工程科学学报.第43卷.第8期：1032-1036.2021年8月 Chinese Journal of Engineering,Vol.43,No.8:1032-1036,August 2021 https://doi.org/10.13374/j.issn2095-9389.2020.12.03.003;http://cje.ustb.edu.cn Ba3Ca1+xNb2-xOg-s复合钙钛矿型固体电解质性能研究 丁玉石2)，厉 英1,2)四 1)东北大学治金学院.沈阳1108192)辽宁省治金传感器材料及技术重点实验室，沈阳110819 ☒通信作者，E-mail:liying@mail.neu.edu.cn 摘要高温质子导体固体电解质Ba3Ca1+rNb2-Og-s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Ba3Ca1+Nb2-Og-(x=0、0.10、0.18、0.30)材料.随着Ca掺杂量的增加BaCa1+Nb2-Og-s样 品的电导率先增加后降低，x=0.18的样品电导率最高.Ba,Ca1+Nb2-Og-s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 关键词质子导体：钙钛矿：电导率：载流子：迁移数 分类号TF01:077 Transport properties of Ba3Ca+xNb2-Oo-s composite perovskite oxides DING Yu-shi2),LI Ying2 1)School of Metallurgy,Northeastern University,Shenyang 110819,China 2)Liaoning Key Laboratory for Metallurgical Sensor Materials and Technology,Shenyang 110819,China Corresponding author,E-mail:liying@mail.neu.edu.cn ABSTRACT ABO3-type perovskite oxides and A3B'B"2O-type composite perovskite oxides exhibit proton conduction from 200 C to 1000 C.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 BaCaNb2-Os 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 Ba CaNbin 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 Ca dopant in Ba CaNb2O due to a lack of positive charge.Meanwhile,the proton and electron-hole concentrations increase with oxygen vacancies,and the conductivity of Ba CaNb2Ocan be improved.However,the crystal structure of BaCaNb2O can be changed with Cadoping,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 Cadoping,with different effects of crystal structure for protons,oxygen vacancies,and electron-hole conduction.Ba CaNbhas high conductivity in a humid atmosphere,and the proton transport number with doping amount needs to be further studied.In this work,BaCaNb2O(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 Ca doping amount,the conductivity of Ba CaNbsamples first increased and then decreased,and the conductivity of the sample with x=0.18 was the highest.The electron-hole transport number of Ba;Ca+Nb2_0o under the atmosphere containing hydrogen was 收稿日期：2020-12-03 基金项目：国家自然科学基金资助项目(51774076.51834004,51704063)Ba3Ca1+xNb2−xO9−δ 复合钙钛矿型固体电解质性能研究 丁玉石1,2)，厉    英1,2) 苣 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 苣通信作者，E-mail：liying@mail.neu.edu.cn 摘    要    高温质子导体固体电解质 Ba3Ca1+xNb2−xO9−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 Ba3Ca1+xNb2−xO9−δ（x=0、0.10、0.18、0.30）材料. 随着 Ca 掺杂量的增加 Ba3Ca1+xNb2−xO9−δ 样 品的电导率先增加后降低，x=0.18 的样品电导率最高. Ba3Ca1+xNb2−xO9−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. 关键词    质子导体；钙钛矿；电导率；载流子；迁移数 分类号    TF01；O77 Transport properties of Ba3Ca1+xNb2−xO9−δ composite perovskite oxides DING Yu-shi1,2) ，LI Ying1,2) 苣 1) School of Metallurgy, Northeastern University, Shenyang 110819, China 2) Liaoning Key Laboratory for Metallurgical Sensor Materials and Technology, Shenyang 110819, China 苣 Corresponding author, E-mail: liying@mail.neu.edu.cn 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  Ba3Ca1+xNb2−xO9−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 Ba3Ca1+xNb2−xO9−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 Ba3Ca1+xNb2−xO9−δ due  to  a  lack  of  positive  charge.  Meanwhile,  the  proton  and  electron-hole  concentrations  increase  with  oxygen vacancies,  and  the  conductivity  of  Ba3Ca1+xNb2−xO9−δ can  be  improved.  However,  the  crystal  structure  of  Ba3Ca1+xNb2−xO9−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.  Ba3Ca1+xNb2−xO9−δ has  high  conductivity  in  a  humid atmosphere, and the proton transport number with doping amount needs to be further studied. In this work, Ba3Ca1+xNb2−xO9−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 Ba3Ca1+xNb2−xO9−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 Ba3Ca1+xNb2−xO9−δ under the atmosphere containing hydrogen was 收稿日期: 2020−12−03 基金项目: 国家自然科学基金资助项目（51774076，51834004，51704063） 工程科学学报，第 43 卷，第 8 期：1032−1036，2021 年 8 月 Chinese Journal of Engineering, Vol. 43, No. 8: 1032−1036, August 2021 https://doi.org/10.13374/j.issn2095-9389.2020.12.03.003; http://cje.ustb.edu.cn