Sr和Co共掺杂对PrAlO<sub>3</sub>钙钛矿氧化物的结构和电性能的影响

引用本文: 郭银涛, 叶芹, 向军, 徐加焕. Sr和Co共掺杂对PrAlO₃钙钛矿氧化物的结构和电性能的影响[J]. 无机化学学报, 2013, 29(5): 958-964. doi: 10.3969/j.issn.1001-4861.2013.00.155 shu

Citation: GUO Yin-Tao, YE Qin, XIANG Jun, XU Jia-Huan. Effect of Strontium and Cobalt Co-doping on the Structural and Electrical Properties of PrAlO₃ Perovskite Oxides[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(5): 958-964. doi: 10.3969/j.issn.1001-4861.2013.00.155 shu

Sr和Co共掺杂对PrAlO₃钙钛矿氧化物的结构和电性能的影响

通讯作者: 向军,E-mail:junx93@sina.com

基金项目:
国家自然科学基金(No.11204108) (No.11204108)

江苏省高校自然科学基金(No.11KJB430006) (No.11KJB430006)

江苏省普通高校研究生科研创新计划(No.CXLX11-0293) 资助项目。 (No.CXLX11-0293)

摘要: 采用柠檬酸盐法结合高温烧结制备了(Pr,Sr)(Al,Co)O_3-δ系列钙钛矿氧化物导电陶瓷。使用X射线衍射(XRD)、扫描电镜(SEM)和直流四线法等手段对样品的物相、微观结构和电性能进行了表征。结果表明:所制备的Pr_0.9Sr_0.1Al_1-yCoyO_3-δ(y=0.1～0.5)陶瓷均为单相菱方钙钛矿结构,在掺杂范围内其晶胞体积、相对密度和电导率都随Co掺杂量y的增加而增大,但电导率的增幅在逐步减小;所有陶瓷样品在空气中都是氧离子与电子空穴的混合导体,电导行为符合小极化子跳跃机制。对于Pr_1-xSr_xAl_0.5Co_0.5O_3-δ(x=0.1～0.4)陶瓷,当x=0.2时样品有较明显的第二相(Pr,Sr)CoO₃析出,说明Sr在该体系的固溶限在10～20at%之间,而且随着x的进一步增加,(Pr,Sr)CoO₃增多并成为主相;在测量温度范围内,Pr_1-xSr_xAl_0.5Co_0.5O_3-δ的电导率随x的增加大体呈现出一个先增大后减小的变化趋势,在x=0.3附近达到一个最大值,当x≥0.2时还可观察到明显的半导体-金属性转变,且转变温度随x的增加而逐渐降低。

关键词:

共掺杂;PrAlO₃;电性能;混合导体;半导体-金属转变

English

Effect of Strontium and Cobalt Co-doping on the Structural and Electrical Properties of PrAlO₃ Perovskite Oxides

1.
School of Mathematics and Physics, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, China

Corresponding author: 向军,E-mail:junx93@sina.com

Received Date: 25 December 2012
Fund Project:
国家自然科学基金(No.11204108)

江苏省高校自然科学基金(No.11KJB430006)

江苏省普通高校研究生科研创新计划(No.CXLX11-0293) 资助项目。

Abstract: Novel Sr- and Co-codoped (Pr,Sr)(Al,Co)O_3-δ perovskite oxide conducting ceramics were prepared by citrate process combined with subsequent high-temperature sintering. The phase composition, microstructure and electrical properties of the obtained ceramics were characterized by XRD, SEM and direct current four-wire method. The experimental results show that all the as-prepared Pr_0.9Sr_0.1Al_1-yCoyO_3-δ(y=0.1～0.5) ceramics are a single-phase rhombohedral perovskite structure, and their unit cell volumes, relative densities and electrical conductivities increase with increasing y in the doping range, while the increasing rate in electrical conductivity progressively decrease. Furthermore, these samples are a mixed conductor of oxygen ion and hole in air and their electrical conductivities are absolutely dominated by p-type conduction. The temperature dependence of electrical conductivity for Pr_0.9Sr_0.1Al_1-yCoyO_3-δ can be described by the small polaron hopping mechanism. For the as-prepared Pr_1-xSr_xAl_0.5Co_0.5O_3-δ(x=0.1～0.4) ceramics, a second phase (Pr,Sr)CoO₃ obviously precipitates when x=0.2, indicating that the solid solubility limit of Sr on A site in this system is between 10at% and 20at%, and the (Pr, Sr)CoO₃ phase in samples increases gradually and finally becomes the main phase with further increase in Sr content. It is found that the electrical conductivity of Pr_1-xSr_xAl_0.5Co_0.5O_3-δ ceramics roughly exhibits a trend of first increase and then decrease with increasing x in the whole examined temperature range, and reaches the maximum value at around x=0.3. Additionally, the semiconductor-to-metal transition in the conduction behavior is obviously observed for the samples with x≥0.2, and the transition temperature gradually decreases with increasing Sr content.

Key words:

co-doping;PrAlO₃;electrical properties;mixed conductor;semiconductor-metal transition

1. [1] CHEN Yong-Hong(陈永红), WEI Yi-Jun(魏亦军), LIU Xing-Qin(刘杏芹), et al. Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2006,22(1):31-36[1] CHEN Yong-Hong(陈永红), WEI Yi-Jun(魏亦军), LIU Xing-Qin(刘杏芹), et al. Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2006,22(1):31-36
2. [2] SHAO Zong-Ping(邵宗平). Prog. Chem. (Huaxue Jinzhan), 2011, 23(2/3):418-429[2] SHAO Zong-Ping(邵宗平). Prog. Chem. (Huaxue Jinzhan), 2011, 23(2/3):418-429
3. [3] XU Hong-Mei(徐红梅). Mater. Rev. (Cailiao Daobao), 2012,26(7):16-19[3] XU Hong-Mei(徐红梅). Mater. Rev. (Cailiao Daobao), 2012,26(7):16-19
4. [4] Yin Y M, Xiong M W, Yang N T, et al. Int. J. Hydrogen. Energy, 2011,36:3989-3996[4] Yin Y M, Xiong M W, Yang N T, et al. Int. J. Hydrogen. Energy, 2011,36:3989-3996
5. [5] Park S, Choi S H, Shin J Y, et al. J. Power Sources, 2012, 210:172-177[5] Park S, Choi S H, Shin J Y, et al. J. Power Sources, 2012, 210:172-177
6. [6] Choi S H, Yoo S, Shin J Y, et al. J. Electrochem. Soc., 2011,158(8):B995-B999[6] Choi S H, Yoo S, Shin J Y, et al. J. Electrochem. Soc., 2011,158(8):B995-B999
7. [7] Guo Y, Shi H, Ran R, et al. J. Hydrogen. Energy, 2009,34: 9496-9504[7] Guo Y, Shi H, Ran R, et al. J. Hydrogen. Energy, 2009,34: 9496-9504
8. [8] Baek S W, Bae J, Yoo Y S. J. Power Sources, 2009,193:431- 440[8] Baek S W, Bae J, Yoo Y S. J. Power Sources, 2009,193:431- 440
9. [9] Meng X W, Lü S Q, Ji Y, et al. J. Power Sources, 2008, 183:581-585[9] Meng X W, Lü S Q, Ji Y, et al. J. Power Sources, 2008, 183:581-585
10. [10] Torres-Garibay C, Kovar D, Manthiram A. J. Power Sources, 2009,187:480-486[10] Torres-Garibay C, Kovar D, Manthiram A. J. Power Sources, 2009,187:480-486
11. [11] Ren Y Z, Li B A, Wang J Y, et al. J. Solid State Chem., 2004,177:3977-3980[11] Ren Y Z, Li B A, Wang J Y, et al. J. Solid State Chem., 2004,177:3977-3980
12. [12] YANG Nai-Tao(杨乃涛), FENG Liu(冯柳), TAN Xiao-Yao (谭小耀), et al. Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2005,21(11):1623-1626[12] YANG Nai-Tao(杨乃涛), FENG Liu(冯柳), TAN Xiao-Yao (谭小耀), et al. Chinese J. Inorg. Chem. (Wuji Huaxue Xuebao), 2005,21(11):1623-1626
13. [13] Lee K T, Manthiram A. J. Electrochem. Soc., 2006,153(4): A794-A798[13] Lee K T, Manthiram A. J. Electrochem. Soc., 2006,153(4): A794-A798
14. [14] Zhu C J, Liu X M, Xu D, et al. J. Power Sources, 2008, 185:212-216[14] Zhu C J, Liu X M, Xu D, et al. J. Power Sources, 2008, 185:212-216
15. [15] Fu Q X, Tietz F, Lersch P, et al. Solid State Ionics, 2006, 177:1059-1069[15] Fu Q X, Tietz F, Lersch P, et al. Solid State Ionics, 2006, 177:1059-1069
16. [16] Tsipis E V, Kharton V V, Waerenborgh J C, et al. J. Alloys Compd., 2006,413:244-250[16] Tsipis E V, Kharton V V, Waerenborgh J C, et al. J. Alloys Compd., 2006,413:244-250
17. [17] XIANG Jun(向军), GUO Ying-Tao(郭银涛), CHU Yan-Qiu (褚艳秋), et al. Acta Phys. Sin. (Wuli Xuebao), 2011,60(2): 027203[17] XIANG Jun(向军), GUO Ying-Tao(郭银涛), CHU Yan-Qiu (褚艳秋), et al. Acta Phys. Sin. (Wuli Xuebao), 2011,60(2): 027203
18. [18] XIANG Jun(向军), GUO Ying-Tao(郭银涛), ZHOU Guang- Zhen(周广振), et al. Acta Phys. Sin. (Wuli Xuebao), 2012, 61(22): 227201[18] XIANG Jun(向军), GUO Ying-Tao(郭银涛), ZHOU Guang- Zhen(周广振), et al. Acta Phys. Sin. (Wuli Xuebao), 2012, 61(22): 227201
19. [19] Ishihara T. Perovskite Oxide for Solid Oxide Fuel Cells. New York: Springer, 2009:68-69[19] Ishihara T. Perovskite Oxide for Solid Oxide Fuel Cells. New York: Springer, 2009:68-69
20. [20] XU Jia-Huan(徐加焕), HUANG Xi-Qiang(黄喜强), LV Zhe (吕喆), et al. Acta Chim. Sin. (Huaxue Xuebao), 2006,64(5): 449- 452[20] XU Jia-Huan(徐加焕), HUANG Xi-Qiang(黄喜强), LV Zhe (吕喆), et al. Acta Chim. Sin. (Huaxue Xuebao), 2006,64(5): 449- 452
21. [21] XU Qing(徐庆), HUANG Duan-Ping(黄端平), CHEN Wen (陈文), et al. J. Chinese Rare Earth Soc. (Zhongguo Xitu Xuebao), 2003,21(5):541-545[21] XU Qing(徐庆), HUANG Duan-Ping(黄端平), CHEN Wen (陈文), et al. J. Chinese Rare Earth Soc. (Zhongguo Xitu Xuebao), 2003,21(5):541-545
22. [22] Kostogloudis G Ch, Ftikos Ch. J. Eur. Ceram. Soc., 2007, 27:273-277[22] Kostogloudis G Ch, Ftikos Ch. J. Eur. Ceram. Soc., 2007, 27:273-277
23. [23] Basu S, Chakraborty A, Devi P S, et al. J. Am. Ceram. Soc., 2005,88:2110-2113[23] Basu S, Chakraborty A, Devi P S, et al. J. Am. Ceram. Soc., 2005,88:2110-2113
24. [24] Kostogloudis G Ch, Vasilakos N, Ftikos Ch. Solid State Ionics, 1998,106:207-218[24] Kostogloudis G Ch, Vasilakos N, Ftikos Ch. Solid State Ionics, 1998,106:207-218
25. [25] Fu Q X, Xu Z Y, Peng D K, et al. J. Mater. Sci., 2003,38: 2901-2906[25] Fu Q X, Xu Z Y, Peng D K, et al. J. Mater. Sci., 2003,38: 2901-2906

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Sr和Co共掺杂对PrAlO₃钙钛矿氧化物的结构和电性能的影响

通讯作者: 向军,E-mail:junx93@sina.com

English

Effect of Strontium and Cobalt Co-doping on the Structural and Electrical Properties of PrAlO₃ Perovskite Oxides

Corresponding author: 向军,E-mail:junx93@sina.com

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Sr和Co共掺杂对PrAlO3钙钛矿氧化物的结构和电性能的影响

通讯作者: 向军,E-mail:junx93@sina.com

English

Effect of Strontium and Cobalt Co-doping on the Structural and Electrical Properties of PrAlO3 Perovskite Oxides

Corresponding author: 向军,E-mail:junx93@sina.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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Sr和Co共掺杂对PrAlO₃钙钛矿氧化物的结构和电性能的影响

Effect of Strontium and Cobalt Co-doping on the Structural and Electrical Properties of PrAlO₃ Perovskite Oxides

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