Transport properties of Ba3Ca1+xNb2?xO9?δ composite perovskite oxides

DING Yu-shi; LI Ying

doi:10.13374/j.issn2095-9389.2020.12.03.003

Volume 43 Issue 8

Aug. 2021

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DING Yu-shi, LI Ying. Transport properties of Ba3Ca1+xNb2?xO9?δ composite perovskite oxides[J]. Chinese Journal of Engineering, 2021, 43(8): 1032-1036. doi: 10.13374/j.issn2095-9389.2020.12.03.003

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DING Yu-shi, LI Ying. Transport properties of Ba₃Ca_1+xNb_2?xO_9?δ composite perovskite oxides[J]. Chinese Journal of Engineering, 2021, 43(8): 1032-1036. doi: 10.13374/j.issn2095-9389.2020.12.03.003

DING Yu-shi, LI Ying. Transport properties of Ba3Ca1+xNb2?xO9?δ composite perovskite oxides[J]. Chinese Journal of Engineering, 2021, 43(8): 1032-1036. doi: 10.13374/j.issn2095-9389.2020.12.03.003

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

doi: 10.13374/j.issn2095-9389.2020.12.03.003

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
Received Date: 2020-12-03
Available Online: 2021-03-13
Publish Date: 2021-08-25

Abstract

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

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References(25)

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