錯体水素化物でのリチウム超イオン伝導-その機構解明と新材料創製

• Project/Area Number: 21246100
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Structural/Functional materials
• Research Institution: Tohoku University
• Principal Investigator: 折茂 慎一 Tohoku University, 金属材料研究所, 教授 (40284129)
• Co-Investigator(Kenkyū-buntansha): 大山 研司 東北大学, 金属材料研究所, 准教授 (60241569) ; 湯川 宏 名古屋大学, 工学研究科, 助教 (50293676) ; 上床 美也 東京大学, 物性研究所, 准教授 (40213524)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥39,780,000 (Direct Cost: ¥30,600,000、Indirect Cost: ¥9,180,000); Fiscal Year 2011: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000); Fiscal Year 2010: ¥11,830,000 (Direct Cost: ¥9,100,000、Indirect Cost: ¥2,730,000); Fiscal Year 2009: ¥16,900,000 (Direct Cost: ¥13,000,000、Indirect Cost: ¥3,900,000)
• Keywords: リチウム / 水素 / 錯体水素化物 / 超イオン伝導 / 構造相転移 / 錯イオン / リチウムイオン二次電池 / エネルギー

Research Abstract

リチウム超(高速)イオン伝導特性を示すLiBH_4をベースとした水素化物群の合成やその伝導機構の解明、そして関連する新たな水素化物群の創製などを目的とした研究を進めている。今年度、[BH_4]-錯イオンに加えて、[NH_2]-錯イオンや[AlH_4]-錯イオンを含む新たな水素化物群を合成し、結晶構造・格子振動・融解などの諸特性やイオン伝導率の温度依存性などを系統的に評価したところ、以下の結果が得られた。(1)[NH_2]-錯イオンから形成されるLiNH_2の場合、それ自体のイオン伝導度は室温で10^<-9>/cmと低い(LiIも同様の低い伝導度を示す)が、I^-を用いて[NH_2]-錯イオンを部分的に置換することで特徴的な層状構造を有する新しい錯体水素化物Li_3(NH_2)_2Iが生成し、さらにそのイオン伝導特性を評価したところ出発原料であるLiNH_2やLiIより4桁も高い値(室温で10^<-5>S/cm)を示すことが明らかとなった。この特徴的な層状構造は、ラーベス相構造を示す金属水素化物との類似性も強く、錯体水素化物と金属水素化物を繋ぐ新たな水素化物の最初の合成例としての学術意的な意味も大きい。(2)[AlH_4]-錯イオンや[AlH_6]^<3->錯イオンから構成されるLiAlH_4やLi_3AlH_6などの錯体水素化物でも高いイオン伝導度を示すことが明らかとなった。これらの知見は、[BH_4]^-や[NH_2]^-、[AlH_4]^-や[AlH_6]^<3->などに加えて、[NiH_4]^<4->、[CoH_5]^<4->、[MnH_6]^<5->などの錯イオンも含めた多様な錯体水素化物群を次世代リチウムイオン電池電解質として機能化する上、さらにリチウムイオン伝導と水素の(または水素を含む錯イオンの)ダイナミクスとの相関を解明する上で、極めて重要である。

Research Products

• [Journal Article] Diffuse and doubly split atom occupation in hexagonal LiBH_4 (2011)
  • Author(s): T.Ikeshoji, et.al.
  • Journal Title: Physical Review Letters Volume: 83
  • Peer Reviewed
• [Journal Article] Lithium fast-ionic conduction in complex hydrides : Review and prospects (2011)
  • Author(s): M.Matsuo, S.Orimo
  • Journal Title: Advanced Energy Materials Volume: 1 Pages: 161-172
  • Peer Reviewed
• [Journal Article] Order and disorder in lithium tetrahydroborate (2011)
  • Author(s): S.K.Callear, et.al.
  • Journal Title: Journal of Materials Sciences Volume: 46 Pages: 566-569
  • Peer Reviewed
• [Journal Article] Lithium ion conduction in lithtum borohydrides under high pressure (2011)
  • Author(s): H.Takamura, et.al.
  • Journal Title: Solid State Ionics Volume: (In press)
  • Peer Reviewed
• [Journal Article] Room temperature lithium fast-ion conduction and phase relationship of LiI stabilized LiBH_4 (2011)
  • Author(s): R.Miyazaki, et.al.
  • Journal Title: Solid State Ionics Volume: (In press)
  • Peer Reviewed
• [Journal Article] Synthesis and Lithium Fast-Ion Conductivity of a New Complex Hydride with Double-Layered Structure (2010)
  • Author(s): M.Matsuo, et.al.
  • Journal Title: Chemistry of Materials Volume: 22 Pages: 2702-2704
  • Peer Reviewed
• [Journal Article] Lithium-ion conduction in complex hydrides LiAlH_4 and Li_3AlH_6 (2010)
  • Author(s): H.Oguchi, et.al.
  • Journal Title: Journal of Applied Physics Volume: 107
  • Peer Reviewed
• [Journal Article] Anharmonicity in LiBH_4-LiI induced by anion exchange and temperature (2010)
  • Author(s): A.Borgschulte, et.al.
  • Journal Title: Applied Physics Letters Volume: 97
  • Peer Reviewed
• [Journal Article] Complex hydrides : a new category of solid-state lithium fast-ion conductors (2010)
  • Author(s): M.Matsuo, et.al.
  • Journal Title: Materials Matter Volume: 5 Pages: 105-107
  • Peer Reviewed
• [Journal Article] Stabilization of lithium superionic conduction phase and enhancement of conductivity of LiBH_4 by LiCl addition (2009)
  • Author(s): M.Matsuo, et.al.
  • Journal Title: Applied Physics Letters 94
  • Peer Reviewed
• [Journal Article] Halide-stabilized LiBH_4, a room-temperature lithium fast-ion conductor (2009)
  • Author(s): H.Maekawa, et.al.
  • Journal Title: Journal of the American Chemical Society 131 Pages: 894-895
  • Peer Reviewed
• [Journal Article] Complex hydrides with(BH_4)^- and(NH_2)^- anions as new lithium fast-ion conductors (2009)
  • Author(s): M.Matsuo, et.al.
  • Journal Title: Journal of the American Chemical Society 131 Pages: 16389-16391
  • Peer Reviewed
• [Journal Article] Experimental and computational studies on structural transitions in the LiBH_4-LiI pseudobinary system (2009)
  • Author(s): H.Oguchi, et.al.
  • Journal Title: Applied Physics Letters 94
  • Peer Reviewed
• [Journal Article] Diffuse and doubly split atom occupation in hexagonal LiBH_4 (2009)
  • Author(s): T.Ikeshoji, et.al.
  • Journal Title: Applied Physics Letters 95
  • Peer Reviewed
• [Journal Article] Formation of intermediate compound with B_<12>H_<12> cluster : Experimental and theoretical studies on magnesium borohydride Mg(BH_4)_2 (2009)
  • Author(s): H-.W. Li, et.al.
  • Journal Title: Nanotechnology 20
  • Peer Reviewed
• [Journal Article] Synthesis and partial dehydrogenation of the impregnated lithium borohydride, LiBH_4 (2009)
  • Author(s): M.Menjo, et.al.
  • Journal Title: Journal of the Ceramic Society of Japan 117 Pages: 457-460
  • Peer Reviewed
• [Presentation] Stability and Dynamics of Metal Borohydrides for Energy Applications (2011)
  • Author(s): S.Orimo
  • Organizer: 8th International Workshop on WATER DYNAMICS
  • Place of Presentation: 日本,仙台(招待講演)
  • Year and Date: 2011-03-10
• [Presentation] エネルギー利用を目指した錯体水素化物の機能設計 (2011)
  • Author(s): 折茂慎一
  • Organizer: 環境調和型水素製造システムにおける生成と吸藏貯蔵の一体化研究会
  • Place of Presentation: 日本,名古屋(招待講演)
  • Year and Date: 2011-02-23
• [Presentation] Complex Hydride Ionics (2011)
  • Author(s): S.Orimo
  • Organizer: 5th International Symposium Hydrogen and Energy
  • Place of Presentation: スイス,シュトース(招待講演)
  • Year and Date: 2011-01-25
• [Presentation] Hydrogen Storage and Ionics in Complex Hydrides (2010)
  • Author(s): S.Orimo
  • Organizer: Workshop on Computational Materials Science on Hydrogen Storage
  • Place of Presentation: 日本,仙台(招待講演)
  • Year and Date: 2010-12-12
• [Presentation] エネルギー利用を目指した水素化物の機能設計 (2010)
  • Author(s): 折茂慎一
  • Organizer: 第8回水素量子アトミクス研究会
  • Place of Presentation: 日本,愛媛(招待講演)
  • Year and Date: 2010-10-28
• [Presentation] Complex Hydrides for Alternative Energy Sources (2010)
  • Author(s): S.Orimo
  • Organizer: E-MRS 2010 Fall Meeting
  • Place of Presentation: ポーランド,ワルシャワ(招待講演)
  • Year and Date: 2010-09-13
• [Presentation] Complex Hydrides as Advanced Energy Storage Materials (2010)
  • Author(s): S.Orimo
  • Organizer: The 7th Pacific Rim International Conference on Advanced Materials and Processing (PRICM-7)
  • Place of Presentation: オーストラリア,ケアンズ(基調講演)
  • Year and Date: 2010-08-03
• [Presentation] "High-Density Hydrogen Storage" and "Lithium Super(Fast)-Ionic Conduction" in Metal Borohydrides (2010)
  • Author(s): S.Orimo
  • Organizer: International Symposium on Metal-Hydrogen Systems (MH2010)
  • Place of Presentation: ロシア,モスクワ(招待講演)
  • Year and Date: 2010-07-19
• [Presentation] ボロハイドライドのリチウム高速イオン伝導機能(基調講演) (2010)
  • Author(s): 折茂慎一
  • Organizer: 日本金属学会2010年春期(第146回)大会
  • Place of Presentation: 日本,つくば
  • Year and Date: 2010-03-28
• [Presentation] High-density hydrogen storage and lithium super-ionic conduction in metal borohydrides(招待講演) (2010)
  • Author(s): 折茂慎一
  • Organizer: American Physical Society(APS)March Meeting 2010
  • Place of Presentation: 米国,ポートランド
  • Year and Date: 2010-03-15
• [Presentation] Physics and chemistry of hydrogen storage materials(基調講演) (2010)
  • Author(s): 折茂慎一
  • Organizer: JAEA-Symposium on Synchrotron Radiation Research 2010 -Material Science on Metal Hydride-
  • Place of Presentation: 日本,佐用
  • Year and Date: 2010-02-26
• [Presentation] Stability and dynamics of metal borohydrides(招待講演) (2009)
  • Author(s): 折茂慎一
  • Organizer: 2009 MRS Fall Meeting
  • Place of Presentation: 米国,ボストン
  • Year and Date: 2009-12-02
• [Presentation] High-density hydrogen storage and lithium super-ionic conductivity in metal borohydrides(基調講演) (2009)
  • Author(s): 折茂慎一
  • Organizer: 5th IUPAC & 19th FCFP & 3rd Symposium on Power Sources for Energy Storage and their Key Materials
  • Place of Presentation: 中国,上海
  • Year and Date: 2009-10-20
• [Presentation] Metal borohydrides for energy storage(招待講演) (2009)
  • Author(s): 折茂慎一
  • Organizer: 42nd IUPAC CONGRESS "Chemistry Solutions, Materials, Hydrogen Storage"
  • Place of Presentation: 英国,グラスゴー
  • Year and Date: 2009-08-03
• [Presentation] 水素機能材料における新物質探索(招待講演) (2009)
  • Author(s): 折茂慎一
  • Organizer: 応用物理学会超伝導分科会第39回研究会
  • Place of Presentation: 日本,東京
  • Year and Date: 2009-06-07
• [Book] 未来材料 (2011)
  • Author(s): 松尾元彰, 折茂慎一
  • Publisher: エヌ・ティー・エス
• [Book] セラミックデータブック2009/10年版,「錯体水素化物LiBH_4におけるリチウム超イオン伝導」 (2009)
  • Author(s): 松尾元彰, 折茂慎一
  • Total Pages: 186
  • Publisher: 工業製品技術協会
• [Remarks]
  • URL: http://www.hydrogen.imr.tohoku.ac.jp/
• [Remarks]
  • URL: http://www.hydrogen.imr.tohoku.ac.jp/