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Sm0.2Ce0.8O1.9/Na2CO3 纳米复合电解质的研究:制备、界面微观结构和离子电导率。

Investigation of Sm0.2Ce0.8O1.9/Na2CO3 nanocomposite electrolytes: preparation, interfacial microstructures, and ionic conductivities.

机构信息

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing University of Technology , 5 New Model Road, Nanjing 210009, P. R. China.

出版信息

ACS Appl Mater Interfaces. 2013 Dec 26;5(24):12876-86. doi: 10.1021/am403198x. Epub 2013 Dec 9.

DOI:10.1021/am403198x
PMID:24251947
Abstract

With the analytical grade Ce(NO3)3·6H2O, Sm(NO3)3·6H2O, and Na2CO3 as starting materials, Sm0.2Ce0.8O1.9(SDC)/Na2CO3 nanocomposite electrolytes were prepared through a rare-earth/sodium carbonate complex precipitation, prefiring, and sintering operations. The phase components and microstructures were studied and characterized by XRD, FESEM, TEM, and TG-DSC. In particular, the interfacial interactions between the phases of SDC crystallites and amorphous Na2CO3 were deliberately probed by Raman and infrared spectroscopies. It has been found that the amorphous carbonates in the SDC/Na2CO3 composites are tightly bound to the surface of SDC nanocrystals to form an intimate shell-layer via a long-range interface interaction, characterized by ∼8 nm in thickness and a red-shift of 15 cm(-1) for the Raman symmetrical vibration mode of carbonate ions with reference to the crystalline Na2CO3, which is practically enabled to frustrate the crystallization of Na2CO3 and enhance the transport properties of oxide ions in the SDC/Na2CO3 composite electrolytes because of the disordered interface microstructures. Moreover, smaller SDC nanocrystals were found to achieve higher conductivity enhancements for the SDC/Na2CO3 composite electrolytes and the {100} facets on the surface of SDC nanocrystals are believed to be more important than the other facets because of their strong electropositivity. This effect makes the SDC/Na2CO3 composite sample prefired at 600 °C realize a much higher ionic conductivity than the samples prefired at the other temperatures.

摘要

以分析纯 Ce(NO3)3·6H2O、Sm(NO3)3·6H2O 和 Na2CO3 为原料,通过稀土/碳酸钠复合沉淀、预烧和烧结工艺制备了 Sm0.2Ce0.8O1.9(SDC)/Na2CO3 纳米复合电解质。采用 XRD、FESEM、TEM 和 TG-DSC 对相组成和微观结构进行了研究和表征。特别是,通过拉曼和红外光谱对 SDC 晶相和非晶态 Na2CO3 之间的相界面相互作用进行了有意探测。结果发现,SDC/Na2CO3 复合材料中的非晶态碳酸盐通过长程界面相互作用紧密结合在 SDC 纳米晶表面,形成紧密的壳层,其厚度约为 8nm,碳酸根离子的拉曼对称振动模式发生 15cm-1 的红移,相对于晶态 Na2CO3,这实际上可以阻止 Na2CO3 的结晶,并由于无序界面微结构而提高 SDC/Na2CO3 复合电解质中氧化物离子的输运性能。此外,较小的 SDC 纳米晶使 SDC/Na2CO3 复合电解质具有更高的电导率增强,并且 SDC 纳米晶表面的{100}面比其他面更为重要,因为它们具有较强的正电性。这种效应使得在 600°C 预烧的 SDC/Na2CO3 复合样品比在其他温度下预烧的样品具有更高的离子电导率。

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