{"title":"热电钙钛矿:固态合成与热特性","authors":"Dong Hwi Kim, Sang Yun, Il-Ho Kim","doi":"10.3365/kjmm.2024.62.6.480","DOIUrl":null,"url":null,"abstract":"In this study, thermoelectric chalcostibite (CuSbS2) compounds were fabricated using mechanical alloying (MA) and hot pressing (HP), and phase identification, microstructural observation, and thermal analysis were conducted. The thermal properties were then measured and compared with those of other Cu–Sb–S ternary compounds synthesized by the same solid-state process, namely, skinnerite (Cu3SbS3), famatinite (Cu3SbS4), and tetrahedrite (Cu12Sb4S13). Both the MA powder and HP-sintered samples contained a single-phase chalcostibite with an orthorhombic structure, and relative densities of 94.6–99.7% were obtained based on HP temperature. The full width at half maximum of the X-ray diffraction peak was significantly reduced for the HP specimens compared to that of the MA powder due to stress relaxation and grain growth during HP at elevated temperatures. However, practically no changes were observed in the lattice constants based on HP temperature. Differential scanning calorimetric analysis revealed that one endothermic reaction occurred at 814–815 K for the MA powder and at 818–821 K for the HP specimen, which were interpreted as the melting points of chalcostibite. Densely sintered compacts with densities close to the theoretical density were obtained using HP at temperatures of 623 K or higher. The constituent elements of the chalcostibites were uniformly distributed. As the HP temperature increased, thermal diffusivity and conductivity increased, but they decreased significantly as the measurement temperature increased. For the chalcostibite specimen hot-pressed at 623 K, the thermal diffusivity and conductivity were (0.75–0.36) × 10-2 cm2 s-1 and 1.47–0.72 W m-1 K-1 at 323–623 K, respectively. Compared with other Cu–Sb–S ternary compounds, the thermal diffusivity was higher at low temperatures but similar at high temperatures, and the thermal conductivity above 500 K was lower than 1 W m-1 K-1.","PeriodicalId":17894,"journal":{"name":"Korean Journal of Metals and Materials","volume":null,"pages":null},"PeriodicalIF":1.1000,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Thermoelectric Chalcostibite: Solid-State Synthesis and Thermal Properties\",\"authors\":\"Dong Hwi Kim, Sang Yun, Il-Ho Kim\",\"doi\":\"10.3365/kjmm.2024.62.6.480\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"In this study, thermoelectric chalcostibite (CuSbS2) compounds were fabricated using mechanical alloying (MA) and hot pressing (HP), and phase identification, microstructural observation, and thermal analysis were conducted. The thermal properties were then measured and compared with those of other Cu–Sb–S ternary compounds synthesized by the same solid-state process, namely, skinnerite (Cu3SbS3), famatinite (Cu3SbS4), and tetrahedrite (Cu12Sb4S13). Both the MA powder and HP-sintered samples contained a single-phase chalcostibite with an orthorhombic structure, and relative densities of 94.6–99.7% were obtained based on HP temperature. The full width at half maximum of the X-ray diffraction peak was significantly reduced for the HP specimens compared to that of the MA powder due to stress relaxation and grain growth during HP at elevated temperatures. However, practically no changes were observed in the lattice constants based on HP temperature. Differential scanning calorimetric analysis revealed that one endothermic reaction occurred at 814–815 K for the MA powder and at 818–821 K for the HP specimen, which were interpreted as the melting points of chalcostibite. Densely sintered compacts with densities close to the theoretical density were obtained using HP at temperatures of 623 K or higher. The constituent elements of the chalcostibites were uniformly distributed. As the HP temperature increased, thermal diffusivity and conductivity increased, but they decreased significantly as the measurement temperature increased. For the chalcostibite specimen hot-pressed at 623 K, the thermal diffusivity and conductivity were (0.75–0.36) × 10-2 cm2 s-1 and 1.47–0.72 W m-1 K-1 at 323–623 K, respectively. 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引用次数: 0
摘要
本研究采用机械合金化(MA)和热压(HP)工艺制备了热电霞石(CuSbS2)化合物,并进行了相鉴定、微观结构观察和热分析。然后测量了这些化合物的热性能,并与采用相同固态工艺合成的其他铜-锑-锑三元化合物(即矽卡岩(Cu3SbS3)、法曼石(Cu3SbS4)和四面体(Cu12Sb4S13))的热性能进行了比较。MA粉末和HP烧结样品中都含有具有正方体结构的单相菱锰矿,根据HP温度可获得94.6-99.7%的相对密度。与 MA 粉末相比,HP 试样的 X 射线衍射峰的半最大全宽明显减小,这是由于在高温下进行 HP 时发生了应力松弛和晶粒生长。然而,根据 HP 温度,晶格常数几乎没有变化。差示扫描量热分析表明,MA粉末在814-815 K和HP试样在818-821 K发生了一个内热反应,这两个温度点被解释为钙钛矿的熔点。使用 HP 在 623 K 或更高温度下获得了密度接近理论密度的致密烧结压实物。钙钛矿的组成元素分布均匀。随着 HP 温度的升高,热扩散率和电导率也随之升高,但随着测量温度的升高,热扩散率和电导率显著降低。对于在 623 K 下热压的霞石试样,在 323-623 K 下的热扩散率和电导率分别为 (0.75-0.36) × 10-2 cm2 s-1 和 1.47-0.72 W m-1 K-1。与其他铜-锑-锑三元化合物相比,低温下的热扩散率较高,但高温下的热扩散率相近,500 K 以上的热导率低于 1 W m-1 K-1。
Thermoelectric Chalcostibite: Solid-State Synthesis and Thermal Properties
In this study, thermoelectric chalcostibite (CuSbS2) compounds were fabricated using mechanical alloying (MA) and hot pressing (HP), and phase identification, microstructural observation, and thermal analysis were conducted. The thermal properties were then measured and compared with those of other Cu–Sb–S ternary compounds synthesized by the same solid-state process, namely, skinnerite (Cu3SbS3), famatinite (Cu3SbS4), and tetrahedrite (Cu12Sb4S13). Both the MA powder and HP-sintered samples contained a single-phase chalcostibite with an orthorhombic structure, and relative densities of 94.6–99.7% were obtained based on HP temperature. The full width at half maximum of the X-ray diffraction peak was significantly reduced for the HP specimens compared to that of the MA powder due to stress relaxation and grain growth during HP at elevated temperatures. However, practically no changes were observed in the lattice constants based on HP temperature. Differential scanning calorimetric analysis revealed that one endothermic reaction occurred at 814–815 K for the MA powder and at 818–821 K for the HP specimen, which were interpreted as the melting points of chalcostibite. Densely sintered compacts with densities close to the theoretical density were obtained using HP at temperatures of 623 K or higher. The constituent elements of the chalcostibites were uniformly distributed. As the HP temperature increased, thermal diffusivity and conductivity increased, but they decreased significantly as the measurement temperature increased. For the chalcostibite specimen hot-pressed at 623 K, the thermal diffusivity and conductivity were (0.75–0.36) × 10-2 cm2 s-1 and 1.47–0.72 W m-1 K-1 at 323–623 K, respectively. Compared with other Cu–Sb–S ternary compounds, the thermal diffusivity was higher at low temperatures but similar at high temperatures, and the thermal conductivity above 500 K was lower than 1 W m-1 K-1.
期刊介绍:
The Korean Journal of Metals and Materials is a representative Korean-language journal of the Korean Institute of Metals and Materials (KIM); it publishes domestic and foreign academic papers related to metals and materials, in abroad range of fields from metals and materials to nano-materials, biomaterials, functional materials, energy materials, and new materials, and its official ISO designation is Korean J. Met. Mater.