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

Research Project

Project/Area Number 13555237
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 工業物理化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

HAGAIWARA Rika  Kyoto Univ., Energy Science, Associate Professor, エネルギー科学研究科, 助教授 (30237911)

Co-Investigator(Kenkyū-buntansha) MOMOTA Kunitaka  Director and Chemical Division, Manager, 精密化学薬品事業部, 取締役事業部長
GOTO Takuya  Kyoto Univ., Energy Science, Research Associate, エネルギー科学研究科, 助手 (60296754)
NOHIRA Tashiyuki  Kyoto Univ., Energy Science, Research Associate, エネルギー科学研究科, 助手 (00303876)
Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥13,700,000 (Direct Cost: ¥13,700,000)
Fiscal Year 2003: ¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2002: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2001: ¥9,000,000 (Direct Cost: ¥9,000,000)
Keywordsmolten salt / ionic liquid / room temperature / ambient temperature / imidazolium / hydrogen fluoride / fluoride / electrolyte
Research Abstract

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

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (35 results)

All Other

All Publications (35 results)

  • [Publications] 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 fluorocomplex anions"J.Chem.Soc., Dalton Trans.. No.1. 144-149 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Hagiwara, Kazuhiko Matsumoto, Yoji Nakamori, Tetsuya Tsuda, Yasuhiko Ito, Hajime Matsumoto, Kunitaka Kunita: "Physicochemical properties of 1,3-dialkylimidazolium fluorohydrogenates room temperature molten salts"J.Electrochem.Soc.. 150, No.12. D195-D199 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Makoto Ue, Masayuki Takeda, Akiko Toriumi, Asao Kominato, Rika Hagiwara, Yashiko Ito: "Application of low-viscosity ionic liquid to the electrolyte of double-layer capacitors"J.Electrochem.Soc.. 150, No.4. A499-A502 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Tetsuya Tsuda, Toshiyuki Nohira, Yoji Nakamori, Kazuhiko Matsumoto, Rika Hagiwara, Yasuhiko Ito: "A highly conductive composite electrolyte consisting of polymer and room temperature molten fluorohydrogenates"Solid St. Ionics. 149, No.3-4. 295-298 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Matsumoto, R.Hagiwara, T.Tsuda, Y.Ito, O.Tamada: "Structural characteristics of 1-ethyl-3-methylimidazolium bifluoride : HF- deficient form of a highly conductive room temperature molten salt"Solid St.Sci.. 4, No.1. 23-26 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Hagiwara, Takayuki Hirashige, Tetsuya Tsuda, Yasuhiko Ito: "A highly conductive room temperature molten fluoride ; EMIF・2.3HF"J.Electrochem.Soc.. 149. D1-D6 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 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 fluorocomplex anions"J.Chem.Soc., Dalton Trans.. No.1. 144-149 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideaki Yoshino, Seijiro Matsubara, Koichiro Oshima, Kazuhiko Matsumoto, Rika Hagiwara, Yasuhiko Ito: "Halofluormation of alkenes with ionic liquid EMIMF(HF)_<2.3>"J.Fluor.Chem. 125. 455-458 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Hagiwara, Kazuhiko Matsumoto, Yoji Nakamori, Tetsuya Tsuda, Yasuhiko Ito, Hajime Matsumoto, Kunitaka Kunita: "Physicochemical properties of 1,3-dialkylimidazolium fluorohydrogenates room temperature molten salts"J.Electrochem.Soc.. 150, No.12. D195-D199 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Makoto Ue, Masayuki Takeda, Akiko Toriumi, Asao Kominato, Rika Hagiwara, Yasuhiko Ito: "Application of low-viscosity ionic liquid to the electrolyte of double-layer capacitors"J.Electrochem.Soc.. 150, No.4. A499-A502 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Kazuhiko Matsumoto, Rika Hagiwara, Tetsuya Tsuda, Yasuhiko Ito, Shmji Kohara, Kentaro Suzuya: "Structural analysis of 1-ethyl-3-methylimidazolium bifluoride melt"Nuclear Inst.and Methods in Physics Research, B. 199. 29-33 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Tetsuya Tsuda, Toshiyuki Nohira, Yoji.Nakamori, Kazuhiko Matsumoto, Rika Hagiwara, Yasuhiko Ito: "A highly conductive composite electrolyte consisting of polymer and room temperature molten fluorohydrogenates"Solid St.Tonics. 149, No.3-4. 295-298 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] K.Matsumoto, R.Hagiwara, T.Tsuda, Y.Ito, 0.Tamada: "Structural characteristics of 1-ethyl-3-methylimidazolium bifluoride : HF-deficient form of a highly conductive room temperature molten salt"Solid St.Sci.. 4, No.1. 23-26 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Rika Hagiwara, Takayuki Hirashige, Tetsuya Tsuda, Yasuhiko Ito: "A highly conductive room temperature molten fluoride ; EMIF 2.3HF"J.Electrochem.Soc.. 149. D1-D6 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hideaki Yoshino, Seijiro Matsubara, Koichiro Oshima, Kazuhiko Matsumoto, Rika Hagiwara, Yasuhiko Ito: "Halofluorination of alkenes with ionic liquid EMIMF(HF)_<2.3>"J.Fluor.Chem.. 125. 455-458 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Kazuhiko Matsumoto, Rika Hagiwara, Ryuhei Yoshida, Yasuhiko Ito, Zoran Mazej, Primoz Benkic, Boris Zemva, Osamu Tamada, Hideuki Yoshino, Seijiro Matsubara: "Syntheses, structures and thermal properties of 1 ethyl-3-methylimidazolium salts of fluorocomplex anions"J.Chem.Soc., Dalton Trans.. No.1. 144-149 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] Rika Hagiwara, Kazuhiko Matsumoto, Yoji Nakamori, Tetsuya Tsuda, Yasuhiko Ito, Hajime Matsumoto, Kunitaka Momota: "Physicochemical properties of 1,3-dialkylimidazolium fluorohydrogenates room temperature molten salts"J.Electrochem.Soc.. 150,No.12. D195-D199 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Makoto Ue, Masayuki Takeda.Akiko Toriumi, Asao Kominato, Rika Hagiwara, Yashiko Ito: "Application of low-viscosity ionic liquid to the electrolyte of double-layer capacitors"J.Electrochem.Soc.. 150,No.4. A499-A502 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Kazuhiko Matsumoto, Rika Hagiwara, Tetsuya Tsuda, Yasuhiko Ito, Shinji Kohara, Kentaro Suzuya: "Structural analysis of 1-ethyl-3-methylimidazolium bifluoride melt"Nuclear Inst. and Methods in Physics Research, B. 199. 29-33 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 萩原理加 他: "フッ素化学入門-先端テクノロジーに果たすフッ素化学の役割-"独立行政法人日本学術振興会フツ素化学第155委員会 編. 447 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] 萩原理加, 後藤琢也, 野平俊之 他: "溶融塩の応用-エネルギー・環境技術への応用-"伊藤靖彦 編. 374 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] K.Matsumoto, R.Hagiwara, T.Tsuda, Y.Ito, S.Kohara, K.Suzuya: "Structural analysis of 1-ethyl-3-methylimidazolium bifluoride (EMIF ・ HF) : comparison with its solid state and 1-ethyl-3-methylimidazolium fluorohydrogenate (EMIF ・ 2.3HF)"Nuclear Inst.And Methods in Physics Research, B. 199. 29-33 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 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)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Tsuda, T.Nohira, Y.Nakamori, K.Matsumoto, R.Hagiwara, Y.Ito: "A high conductive composite electrolyte consisting of polymer and room temperature molten fluorohydrogenates"Solid St.Ionics. 149,No.3-4. 295-298 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Matsumoto, R.Hagiwara, Y.Ito: "Room temperature molten fluorometallates : 1-ethyl-3-methylimidazolium hexafluoroniobate(V)"J.Fluor.Chem.. 115,No.2. 133-135 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Kohara, R.Hagiwara, K.Matsumoto, Y.Ito, A.Kajinami, K.Suzuya: "High energy x-ray diffraction studies of alkylimidazolium fluorohydrogenate room temperature molten salts at Spring-8 high-energy x-ray diffraction beamline beamline BL04B2"Proc. of 13^<th> International Symposium on Molten Salts, The Electrochemical Society. 2002-19. 1047-1056 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] R.Hagiwara, K.Matsumoto, Y.Nakamori, T.Tsuda, Y.Ito, H.Matsumoto, K.Momota: "Alkylimidazolium fluorohydrogenates room temperature molten salts"Proc.of 13^<th> International Symposium on Molten Salts, The Electrochemical Society. 2002-19. 1007-1013 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 萩原理加 他, 大野弘幸 監修: "イオン性液体"シーエムシー出版. 255 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Rika Hagiwara: "A highly conductive RTMS ; Alkylimidazolium Fluorohydrogenates"Proc. of 6th International Conference on Molten Salt Chemistry and Technology. 136-139 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Rika Hagiwara: "A highly conductive room temperature molten fluoride ; EMIF・2.3HF"J.Electrochem.Soc.. 149. D1-D6 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Matsumoto: "Structural characteristics of 1-ethyl-3-methylimidazolium bifluoride : HF-deficient form of a highly conductive room temperature molten salt"Solid St.Sciences. 4. 23-26 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 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)

    • Related Report
      2001 Annual Research Report
  • [Publications] K.Matsumoto: "Tris(1-ethyl-3-methylimidazolium) hexafluorolanthanate"Acta Crystallographica. C58. m186-m187 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 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)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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