Preparation of Fact-Ion Conductive Thin Films as nano-sized Battery Electrolytes

纳米级电池电解质 FF-Ion 导电薄膜的制备

• 批准号: 04650705
• 负责人: OSAKA Akiyoshi
• 金额: $ 1.2万
• 依托单位: OKAYAMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04650705/
• 关键词: rf-sputtering; thin films; amorphous; ionic conductivity; laser irradiation; optical memory; crystallization; オキシハライド; イオン伝導性; レーザー

The present research was exploited based on a demand for developing optical memory materials and electrolytes for fine scale solid batteries. Thin films of the systems F-O-Si-Pb and CuI-MoO_4-P_2O_5 were prepared with an rf-sputtering technique and their microstructure, electrical conductivity and phase change due to laser irradiation.1. Amorphous thin films of the system F-O-Si-PbAmorphous thin films of the system F-O-Si-Pb were rf-sputtered under the conditions : the Ar chamber pressure : 0.06-0.07 Torr, rf-power : 100W, sputtering time : 45min. X-ray photoelectron spectra showed that the fluorine atoms were homogeneously distributed in the films but the ratio F-Si/F-Pb decreased in the direction from the surface to the film-substrate interface. The results were accounted for by an increase in non-bridging oxygen due to a reaction Si-O-Si->Si-F+Si-O^-. Irradiation of 3mW He-Ne laser beam (lambda=632.8nm) for 1/500s induced crystallization of a quartz in the area of 11mum radium, independent of the fluorine content, but not induced an expected PbF2 phase of high conductivity. Fluorine ionic conductivity obeyed an Arrhenius type temperature dependence with sigma=1.1x10-5 S/cm at 500K, two orders of magnitude larger than the corresponding bulk glass, and activation energy of 106.5kJ/mol.2. Amorphous thin films of the system CuI-MoO_4-P_2O_5A target of a composition 25CuI・25Cu_2O・25MoO_4・25Cu_3(PO_4)_3 was rf-sputtered with the same conditions above to prepare amorphous films. They had a particular microstructure and were insulators below 550K with conductivity as small as 10^<-8> S/cm. The increase in the rf-power grew cubic particles of gamma-CuI while a large fraction of Cu atoms were divalent. The laser irradiation dug holes of 8mum in diameter even at 1/500 s and the holes grew to 12 at 1s irradiation, whereas no crystallization was observed.

本研究是基于开发用于小型固体电池的光存储材料和电解液的需求而开发的。采用射频溅射技术制备了F-O-Si-Pb和CuI-MoO_4-P_2O_5系薄膜，研究了它们的微观结构、电导率和激光辐照下的相变。在Ar气压0.06-0.07Torr，功率100W，溅射时间45min的条件下，对F-O-Si-Pb系非晶态薄膜进行了射频溅射。X射线光电子能谱表明，氟原子在薄膜中均匀分布，但F-Si/F-Pb值在从表面到薄膜-衬底界面的方向上减小。这一结果是由于反应Si-O-Si-&Gt；Si-F+Si-O^-增加了非桥氧。用3 mW He-Ne激光(波长=632.8 nm)照射1/500s，诱导石英晶化，晶化面积为11微米，与氟含量无关，但未诱导出预期的高电导率PbF2相。氟离子电导率服从阿累尼乌斯型温度关系，在500K时，sigma=1.1×10~(-5)S/cm，比相应的块体玻璃大两个数量级，活化能为106.5kJ/mol.用射频溅射方法制备了成分为25CuI·25Cu2O·25MoO_4·25Cu3(PO_4)_3的CuI-MoO_4-P_2O_5A系非晶薄膜。它们具有特殊的微观结构，是550K以下的绝缘体，电导率低至10^~(-8)S/厘米。随着射频功率的增加，γ-CuI的立方粒子长大，而大部分的铜原子是二价的。在S激光照射下，即使在1/500时也能挖出直径为8微米的孔洞，1s时孔洞扩大到12个，但没有观察到结晶现象。

项目成果

Akiyoshi OSAKA,Haruyuki KAWAMURA and Yoshinari MIURA: ""Chemical states of fluorine atoms and laser-induced crystallization in rf-sputtered thin films of amorphous lead fluorosilicate"" Memoirs of the Faculty of Engineering, Okayama University. 28[2]. 215

Akiyoshi OSAKA、Haruyuki KAWAMURA 和 Yoshinari MIURA：“非晶氟硅酸铅射频溅射薄膜中氟原子的化学状态和激光诱导结晶”，冈山大学工学院回忆录。

Akiyoshi OSAKA: "Chemical states of fluorine atoms and laser-induced crystallization in rf-sputtered thin films of amorphous lead fluorosilicate" Memoirs of the Faculty of Engineering,Okayama University. 28. 77-84 (1994)

Akiyoshi OSAKA：“非晶氟硅酸铅射频溅射薄膜中氟原子的化学状态和激光诱导结晶”冈山大学工学院回忆录。

A.Osaka: "Chemical states of fluorine atoms and laser-induced crystallization in rfsputtered thin films of amorphous lead fluorosilicate" Memoirs of Faculty of Engineering,Okayama University. 27 (印刷中).

A.Osaka：“非晶氟硅酸铅射频溅射薄膜中氟原子的化学状态和激光诱导结晶”冈山大学工学院回忆录27（出版中）。