• 한국전기전자재료학회논문지
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• 제33권6호
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• pp.495-499
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• 2020

Power factor improvement at high temperatures has been a major research topic for the development of skutterudite thermoelectric materials. Here, we attempted to optimize the process parameters for manufacturing skutterudite materials, especially for p-type systems. We focused on the effect of aging time variation to maximize the high-temperature performance of the Ce-filled Fe³CoSb¹² skutterudite system. The optimized aging time was concluded to be a key parameter for the formation of single-phase nanostructures in this p-type skutterudite system. The optimized condition was effective in reducing the bipolar effect at high temperature ranges by increasing the carrier concentration in the p-type system. To confirm the conclusions, the electrical conductivity, Seebeck coefficient, and power factor were measured. The results matched well with the microstructure and with those of an XRD analysis performed for the system.

• 한국재료학회지
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• 제14권11호
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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.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2005년도 춘계학술발표대회 및 제8회 신소재 심포지엄 논문개요집
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• pp.29-29
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• 2005

• 한국재료학회지
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• 제16권9호
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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.

• 한국재료학회지
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• 제16권5호
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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 ${\delta}-CoSb_3$.

• 한국전기전자재료학회논문지
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• 제29권11호
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• pp.671-675
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• 2016

Skutterudite materials show PGEC (phonon glass electron crystal) characteristics which is an optimal strategy for designing high performance thermoelectric materials. Now two methods are in parallel to control thermal conductivity of skutterudites, a rattler-atoms doping method and a process for nanostructured bulk materials. Amount of rattler atoms in p-type skutterudite are depends on a Fe/Co ratio of matrix, and the optimal Fe/Co ratio has been reported about from 3:1 to 3.5:0.5 in $R(Fe,Co)_4Sb_{12}$ structure. In this paper, our discussion for rattler doping research was concentrated on double-rattler systems and DD-doped systems in p-type skutterudites. A melt spinning precess combined with high energy ball milling were suggested as a strategy for nanostructured bulk materials with PGEC (phonon glass electron crystal) characteristics in p-type skutterudites.

• 한국전기전자재료학회논문지
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• 제32권6호
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• pp.496-500
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• 2019

In this study, we investigate the effect of an Sb-deficiency on the thermoelectric properties of double-filled n-type skutterudite ($In_{0.05}Yb_{0.15}Co_4Sb_{12-x}$). Samples were prepared by encapsulated induction melting, consecutive long-time annealing, and finally spark plasma sintering processes. The Sb-deficient sample contained a $CoSb_2$ secondary phase. Both the double-filled n-type skutterudite pristine and Sb-deficient samples showed metallic behavior in electrical conductivity with increasing temperature. The carrier concentration of the Sb-deficient sample decreased compared with that of the pristine sample. Due to a decrease in carrier concentration, the Sb deficient sample showed decreased electrical conductivity and an increased Seebeck coefficient compared with the conductivity and coefficient of the pristine sample. Furthermore, the Sb deficient sample showed an increase in the power factor (${\sigma}{\cdot}S^2$); the power factor maximum shifted to athe lower temperature side than ones of the pristine sample. As a result, the Sb-deficient sample represents an improved average figure of merit (ZT) and a $ZT_{max}$ temperature lower than that of the pristine sample. Therefore, we propose that Sb-deficient double-filled n-type skutterudite thermoelectric material ($In_{0.05}Yb_{0.15}Co_4Sb_{12-x}$) be used in the 573~673 K temperature range.

• 한국분말야금학회:학술대회논문집
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• 한국분말야금학회 2005년도 추계학술강연 및 발표대회강연 및 발표논문 초록집
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• pp.104-105
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• 2005

• 한국재료학회지
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• 제15권10호
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• pp.667-670
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• 2005

Binary skutterudite $CoSb_3$ compounds were prepared by the arc melting and hot pressing processes and their thermoelectric properties were investigated in the range from 300 to 600 K. Annealing effect was correlated to phase transformation and homogenization. Thermoelectric properties of the arc-melted and hot-pressed $CoSb_3$ were discussed and compared. Undoped intrinsic $CoSb_3$ prepared by the arc melting showed p-type conduction, while it showed metallic behavior with increasing measuring temperature. However, hot pressed specimens showed n-type conduction, possibly due to Sb evaporation. Thermoelectric properties were remarkably improved by annealing In vacuum and they were closely related to phase transformation.

• 한국분말재료학회지
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• 제12권5호
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• pp.357-361
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• 2005

Fe-doped skutterudite $CoSb_3$ with a nominal composition of $Fe_{x}Co_{4-x}Sb_{12}(0\;{\le}\;x\;{\le}\;2.5)$ has been synthesized by mechanical alloying (MA) of elemental powders, followed by hot pressing. Phase transformations during mechanical alloying and hot pressing were systematically investigated using XRD. Single phase skutterudite was successfully produced by vacuum hot pressing using as-milled powders without subsequent annealing. However, second phase in the form of marcasite structure $FeSb_2$ was found to exist in case of $x\;{\ge}\;2$, suggesting the solubility limit of Fe with Co in this system. Thermoelectric properties as functions of temperature and Fe contents were evaluated for the hot pressed specimens. Fe substitution up to x=1.5 with Co in $Fe_{x}Co_{4-x}Sb_{12}$ appeared to increase thermoelectric figure of merit (ZT) and the maximum ZT was found to be 0.78 at 525K in this study.