Functional ionic liquids for electrochemical devices

2009 Fiscal Year Final Research Report

• Project/Area Number: 17073013
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: HAGIWARA Rika Kyoto University, 大学院・エネルギー科学研究科, 教授 (30237911)
• Co-Investigator(Kenkyū-buntansha): NOHIRA Toshiyuki 京都大学, 大学院・エネルギー科学研究科, 准教授 (00303876)
• Co-Investigator(Renkei-kenkyūsha): UI Koichi 岩手大学, 大学院・工学研究科, 准教授 (60360161)
• Project Period (FY): 2005 – 2009
• Keywords: イオン液体 / 溶融塩 / 電気化学 / イオン導電性 / 粘性率 / 燃料電池 / キャパシタ / リチウム電池

Research Abstract

Electrochemical capacitors using fluorohydrogenate ionic liquids exhibit excellent performance in a wide temperature range especially below room temperatures down to -40℃. DMIm(FH)_2.3F has given the highest capacitance of 178 F g^<-1> at room temperature and a wide temperature range of operation above and below 0℃. A fuel cell using fluorohydrogenate salts as the electrolyte has demonstrated to operate at 120℃ under unhumidified condition. A lithium/LiFePO_4 battery using mixed alkali TFSA salts as the electrolyte has exhibited capacity of 90 mAhg^<-1> at 5C rate. Na/NaCrO_2 secondary battery with NaTFSA-CsTFSA binary molten salt has shown an excellent performance with a potential plateau at 2.8 V vs Na^+/Na at a rate of 10 mA (g-NaCrO_2)^<-1>.

Research Products

• [Journal Article] A new series of ionic liquids based on the difluorophosphate anion (2009)
  • Author(s): Kazuhiko Matsumoto, Rika Hagiwara
  • Journal Title: Inorganic Chemistry 48 Pages: 7350-7358
  • Peer Reviewed
• [Journal Article] Electrochemical properties of alkali bis(trifluoromethylsulfonyl)amides and their eutectic mixtures (2009)
  • Author(s): Keigo Kubota, Kenichiro Tamaki, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Journal Title: Electrochimica Acta 55 Pages: 1113-1119
  • Peer Reviewed
• [Journal Article] Electrochemically stable fluorohydrogenate ionic liquids based on quaternary phosphonium cations (2009)
  • Author(s): Shunsuke Kanematsu, Kazuhiko Matsumoto, Rika Hagiwara
  • Journal Title: Electrochemistry Communications 11 Pages: 1312-1315
  • Peer Reviewed
• [Journal Article] A rechargeable lithium metal battery operating at intermediate temperatures using molten alkali bis(trifluoromethylsulfonyl)amide mixture as an electrolyte (2008)
  • Author(s): Atsushi Watarai, Keigo Kubota, Masaki Yamagata, Takuya Goto, Toshiyuki Nohira, Rika Hagiwara, Koichi Ui, Naoaki Kumagai
  • Journal Title: J. Power Sources 183 Pages: 724-729
  • Peer Reviewed
• [Journal Article] Novel inorganic ionic liquids possessing low melting temperatures and wide electrochemical windows: Binary mixtures of alkali bis(fluorosulfonyl)amides (2008)
  • Author(s): Keigo Kubota, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Journal Title: Electrochem. Commun. 10 Pages: 1886-1888
  • Peer Reviewed
• [Journal Article] Ternary (trifluoromethyl sulfonyl)amides (2008)
  • Author(s): Keigo Kubota, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Journal Title: J. Chem. & Eng. Data 53 Pages: 2144-2147
  • Peer Reviewed
• [Journal Article] Very strong hydrogen bonds in a bent chain structure of fluorohydrogenate anions in liquid Cs(FH)2. 3F (2008)
  • Author(s): Shinji Kohara, Masaki Takata, Kazuhiko Matsumoto, Rika Hagiwara, Kentaro Suzuya, Hidetoshi Morita, Joan E. Siewenie, Chris J. Benmore
  • Journal Title: J. Chem. Phys. 129 Pages: 014512/1-014512/6
  • Peer Reviewed
• [Journal Article] Thermal of (trifluoromethy- sulfonyl) amides (2008)
  • Author(s): Rika Hagiwara, Kenichiro Tamaki, Keigo Kubota, Takuya Goto, Toshiyuki Nohira
  • Journal Title: J. Chem. & Eng. Data 53 Pages: 355-358
  • Peer Reviewed
• [Journal Article] Electric Double Layer Capacitance of Activated Carbon Nanofibers in Ionic Liquid: EMImBF4 (2007)
  • Author(s): S. Shiraishi, T. Miyauchi, R. Sasaki, N. Nishina, A. Oya, R. Hagiwara
  • Journal Title: Electrochemistry 75 Pages: 619-621
  • Peer Reviewed
• [Journal Article] Crystal structures of frozen room temperature ionic liquids, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4), hexafluoroniobate (EMImNbF6) and hexafluorotantalate (EMImTaF6), determined by low-temperature X-ray diffraction (2007)
  • Author(s): Kazuhiko Matsumoto, Rika Hagiwara, Zoran Mazej, Primoz Benkic, Boris Zemva
  • Journal Title: Solid State Sciences 9 Pages: 761
  • Peer Reviewed
• [Journal Article] Coordination environment around the lithium cation in solid Li2(EMIm)(N(SO2CF3)2)3 (EMIm=1-ethyl-3-methylimidazolium): Structural clue of ionic liquid electrolytes for lithium batteries (2006)
  • Author(s): Kazuhiko Matsumoto, Rika Hagiwara, Osamu Tamada
  • Journal Title: Solid State Sciences 8 Pages: 1103-1107
  • Peer Reviewed
• [Journal Article] Crystal structures of frozen room temperature ionic liquids, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4), hexafluoroniobate (EMImNbF6) and hexafluorotantalate (EMImTaF6), determined by low-temperature X-ray diffraction (2006)
  • Author(s): Kazuhiko Matsumoto, Rika Hagiwara, Zolan Mazej, Primoz Benkic, Boris Zemva
  • Journal Title: Solid State Sciences 8(10) Pages: 1250-1257
  • Peer Reviewed
• [Journal Article] Anodic hydrogen electrode reaction in aluminum chloride-1-ethyl- 3-methylimidazolium chloride ionic liquids (2005)
  • Author(s): Tetsuya Tsuda, Charles L. Hussey, Toshiyuki Nohira, Yoshihiro Ikoma, Kasumi Yamauchi, Rika Hagiwara, Yasuhiko Ito
  • Journal Title: Electrochemistry 73(8) Pages: 644-650
  • Peer Reviewed
• [Journal Article] Electric double layer capacitance of activated carbon fibers in ionic liquid: EMImBF4 (2005)
  • Author(s): Soshi Shiraishi, Naoya Nishina, Asao Oya, Rika Hagiwara
  • Journal Title: Electrochemistry 73(8) Pages: 593-596
  • Peer Reviewed
• [Journal Article] Ionization state and ion migration mechanism of room temperature molten dialkylimidazolium fluorohydrogenates (2005)
  • Author(s): Yuria Saito, Kenichi Hirai, Kazuhiko Matsumoto, Rika Hagiwara, Yoshihiro Minamizaki
  • Journal Title: Journal of Physical Chemistry B 109,No.7 Pages: 2942-2948
  • Peer Reviewed
• [Journal Article] A fluorohydrogenate ionic liquid fuel cell operating without humidification (2005)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Kazuhiko Matsumoto, Yuko Tamba
  • Journal Title: Electrochemical and Solid-State Letters 8,No.4 Pages: A231-A233
  • Peer Reviewed
• [Journal Article] The effect of the anion fraction on the physicochemical properties of EMIm(HF)nF (n = 1. 0-2. 6) (2005)
  • Author(s): Rika Hagiwara, Yoji Nakamori, Kazuhiko Matsumoto, Yasuhiko Ito
  • Journal Title: Journal of Physical Chemistry B 109,No.12 Pages: 5445-5449
  • Peer Reviewed
• [Presentation] The Electrochemical Formation Mechanism of Silicon in Non-Aqueous Solvents (2009)
  • Author(s): Yusaku Nishimura, Tetsuo Nishida, Caetano R. Miranda, Yasuhiro Fukunaka, Toshiyuki Nohira, Rika Hagiwara
  • Organizer: 216th Electrochemical Society Meeting
  • Place of Presentation: Vienna, Austria
  • Year and Date: 20091004-20091009
• [Presentation] New ionic liquids based on the difluorophosphate anion (2009)
  • Author(s): Kazuhiko Matsumoto, Rika Hagiwara
  • Organizer: 19th International Symposium on Fluorine Chemistry
  • Place of Presentation: Jackson Hole, Wyoming USA
  • Year and Date: 20090823-20090828
• [Presentation] Fluorohydrogenate Ionic Liquid Fuel Cells Operating at Intermediate Temperature under Unhumidified Condition (2009)
  • Author(s): Toshiyuki Nohira, Kouji Ogasawara, Takashi Hayashida, Rika Hagiwara
  • Organizer: The 4th International Conference on Polymer Batteries and Fuel Cells
  • Place of Presentation: Yokohama, Japan
  • Year and Date: 20090802-20090806
• [Presentation] Mesophase Behavior of Fluorohydrogenate Salts (2009)
  • Author(s): Kazuhiko Matsumoto, Ryosuke Taniki, Fei Xu, Rika Hagiwara
  • Organizer: 3rd Congress on Ionic Liquids
  • Place of Presentation: Cairns, Australia
  • Year and Date: 20090531-20090604
• [Presentation] The Electrodeposition Mechanism of Silicon in a Room-Temperature Ionic Liquid (2009)
  • Author(s): Yusaku Nishimura, Toshiyuki Nohira, Tetsuo Nishida, Caetano R. Miranda, Yasuhiro Fukunaka, Rika Hagiwara
  • Organizer: 3rd Congress on Ionic Liquids
  • Place of Presentation: Cairns, Australia
  • Year and Date: 20090531-20090604
• [Presentation] Unhumidified Fuel Cells Operating at Intermediate Temperature Using Fluorohydrogenate Ionic Liquids (2009)
  • Author(s): Toshiyuki Nohira, Kouji Ogasawara, Takashi Hayashida, Rika Hagiwara
  • Organizer: 3rd Congress on Ionic Liquids
  • Place of Presentation: Cairns, Australia
  • Year and Date: 20090531-20090604
• [Presentation] Fluorohydrogenate ionic liquids- their unique features and new applications- (2008)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Kazuhiko Matsumoto, Shinji Kohara
  • Organizer: 2008 Joint Symposium on Molten Salts
  • Place of Presentation: Kobe, Japan
  • Year and Date: 20081019-20081023
• [Presentation] Fluorohydrogenate ionic liquids - their unique features and new applications- (2008)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Kazuhiko Matsumoto, Shinji Kohara
  • Organizer: 2008 Joint Symposium on Molten Salts
  • Place of Presentation: Kobe, Japan
  • Year and Date: 20081019-20081023
• [Presentation] Physicochemical properties of mixed alkali metal FSI salts (2008)
  • Author(s): Keigo Kubota, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Organizer: 2008 Joint Symposium on Molten Salts
  • Place of Presentation: Kobe, Japan
  • Year and Date: 20081019-20081023
• [Presentation] Recent studies on fluorohydrogenate ionic liquids (2008)
  • Author(s): Rika Hagiwara
  • Organizer: 234th ACS National Meeting
  • Place of Presentation: Boston, USA
  • Year and Date: 20081019-20081023
• [Presentation] Binary mixtures of MFSI (M = Li, Na, K, Rb, Cs) as new inorganic ionic liquids (2008)
  • Author(s): Keigo Kubota, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Organizer: PRiME 2008
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20081012-20081017
• [Presentation] Molten alkali bis (trifluoromethylsulfonyl)amides and their application to rechargeable lithium batteries (2008)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Takuya Goto, Atsushi Watarai, Tetsuya Fujimori, Keigo Kubota, Masaki Yamagata, Koichi Ui, Naoaki Kumagai
  • Organizer: PRiME 2008 Meeting
  • Place of Presentation: Hawaii, USA
  • Year and Date: 20081012-20081017
• [Presentation] Ionic Liquid Fluorohydrogenates- Difference form the conventional fluoride-HF systems- (2007)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto, Shinji Kohara, Yuria Saito
  • Organizer: 2nd International Congress on Ionic Liquids
  • Place of Presentation: Yokohama, Japan
  • Year and Date: 20070805-20070810
• [Presentation] Physicochemical Properties of Ternary MTFSI (M=Li, Na, K, Cs) Mixed Salts (2007)
  • Author(s): Keigo Kubota, Kenichiro Tamaki, Toshiyuki Nohira, Takuya Goto, Rika Hagiwara
  • Organizer: 2nd International Congress on Ionic Liquids
  • Place of Presentation: Yokohama, Japan
  • Year and Date: 20070805-20070810
• [Presentation] New Series of Room-temperature fluorohydrogenate Ionic Liquids with N-Heterocyclic Cations (2007)
  • Author(s): Masaki Yamagata, Soichiro Konno, Rika Hagiwara
  • Organizer: 2nd International Congress on Ionic Liquids
  • Place of Presentation: Yokohama, Japan
  • Year and Date: 20070805-20070810
• [Presentation] Ionic liquid fluorohydrogenates and their applications (2006)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Takashi Shimada, Takashi Fujinaga, Soichiro Konno
  • Organizer: ECS 210th Meeting
  • Place of Presentation: Cancun, Mexico
  • Year and Date: 20061029-20061103
• [Presentation] Ionic Liquid Composite Polymer Electrolyte Membranes for the Unhumidified Intermediate Temperature Fuel Cell (2006)
  • Author(s): Je Seung Lee, Toshiyuki Nohira, Rika Hagiwara
  • Organizer: ECS 210th Meeting
  • Place of Presentation: Cancun, Mexico
  • Year and Date: 20061029-20061103
• [Presentation] Ionic Liquid Fluorohydrogenates and Their Application to Fuel Cell (2006)
  • Author(s): R. Hagiwara, T. Nohira, T. Shimada, T. Fujinaga
  • Organizer: 18th International Symposium on Fluorine Chemistry
  • Place of Presentation: Bremen, Germany
  • Year and Date: 20060730-20060804
• [Presentation] Structural Analyses of Room Temperature Ionic Liquids Containing Fluoroanions (2006)
  • Author(s): K. Matsumoto, R. Hagiwara, Z. Mazej, P. Benkic, B. Zemva
  • Organizer: 18th International Symposium on Fluorine Chemistry
  • Place of Presentation: Bremen, Germany
  • Year and Date: 20060730-20060804
• [Presentation] Studies on some fluorocomplex salts for electrochemical applications (2006)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto
  • Organizer: ACS 231st spring national meeting
  • Place of Presentation: Atlanta, USA
  • Year and Date: 20060326-20090330
• [Presentation] Chemical and electrochemical applications of ionic liqiuid fluorohydrogenates (2006)
  • Author(s): Rika Hagiwara, Toshiyuki Nohira, Kazuhiko Matsumoto, Takashi Shimada, Takuji Fujinaga
  • Organizer: ACS 231st spring national meeting
  • Place of Presentation: Atlanta, USA
  • Year and Date: 20060326-20090330
• [Presentation] Low viscous fluorohydrogenate ionic liquids and their electrochemical applications (2006)
  • Author(s): Rika Hagiwara
  • Organizer: ACS 18th Winter Fluorine Conference
  • Place of Presentation: St. Petersburg, USA
  • Year and Date: 20060114-20060119
• [Presentation] Fluorohydrogenate ionic liquid fuel cell (2005)
  • Author(s): R. Hagiwara, T. Nohira, K. Matsumoto, Y. Tamba, T. Shimada
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 20051214-20051220
• [Presentation] Structural studies of 1-ethyl-3- methylimidazolium salts containing fluoroanions (2005)
  • Author(s): K. Matsumoto, R. Hagiwara, Z. Mazej, P. Benkic, B. Zemva
  • Organizer: Pacifichem 2005
  • Place of Presentation: Honolulu, USA
  • Year and Date: 20051214-20051220
• [Presentation] Room temperature molten fluorohydrotentates-properties and electrolyte applications- (2005)
  • Author(s): R. Hagiwara, K. Matsumoto, T. Nohira, Y. Nakamori, Y. Tamba, T. Shimada, Y. Saito, S. Kohara
  • Organizer: Proc. of 7th International Conference on Molten Salt Chemistry and Technology
  • Place of Presentation: Toulouse
  • Year and Date: 20050831-20050902
• [Presentation] Room Temperature Molten Fluorohydrogenate - Properties and Electrolyte Applications (2005)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto, Toshiyuki Nohira, Youji Nakamori, Yuko Tamba, Takashi Shimada, Y. Saito, S. Kohara
  • Organizer: The 7th International Symposium on Molten Salts Chemistry
  • Place of Presentation: Toulouse, France
  • Year and Date: 20050829-20080902
• [Presentation] Room temperature ionic liquid fluoride (2005)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto, Toshiyuki Nohira, Yuko Tamba, Zoran Mazej, Boris Zemva
  • Organizer: 17th International Symposium on Fluorine Chemistry
  • Place of Presentation: Shanghai, China
  • Year and Date: 20050724-20050729
• [Book] Ionic Liquids:Not Just Solvents Anymore (2007)
  • Author(s): C. Larriba, D. Garoz, C. Bueno, I. Romero-Sanz, S. Castro, J. Fernandez de la Mora, Y. Yoshida, G. Saito, R. Hagiwara, K. Matsumoto, J. Wilkes
  • Total Pages: 308-319
  • Publisher: Oxford University Press
• [Book] 化学フロンティア17新エネルギー最前線(吉川暹編, 化学同人) (2006)
  • Author(s): 萩原理加, 野平俊之
  • Total Pages: 55-60
• [Book] イオン液体II(大野弘幸監修) (2006)
  • Author(s): 萩原理加
  • Total Pages: 179-186
  • Publisher: シーエムシー出版
• [Book] Electrochemical Aspects of Ionic Liquids(Hiroyuki Ohno Ed. ) (2005)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto, Novel Fluoroanion Salts
  • Total Pages: 227-235
  • Publisher: Wiley Interscience
• [Book] Fluorinated Materials for Energy Conversion(Tsuyoshi Nakajima and Henri Groult Eds. ) (2005)
  • Author(s): Rika Hagiwara, Kazuhiko Matsumoto
  • Total Pages: 349-368
  • Publisher: Wiley Interscience
• [Remarks] ホームページ等
  • URL: http://www.echem.energy.kyoto-u.ac.jp/
• [Patent(Industrial Property Rights)] 電気二重層キャパシタ (2010)
  • Inventor(s): 萩原理加, 伊藤靖彦, 宇恵誠, 鳥海明子
  • Industrial Property Rights Holder: 三菱化学株式会社
  • Industrial Property Number: 特許・特許第4453174号
  • Acquisition Date: 2010-02-12
• [Patent(Industrial Property Rights)] 溶融塩組成物及びその利用 (2009)
  • Inventor(s): 萩原理加, 後藤琢也, 野平俊之, 窪田啓吾
  • Industrial Property Rights Holder: 国立大学法人京都大学
  • Patent Publication Number: 特許・特開2009-067644
  • Filing Date: 2009-04-02
• [Patent(Industrial Property Rights)] ウランの濃縮方法 (2008)
  • Inventor(s): 萩原理加, 松本一彦, 金谷崇系
  • Industrial Property Rights Holder: 国立大学法人京都大学
  • Industrial Property Number: 特許・特願2008-331055
  • Filing Date: 2008-12-25
• [Patent(Industrial Property Rights)] 燃料電池用触媒電極およびその製造方法 (2008)
  • Inventor(s): 上條元久, 岩崎靖和, 萩原理加, 野平俊之
  • Industrial Property Rights Holder: 日産自動車株式会社, 国立大学法人京都大学
  • Patent Publication Number: 特許・特開2008-177136
  • Filing Date: 2008-07-31
• [Patent(Industrial Property Rights)] 膜電極接合体、および, これを用いた燃料電池 (2007)
  • Inventor(s): 小川弘志, 竹川寿弘, 萩原理加, 野平俊之, 嶋田隆
  • Industrial Property Rights Holder: 日産自動車株式会社, 国立大学法人京都大学
  • Industrial Property Number: 特許・特開JP2007066765
  • Filing Date: 2007-03-15
• [Patent(Industrial Property Rights)] Molten salt composition for secondary battery electrolyte (2006)
  • Inventor(s): Hagiwara, Rika; Matsumoto, Kazuhiko; Tamaki, Kenichiro; Nohira, Toshiyuki; Goto, Takuya
  • Industrial Property Rights Holder: (米国を除くすべての指定国について)国立大学法人京都大学、(米国についてのみ):Hagiwara, Rika; Matsumoto, Kazuhiko; Tamaki, Kenichiro; Nohira, Toshiyuki; Goto, Takuya
  • Industrial Property Number: 特許・WO2006/101141A1
  • Filing Date: 2006-09-28
• [Patent(Industrial Property Rights)] 溶融塩組成物及びその利用 (2006)
  • Inventor(s): 萩原理加, 松本一彦, 玉木健一郎, 野平俊之, 後藤琢也
  • Industrial Property Rights Holder: 国立大学法人京都大学
  • Patent Publication Number: 特許・特開2006-305736
  • Filing Date: 2006-03-22
• [Patent(Industrial Property Rights)] 燃料電池電解質および燃料電池 (2005)
  • Inventor(s): 大井亮, 山内昇, 萩原理加, 野平俊之, 松本一彦, 丹波悠子, 伊藤靖彦
  • Industrial Property Rights Holder: 日産自動車株式会社
  • Patent Publication Number: 特許・特開2005-251466
  • Filing Date: 2005-09-15