Establishment of anhydrous synthesis process using molten salts as reaction media

以熔盐为反应介质的无水合成工艺的建立

• 批准号: 11450327
• 负责人: ITO Yasuhiko
• 金额: $ 9.73万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450327/
• 关键词: Molten salt; anhydrous; material synthesis process; Electrochemistry; dehydration; room temperature molten salt; 材料評価プロセス

The purpose of this project is to establish the anhydrous synthesis process that consists of purification of molten slats and separation/recovery of products. In year 1999, we succeeded in reducing the size of electrolysis cell to one half and the volume of molten salts to one tenth. In year 2000, we constructed a new electrolysis cell in an argon glove box having a gas purification equipment. By using this apparatus, it was found that water contamination level in LiCl-KCl melts could be reduced to one tenth compared to a conventional preparation method. In LiCl-KCl-DyCl_3 melts, a DyNi_2 film having 60 μm thickness was formed by potentiostatic cathodic electrolysis at a Ni electrode for 2 hours at 723 K. In LiCl-KCl-SmCl_3 melts, a SmNi_2 film having 20μm thickness was formed by galvanostatic cathodic electrolysis at a Ni electrode for 1hour at 723 K. In year 2001, we synthesized and/or searched for new room-and middle-temperature molten salts. At middle temperature range (200-300℃), it was found that the melting point of LiBr-KBr-CsBr was around 230℃, which was the lowest value among molten alkali halides. When LiH was added to this melt, it was found that hydride ion was formed. By using the electrode reaction of hydride ions, hydrogen absorption properties were evaluated for Ti electrode. At room temperature range, we succeeded in synthesizing a novel room temperature molten salt, EMIF-2.3HF, that has the highest conductivity among all room temperature molten salts at 25℃. It was found that EMIF-2.3HF had a electrochemical window of about 3.2 V. A high performance capacitor was constructed by using this melt.

该项目的目的是建立无水合成工艺，包括熔板净化和产物分离/回收。 1999年，我们成功地将电解槽尺寸缩小到一半，熔盐体积缩小到十分之一。 2000年，我们在氩气手套箱中建造了一个新的电解槽，并配有气体净化设备。通过使用该设备，发现与传统制备方法相比，LiCl-KCl熔体中的水污染水平可降低至十分之一。在LiCl-KCl-DyCl_3熔体中，通过在Ni电极上于723K进行恒电位阴极电解2小时，形成厚度为60μm的DyNi_2膜。在LiCl-KCl-SmCl_3熔体中，通过在Ni电极上于723K进行恒电位阴极电解1小时，形成厚度为20μm的SmNi_2膜。 2001年，我们合成和/或寻找新的室温和中温熔盐。在中间温度范围（200-300℃），发现LiBr-KBr-CsBr的熔点在230℃左右，是熔融碱卤化物中最低的值。当向该熔体中添加LiH时，发现形成了氢负离子。利用氢阴离子的电极反应，评价Ti电极的吸氢性能。在室温范围内，我们成功合成了一种新型室温熔盐EMIF-2.3HF，其在25℃时具有所有室温熔盐中最高的电导率。结果发现EMIF-2.3HF的电化学窗口约为3.2 V。使用该熔体构建了高性能电容器。

项目成果

T.Tsuda: "Electrochmeical behavior of lanthanum ion in basic AlCl_3-EMIC melts"Progress in Molten Salt Chemistry. Vol.1. 543-547 (2000)

T.Tsuda：“镧离子在碱性 AlCl_3-EMIC 熔体中的电化学行为”熔盐化学进展。

T.Nishikiori, T.Nohira, Y.Ito: "Kinetic Investigation of the Ti-H System by a Molten Salt Electrochemical Technique"J. Electrochem. Soc.. Vol.148. E127-E132 (2001)

T.Nishikiori、T.Nohira、Y.Ito：“通过熔盐电化学技术对 Ti-H 体系进行动力学研究”J。

R.Hagiwara: "A highly conductive room temperature molten fluoride : EMIF・2.3HF"J. Electrochem. Soc.. Vol.149. D1-D6 (2002)

R.Hagiwara：“高导电性室温熔融氟化物：EMIF·2.3HF”J.Electrochem.Vol.149。

T. Nishikiori, T. Nohira, Y. Ito: "Kinetic Investigation of the Ti-H System by a Molten Salt Electrochemical Technique"J. Electrochem. Soc.. Vol.148(3). E127-E132 (2001)

T. Nishikiori、T. Nohira、Y. Ito：“通过熔盐电化学技术对 Ti-H 体系进行动力学研究”J。

R. Hagiwara, T. Hirashige, T. Tsuda, Y. Ito: "A highly conductive room temperature molten fluoride : EMIF-2.3HF"J. Electrochem. Soc.. Vol.149(1). D1-D6 (2002)

R. Hagiwara、T. Hirashige、T. Tsuda、Y. Ito：“高导电性室温熔融氟化物：EMIF-2.3HF”J。