Study on fast ion dynamics in superionic conductors

超离子导体中快离子动力学研究

• 批准号: 07239101
• 负责人: ISGIGAME Mareo
• 金额: $ 77.38万
• 依托单位: Research Institute for Science Measurement, Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-07239101/
• 关键词: proton conductor; perovskite-type oxides; superlattice; laser ablation; photoemission; EXAFS; molecular dynamics; ion dynamics

In this study, proton conducting superlattice was fabricated and their fundamental characterization has been investigated (Ishigame) and the ion dynamics in perovskite-type proton conductors have been investigated experimentally from the view points of crystal structure (Koto) and electronic structure (Shin). Furthermore, fundamental theory on ion dynamics including electrons was investigated (Ishii) and molecular dynamics simulation in superlattice (Okazaki) and the ab initio molecular-dynamics of proton migration (Kawazoe) have been performed.(Ishigame) SrCeィイD20.95ィエD2YbィイD20.05ィエD2OィイD23ィエD2-SrZrィイD20.95ィエD2YbィイD20.05ィエD2OィイD23ィエD2 superlattices were synthesized by laser ablation method and their fundamental characterization was performed by XRD, RBS, Raman scattering and optical absorption measurements. The electrical conductivity and FTIR-ATR studies showed that those superlattices has proton conductivity.(Shin) Photoemission study of the electronic structure of p-type SrTiィイD2l- … More xィエD2ScィイD2xィエD2OィイD23ィエD2 suggests that the hybridization effect between the Ti 3d and O2p states becomes stronger than undoped SrTiOィイD23ィエD2. The dopant concentration dependence shows that the covalency is the strongest when the Sc concentration is 2 mol%. These facts suggest that the covalency related with the protonic conduction.(Koto) SrZrィイD21-xィエD2YbィイD2xィエD2OィイD23ィエD2 was studied by XAFS and powder XRD to elucidate the crystal and local structures. The interatomic distances Zr-O and Yb-O decrease with increasing temperature though the lattice-constants increase with increasing temperature indicating a higher symmetry of the polyhedron around Zr and Yb ions at higher temperatures. The increase of oxide ion vacancies must play an important role in the promotion of the proton conductivity at high temperature.(Okazaki) Molecular dynamics calculation has been applied to YSZ and CSZ superlattices and AgI-type ionic conductor. It was found that the oxygen ion diffusion takes place frequently in regions near Y or Ca rich layer. The results showed that collaborative motion between two ions plays an important role for ion dynamics in AgI-type ionic conductor.(Ishii) It was found that the mechanism of "universal law" in the dynamic conductivity on regular and randam superlattices originates in the structure of inherent relaxation mode miniband and that the coupling of disorder of mobile ions and lattice distortion indaces the 1st-order phase transition, such that the larger the coupling is, material becomes more unstable.(Kawazoe) Proton absorption and diffusion in SrTiOィイD23ィエD2 with and without oxygen vacancies have been studied by the ab initio molecular-dynamics within local density functional theory using ultrasoft pseucbpotentials. In the SrTiOィイD23ィエD2 with oxygen vacancy, proton tends to move to the vacancy position. Less

在这项研究中，制造了质子传导超晶格，并研究了它们的基本表征（Ishigame），并从晶体结构（KOTO）和电子结构（SHIN）（SHIN）的观察点对钙钛矿型质子导体的离子动力学进行了实验研究。此外，研究了质子迁移（kawazazoe）的超突变（Okazaki）中的有关电子动力学的基本理论（ISHII）和分子动力学模拟（Okazaki）和Ab Inli算分子 - 动力学（Kawazoe）。 D2YBRI D20.05 D2OI D23 D2 D2超晶格是通过激光消融方法合成的，其基本表征是由XRD，RBS，RAMAN散射和光学滥用测量进行的。电导率和FTIR-ATR研究表明，这些近晶格具有质子的电导率。（Shin）对P型SRTII D2L-的电子结构的光发射研究…更多XIE D2SCII D2XII D2XIE D2OI D23D2 D23D2表明TI 3D和O2 PET的杂交效应变得强大了。掺杂剂浓度依赖性表明，当SC浓度为2 mol％时，共价是强的。这些事实表明，与质子传导相关的共价。（Koto）Srzrii D21-XIE D2YBIY D2XIE D2XIE D23Y D23Y D2通过XAFS和粉末XRD进行了研究，以阐明晶体和局部结构。原子间距离ZR-O和YB-O随温度的升高而降低，尽管晶状体组合体随温度的升高而增加，表明在较高温度下，Zr和YB离子周围多面体的对称性更高。氧化离子空位的增加必须在高温下质子电导率的促进中起重要作用。（Okazaki）分子动力学计算已应用于YSZ和CSZ超级晶格和Agi-Type离子导体。发现氧离子扩散经常在Y或CA富含Ca层附近的区域发生。结果表明，两个离子之间的协作运动在Agi型离子导体中起着离子动力学的重要作用。（ISHII）发现，在常规和Randam超级晶格的动态电导率中，“通用定律”的机制起源于继承模式的结构，该结构是遗传模式和较大的阶段差异，该阶段是该阶段的型号，该阶段是该阶段的分数，该型号是该型号的分数，该型号是1个分数。耦合是，材料变得更加不稳定。（Kawazoe）质子滥用和Srtioi D2中有和没有氧空位的质子扩散已被局部分子 - 动力学在局部密度功能理论中使用Ultrasoft Pseucbotentials进行了研究。在具有氧空位的SRTIOI D23E D2中，质子倾向于移至空位位置。较少的

项目成果

K. Ihata and H. Okazaki: "Structural and dynamical properties of α-CuI : A molecular dynamics calculation"I. Phys. Condens. Matter. 9. 1477 (1997)

K. Ihata 和 H. Okazaki：“α-CuI 的结构和动力学特性：分子动力学计算”I. Phys。 9. 1477 (1997)

N.Sata, H.Yugami, Y.Akiyama, T.Hattori, S.Yamaguchi, M.Ishigame: "Studies on superlattice of Perovskite-Type Proton Conductors Synthesized by Pulsed Laser Ablation" Solid State Ionicsに投稿中.

N.Sata、H.Yugami、Y.Akiyama、T.Hattori、S.Yamaguchi、M.Ishigame：“通过脉冲激光烧蚀合成的钙钛矿型质子导体的超晶格研究”提交给固体离子学。

N. Sata, H. Matsuta, Y. Akiyama, Y. Chiba, M. Ishigame, and S. Shin: "Fabrication of the Thin Films of Acceotor Doped-SrZrO_3 and SrCeO_3 and Their Characterization" Proceedings of the 5th Asian Conference on Solid State Ionics. 545-549 (1996)

N. Sata、H. Matsuta、Y. Akiyama、Y. Chiba、M. Ishigame 和 S. Shin：“Acceetor Doped-SrZrO_3 和 SrCeO_3 薄膜的制作及其表征”第五届亚洲固体会议论文集

T. Ishii and T. Abe: "Non-Debye behaviors of dynamic conductivity in a superionic conductor superlattice" Solid State Ionics. 86-88. 1331-1334 (1996)

T. Ishii 和 T. Abe：“超离子导体超晶格中动态电导率的非德拜行为”固态离子学。

Y.Kobayashi,S.Endo,K.Koto and K.Deguchi: "X-ray differaction and dielectric constant measurement of KH_2PO_4 under high pressure"High Pressure Science and Tecnology. 475-477 (1996)

Y.Kobayashi，S.Endo，K.Koto和K.Deguchi：“高压下KH_2PO_4的X射线差分和介电常数测量”高压科学与技术。