Ba3Ca1+xNb2−xO9−δ复合钙钛矿型固体电解质性能研究

丁玉石; 厉英

doi:10.13374/j.issn2095-9389.2020.12.03.003

Ba₃Ca_1+xNb_2−xO_9−δ复合钙钛矿型固体电解质性能研究

doi: 10.13374/j.issn2095-9389.2020.12.03.003

丁玉石^{1, 2},
厉英^{1, 2, ,}

1.
东北大学冶金学院，沈阳 110819
2.
辽宁省冶金传感器材料及技术重点实验室，沈阳 110819

基金项目: 国家自然科学基金资助项目（51774076，51834004，51704063）

详细信息

通讯作者:
E-mail：liying@mail.neu.edu.cn

中图分类号: TF01；O77
计量
- 文章访问数: 134
- HTML全文浏览量: 70
- PDF下载量: 10
- 被引次数: 0
出版历程
- 收稿日期: 2020-12-03
- 网络出版日期: 2021-03-13
- 刊出日期: 2021-08-25

Transport properties of Ba₃Ca_1+xNb_2−xO_9−δ composite perovskite oxides

DING Yu-shi^{1, 2},
LI Ying^{1, 2
, ,}

1.
School of Metallurgy, Northeastern University, Shenyang 110819, China
2.
Liaoning Key Laboratory for Metallurgical Sensor Materials and Technology, Shenyang 110819, China

More Information

Corresponding author: E-mail: liying@mail.neu.edu.cn

摘要

摘要: 高温质子导体固体电解质Ba₃Ca_1+xNb_2−xO_9−δ化学性质稳定，中低温电导率较高，具有较好的应用前景。采用固相合成法制备得到了复合钙钛矿相的Ba₃Ca_1+xNb_2−xO_9−δ（x=0、0.10、0.18、0.30）材料。随着Ca掺杂量的增加Ba₃Ca_1+xNb_2−xO_9−δ样品的电导率先增加后降低，x=0.18的样品电导率最高。Ba₃Ca_1+xNb_2−xO_9−δ材料在含氢中的电子空穴迁移数较低，当温度低于750 ℃时，材料中质子导电为主；当温度达800 ℃后，材料中氧离子导电为主。x=0.10的样品质子迁移数最高，随着掺杂量的增加样品氧离子迁移数逐渐增大，质子迁移数逐渐降低。
- 质子导体 /
- 钙钛矿 /
- 电导率 /
- 载流子 /
- 迁移数
Abstract: ABO₃-type perovskite oxides and A₃B′B′′₂O₉-type composite perovskite oxides exhibit proton conduction from 200 ℃ to 1000 ℃. These high-temperature proton conductors have received considerable attention due to their promise as electrolytes in fuel cells, electrolytic hydrogen production, hydrogen separation, electrochemical reactors, sensors, etc. The Ba₃Ca_1+xNb_2−xO_9−δ composite perovskite-type solid electrolyte has stable chemical properties and corrosion resistance to CO₂ and H₂O, so it can be used in long-term electrochemical devices. Protons are incorporated into Ba₃Ca_1+xNb_2−xO_9−δ in a humid or hydrogen-containing atmosphere because of the reaction of H₂O and oxygen vacancies in proton conductors. However, proton conductors also exhibit oxygen vacancy conduction in the high-temperature range. In addition, electron holes can be generated by an oxygen vacancy reaction with atmospheric oxygen, causing proton conductors to exhibit electron-hole conduction. Hence, more oxygen vacancies can be produced with more Ca²⁺ dopant in Ba₃Ca_1+xNb_2−xO_9−δ due to a lack of positive charge. Meanwhile, the proton and electron-hole concentrations increase with oxygen vacancies, and the conductivity of Ba₃Ca_1+xNb_2−xO_9−δ can be improved. However, the crystal structure of Ba₃Ca_1+xNb_2−xO_9−δ can be changed with Ca²⁺ doping, and changes in proton, oxygen vacancy, and electron-hole transport numbers, the ratio of protons, oxygen vacancies, and electron-hole conductivity to total conductivity respectively, are unknown with Ca²⁺ doping, with different effects of crystal structure for protons, oxygen vacancies, and electron-hole conduction. Ba₃Ca_1+xNb_2−xO_9−δ has high conductivity in a humid atmosphere, and the proton transport number with doping amount needs to be further studied. In this work, Ba₃Ca_1+xNb_2−xO_9−δ (x=0, 0.10, 0.18, and 0.30) with a composite perovskite phase was prepared using a solid-state reaction method. With the increase in Ca²⁺ doping amount, the conductivity of Ba₃Ca_1+xNb_2−xO_9−δ samples first increased and then decreased, and the conductivity of the sample with x=0.18 was the highest. The electron-hole transport number of Ba₃Ca_1+xNb_2−xO_9−δ under the atmosphere containing hydrogen was relatively low. Protons were mainly conductive carriers in Ba₃Ca_1+xNb_2−xO_9−δ below 750 ℃, while Ba₃Ca_1+xNb_2−xO_9−δ exhibited mainly oxygen vacancy conduction at 800 ℃. With the increase in dopant amount, the oxygen vacancy transport number of Ba₃Ca_1+xNb_2−xO_9−δ increased gradually, while the proton transport number decreased gradually.
- proton conductor /
- perovskite /
- conductivity /
- carriers /
- transport number

HTML全文

图 1 在1600 ℃烧结10 h后的Ba₃Ca_1+xNb_2−xO_9−δ（x=0、0.10、0.18、0.30）样品的XRD图

Figure 1. XRD pattern of Ba₃Ca_1+xNb_2−xO_9−δ (x=0, 0.10, 0.18, and 0.30) specimen, sintered at 1600 ℃ for 10 h

下载: 全尺寸图片幻灯片

图 2 Ba₃Ca_1+xNb_2−xO_9−δ（x=0、0.10、0.18、0.30）样品的电导率随温度变化曲线

Figure 2. Temperature‒dependent conductivity of Ba₃Ca_1+xNb_2−xO_9−δ (x=0, 0.10, 0.18, and 0.30) specimen

下载: 全尺寸图片幻灯片

图 3 Ba₃Ca_1.18Nb_1.82O_9−δ样品的电导率随氧分压的变化曲线。（a）$ {P_{{{\rm{H}}_2}{\rm{O}}}}$=0.62 kPa；（b）$ {P_{{{\rm{H}}_2}{\rm{O}}}}$=3.17 kPa

Figure 3. Oxygen partial pressure‒dependent conductivity of Ba₃Ca_1.18Nb_1.82O_9−δ: (a) $ {P_{{{\rm{H}}_2}{\rm{O}}}}$=0.62 kPa; (b) $ {P_{{{\rm{H}}_2}{\rm{O}}}}$=3.17 kPa

下载: 全尺寸图片幻灯片

图 4 含氢气氛中Ba₃Ca_1+xNb_2−xO_9−δ（x=0、0.10、0.18、0.30）样品的载流子迁移数随温度变化曲线

Figure 4. Change in the proton, oxygen vacancy, and hole transport numbers of Ba₃Ca_1+xNb_2−xO_9−δ (x=0, 0.10, 0.18, and 0.30) in Ar−2%H₂

下载: 全尺寸图片幻灯片

参考文献(25)

[1]	Kreuer K D. Proton-conducting oxides. Annu Rev Mater Res, 2003, 33(1): 333 doi: 10.1146/annurev.matsci.33.022802.091825
[2]	Marthinsen A, Wahnström G. Percolation transition in hole-conducting acceptor-doped Barium zirconate. Chem Mater, 2020, 32(13): 5558 doi: 10.1021/acs.chemmater.0c00515
[3]	Zhang J Y, Zhang Z T. Solid electrolyte based on perovskite-type BaCeO₃ and SrCeO₃. J Univ Sci Technol Beijing, 2000, 22(3): 249 doi: 10.3321/j.issn:1001-053X.2000.03.016 张俊英, 张中太. BaCeO₃和SrCeO₃基钙钛矿型固体电解质. 北京科技大学学报, 2000, 22(3):249 doi: 10.3321/j.issn:1001-053X.2000.03.016
[4]	Zheng M H, Zhen X X, Zhao Z G. Preparation and characterization of Yb doped SrCeO₃ based high temperature proton conductor. J Univ Sci Technol Beijing, 1993, 15(3): 310 郑敏辉, 甄秀欣, 赵志刚. SrCeO₃基高温质子导体的制备与性能测定. 北京科技大学学报, 1993, 15(3):310
[5]	Zhou Y, Guan X, Zhou H, et al. Strongly correlated perovskite fuel cells. Nature, 2016, 534(7606): 231 doi: 10.1038/nature17653
[6]	Bi L, Da'As E H, Shafi S P. Proton-conducting solid oxide fuel cell (SOFC) with Y-doped BaZrO₃ electrolyte. Electrochem Commun, 2017, 80: 20 doi: 10.1016/j.elecom.2017.05.006
[7]	Xie D, Ling A, Yan D, et al. A comparative study on the composite cathodes with proton conductor and oxygen ion conductor for proton-conducting solid oxide fuel cell. Electrochimica Acta, 2020, 344: 136143 doi: 10.1016/j.electacta.2020.136143
[8]	Tong Y C, Wang Y, Cui C S, et al. Preparation and characterization of symmetrical protonic ceramic fuel cells as electrochemical hydrogen pumps. J Power Sources, 2020, 457: 228036 doi: 10.1016/j.jpowsour.2020.228036
[9]	Ishiyama T, Kishimoto H, Develos-Bagarinao K, et al. Correlation between dissolved protons in nickel-doped BaZr_0.1Ce_0.7Y_0.1 Yb_0.1O_3−δ and its electrical conductive properties. Inorg Chem, 2017, 56(19): 11876 doi: 10.1021/acs.inorgchem.7b01875
[10]	Tong Y C, Meng X, Luo T, et al. Protonic ceramic electrochemical cell for efficient separation of hydrogen. ACS Appl Mater Interfaces, 2020, 12(23): 25809 doi: 10.1021/acsami.0c04024
[11]	Montaleone D, Mercadelli E, Escolástico S, et al. All-ceramic asymmetric membranes with superior hydrogen permeation. J Mater Chem A, 2018, 6(32): 15718 doi: 10.1039/C8TA04764B
[12]	Morejudo S H, Zanón R, Escolástico S, et al. Direct conversion of methane to aromatics in a catalytic co-ionic membrane reactor. Science, 2016, 353(6299): 563 doi: 10.1126/science.aag0274
[13]	Li Y, Wang C Z, Zhang Z L, et al. A hydrogen sensor using SrCe_0.95Yb_0.05O_3−α as proton conductor and YH_x+YH_2−z as reference electrode for determining hydrogen pressure in solid steel. J Mater Sci Technol, 2010, 26(10): 957 doi: 10.1016/S1005-0302(10)60155-7
[14]	Kalyakin A S, Lyagaeva J G, Chuikin A Y, et al. A high-temperature electrochemical sensor based on CaZr_0.95Sc_0.05O_3−δ for humidity analysis in oxidation atmospheres. J Solid State Electrochem, 2019, 23(1): 73 doi: 10.1007/s10008-018-4108-7
[15]	Ju L C, L Y, Man W K, et al. Preparation and property of silicon sensor auxiliary electrodes based on the CaF₂—SiO₂ system. Chin J Eng, 2016, 38(4): 476 鞠靓辰, 李杨, 满文宽, 等. CaF₂—SiO₂型硅传感器辅助电极的制备及其定硅性能. 工程科技学报, 2016, 38(4):476
[16]	Zhu Z W, Guo E Y, Wei Z L, et al. Tailoring Ba₃Ca_1.18Nb_1.82O_9−δ with NiO as electrolyte for proton-conducting solid oxide fuel cells. J Power Sources, 2018, 373: 132 doi: 10.1016/j.jpowsour.2017.10.091
[17]	Jaiswal S K, Yoon K J, Son J W, et al. Synthesis and investigation on stability and electrical conductivity of Ti-doped Ba₃CaTa_2−xTi_xO₉ (0≤x≤1.0) complex oxides. J Alloys Compd, 2019, 775: 736 doi: 10.1016/j.jallcom.2018.10.185
[18]	Wang S W, Chen Y, Fang S M, et al. Novel chemically stable Ba₃Ca_1.18Nb_1.82−xY_xO_9−δ proton conductor: Improved proton conductivity through tailored cation ordering. Chem Mater, 2014, 26(6): 2021 doi: 10.1021/cm403684b
[19]	Ananyev M V, Farlenkov A S, Kurumchin E K. Isotopic exchange between hydrogen from the gas phase and proton-conducting oxides: Theory and experiment. Int J Hydrog Energy, 2018, 43(29): 13373 doi: 10.1016/j.ijhydene.2018.05.150
[20]	Sažinas R, Einarsrud M A, Grande T. Toughening of Y-doped BaZrO₃ proton conducting electrolytes by hydration. J Mater Chem A, 2017, 5(12): 5846 doi: 10.1039/C6TA11022C
[21]	Bohn H G, Schober T, Mono T, et al. The high temperature proton conductor Ba₃Ca_1.18Nb_1.82O_9−δ. I. Electrical conductivity. Solid State Ionics, 1999, 117(3-4): 219 doi: 10.1016/S0167-2738(98)00420-2
[22]	Liang K C, Du Y, Nowick A S. Fast high-temperature proton transport in nonstoichiometric mixed perovskites. Solid State Ionics, 1994, 69(2): 117 doi: 10.1016/0167-2738(94)90399-9
[23]	Ding Y S, Li Y, Huang W L. Influence of grain interior and grain boundaries on transport properties of scandium-doped calcium zirconate. J Am Ceram Soc, 2020, 103(4): 2653 doi: 10.1111/jace.16968
[24]	Ding Y S, Li Y, Zhang C J, et al. Effect of grain interior and grain boundaries on transport properties of Sc-doped CaHfO₃. J Alloys Compd, 2020, 834: 155126 doi: 10.1016/j.jallcom.2020.155126
[25]	Frade J R. Theoretical behaviour of concentration cells based on ABO₃ perovskite materials with protonic and oxygen ion conduction. Solid State Ionics, 1995, 78(1-2): 87 doi: 10.1016/0167-2738(95)00008-T