Studies on synthesis of mixed ion conducting ceramics and their applications

混合离子导电陶瓷的合成及其应用研究

• 批准号: 05453084
• 负责人: IWAHARA Hiroyasu
• 金额: $ 4.8万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453084/
• 关键词: Ionic conduction; Protonic conduction; Perovskite-type oxide; Membrane reactor; Fuel cell; Chemical cogeneration; 導電率; 燃料電池; 電気化学的反応器

Perovskite-type oxide solid solutions based on BaCeO_3 were synthesized and their ceramics were studied with respect to their ionic conduction at elevated temperatures. Partial substitution of trivalent cations for Ce in BaCeO_3 made the resultant oxide ceramic a mixed ionic conductor of protons and oxide ions under fuel cell condition (H_2/Air). Change in conductivity with ionic radius r of dopant cation was investigated. It was found that the maximum conductivity lay on about r = 0.90-0.95A and that the contribution of oxide ion conduction to the total ionic conductivity under fuel cell condition became marked as the ionic radius grew larger. When BaCeO_3 is doped with divalent cation, both the protonic and oxide ionic conductivities were observed to decrease. Using a temperature programd water vapor desorption experiment and an electrochemical tracer experiment of hydrogen isotope, it could be clarified that low protonic conductivity of the oxide doped with divalent cation was ascribed to small content of proton and its low mobility compared to those in trivalent doped specimens.These mixed ionic conductors were verified experimentally to be applied to an electrochemical membrane reactor for ethylene production form ethane, a chemical reactor for C_2-hydrocarbon production from methane and a fuel cell for chemical cogeneration which could produce both chemical products and electric power.

合成了BaCeO_3基钙钛矿型氧化物固溶体，研究了其陶瓷的高温离子导电性能。在燃料电池（H_2/Air）条件下，部分三价阳离子取代BaCeO_3中的Ce，使氧化物陶瓷成为质子和氧离子的混合离子导体。研究了电导率随掺杂剂阳离子离子半径r的变化。结果表明，电导率在r = 0.90-0.95A之间达到最大值，且随着离子半径的增大，氧离子电导对总电导率的贡献也越来越大。当BaCeO_3中掺杂二价阳离子时，其质子电导率和氧化物离子电导率均降低。通过程序升温水蒸气脱附实验和氢同位素电化学示踪实验，证实了二价阳离子掺杂氧化物的低质子电导率是由于其质子含量少和迁移率低所致，并将其应用于乙烷制乙烯的电化学膜反应器中。一种由甲烷生产C_2烃的化学反应器和一种既能生产化学产品又能发电的化学联产燃料电池。

项目成果

H.Iwahara: "Effect of Ionic Radii of Dopants on Mixed Ionic Conduction (H^++O^<2->) in BaCeO_3-based Electrolytes" Solid State Ionics. Vol.70/71. 267-271 (1994)

H.Iwahara：“掺杂剂离子半径对 BaCeO_3 基电解质中混合离子传导 (H^O^<2->) 的影响”固态离子学。

H.Itoh: "Microstructural Control of Boundary Region Between CVD Diamond Film and Cemented Carbides Substrates" J.Mater.Sci. Vol.29. 1404-1410 (1994)

H.Itoh：“CVD 金刚石薄膜和硬质合金基材之间边界区域的微观结构控制”J.Mater.Sci。

H.Iwahara: "Effect of Ionic Radii of Dopants on Mixed Ionic Conduction(H^++O^<2->) in BaCeO_3‐based Electrolytes" Solid State Ionics. 70/71. 267-271 (1994)

H.Iwahara：“掺杂剂的离子半径对 BaCeO_3 基电解质中混合离子传导 (H^++O^<2->) 的影响”固态离子学 70/71 (1994)。

T.Hibino: "Recycling of Carbon Dioxide Using Proton Conductor as a Solid Electrolyte" J.Appl.Electrochem.24. 126-130 (1994)

T.Hibino：“使用质子导体作为固体电解质回收二氧化碳”J.Appl.Electrochem.24。

日比野高士: "固体電解質をメンブレンリアクターに用いたエタンの脱水素" 日本化学会誌. 1993. 238-242 (1993)

Takashi Hibino：“在膜反应器中使用固体电解质进行乙烷脱氢”日本化学会杂志 1993 年。238-242 (1993)。