Development of super high temperature-type proton conductor based on alpha alumina.

基于α氧化铝的超高温型质子导体的开发。

• 批准号: 13450308
• 负责人: FUKATSU Norihiko
• 金额: $ 9.47万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450308/
• 关键词: alpha-alumina; proton conduction; hydrogen solubility; solid electrolyte; hydrogen sensor; Proton conductor; hydrogen concentration cell; OH stretching vibration; プロトン電導; スピネル

Firstly, the most appropriate dopant for incorporation of hydrogen was studied using single crystal of alpha alumina. With the measurements of IR absorption of OH stretching vibration, the magnesium is found most effective dopant among Mg,Ni,Co, and Ti. In order to improve the low yield of crystal growth due to the thermal stress, the additions of Cr,Y,B,Sm,Nd,La,Ce as the second dopant were examined. However, the any explicit improvements were not obtained.The location of the incorporated hydrogen in the crystal structure of alpha-alumina was investigated with the Mg doped samples. The polarization angle dependency of the absorption of OH stretching vibration was examined for several sets of the directions of the incident beam and crystal faces. The comparison between the measurement and the theoretically calculated results showed that hydrogen is located between one of the 0-0 bond constituting the edges of oxygen octahedron in the corundum structure with making the hydrogen bond. Am … More ong the four 0-0 bonds of different spacing, one whose spacing is 272 pm is found preferred for hydrogen location. The same tendency was observed for Ti doped alpha-alumina.The H/D isotope effect of electrical conductivity was examined for Mg doped single crystal samples. The proton was confirmed to be the most dominant charge carrier in the low oxygen potentials region. The anisotropy was observed also in the electrical conduction. The conductivity was higher when the direction of the electric field is perpendicular to c-axis than pararell, which was reasonably explained by the preference of hydrogen location among the O-O bonds.As the Mg was found to be the most appropriate dopant, the electrochemical properties were studied with the commercially supplied polycrystalline- alumina tube whose main impurities were magnesium. The emf of the hydrogen concentration cells using these tubes as the electrolyte were measured for various hydrogen and oxygen potential gradients. These values were analyzed theoretically based on the model of the crystal defects and the equation between the emf of the cell and the potentials difference on the electrodes was derived. The parameter appeared in the equation was determined as a function of the temperature.The electrochemical properties of magnesium-aluminate spinel which is almost always the co-existing phase of Mg-doped polycrystalline -alumina were also studied to know the effect of second phase on the properties of the proton conduction. It was confirmed that hydrogen might be incorporated into magnesium-aluminate spinel as proton and that the it was movable. However, the conductivity due to magnesium ion was found far higher and the contribution of proton to the electrical conductivity could be ignored. Less

首先，使用α氧化铝的单晶研究了最合适的氢掺杂剂。随着OH拉伸振动的IR吸收的测量，发现镁在Mg，Ni，Co和Ti中最有效的掺杂剂。为了提高由于热应力而提高晶体生长的低产量，研究了CR，Y，B，SM，ND，LA，CE的添加为第二个掺杂剂。但是，未获得任何明确的改进。使用MG掺杂样品研究了掺入氢的位置。检查了入射梁和晶体面的几组方向的OH拉伸振动的抽象的极化角度依赖性。测量和理论计算结果之间的比较表明，氢位于0-0键之间，该键是由刚毛结构中的氧气八面体的边缘组成的，并使氢键产生氢键。 AM…更多关于不同间距的四个0-0键的更多信息，该键的间距为272 pm是氢位置的首选。观察到Ti掺杂的α-铝的趋势相同。检查了电导率的H/D同位素效应，用于MG掺杂的单晶样品。质子被确认为低氧电位区域中最主的电荷载体。在电导传导中也观察到各向异性。当电场的方向垂直于C轴高于Pararell时，电导率高于Pararell，这是通过在O-O键中偏爱氢位置来合理地解释的。由于发现MG是最合适的毒剂，因此电化学性质是在社会上提供的多型铝粉Tube and Impagriim with Maggurium with Mimprise waysmagriim waysmagrium with Maggrium waysmagrium ways immpains with Mimprim ways impagn的。使用这些管作为电解质的氢浓度细胞的EMF测量各种氢和氧势梯。根据晶体缺陷的模型和细胞EMF之间的方程和电极上的潜在差异，对这些值进行了分析。该参数出现在方程式中是根据温度的函数确定的。还研究了MG掺杂的多晶 - 氧化铝的共存相位的镁铝酸酯的电化学性能，还研究了第二相对第二相对Proton传导性能的影响。已经证实，可以将氢作为质子掺入镁氧尖晶石中，并且它是可移动的。但是，发现由于镁离子引起的电导率较高，并且可以忽略质子对电导率的贡献。较少的

项目成果

奥山勇治, 栗田典明, 武津典彦: "アルミナ過剰の不定比マグネシウム・アルミネートスピネルの欠陥構造"固体イオニクス討論会講演要旨集. 29. 152-153 (2003)

Yuji Okuyama、Noriaki Kurita、Norihiko Taketsu：“含过量氧化铝的非化学计量铝酸镁尖晶石的缺陷结构”固态离子研讨会摘要 29. 152-153 (2003)。

N.Fukatsu et al.: "Incorporation of Hydrogen into Magnesium Doped α-alumina"Extended Abstract of 11^<th> International Conference on Solid State Protonic Conductors. PA2 (2002)

N.Fukatsu 等人：“Incorporation of Hydrogen into Magnesium Doped α-alumina”Extend Abstract of 11^<th>International Conference on Solid State Protonic Conductors (2002)。

栗田典明, 堀田和宏, 武津典彦: "アルミナ表面酸化膜の電気化学的特性"日本金属学会講演概要. 134(発表予定). (2004)

Noriaki Kurita、Kazuhiro Hotta、Norihiko Taketsu：“氧化铝表面氧化膜的电化学性质”日本金属研究所的演讲摘要 134（即将发表）。

N.Kurita et al.: "Hydrogen Concentration Cell using α-Alumina as a Solid Electrolyte"Extended Abstract of 11^<th> International Conference on Solid State Protonic Conductors. PA3 (2002)

N.Kurita 等人：“使用 α-氧化铝作为固体电解质的氢浓缩池”第 11 届固体质子导体国际会议的扩展摘要 (2002)。

N.Fukatsu et al.: "Incorporation of Hydrogen into Magnesium Aluminate Spinel"Solid State Ionics. 152-153C. 809-817 (2002)

N.Fukatsu 等人：“将氢掺入镁铝尖晶石”固态离子学。