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钙钛矿型金属氧化物表现出对总电导率可忽略不计的晶界电阻。

Perovskite-type metal oxides exhibiting negligible grain boundary resistance to total electrical conductivity.

机构信息

Department of Calgary, University of Calgary, 2500 University Drive Northwest, Calgary, AB T2N 1N4, Canada.

出版信息

Inorg Chem. 2011 Jan 17;50(2):647-55. doi: 10.1021/ic101846f. Epub 2010 Dec 9.

Abstract

In this paper, we report the synthesis, structure and electrical properties of the perovskite-type AZn0.33+xNb0.67-xO3-δ (A = Sr or Ba; 0 ≤ x ≤ 0.08). The investigated compounds were prepared by employing the solid-state (ceramic) reaction using alkaline nitrates, zinc oxide, and niobium oxide at elevated temperatures in air. Powder X-ray diffraction (PXRD) showed the formation of disordered Zn and Nb at the B-sites of space group Pm3̅m with cubic structure and a lattice constant comparable to that of the literature. The AC impedance study showed mainly bulk contribution to the total electrical conductivity over the investigated frequency range of 0.01 Hz to 1 MHz in all the investigated atmospheres even at low temperatures, which is significantly different from that of the well-known perovskite-type B-site ordered BaCa0.33+xNb0.67-xO3-δ and the disordered acceptor-doped BaCeO3. The bulk dielectric constant determined at 500 and 700 °C in air was found to be in the range of 35-100. In air, the isothermal bulk dielectric constant seems to increase with an increasing Zn content, and a similar trend was observed for total electrical conductivity. In dry and wet H2, the electrical conductivity decreases with an increasing Zn content in AZn0.33+xNb0.67-xO3-δ, and the x = 0 member of the Ba compound exhibits the highest total conductivity of 7.2 × 10(-3) S cm(-1) in dry H2 at 800 °C. Both Sr and Ba compounds were found to be stable against the reaction with pure CO2 at 700 °C and H2O at 100 °C for a long period of time. SrZn0.33+xNb0.67-xO3-δ was found to be stable in 30 ppm H2S at 800 °C, while the corresponding Ba compound formed reaction products such as BaS (JCPDS Card 01-0757), BaS2 (JCPDS Card 21-0087), and BaS3 (JCPDS Card 03-0824).

摘要

本文报道了钙钛矿型 AZn0.33+xNb0.67-xO3-δ(A = Sr 或 Ba;0 ≤ x ≤ 0.08)的合成、结构和电学性能。所研究的化合物通过在空气中使用碱性硝酸盐、氧化锌和氧化铌在高温下采用固态(陶瓷)反应制备。粉末 X 射线衍射(PXRD)表明,在空间群 Pm3̅m 中,无序的 Zn 和 Nb 占据 B 位,形成具有立方结构和与文献相当的晶格常数的化合物。在所有研究的气氛中,即使在低温下,交流阻抗研究表明,在 0.01 Hz 至 1 MHz 的研究频率范围内,总电导率主要来自体贡献,这与众所周知的 B 位有序 BaCa0.33+xNb0.67-xO3-δ 和无序受主掺杂 BaCeO3 明显不同。在空气中于 500 和 700°C 下测定的体介电常数在 35-100 范围内。在空气中,随 Zn 含量的增加,等温体介电常数似乎增加,总电导率也表现出相似的趋势。在干燥和湿 H2 中,随 Zn 含量的增加,AZn0.33+xNb0.67-xO3-δ 的电导率降低,Ba 化合物的 x = 0 成员在 800°C 的干燥 H2 中表现出最高的总电导率 7.2×10(-3) S cm(-1)。在 700°C 下与纯 CO2 和 100°C 下与 H2O 长时间反应,Sr 和 Ba 化合物均表现出稳定性。SrZn0.33+xNb0.67-xO3-δ 在 800°C 下的 30 ppm H2S 中表现出稳定性,而相应的 Ba 化合物形成了反应产物,如 BaS(JCPDS 卡片 01-0757)、BaS2(JCPDS 卡片 21-0087)和 BaS3(JCPDS 卡片 03-0824)。

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