ANALYSIS ON CORRELATION BETWEEN STRUCTURE OF SPECIES IN ROOM-TEMPERATURE MOLTEN SALTAND MECHANISM OF ELECTRODE REACTION

室温熔盐中物种结构相关性分析及电极反应机理

基本信息

批准号：
15550131
负责人：
TASAKA Akimasa
金额：
$ 2.43万
依托单位：
DOSHISHA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550131/
关键词：
Room-temperature molten salt Ionic liquid Tetramethylammonium fluoride High-energy X-ray diffraction Analysis of structure of liquid Electrochemical fluorination Atmosphere plasma spraying technique Sol-gel method テトラメチルアンモニウムフロライド Sol-G

项目摘要

(CH_3)_4NF・mHF (m=3〜5) and (CH_3)_4NF・mDF (m=3.0, 3.5, 4.0) melts were prepared by reaction of (CH_3)_4NF with HF and DE respectively. Analysis of high-energy X-ray diffraction of (CH_3)_4NF・mHF and NH_4F・nHF melts indicated that (CH_3)_4NF・mHF melts had the intermolecular correlations of the (CH_3)_4N^+ cation in liquid state and hence the tetrahedral NC_4 short-range structure was maintained. Comparison of the measured Raman and IR spectra of (CH_3)_4NF・mHF melts with ab initio calculation revealed that a HF molecule in addition to (FH)F^-, (FT)_2F^-, and (FD)_3F^- existed in the melts and that (FH)_2F^- was the most species among them having HF. The frequencies observed in Raman and IR spectra of (CH_3)_4NF・mDF melts were compared with ab initio calculation. Consequently, it is confirmed that (FD)F^-, (FD)_2F^-, and (FD)_3F^- also existed in the melts. Electrolytic conductivity of (CH_3)_4NF・mHF melts increased with increasing m value, whereas their viscosity decreased with the increase of m value, because the concentration of HF molecule in the melts increased with increasing m value. In electrolysis of (CH_3)_4NF・mHF melts containing CsF with a nickel anode, the best ratio of (CF_3)_3N to the overall anode gas was 40.5%. In electrolysis of only (CH_3)_4NF・mHF melts with the LiNiO_2 and the LaNiO_3 coated Ni sheet anodes prepared by atmosphere plasma spraying technique and sol-gel method, an insulating NiF_2 was prevented from formation in the surface layer on the anodes and resistance of the surface layer was decreased. The best ratio of (CF_3)_3N to the overall anode gas on the LiNiO_2 coated Ni sheet anode prepared by atmosphere plasma spraying technique was 33.1%. Those on the LiNiO_2 and the LaNiO_3 coated Ni sheet anodes prepared by sol-gel method were 27% and 25%, respectively.

（CH_3）_4NF ・MHF（M = 3 ～5）和（CH_3）_4NF・MDF（M = 3.0，3.5，4.0）通过（CH_3）_4NF与HF和DE的反应制备熔体。 Analysis of high-energy X-ray diffraction of (CH_3)_4NF・mHF and NH_4F・nHF melts indicated that (CH_3)_4NF・mHF melts had the intermolecular correlations of the (CH_3)_4N^+ cation in liquid state and hence the tetrahedral NC_4 short-range structure was maintained. （CH_3）_4NF ・MHF的测量拉曼和IR光谱的比较与从头算的计算融化，表明除了（fh）f^ - ，（ft）_2f^ - 和（fd）_3f^ - 中存在HF分子，并且在MELT和（FH）中存在（FH）_2F^ - 是最大的物种。将（CH_3）_4NF的RAMAN和IR光谱观察到的频率与从头算计算进行了比较。因此，已经证实（fd）f^ - ，（fd）_2f^ - 和（fd）_3f^ - 也存在于熔体中。（CH_3）_4NF ・MHF熔体的电解电导率随着M值的增加而增加，而其粘度随着M值的增加而降低，因为熔体中HF分子的浓度随着M值的增加而增加。在（CH_3）_4NF的电解中，含有镍阳极的CSF的MHF融化，（CF_3）_3n与总阳极气体的最佳比率为40.5％。在仅（CH_3）_4NF的电解中，MHF与Linio_2融化，LANIO_3涂层的Ni片阳极由大气等离子体喷涂技术和SOL-GEL方法和Sol-Gel方法制备，防止NIF_2的绝缘NIF_2在表面层的表面层和表面层的阻力上得到了改善。（CF_3）_3N与Linio_2涂层Ni板阳极在大气等离子体喷涂技术中的最佳比率为33.1％。 Linio_2和LANIO_3涂层的Ni片阳极在Sol-Gel方法中制备的那些分别为27％和25％。