固体电解质Ce0.9Er0.1-xPrxO1.95+δ的微观结构及电性能

doi:10.7503/cjcu20140591

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (1): 61.doi: 10.7503/cjcu20140591

• 研究论文: 无机化学 • 上一篇下一篇

固体电解质Ce_0.9Er_0.1-_xPr_xO_1.95+_δ的微观结构及电性能

林晓敏¹(), 朱丽丽¹, 韩健¹, 刘晓梅²

1.北华大学物理学院, 吉林 132013
2. 吉林大学物理学院, 长春 130021

收稿日期:2014-06-27 修回日期:2014-12-16 出版日期:2015-01-10 发布日期:2014-12-16
作者简介:联系人简介: 林晓敏, 女, 博士, 教授, 主要从事无机固体电解质材料研究. E-mai:xiaominlin666@163.com
基金资助:
国家自然科学基金(批准号: 51272087)和吉林省教育厅科学技术研究项目(批准号: 2014181)资助.

Microstructure and Electrical Properties of Solid Electrolytes Ce_0.9Er_0.1-_xPr_x

LIN Xiaomin^1,^*(), ZHU Lili¹, HAN Jian¹, LIU Xiaomei²

1. College of Physics, Beihua University, Jilin 132013, China
2. College of Physics, Jilin University, Changchun 130021, China

Received:2014-06-27 Revised:2014-12-16 Online:2015-01-10 Published:2014-12-16
Contact: LIN Xiaomin E-mail:xiaominlin666@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.51272087) and the Scientific Resesrch Foundation of Jilin Province Education Institute, China(No.2014181)

摘要/Abstract

摘要：

采用柠檬酸溶胶-凝胶法制备了固体电解质Ce_0.9Er_0.1-_xPr_xO_1.95+_δ(x= 0.02~0.08), 利用X射线粉末衍射(XRD)、原子力显微镜(AFM)、拉曼光谱(Raman)、 X射线光电子能谱(XPS)和交流阻抗谱研究了样品的微观结构和电性能. XRD结果表明, 800 ℃煅烧的所有样品均形成了单相立方萤石结构; Raman光谱结果表明, Ce_0.9Er_0.05Pr_0.05O_1.95+_δ具有氧缺位的立方萤石结构; XPS分析表明, Ce_0.9Er_0.05Pr_0.05O_1.95+_δ存在氧缺位, Pr³⁺离子和Pr⁴⁺离子共存; AFM观测结果表明, 1300 ℃下烧结的样品比1400 ℃下烧结的样品致密; 交流阻抗谱结果表明, Pr掺杂量x=0.05时, Ce_0.9Er_0.05Pr_0.05O_1.95+_δ的电导率最高(σ_{600 ℃}=1.34×10^-2 S/cm, E_a=0.90 eV), 比未掺杂Pr的Ce_0.9Er_0.1O_1.95(σ_{600 ℃}=8.81×10^-3 S/cm, E_a=0.92 eV)提高了52%, 说明在Ce_0.9Er_0.1O_1.95中适量掺杂Pr可提高材料的电导率, 降低活化能.

关键词: 固体电解质, 铒和镨双掺杂氧化铈, 拉曼光谱, X射线光电子能谱, 电导率

Abstract:

The microstructure and electrical conductivity of Ce_0.9Er_0.1-_xPr_xO_1.95+_δ(x=0—0.08) solid electrolytes synthesized by citric sol-gel method were characterized by means of X-ray diffraction(XRD), atomic force microscopy(AFM), Raman, X-ray photoelectron spectroscopy and impedance spectroscopy. XRD measurements show that all the samples calcined at 800 ℃ crystallize in single cubic fluorite structure. The Raman spectra indicate that the Ce_0.9Er_0.05Pr_0.05O_1.95+_δ is cubic fluorite structure with oxygen vacancies. X-ray photoelectron spectroscopy analysis suggest that oxygen vacancies and the mixed valence Pr³⁺ and Pr⁴⁺ions exist in Ce_0.9Er_0.05Pr_0.05O_1.95+_δ. AFM results show that sample Ce_0.9Er_0.05Pr_0.05O_1.95+_δ sintered at 1300 ℃ is denser than that sintered at 1400 ℃. The maximum conductivity of Ce_0.9Er_0.05Pr_0.05O_1.95+_δ is found at x=0.05(σ_{600 ℃}=1.34×10^-2 S/cm, E_a=0.90 eV). The conductivity of Ce_0.9Er_0.05Pr_0.05O_1.95+_δ increases by 52% in comparison with that of Ce_0.9Er_0.1O_1.95without Pr(σ_{600 ℃}=8.81×10^-3 S/cm, E_a=0.92 eV), which suggests that co-doping with appropriate ratio of Pr can further improve the electrical performance of Ce_0.9Er_0.1O_1.95.

Key words: Solid electrolyte, Erbium and praseodymium doped ceria, Raman spectrum, X-ray photoelectron spectroscopy, Conductivity

中图分类号:

O614.33
O646

TrendMD:

林晓敏, 朱丽丽, 韩健, 刘晓梅. 固体电解质Ce_0.9Er_0.1-_xPr_xO_1.95+_δ的微观结构及电性能. 高等学校化学学报, 2015, 36(1): 61.

LIN Xiaomin, ZHU Lili, HAN Jian, LIU Xiaomei. Microstructure and Electrical Properties of Solid Electrolytes Ce_0.9Er_0.1-_xPr_x. Chem. J. Chinese Universities, 2015, 36(1): 61.

图/表 8

Fig.1 XRD patterns of Ce0.9Er0.1-xPrxO1.95+δ (x=0—0.08) powder samples calcined at 800 ℃ x: a. 0; b. 0.02; c. 0.04; d. 0.05; e.0.06; f. 0.08.

Table 1 Lattice parameter, crystal size, electrical conductivity and active energy of Ce0.9Er0.1-xPrxO1.95+δ samples

x of Ce_0.9Er_0.1-_xPr_xO_1.95+_δ	Lattice parameter, a/nm	D/nm	σ/(S·cm^-1)				E_a/eV
x of Ce_0.9Er_0.1-_xPr_xO_1.95+_δ	Lattice parameter, a/nm	D/nm	500 ℃		600 ℃	700 ℃	800 ℃
0	0.54250	42	2.11×10^-3	8.81×10^-3	2.56×10^-2	5.82×10^-2	0.92
0.02	0.54113	43	1.59×10^-3	7.84×10^-3	2.49×10^-2	5.92×10^-2	0.96
0.04	0.54098	44	1.84×10^-3	8.12×10^-3	3.22×10^-2	6.36×10^-2	0.91
0.05	0.54116	45	2.73×10^-3	1.34×10^-2	3.50×10^-2	7.74×10^-2	0.90
0.06	0.54207	40	7.01×10^-4	2.58×10^-3	6.90×10^-3	1.39×10^-2	0.80
0.08	0.54097	39	6.99×10^-4	2.30×10^-2	5.72×10^-3	1.12×10^-2	0.73

Fig.2 AFM images of Ce0.9Er0.05Pr0.05O1.95+δ sintered at 1300 ℃(A) and 1400 ℃(B)

Fig.3 Raman spectra of CeO2(a) and Ce0.9Er0.05Pr0.05O1.95+δ(b)

Fig.4 X-ray photoelectron spectra of Ce0.9Er0.05Pr0.05O1.95+δ (A) O1s; (B) Pr3d.

Fig.5 Impedance spectrum and equivalent circuit model(inset) of Ce0.9Er0.05Pr0.05O1.95+δat 600 ℃

Fig.6 Arrhenius plots of Ce0.9Er0.1-xPrxO1.95+δ sintered at 1300 ℃

Fig.7 Arrhenius plots of Ce0.9Er0.1-xPrxO1.95+δ sintered at 1300 ℃(a) and 1400 ℃(b) (A) x=0.02; (B) x=0.04; (C) x=0.05.

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固体电解质Ce_0.9Er_0.1-_xPr_xO_1.95+_δ的微观结构及电性能

Microstructure and Electrical Properties of Solid Electrolytes Ce_0.9Er_0.1-_xPr_x

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