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

（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。（CH_3）_4NF·mHF和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。与（CH_3）_4NF·mHF melts的初始计算揭示了HF分子添加到（FH）F^-， （FT）_2F^-，和（FD）_3F^-存在于该melts中的（FH）_2F^-是其中最大的物种。拉曼观察到的频率和（CH_3）_4NF的IR指标·MDF melts与初始计算相比较。顺便说一下，确认（FD）F^-， （FD）_2F^-，和（FD）_3F^-也存在于melts中。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 centration 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%。在仅（CH_3）_4NF·mHF熔体用LiNiO_2和LaNiO_3涂层的镍片阳极由大气层等离子体喷雾技术和溶剂方法制备，绝缘NiF_2从表面层上形成的阳极和表面层的抵抗力被分解。（CF_3）_3 N对LiNiO_2涂覆的镍片阳极气体的最佳比率为33.1%。那些在LiNiO_2和LaNiO_3涂层镍片上制备的阳极分别是27%和25%，相应地。

(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.