole pattern fitting of the powder X-ray diffraction data. Indium occupation of the oversized void-sites was verified by its unusually large thermal displacement parameter. The indium solubility limit approached 0.15. The principal thermoelectric properties were measured from 300 to 600 K. All samples are semiconducting. Indium void-site occupation reduced the lattice thermal conductivity of In_0.15Rh₄Sb₁₂ 30% at 300 K; however, the effect was subverted at elevated temperatures due to a coincident increase in bipolar thermal diffusion. The high-temperature thermoelectric figure of merits (ZT's) are low compared to the isostructural indium-filled In_xCo₄Sb₁₂ skutterudites due to a striking sign change in the Seebeck coefficients at 400 K and relatively high thermal conductivities.     

Synthesis and high-temperature thermoelectric properties of Ni3GaSb and Ni3InSb

Ni₃GaSb and Ni₃InSb were successfully synthesized by the direct reaction of Ni and GaSb or InSb. The XRD patterns and the lattice parameters of these compounds were in good agreement with the literature data. The Seebeck coefficient (S), the electrical resistivity (ρ), and the thermal conductivity (κ) of Ni₃GaSb and Ni₃InSb were examined in the temperature range from room temperature to 1073 K. Both compounds indicated metal-like characteristics. The power factor (S²ρ⁻¹) values increased with temperature and reached maximum at 1073 K. The κ and the dimensionless figure of merit ZT of both samples increased with temperature. The maximum values of the ZT of Ni₃GaSb and Ni₃InSb were obtained at 1073 K to be 0.022 and 0.023, respectively.     

Thermoelectric properties of p-type skutterudites YbxFe3.5Ni0.5Sb12 (0.8 ? x ? 1)

p-Type skutterudites, with nominal compositions Yb_xFe_3.5Ni_0.5Sb₁₂ (0.8 ? x ? 1), have been synthesized by induction melting with subsequent annealing, and their thermoelectric properties evaluated from 3.5 to 745 K to assess their suitability for thermoelectric-based waste heat recovery applications. We report results for the synthesis and measurements of Seebeck coefficient (S), electrical resistivity (ρ), thermal conductivity (κ), Hall coefficient (R_H) and effective mass (m^*/m₀) of Yb_xFe_3.5Ni_0.5Sb₁₂ (0.8 ? x ? 1). Powder X-ray diffraction and electron probe microanalysis show that this system has a narrow filling fraction range of x ∼ 0.84-0.86 for Yb in the crystallographic voids. All samples show positive R_H for the entire temperature range studied, with carrier concentrations ranging from 9.6 × 10²⁰ to 2.8 × 10²¹ cm⁻³ at room temperature. Relatively high values of S result in high power factors up to 17 μW cm⁻¹ K⁻² at room temperature. However, large values of κ and a sharp reduction in the S at high temperature due to bipolar conduction prevent the attainment of high thermoelectric figure of merit.     

Studies on the power factor of (Ba,Sr)Co2+xRu4−xO11 compounds

We have prepared polycrystalline single-phase ACo_2+xRu_4−xO₁₁ (A = Sr, Ba; 0 ≤ x ≤ 0.5) using the ceramic method and we have studied their structure, electrical resistivity and Seebeck coefficient, in order to estimate their power factor (P.F.). These layered compounds show values of electrical resistivity of the order of 10⁻⁵ Ωm and their Seebeck coefficients are positive and range from 1 μV K⁻¹ (T = 100 K) to 20 μV K⁻¹ (T = 450 K). The maximum power factor at room temperature is displayed by BaCo₂Ru₄O₁₁ (P.F.: 0.20 μW K⁻² cm⁻¹), value that is comparable to that shown by compounds such as SrRuO₃ and Sr₆Co₅O₁₅.     

Heat capacity measurements and XPS studies on uranium-lanthanum mixed oxides

Heat capacity measurements were carried out on (U_1−yLa_y)O_2±x (y = 0.2, 0.4, 0.6, and 0.8) using differential scanning calorimeter (DSC) in the temperature range 298-800 K. Enthalpy increment measurements were carried out on the above solid solutions using high temperature drop calorimetry in the temperature range 800-1800 K. Chemical states of U and La in the solid solutions of mixed oxides were determined using X-ray photoelectron spectroscopy (XPS). Oxygen to metal ratios of (U_1−yLa_y)O_2±x were estimated from the ratios of different chemical states of U present in the sample. Anomalous increase in the heat capacity is observed for (U_1−yLa_y)O_2±x (y = 0.4, 0.6 and 0.8) with onset temperatures in the range of 1000-1200 K. The anomalous increase in the heat capacity is attributed to certain thermal excitation process, namely, Frenkel pair defect of oxygen. The heat capacity value of (U_1−yLa_y)O_2±x (y = 0.2, 0.4, 0.6, and 0.8) at 298 K are 65.3, 64.1, 57.7, 51.9 J K⁻¹ mol⁻¹, respectively. From the XPS investigations, it was observed that the O/M ratios at the surface are higher than that in the bulk. In uranium rich mixed oxide samples, the surface O/M ratios are greater than 2 whereas that in La rich mixed oxides, they are less than 2, though the bulk O/M in all the samples are less than 2.     

Thermoelectric properties of Bi2SexTe3−x prepared by Bridgman method

Bi₂Se_xTe_3−x crystals with various x values were grown by Bridgman method. The electrical conductivity, σ, was found to decrease with increasing Se content. The highest σ of 1.6 × 10⁵ S m⁻¹ at room temperature was reached at x = 0.12 with a growth rate of 0.8 mm h⁻¹. The Seebeck coefficient, S, was less dependent on Se content, all with positive values showing p-type characteristics, and the highest S was measured to be 240 μV K⁻¹ at x = 0.24. The lowest thermal conductivity, κ, was 0.7 W m⁻¹ K⁻¹ at x = 0.36. The electronic part of κ, κ_el, showed a decrease with increasing Se content, which implies that the hole concentration as the main carriers was reduced by the addition of Se. The highest dimensionless figure of merit, ZT, at room temperature was 1.2 at x = 0.36, which is attributed to the combination of a rather high electrical conductivity and Seebeck coefficient and low thermal conductivity.     

The studies of phase relation, microstructure, magnetic transition, magnetocaloric effect in (Gd1−xErx)5Si1.7Ge2.3 compounds

The phase relation, microstructure, Curie temperatures (T_C), magnetic transition, and magnetocaloric effect of (Gd_1−xEr_x)₅Si_1.7Ge_2.3 (x = 0, 0.05, 0.1, 0.15, and 0.2) compounds prepared by arc-melting and then annealing at 1523 K (3 h) using purity Gd (99.9 wt.%) are investigated. The results of XRD patterns and SEM show that the main phases in those samples are mono-clinic Gd₅Si₂Ge₂ type structure. With increase of Er content from x = 0 to 0.2, the values of magnetic transition temperatures (T_C) decrease linearly from 228.7 K to 135.3 K. But the (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds display large magnetic entropy near their transition temperatures in a magnetic field of 0-2 T. The maximum magnetic entropy change in (Gd_1−xEr_x)₅Si_1.7Ge_2.3 compounds are 24.56, 14.56, 16.84, 14.20, and 13.22 J/kg K⁻¹ with x = 0, 0.05, 0.1, 0.15, and 0.2, respectively.     

Effect of Ag-doping on crystal structure and high temperature thermoelectric properties of c-axis oriented Ca3Co4O9 thin films by pulsed laser deposition

Ag-doped Ca₃Co₄O₉ thin films with nominal composition of Ca_3−xAg_xCo₄O₉ (x = 0∼0.4) have been prepared on sapphire (0 0 0 1) substrates by pulsed laser deposition (PLD). Structural characterizations and surface chemical states analysis have shown that Ag substitution for Ca in the thin films can be achieved with doping amount of x ≤ 0.15; while x > 0.15, excessive Ag was found as isolated and metallic species, resulting in composite structure. Based on the perfect c-axis orientation of the thin films, Ag-doping has been found to facilitate a remarkable decrease in the in-plane electrical resistivity. However, if doped beyond the substitution limit, excessive Ag was observed to severely reduce the Seebeck coefficient. Through carrier concentration adjustment by Ag-substitution, power factor of the Ag-Ca₃Co₄O₉ thin films could reach 0.73 mW m⁻¹ K⁻² at around 700 K, which was about 16% higher than that of the pure Ca₃Co₄O₉ thin film.     

Resistivity, thermopower, and thermal conductivity of nickel doped compounds Cr1−xNixSb2 at low temperatures

Substitutional compounds Cr_1−xNi_xSb₂ (0 ≤ x ≤ 0.1) were synthesized, and the effect of Ni substitution on transport and thermoelectric properties of Cr_1−xNi_xSb₂ were investigated at the temperatures from 7 to 310 K. The results indicated that the magnitudes of the resistivity and thermopower of Cr_1−xNi_xSb₂ decreased greatly with increasing Ni content at low temperatures, owing to an increase in electron concentration caused by Ni substitution for Cr. Experiments also showed that the low-temperature lattice thermal conductivity of Cr_1−xNi_xSb₂ decreased substantially with increasing Ni content due to an enhancement of phonon scattering by the increased number of Ni atoms. As a result, the figure of merit, ZT, of lightly doped Cr_0.99Ni_0.01Sb₂ was improved at T > ∼230 K. Specifically, the ZT of Cr_0.99Ni_0.01Sb₂ at 310 K was approximately ∼29% larger than that of CrSb₂, indicating that thermoelectric properties of CrSb₂ can be improved by an appropriate substitution of Ni for Cr.     

Magnetic and magnetocaloric properties of ternary Gd-Co-Al bulk metallic glasses

Bulk metallic glasses (BMGs) with compositions of Gd₅₅Co_xAl_45−x (15 ≤ x ≤ 30) and Gd₆₀Co_yAl_40−y (15 ≤ y ≤ 30) were synthesized by an injection casting technique. Temperature dependence of magnetization of the BMGs indicates that their Curie temperatures can be tailored between 96 and 143 K by varying Gd and Co concentration. The magnetic entropy changes of the BMGs are greater than 9.0 J/kg K except for the Gd₅₅Co₃₀Al₁₅ glass that exhibits a reduced magnetization due to its large Co content. The relative cooling powers of the BMGs are greater than those of any other crystalline compounds and decrease with the increasing Co content.     

Power factor enhancement in Zn-doped Na0.8CoO2

The thermoelectric properties of Na_0.8Zn_xCo_1−xO₂/(ZnO)_y (x ≤ 0.01, 0 ≤ y ≤ 0.14) have been systematically investigated. The results suggest that doping divalent Zn ions within solubility limit x^* ∼ 0.01 leads to simultaneous reduction in resistivity and enhancement of thermopower. Analysis of the results show that the reduction of resistivity may be attributed to improved mobility of carriers, while the enhancement of thermopower may originate from the geometric relaxation of distorted CoO₆ octahedra caused by partial Zn substitution, leading to a narrower band width in the strongly correlated environment, consequently resulting in a remarkable 20% improvement in power factor.     

Phase range and physical properties of the thallium tin tellurides Tl10−xSnxTe6 (x ≤ 2.2)

Crystal structures and physical property measurements were determined for Tl_10−xSn_xTe₆ with a phase range of 0 ≤ x ≤ 2.2. These tellurides are substitution variants of Tl₅Te₃. Electronic structure calculations indicate that Tl₈Sn₂Te₆ should be an intrinsic semiconductor, and the Sn-poor variants, extrinsic ones with p-type conduction. The positive Seebeck values increase with increasing Sn content, while the electrical and thermal conductivity values decrease. Low thermal conductivity values, well below 1 W m⁻¹ K⁻¹, are the best asset of these materials with respect to thermoelectric performance. At x = 2.2, the best thermoelectric properties were obtained, with a figure-of-merit ZT = 0.60 at 617 K as determined on sintered cold-pressed pellets.     

Synthesis and thermal conductivities of ZnIn2Te4 and CdIn2Te4 with defect-chalcopyrite structure

ZnIn₂Te₄ and CdIn₂Te₄ have a defect-chalcopyrite tetragonal crystal structure with structural vacancies. In order to investigate the effects of vacancies on the lattice thermal conductivity (κ_lat), single phase samples of ZnIn₂Te₄ and CdIn₂Te₄ were synthesized and their κ_lat values were examined in the temperature range from room temperature to 850 K. The κ_lat data for ZnIn₂Te₄ and CdIn₂Te₄ were compared with those of Zn- and Cd-series chalcopyrite compounds with no vacancies. The results revealed that the presence of vacancies alone in the defect-chalcopyrite structure does not result in effective phonon scattering.     

Preparation, structure and electrical conductivity of the pyrochlore-type phase Sm2Zr2O7 codoped with bivalent magnesium and trivalent dysprosium cations

The pyrochlore-type phases with the compositions of SmDy_1−xMg_xZr₂O_7−x/2 (0 ≤ x ≤ 0.20) have been prepared by pressureless-sintering method for the first time as possible solid electrolytes. The structure and electrical conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics have been studied by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy measurements. SmDy_1−xMg_xZr₂O_7−x/2 (x = 0, 0.05, 0.10) ceramics exhibit a single phase of pyrochlore-type structure, and SmDy_1−xMg_xZr₂O_7−x/2 (x = 0.15, 0.20) ceramics consist of pyrochlore phase and a small amount of the second phase magnesia. The total conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics obeys the Arrhenius relation, and the total conductivity of each composition increases with increasing temperature from 673 to 1173 K. SmDy_1−xMg_xZr₂O_7−x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest total conductivity value is about 8 × 10⁻³ S cm⁻¹ at 1173 K for SmDy_1−xMg_xZr₂O_7−x/2 ceramics.     

W-type hexaferrite nanoparticles: A consideration for microwave attenuation at wide frequency band of 0.5-10 GHz

The static and dynamic magnetic properties of W-type hexaferrites are tuned to meet the requirements of wide band frequencies for attenuation of electromagnetic interference and microwave absorptions purposes. For this purpose, the W-type hexaferrite of entirely new composition of BaCoZnFe_16−2yAl_yCe_yO₂₇ (y = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) has been synthesized by the chemical co-precipitation. The material is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The complex permittivity (?_r = ?′ − j?″) and permeability (μ_r = μ′ − jμ″) spectra are determined using Vector Network Analyzer (VNA) in a range from 0.5 GHz to 10 GHz. During this study, it is noticeable that the Al³⁺ and Ce³⁺ ions have considerable effect on the shape of the nanoparticles. Samples having Al-Ce contents y = 0.2 and y = 0.4 showed large values for magnetization (70.5 emu/g) and remanent magnetization (32.9 emu/g). In addition, more than 99% absorption (>−20 dB) is noted for this sample composition. Based on these results it is concluded that the microwave absorption characteristics of these compounds can be tuned for the required frequency by varying the thickness of the absorber. Due to this reason, potential employment of the synthesized nanoparticles for absorption of electromagnetic radiations at wide frequency band of 0.5-10 GHz has been proposed.     

Structural, morphological and optical properties of Bi2−xSbxSe3 thin films grown by electrodeposition

Ternary single-phase Bi_2−xSb_xSe₃ alloy thin films were synthesized onto Au(1 1 1) substrates from an aqueous solution containing Bi(NO₃)₃, SbCl₃, and SeO₂ at room temperature for the first time via the electrodeposition technique. The electrodeposition of the thin films was studied using cyclic voltammetry, compositional, structural, optical measurements and surface morphology. It was found that the thin films with different stoichiometry can be obtained by controlling the electrolyte composition. The as-deposited films were crystallized in the preferential orientation along the (0 1 5) plane. The SEM investigations show that the film growth proceeds via nucleation, growth of film layer and formation of spherical particles on the film layer. The particle size and shape of Bi_2−xSb_xSe₃ films could be changed by tuning the electrolyte composition. The optical absorption spectra suggest that the band gap of this alloy varied from 0.24 to 0.38 eV with increasing Sb content from x = 0 to x = 0.2.     

Preparation and electrical properties of perovskite ceramics in the system BaBi1−xSbxO3 (0 ≤ x ≤ 0.5)

The effect of the composition on the electrical properties of BaBi_1−xSb_xO₃ (0 ≤ x ≤ 0.5) negative temperature coefficient (NTC) thermistors was studied. Major phases present in the sintered bodies of BaBi_1−xSb_xO₃ (0 < x < 0.5) ceramics were BaBi_0.5Sb_0.5O₃ compounds with a rhombohedral structure and BaBiO₃ compounds with a monoclinal structure. Most pores were located in the grains of BaBiO₃ and BaBi_0.5Sb_0.5O₃ ceramics. It was apparent that the ρ₂₅ and B_25/85 constant of the thermistors increased with increasing Sb content.