• Korean Journal of Materials Research
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• v.22 no.12
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• pp.682-688
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• 2012

In this study we aimed to examine the co-doping effects of 1/6 mol% $Co_3O_4$ and 1/4 mol% $Cr_2O_3$ (Co:Cr = 1:1) on the reaction, microstructure, and electrical properties, such as the bulk defects and the grain boundary properties, of ZnO-$Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi = 0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Co,Cr-doped ZBS, ZBS(CoCr) varistors were controlled using the Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$), ${\alpha}$-spinel ($Zn_7Sb_2O_{12}$), and ${\delta}-Bi_2O_3$ were formed in all systems. Pyrochlore was decomposed and promoted densification at lower temperature on heating in Sb/Bi = 1.0 by Cr rather than Co. A more homogeneous microstructure was obtained in all systems affected by ${\alpha}$-spinel. In ZBS(CoCr), the varistor characteristics were improved (non-linear coefficient, ${\alpha}$ = 20~63), and seemed to form ${Zn_i}^{{\cdot}{\cdot}}$(0.20 eV) and ${V_o}^{\cdot}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy, the grain boundaries were found to be composed of an electrically single barrier (0.94~1.1 eV) that is, however, somewhat sensitive to ambient oxygen with temperature. The phase development, densification, and microstructure were controlled by Cr rather than by Co but the electrical and grain boundary properties were controlled by Co rather than by Cr.

• Korean Journal of Materials Research
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• v.20 no.6
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• pp.326-330
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• 2010

$CoSb_3$ Skutterudites materials have high potential for thermoelectric application at mid-temperature range because of their superior thermoelectric properties via control of charge carrier density and substitution of foreign atoms. Improvement of thermoelectric properties is expected for the ternary solid solution developed by substitution of foreign atoms having different valances into the $CoSb_3$ matrix. In this study, ternary solid solutions with a stoichiometry of $Co_{1-x}Ni_xSb_3$ x = 0.01, 0.05, 0.1, 0.2, $CoSb_{3-y}Te_y$, y = 0.1, 0.2, 0.3 were prepared by the Spark Plasma Sintering (SPS) system. Before the SPS synthesis, the ingots were synthesized by vacuum induction melting and followed by annealing. For phase analysis X-ray powder diffraction patterns were checked. All the samples were confirmed as single phase; however, with samples that were more doped than the solubility limit some secondary phases were detected. All the samples doped with Ni and Te atoms showed a negative Seebeck coefficient and their electrical conductivities increased with the doping amount up to the solubility limit. For the samples prepared by SPS the maximum value for dimensionless figure of merit reached 0.26, 0.42 for $Co_{0.9}Ni_{0.1}Sb_3$, $CoSb_{2.8}Te_{0.2}$ at 690 K, respectively. These results show that the SPS method is effective in this system and Ni/Te dopants are also effective for increasing thermoelectric properties of this system.

• Journal of the Korean Ceramic Society
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• v.50 no.6
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• pp.476-479
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• 2013

$CoSb_3$ with its high electrical conductivity, Seebeck coefficient and rather low thermal conductivity is quite a promising material for thermoelectric conversion applications. A potentially high figure of merit (ZT) can be achieved by a nanostructure evolution of thermoelectric materials. In this work, $CoSb_3$ nanoparticles were synthesized through a thermal decomposition method in cooperation with a hot injection technique. Nano-sized $CoSb_3$ particles were obtained through the thermal decomposition reaction between the pre-heated cobalt-oleate at $320^{\circ}C$ and the injected antimony oleate with room temperature. The results showed that the particle size was increased with increasing synthesis temperature and the crystallinity of particles was improved with temperature but the decomposition of $CoSb_3$ was observed at $320^{\circ}C$. The $CoSb_3$ particles synthesized at $300^{\circ}C$ showed a high purity and an homogeneous shape with average particle size of 26 nm.

• Korean Journal of Materials Research
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• v.16 no.9
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• pp.529-532
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• 2006

Sn-filled $Co_8Sb_{24}$ skutterudites were synthesized by the encapsulated induction melting process. Single ${\delta}-phase$ was successfully obtained by subsequent annealing and confirmed by X-ray diffraction analysis. Temperature dependences of Seebeck coefficient, electrical resistivity and thermal conductivity were examined from 300 K to 700 K. The positive Seebeck coefficient confirmed the p-type conductivity of the Sn-filled $Co_8Sb_{24}$. Electrical resistivity increased with increasing temperature, which shows that the Sn-filled $Co_8Sb_{24}$ skutterudite is a highly degenerate semiconductor. Thermal conductivity was reduced by Sn-filling because the filler atoms acted as phonon scattering centers in the skutterudite lattice. Thermoelectric figure of merit was enhanced by Sn filling and its optimum filling content was considered to be $z{\leq}0.5$ in the $Sn_zCo_8Sb_{24}$ system.

• Korean Journal of Materials Research
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• v.16 no.7
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• pp.435-438
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• 2006

The hot pressing was employed to prepare Fe-doped $CoSb_3$ skutterudites and their thermoelectric properties were investigated. Single phase ${\delta}-CoSb_3$ was successfully obtained by the hot pressing under 60MPa at 773 K for 2 hrs. Iron atoms acted as electron acceptors by substituting cobalt atoms. Thermoelectric properties were remarkably improved by the appropriate doping. $Co_{0.7}Fe_{0.3}Sb_3$ was found as an optimum composition for the best thermoelectric property in this work.

• Journal of the Korean Ceramic Society
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• v.53 no.3
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• pp.367-375
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• 2016

A novel strategy for the synthesis of $CoSb_2$ nanoparticles is demonstrated via preparation of novel organometallic complexes. Hydrated cobalt oleate (CoOl) and non-hydrated antimony oleate (SbOl) complexes are synthesized as precursors. The $CoSb_2$ nanoparticles are prepared by hot injection, which involves thermolysis of CoOl and SbOl in a non-coordinating solvent at $320^{\circ}C$. The coordination modes and distinct thermal behaviors of the intermediate non-hydrated SbOl complexes are comparatively investigated by thermo-analytical techniques. When the reaction temperature is increased, the particle size is found to increase linearly. The crystallinity of the $CoSb_2$ nanoparticles prepared at $250^{\circ}C$ is amorphous phase without any peaks. $CoSb_2$ structural peaks start to appear at $300^{\circ}C$ and dominant peaks with high crystallinity are synthesized at $320^{\circ}C$. The potential chemical structures of non-hydrated SbOl and their reaction mechanisms by thermolysis are elucidated. The elemental composition and crystallographic structure of $CoSb_2$ nanoparticles suggest a bimodal interaction of the organic shell and the nanoparticle surface, with a chemical absorbed inner layer and physically absorbed outer layer of carboxylic acid.

• Korean Journal of Materials Research
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• v.14 no.11
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• pp.802-806
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• 2004

Skutterudite $CoSb_3$ powders were produced by mechanical alloying (MA) of elemental powders using a nominal stoichiometric composition. Annealing of MA powders under specific condition led to a complete phase transformation to a semiconducting ${\delta}-CoSb_3$. Single phase $CoSb_3$ was successfully produced by vacuum hot pressing using MA powders without subsequent annealing. Phase transformations during mechanical alloying and hot pressing were systematically investigated using XRD and SEM. Thermoelectric properties as a function of temperature were evaluated for the hot pressed specimens and compared with results of analogous studies.

• Korean Journal of Materials Research
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• v.16 no.5
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• pp.312-317
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• 2006

Binary skutterudite $CoSb_3$ compounds were prepared by the encapsulated induction melting (EIM) process, and their thermoelectric, microstructural and mechanical properties were examined. Single-phase ${\delta}-CoSb_3$ was successfully produced by the EIM and subsequent heat treatment at 773 K-873 K for 24 hours in vacuum. Seebeck coefficient increased with increasing heat treatment temperature up to 673 K, showing the positive signs in the range of measuring temperature. However, the samples heat-treated at 773 K-873 K showed negative Seebeck coefficient from room temperature to 400 K, while it showed positive signs above 400 K. Electrical resistivity decreased with increasing temperature, showing typical semiconducting conductivity. Thermal conductivity decreased drastically with increasing heat-treatment temperature. This is closely related with the phase transition to ${\delta}-CoSb_3$.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.25 no.11
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• pp.878-885
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• 2012

In this study we aims to examine the co-doping effects of 1/3 mol% $Mn_3O_4+Co_3O_4$ (1:1) on the reaction, microstructure, and electrical properties such as the bulk defects and grain boundary properties of $ZnO-Bi_2O_3-Sb_2O_3$ (ZBS; Sb/Bi=0.5, 1.0, and 2.0) varistors. The sintering and electrical properties of Mn,Co-doped ZBS, ZBS(MCo) varistors were controlled by Sb/Bi ratio. Pyrochlore ($Zn_2Bi_3Sb_3O_{14}$) was decomposed and promoted densification at lower temperature on heating in Sb/Bi=1.0 by Mn rather than Co. Pyrochlore on cooling was reproduced in all systems however, spinel (${\alpha}$- or ${\beta}$-polymorph) did not formed in Sb/Bi=0.5. More homogeneous microstructure was obtained in $Sb/Bi{\geq}1.0$ In ZBS(MCo), the varistor characteristics were improved drastically (non-linear coefficient, ${\alpha}$=30~49), and seemed to form $Zn_i^{..}$(0.17 eV) and $V_o^{\bullet}$(0.33 eV) as dominant defects. From impedance and modulus spectroscopy (IS & MS), the grain boundaries have divided into two types, i.e. the one is tentatively assign to $ZnO/Bi_2O_3(Mn,Co)/ZnO$ (0.47 eV) and the other ZnO/ZnO (0.80~0.89 eV) homojunctions.

• Korean Journal of Materials Research
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• v.16 no.7
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• pp.412-415
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• 2006

Te-doped $CoSb_3$ was prepared by the encapsulated induction melting, and its doping effects on the thermoelectric properties were investigated. Single phase ${\delta}-CoSb_3$ was successfully obtained by the subsequent annealing at 773 K for 24 hrs. Tellurium atoms acted as electron donors by substituting antimony atoms. Thermoelectric properties were remarkably improved by the appropriate doping. Dimensionless figure of merit was obtained to be 0.83 at 700K for the $CoSb_{2.8}Te_{0.2}$ specimen.