Novel ambient temperature molten fluorides Scale up of syntheses and application to electrochemical systems

新型环境温度熔融氟化物的合成放大及其在电化学系统中的应用

• 批准号: 13555237
• 负责人: HAGAIWARA Rika
• 金额: $ 8.77万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555237/
• 关键词: molten salt; ionic liquid; room temperature; ambient temperature; imidazolium; hydrogen fluoride; fluoride; electrolyte

Room temperature molten salts have received an attention for their excellent characteristics from the viewpoint of electrochemical and synthetic applications. In 1999, we developed a new ionic liquid, 1-ethyl-3-methylimidazolium fluorohydrogenate, EMIm(HF)_<2.3>F, having a high ionic conductivity (100 mScm^<-1>). In a series of studies supported by this grant, we have reported some studies on their physical and chemical properties, and practical applications for electrolytes of some electrochemical systems. EMIm(HF)_<2.3>F is prepared by metathesis of starting chloride and anhydrous hydrogen fluoride. EMImHF_2 prepared by thermal decomposition of EMIm(HF)_<2.3>F is a colorless crystalline solid at room temperature. The reaction of the salt with stoichiometric amount of aHF gives EMIm(HF)_nF (1<n<2.5) with negligibly small HF dissociation pressures at room temperature. A phase diagram of EMIm(HF)_nF has been constructed in this composition range. The melting points of lower than room te … More mperature are observed for the salts with n>1.2. A series of syntheses, physical and electrochemical characterization of 1,3-dialkylimidazolium fluorohydrogenates have been performed in order to develop ionic liquids with high conductivities and large breaking up voltages. As a result, 1,3-dimethylimidazolium fluorohydrogenate, DMIm(HF)_<2.3>F has been found to give a higher conductivity (110 mScm^<-1>) than that of EMIm(HF)_<2.3>F. Extension of the alkyl side chain on the cation increases the electrochemical window of these ionic liquids. The conductivities of these salts are higher than those found for the other ionic liquids by one order of magnitude. High energy X-ray diffraction studies of these ionic liquids show ordering of the planar molecular ions in liquid state, which is considered to be related to their low viscosity and high conductivity. Application of these room temperature molten salts has been investigated as the electrolytes of electrical double layer capacitors, exhibit excellent, charge-discharge 'performances in wide temperature ranges. Also, these fluorohydrogenates has been turned out to act as good fluorobases against some binary fluorides to give fluorometallate ionic liquids with high purities. Less

从电化学和合成应用的角度来看，室温熔融盐的出色特征引起了人们的关注。 1999年，我们开发了一种新的离子液体，1-乙基-3-甲基咪唑唑磺酸盐，EMIM（HF）_ <2.3> F，具有高离子电导率（100 mSCM^<-1>）。在这笔赠款支持的一系列研究中，我们报告了一些有关其物理和化学特性的研究，以及对某些电化学系统的电解质的实际应用。 EMIM（HF）_ <2.3> F是通过开始氯化氯化物和无水氟化物来制备的。 EMIMHF_2通过EMIM（HF）_ <2.3> F的热分解制备是在室温下无色晶体固体。盐与化学计量量的AHF的反应使EMIM（HF）_nf（1 <n <2.5）在室温下可忽略不计的HF解离压力小。 EMIM（HF）_NF的相图已在此组合范围内构建。 n> 1.2的沙拉观察到了低于TE的低熔点。为了开发具有高电导率和较大分解电压的离子液体，已经进行了一系列合成，即1,3-二烷基咪唑烷氟化物的物理和电化学表征。结果，已经发现1,3-二甲基咪唑烷氟氢氢盐，DMIM（HF）_ <2.3> F比EMIM（HF）_ <2.3> f的电导率（110 MSCM^<-1>）具有更高的电导率（110 MSCM^-1>）。阳离子上烷基侧链的延伸增加了这些离子液体的电化学窗口。这些盐的电导率高于其他离子液体通过一个数量级的电导率。这些离子液体的高能量X射线衍射研究表明，液态下平面分子离子的排序，这被认为与它们的低粘度和高电导率有关。这些室温熔融销售的应用已被研究为电动双层电容器的电解质，在广泛的温度范围内暴露了出色的，充电量的表现。同样，这些氟氢化物已被证明是对某些二元荧光座的良好氟化物，从而使含有较高纯度的氟化离子液体具有。较少的

项目成果

Kazuhiko Matsumoto, Tetsuya Tsuda, Toshiyuki Nohira, Rika Hagiwara, Yasuhiko Ito, Osamu Tamada: "Tris(1-ethyl-3-methylimidazolium) hexachlorolanthanate"Acta Cryst.. C58(3), Part 3. ml86-ml87 (2002)

Kazuhiko Matsumoto、Tetsuya Tsuda、Toshiyuki Nohira、Rika Hagiwara、Yasuhiko Ito、Osamu Tamada：“三(1-乙基-3-甲基咪唑)六氯镧酸盐”Acta Cryst.. C58(3)，第 3 部分。 ml86-ml87 (2002)

萩原理加: "HF系アルキルイミダゾリウム室温溶融塩"溶融塩および高温化学. 45. 7-16 (2002)

Hagiwara，R.：“HF基烷基咪唑室温熔盐”熔盐和高温化学45. 7-16 (2002)。

萩原理加: "室温溶融塩-電気を流す新しい液体-"化学. 57, No.1. 62-63 (2002)

Hagiwara, R.：“室温熔盐 - 一种导电的新液体”，化学 57，第 1. 62-63 (2002)。

R.Hagiwara, K.Matsumoto, T.Tauda, Y.Ito, S.Kohara, K.Suzuya, H.Matumoto, Y.Miyazaki: "The structures of alkylimidazolium fluorohydrogenate molten salts studied by high-energy X-ray diffraction"J.Noncryst.Solids. 312-314. 414-418 (2002)

R.Hagiwara、K.Matsumoto、T.Tauda、Y.Ito、S.Kohara、K.Suzuya、H.Matumoto、Y.Miyazaki：“通过高能 X 射线衍射研究烷基咪唑氟氢化熔盐的结构”

Kazuhiko Matsumoto, Rika Hagiwara, Ryuhei Yoshida, Yasuhiko Ito, Zoran Mazej, Primoz Benkic, Boris Zemva, Osamu Tamada, Hideaki, Yoshino, Seijiro Matsubara: "Syntheses, structures and thermal properties of 1 ethyl-3-methylimidazolium salts of fluorocomple

Kazuhiko Matsumoto、Rika Hagiwara、Ryuhei Yoshida、Yasuhiko Ito、Zoran Mazej、Primoz Benkic、Boris Zemva、Osamu Tamada、Hideaki、Yoshino、Seijiro Matsubara：“氟络合物 1 乙基-3-甲基咪唑鎓盐的合成、结构和热性质