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实现稀土取代的SrTiO₃的高热电性能:强还原烧结条件所带来的影响。

Towards a high thermoelectric performance in rare-earth substituted SrTiO3: effects provided by strongly-reducing sintering conditions.

作者信息

Kovalevsky A V, Yaremchenko A A, Populoh S, Thiel P, Fagg D P, Weidenkaff A, Frade J R

机构信息

Department of Materials and Ceramic Engineering, CICECO, University of Aveiro, 3810-193 Aveiro, Portugal.

出版信息

Phys Chem Chem Phys. 2014 Dec 28;16(48):26946-54. doi: 10.1039/c4cp04127e.

Abstract

Donor-substituted strontium titanate ceramics demonstrate one of the most promising performances among n-type oxide thermoelectrics. Here we report a marked improvement of the thermoelectric properties in rare-earth substituted titanates Sr0.9R0.1TiO3±δ (R = La, Ce, Pr, Nd, Sm, Gd, Dy, Y) to achieve maximal ZT values of as high as 0.42 at 1190 K < T < 1225 K, prepared via a conventional solid state route followed by sintering under strongly reducing conditions (10%H2-90%N2, 1773 K). As a result of complex defect chemistry, both electrical and thermal properties were found to be dependent on the nature of the rare-earth cation and exhibit an apparent correlation with the unit cell size. High power factors of 1350-1550 μW m(-1) K(-2) at 400-550 K were observed for R = Nd, Sm, Pr and Y, being among the largest reported so far for n-type conducting bulk-ceramic SrTiO3-based materials. Attractive ZT values at high temperatures arise primarily from low thermal conductivity, which, in turn, stem from effective phonon scattering in oxygen-deficient perovskite layers formed upon reduction. The results suggest that highly-reducing conditions are essential and should be employed, whenever possible, in other related micro/nanostructural engineering approaches to suppress the thermal conductivity in target titanate-based ceramics.

摘要

施主取代的钛酸锶陶瓷在n型氧化物热电材料中展现出最具前景的性能之一。在此,我们报道了通过传统固态路线制备并在强还原条件(10%H₂ - 90%N₂,1773 K)下烧结的稀土取代钛酸盐Sr₀.₉R₀.₁TiO₃±δ(R = La、Ce、Pr、Nd、Sm、Gd、Dy、Y)的热电性能有显著改善,在1190 K < T < 1225 K时实现了高达0.42的最大ZT值。由于复杂的缺陷化学,发现电学和热学性能均取决于稀土阳离子的性质,并且与晶胞尺寸呈现明显的相关性。对于R = Nd、Sm、Pr和Y,在400 - 550 K时观察到1350 - 1550 μW m⁻¹ K⁻²的高功率因子,这是迄今为止报道的n型导电块状陶瓷SrTiO₃基材料中最大的功率因子之一。高温下有吸引力的ZT值主要源于低热导率,而低热导率又源于还原时形成的缺氧钙钛矿层中的有效声子散射。结果表明,强还原条件至关重要,并且在其他相关的微/纳米结构工程方法中,只要有可能,都应采用该条件来抑制目标钛酸盐基陶瓷的热导率。

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