Improving thermoelectric properties of Ca 3 Co 4 O 9+d through both Na doping and K addition at optimal values

Ca 2.93 Na 0.07 Co 4 O y /x wt% K 2 CO 3 (x = 0.00, 0.01, and 0.03) polycrystalline ceramics were prepared by conventional solid-state method. XRD results have shown that all samples predominantly include Ca 3 Co 4 O 9 phase together with small amounts of secondary phases. SEM images show that all samples have randomly oriented plate-like grains in different sizes. The electrical resistivity measurement showed that electrical properties of Ca 3 Co 4 O 9 ceramics can be improved significantly by both, Na doping and K addition at their optimal values. The effect of dopants on thermoelectric properties of Ca 3 Co 4 O 9 was examined by both, Seebeck coefficient and power factor, being higher in K-added than in the pure samples, indicating that thermoelectric properties of samples are positively affected when alkaline elements enter into their structure

Thermoelectrics

Metallic Ag microsphere in a ceramic matrix Thermoelectricity is the direct solid-state conversion between thermal and electrical energy, without any moving parts, due to the well-known Seebeck effect. Currently, more than half of the energy produced ends up in the form of wasted heat: thermoelectric harvesting and energy conversion constitutes an solution to improve the energy efficiency of classical industrial and domestic energy transforming processes, through thermoelectric modules

Effect of Yttrium substitution on superconductivity in Bi-2212 textured rods prepared by a LFZ technique

In this study, the physical and superconducting properties of the Bi2Sr2Ca1-xYxCu2O8+delta with x=0.0, 0.05, 0.075 0.1, and 0.20 textured superconducting rods prepared by a laser floating zone technique were presented. The effects of Y3+ substitution for Ca2+ have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), dc-magnetization, magnetic hysteresis and critical current density calculation by using the Bean''s critical state model. The powder XRD patterns of the samples have shown the Bi-2212 phase is the major one. Along with the powder samples, the textured rod surfaces also were investigated by XRD. The grains found to be well-oriented along the longitudinal rod axis which is a typical result for superconductors prepared by laser floating zone (LFZ) method, has been observed. The best critical temperature, T-C, has been found as 92.9 K for the sample with 0.15Y substitution, under DC magnetic field of 50 Oe in ZFC mode. It has also been observed that the critical current density decreases with increasing Y-substitution. Using those values, the maximum J(C) value has been determined as 2.37 x 10(5) A/cm(2) for the undoped sample

Thermal Conductivity and Thermoelectric Power of Yb-Substituted Bi-2212 Superconductor

In the present study, Bi2Sr2CaCu2-xYbxO8+y where x = 0.0, 0.05, 0.1 and 0.25, superconductor materials were textured using the Laser Floating Zone technique. After annealing the as-grown materials, they were characterized by thermal conductivity (¿-T), thermoelectric power (S-T), and electrical resistivity (R-T) measurements performed from room temperature down to 20 K. The thermoelectric power is positive in all cases and is found to increase with decreasing temperature, reaching the maximum value (peak) around the samples TC values and dropping rapidly to zero below TC. Electrical resistivity measurements show a slight decrease of TC when Yb substitution is raised. In spite of this effect, TC values are higher than 90 K in all cases. On the other hand, Yb substitution also decreases thermal conductivity, compared with the undoped samples

Influence of Ca substitution by Mg on the Ca3Co4O9 performances

Ca3-xMgxCo4O9 polycrystalline thermoelectric ceramics with small amounts of Mg have been synthesized by the classical solid state method. Microstructural characterizations have shown that all the Mg has been incorporated into the Ca3Co4O9 structure and no Mg-based secondary phases have been identified. Apparent density measurements have shown that samples do not modify their density until 0.05 Mg content, decreasing for higher contents. Electrical resistivity decreases and Seebeck coefficient slightly raises when Mg content increases until 0.05 Mg addition. The improvement in both parameters leads to higher power factor values than the usually obtained in samples prepared by the conventional solid state routes and close to those obtained in textured materials.Se han preparado cerámicas termoeléctricas policristalinas de Ca3-xMgxCo4O9, con pequeñas cantidades de Mg, utilizando el método clásico de estado sólido. La caracterización microestructural ha mostrado que el Mg se ha incorporado en la estructura del Ca3Co4O9 y que no se han formado fases secundarias con el Mg. Las medidas de densidad aparente han mostrado que las muestras prácticamente poseen la misma densidad hasta un contenido de 0.05 Mg, disminuyendo para contenidos mayores. La resistividad eléctrica disminuye y el coeficiente Seebeck aumenta cuando el contenido de Mg se incrementa hasta valores de 0.05. La mejora de ambos parámetros conduce a valores del factor de potencia mayores que los obtenidos en muestras preparadas por la vía convencional de estado sólido, alcanzando valores próximos a los que se encuentran en materiales texturados

Thermoelectric doping effect in Ca3Co4-xNixO9 ceramics

Ca3Co4-xNixO9 (x=0.01, 0.03, and 0.05) polycrystalline thermoelectric ceramics have been prepared by the classical solid state method. As a result of the Ni addition an increase in porosity has been detected. Moreover, the presence of Ni has been related with the increase of Ca2Co3O6 secondary phase and the appearance of a new NiO-CoO solid solution. However, for the 0.01-Ni doped samples an improvement in the thermoelectric performances has been measured. This effect has been related with a decrease in the resistivity values and an increase in the Seebeck coefficient. The raise in the power factor for the 0.01-Ni doped samples, compared with the undoped ones, is between 10 and 25% at 50 and 800 °C respectively. Moreover, the maximum power at 800 °C, around 0.25 mW/K2.m, is significantly higher than the best results obtained in Ni doped samples reported previously in the literature

Influence of Ca substitution by Mg on the Ca3Co4O9 performances

Ca3-xMgxCo4O9 polycrystalline thermoelectric ceramics with small amounts of Mg have been synthesized by the classical solid state method. Microstructural characterizations have shown that all the Mg has been incorporated into the Ca3Co4O9 structure and no Mg-based secondary phases have been identified. Apparent density measurements have shown that samples do not modify their density until 0.05 Mg content, decreasing for higher contents. Electrical resistivity decreases and Seebeck coefficient slightly raises when Mg content increases until 0.05 Mg addition. The improvement in both parameters leads to higher power factor values than the usually obtained in samples prepared by the conventional solid state routes and close to those obtained in textured materials.Se han preparado cerámicas termoeléctricas policristalinas de Ca3-xMgxCo4O9, con pequeñas cantidades de Mg, utilizando el método clásico de estado sólido. La caracterización microestructural ha mostrado que el Mg se ha incorporado en la estructura del Ca3Co4O9 y que no se han formado fases secundarias con el Mg. Las medidas de densidad aparente han mostrado que las muestras prácticamente poseen la misma densidad hasta un contenido de 0.05 Mg, disminuyendo para contenidos mayores. La resistividad eléctrica disminuye y el coeficiente Seebeck aumenta cuando el contenido de Mg se incrementa hasta valores de 0.05. La mejora de ambos parámetros conduce a valores del factor de potencia mayores que los obtenidos en muestras preparadas por la vía convencional de estado sólido, alcanzando valores próximos a los que se encuentran en materiales texturados

Role of Ag in textured-annealed Bi2Ca2Co1.7Ox thermoelectric ceramic

Bi2Ca2Co1.7Ox thermoelectric ceramics with small Ag additions (0, 1, 2, 3, 4, and 5 wt.%) have been successfully grown from the melt, using the laser floating zone method and subsequently annealed at 800 °C for 24 h. The microstructure has shown a reduction of the amount of secondary phases for Ag contents up to 4 wt.%. This microstructural evolution leads to a decrease of the electrical resistivity values until an Ag content of 4 wt.%, whereas Seebeck coefficient has been maintained unchanged. This is in agreement with the presence of metallic Ag in all samples, confirmed not only by Energy Dispersive Spectrometry but also by X-ray photoelectron and Auger spectroscopy. These electrical properties lead to maximum power factor values of about 0.30 mW/K2.m at 650 °C for the 4 wt.% Ag containing samples, which is among the best results obtained for this type of materials

Detail investigation of thermoelectric performance and magnetic properties of Cs-doped Bi2Sr2Co2Oy ceramic materials

Bi2Sr2-xCsxCo2Oy materials with 0 = x = 0.15, have been fabricated via the classical ceramic technique. XRD results have indicated that undoped and Cs-substituted samples are composed of Bi2Sr2Co2Oy phase as the major one. Microstructural studies have demonstrated the formation of a liquid phase, which allows a drastic grain growth. This factor is responsible for a drastic improvement of relative density, reaching about 95% of the theoretical one for 0.125 Cs content. On the other hand, electrical resistivity has been reduced up to 14 mO cm at 650 °C for 0.125 Cs content, around 40% lower than the obtained in undoped samples. As a consequence, Seebeck coefficient has been decreased due to the raise in charge carrier concentration. The highest power factor at 650 °C (0.21 mW/K2 m) has been found for 0.125 Cs substituted sample, about 40% larger than the obtained in undoped samples, and very similar to the notified in single crystals (0.26 mW/K2 m). Magnetisation with respect to temperature results have demonstrated that measured samples have a paramagnetic property above 50 K, except 0.10 Cs. Magnetic hysteresis curves have shown that the slopes and the magnitudes have increased with decreasing temperature

Evaluation of pressure and temperature effect on the structure and properties of Ca2.93Sr0.07Co4O9 ceramic materials

In this work, the effect of hot-pressing conditions on the performances of Sr-doped Ca3Co4O9 materials has been investigated. The samples were prepared from attrition milled precursors, which reduced the processing time. Samples were hot-pressed at temperatures (T) between 800 and 900 °C and pressures (P) from 51 to 71 MPa. The out-of-plane X-ray diffraction (XRD) showed that all samples are formed by the thermoelectric phase, with a good grain orientation which is improved with T, and P, as demonstrated by their Lotgering factor. The observations through Scanning Electron Microscopy (SEM) have revealed that grain sizes and orientation are enhanced with T, and P, as well as density through Archimedes''s method. All these trends are reflected in the flexural strength and microhardness. The electrical resistivity is lower when the T, or P, is increased, reaching 6.4 mO cm for samples processed at 900 °C and 71 MPa, which is about the best reported values in the literature. On the other hand, contrarily to the expected results, they also showed the highest S values, 182 µV/K, which are similar to the best reported values for highly dense textured materials. Thermal conductivity values do not follow a regular evolution with the hot-pressing conditions, probably due to internal stresses, reaching the lowest values at 800 °C in samples processed at 800 °C and 51 MPa (1.51 W/(K*m)) or 900 °C and 61 MPa (1.53 W/(K*m)). Consequently, the highest ZT values have been determined in samples processed at 900 °C and 61 MPa (0.35) which is higher than the best reported values in literature for bulk textured samples, to the best of our knowledge. © 2021 The Author