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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。

基本信息

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

项目摘要

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氧化铝单晶研究了最适合掺入氢的掺杂剂。通过OH伸缩振动的红外吸收测量，发现镁是Mg、Ni、Co和Ti中最有效的掺杂剂。为了改善由于热应力导致的晶体生长的低产率，研究了Cr、Y、B、Sm、Nd、La、Ce作为第二掺杂剂的添加。然而，并没有获得任何明显的改进。用镁掺杂样品研究了α-氧化铝晶体结构中掺入氢的位置。针对几组入射光束和晶面的方向，检查了 OH 伸缩振动吸收的偏振角依赖性。测量结果与理论计算结果的比较表明，氢位于刚玉结构中构成氧八面体边缘的0-0键之一之间并形成氢键。在四个不同间距的0-0键中，发现间距为272 pm的一个是氢位置的首选。对于掺钛的α-氧化铝也观察到了相同的趋势。对掺镁的单晶样品的电导率的H/D同位素效应进行了检查。质子被证实是低氧电势区域最主要的载流子。在电传导中也观察到各向异性。当电场方向垂直于c轴时电导率高于平行电场方向，这是由于氢在O-O键之间的位置优先而合理解释的。由于发现Mg是最合适的掺杂剂，因此用主要杂质为镁的市售多晶氧化铝管研究了其电化学性能。使用这些管作为电解质的氢浓差电池的电动势被测量为各种氢和氧电势梯度。基于晶体缺陷模型对这些值进行了理论分析，并导出了电池的电动势与电极上的电势差之间的方程。方程中出现的参数被确定为温度的函数。我们还研究了镁铝尖晶石的电化学性能，镁铝尖晶石几乎总是掺镁多晶氧化铝的共存相，以了解第二相对质子传导性能的影响。已证实氢可以作为质子并入镁铝尖晶石中并且是可移动的。然而，发现镁离子的电导率要高得多，并且质子对电导率的贡献可以忽略不计。较少的

项目成果

期刊论文数量（58）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

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)。

DOI：
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通讯作者：

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）。

DOI：
发表时间：
期刊：
影响因子：
0
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通讯作者：

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)。