1997 Fiscal Year Annual Research Report

イオン高速輸送機能をもつ固体の創製と評価

Research Project

Project/Area Number	07239105
Research Institution	KYOTO UNIVERSITY
Principal Investigator	小久見善八京都大学, 工学研究科, 教授 (60110764)
Co-Investigator(Kenkyū-buntansha)	渡辺正義静岡国立大学, 工学部, 助教授 (60158657) 藤波達雄静岡大学, 工学部, 教授 (80022010) 岸本昭東京大学, 生産技術研究所, 助教授 (30211874) 江坂淳男鳥取大学, 工学部, 教授 (70116317) 八尾健京都大学, エネルギー科学研究科, 教授 (50115953)
Keywords	イオン導電性 / 固体イオニクス / ポリマー電解質 / 複合化 / 薄膜形成法 / 塩化物 / 酸化物
Research Abstract	前年度までの構造班、ダイナミクス班の成果を活かして、また、応用班の要求を容れた新規高速イオン移動固体の創製を目指すと共に、既知イオンの移動固体の構造制御と新規プロセッシング技術の開発を目指した。得られた成果は以下の通りである。 1.新規高速イオンで移動固体の創製 1)Clを導入した複塩化物水素化物CsCaCl_<3-x>H_xおよびCsCa_<1-y>Na_yCl_<3-x-y>H_x(x<0.05)固溶体を合成し、600℃で10^<-3>Scm^<-1>を越す導電率を示す材料が得られた。 2)800℃で3.4x10^<-2>Scm^1に達する高いイオン導電率を示すPb_<1-x>La_xWO_<4+x/2>及びPb_<1-x>La_<2x/3>WO_4を合成し、その伝導機構を明らかにした。 3)極めて高度に枝分かれしたポリエーテル系のポリマー電解質P(EO/MEEGE)にリチウムイミド塩を複合化したポリマー電解質の導電率が通常のポリエーテル系ポリマー電解質の約10倍高くなることを見いだした。 4)アルミニウムの替わりにホウ素を中心金属とするアート型錯体を用いるポリマー電解質を合成した。このポリマー電解質はアルミニウムを含む物より2倍以上高いイオン導電率を与えることが分かった。 2.高速イオン移動固体の構造制御ナノサイズのアルミナ粒子を分散添加して強化したジルコニアセラミックスの機械特性を評価し、アルミナ添加量10%まではイオン導電性が増大することを明らかにした。 3.新プロセッシング法の開発 1)液相から直接イオン伝導性結晶薄膜を析出させる方法を発展させ、Laの一部をSrで置換したなどの複雑な構造を持つ酸化物を基盤に用いたPET板の上に直径10〜30μm程度の粒子の凝集体で析出させることができた。 2)前年度に開発したNiOを酸素源とし、直径約100μmで湾曲したセリアのホローファイバーを合成した。また、この反応による析出メカニズムを明らかにした。

Research Products

(30 results)

All Other

All Publications (30 results)

[Publications] T.Esaka et al.: "Application of NR to Study the Lithium Ion Transfer Solid Ionic Conductors" Key Engineering Materials. 132-136. 1393-1396 (1997)
[Publications] M.Kamata et al.: "Application of Neutron Radiography to the Study of Lithium Batteries" J.Power Sources. 68. 459-462 (1997)
[Publications] H.Morimoto et al.: "Preparation of the Perovskite-type Oxide Ceramic Ca_<1-x>La_<x/3>MnO_<3/1A> as the Cathode Active Materials in Alkaline Batteries" Material Research Bulletin. 32. 1359-1366 (1997)
[Publications] M.Kamata et al.: "Application of Neutron Radiography to the Research of Lithium Ion Conductors and Lithium Batteries" The Proceedings of 5th World Conference on Neutron Radiography. 650-656 (1997)
[Publications] S.Takai et al.: "Mechanical Alloying of the Perovskite-type structured Powder of La_<2/3-x>Li_<3x>TiO_3 Showing lithium Ion Conduction" The proceedings of Int.Symposium on Metastable,Mechanically Alloyed and Nanocrystalline Materials (LSMANAM,97) in press.
[Publications] S.Takai et al.: "Conductivity Relaxation Studies on (Bi_1O_3)_<1-x>(Y_2O_3)_x and (Bi_2O_3)_<1-x>(Gd_2O_3)_x with the defect fluorite structure" Material Research Bulletin,in press.
[Publications] M.Kamata et al.: "Synthesis and Ionic Conductivity of LiBaF_<3rX>H_X" Denki Kagaku,in press.
[Publications] T.Esaka et al.: "Measurements to Study the Reversible Transfer of Lithium Ion in Lithium Titanium Oxide" The Proceedings of Materials Research Society 1997 Fall Meeting,in press.
[Publications] T.Harada et al.: "Nonlinear current-voltage characteristics of Homojunctions made by zinc oxide single crystals" J.Mat.Res.Soc.458. 343-347 (1997)
[Publications] Y.Nakamura et al.: "High Temperature Strain Sensor Using NiO-CaO Solid Solution" Jpn.Sensor Newsletter,Edison Sensor Technology Center. 11. 19-23 (1997)
[Publications] Y.Nakamura et al.: "Strain-Dependent Electrical Conduction in the System NiO-CaO" J.Am.Ceram.Soc.80. 1609-1611 (1997)
[Publications] Y.Nakamura: "Comparison of the Mechanical and Dielectric Strength Distribution for Hardened Gypsum" J.Mat.Sci.32. 115-118 (1997)
[Publications] T.Fujinami et al.: "Siloxyalminate Polymers with High Li+Ion Conductivity" Chemistry of Materials. 9. 2236-2239 (1997)
[Publications] 藤波達雄: "アート錯体型イオン伝導性高分子" 電池技術. 9. 30-37 (1997)
[Publications] 藤波達雄: "有機無機ハイブリッド型イオン導電体" 高分子加工. 46. 450-454 (1997)
[Publications] 渡邊正義: "高分子中のイオンダイナミクスと高分子固体電解質" 熱測定. 24. 12-21 (1997)
[Publications] K.Ichikawa et al.: "Molecular Relaxation of a Branched Poly (ethylene oxide) Network Polymer" Polym.J.29. 429-433 (1997)
[Publications] A.Nishimoto et al.: "High Ionic Conductivity of New Polymer Electolytes based on High Molecular Weight Polyether Comb Polymers" Electrochim.Acta,. (in press).
[Publications] A.Uedono et al.: "Open Spaces and Molecular Motions of Polyether-Based Network Polymers Probed by Positron Annihilatio" J.Polym.Sci,Part B,Polym.Phys. (in press).
[Publications] M.Kono et al.: "Network Polymer Electrolytes having Free Chain Ends as Internal Plasticizer" J.Electrochem.Soc,. (in press).
[Publications] 渡邊正義: "ゴム状態とポリマーイオニクス材料" 日本ゴム協会誌. 70. 477-484 (1997)
[Publications] 渡邊正義: "高分子固体電解質の最近の進展" 電気化学. 65. 920-925 (1997)
[Publications] T.Yao et al.: "Novel Method for Zirconium Oxide Synthesis from Aqueous Solution" J.Am.Ceram.Soc.79. 3329-3330 (1996)
[Publications] Y.Oka et al.: "Crystal Structures of Cs_2V_4O_<11> with Unusual V-O Coordinations" J.Solid State Chem.134. 52-58 (1997)
[Publications] Y.Oka et al.: "Hydrothermal Synthesis and Structure Refinemient of Alkali-Metal Trivanadates AV_3O_8 (A=K,Rb,Cs)" Mater.Res.Bullet.32. 1201-1209 (1997)
[Publications] M.Inaba et al.: "Growth Rate of Yttria-Stabilized Zircomia Thin Films Formed by Electrochemical Vapor-Deposition Using NiO as an Oxygen Soura" Solid State Ionics. 104. 303-310 (1997)
[Publications] M.Inaba et al.: "Raman Study of Layered Rock-Salt LiCoO_2 and Its Electrochemical Lithium Deintercalation" J.Raman Spectrosc.28. 613-617 (1997)
[Publications] T.Ioroi: "Preparation of Perovskite-Type La_<1-x> Sr_x MnO_3 Films by Vapor-Phase Processes and Their Electrochemical Proper" J.Electrochem.Soc.144. 1362-1370 (1997)
[Publications] 岸本昭: "「工業材料大事典」" 産業調査会, (1997)
[Publications] 岸本昭: "「セラミックス用語辞典」" 日刊工業新聞, (1997)

1997 Fiscal Year Annual Research Report

イオン高速輸送機能をもつ固体の創製と評価

Principal Investigator

小久見 善八 京都大学, 工学研究科, 教授 (60110764)

Research Products

[Publications] T.Esaka et al.: "Application of NR to Study the Lithium Ion Transfer Solid Ionic Conductors" Key Engineering Materials. 132-136. 1393-1396 (1997)

[Publications] M.Kamata et al.: "Application of Neutron Radiography to the Study of Lithium Batteries" J.Power Sources. 68. 459-462 (1997)

[Publications] H.Morimoto et al.: "Preparation of the Perovskite-type Oxide Ceramic Ca_<1-x>La_<x/3>MnO_<3/1A> as the Cathode Active Materials in Alkaline Batteries" Material Research Bulletin. 32. 1359-1366 (1997)

[Publications] M.Kamata et al.: "Application of Neutron Radiography to the Research of Lithium Ion Conductors and Lithium Batteries" The Proceedings of 5th World Conference on Neutron Radiography. 650-656 (1997)

[Publications] S.Takai et al.: "Mechanical Alloying of the Perovskite-type structured Powder of La_<2/3-x>Li_<3x>TiO_3 Showing lithium Ion Conduction" The proceedings of Int.Symposium on Metastable,Mechanically Alloyed and Nanocrystalline Materials (LSMANAM,97) in press.

[Publications] S.Takai et al.: "Conductivity Relaxation Studies on (Bi_1O_3)_<1-x>(Y_2O_3)_x and (Bi_2O_3)_<1-x>(Gd_2O_3)_x with the defect fluorite structure" Material Research Bulletin,in press.

[Publications] M.Kamata et al.: "Synthesis and Ionic Conductivity of LiBaF_<3rX>H_X" Denki Kagaku,in press.

[Publications] T.Esaka et al.: "Measurements to Study the Reversible Transfer of Lithium Ion in Lithium Titanium Oxide" The Proceedings of Materials Research Society 1997 Fall Meeting,in press.

[Publications] T.Harada et al.: "Nonlinear current-voltage characteristics of Homojunctions made by zinc oxide single crystals" J.Mat.Res.Soc.458. 343-347 (1997)

[Publications] Y.Nakamura et al.: "High Temperature Strain Sensor Using NiO-CaO Solid Solution" Jpn.Sensor Newsletter,Edison Sensor Technology Center. 11. 19-23 (1997)

[Publications] Y.Nakamura et al.: "Strain-Dependent Electrical Conduction in the System NiO-CaO" J.Am.Ceram.Soc.80. 1609-1611 (1997)

[Publications] Y.Nakamura: "Comparison of the Mechanical and Dielectric Strength Distribution for Hardened Gypsum" J.Mat.Sci.32. 115-118 (1997)

[Publications] T.Fujinami et al.: "Siloxyalminate Polymers with High Li+Ion Conductivity" Chemistry of Materials. 9. 2236-2239 (1997)

[Publications] 藤波達雄: "アート錯体型イオン伝導性高分子" 電池技術. 9. 30-37 (1997)

[Publications] 藤波達雄: "有機無機ハイブリッド型イオン導電体" 高分子加工. 46. 450-454 (1997)

[Publications] 渡邊正義: "高分子中のイオンダイナミクスと高分子固体電解質" 熱測定. 24. 12-21 (1997)

[Publications] K.Ichikawa et al.: "Molecular Relaxation of a Branched Poly (ethylene oxide) Network Polymer" Polym.J.29. 429-433 (1997)

[Publications] A.Nishimoto et al.: "High Ionic Conductivity of New Polymer Electolytes based on High Molecular Weight Polyether Comb Polymers" Electrochim.Acta,. (in press).

[Publications] A.Uedono et al.: "Open Spaces and Molecular Motions of Polyether-Based Network Polymers Probed by Positron Annihilatio" J.Polym.Sci,Part B,Polym.Phys. (in press).

[Publications] M.Kono et al.: "Network Polymer Electrolytes having Free Chain Ends as Internal Plasticizer" J.Electrochem.Soc,. (in press).

[Publications] 渡邊正義: "ゴム状態とポリマーイオニクス材料" 日本ゴム協会誌. 70. 477-484 (1997)

[Publications] 渡邊正義: "高分子固体電解質の最近の進展" 電気化学. 65. 920-925 (1997)

[Publications] T.Yao et al.: "Novel Method for Zirconium Oxide Synthesis from Aqueous Solution" J.Am.Ceram.Soc.79. 3329-3330 (1996)

[Publications] Y.Oka et al.: "Crystal Structures of Cs_2V_4O_<11> with Unusual V-O Coordinations" J.Solid State Chem.134. 52-58 (1997)

[Publications] Y.Oka et al.: "Hydrothermal Synthesis and Structure Refinemient of Alkali-Metal Trivanadates AV_3O_8 (A=K,Rb,Cs)" Mater.Res.Bullet.32. 1201-1209 (1997)

[Publications] M.Inaba et al.: "Growth Rate of Yttria-Stabilized Zircomia Thin Films Formed by Electrochemical Vapor-Deposition Using NiO as an Oxygen Soura" Solid State Ionics. 104. 303-310 (1997)

[Publications] M.Inaba et al.: "Raman Study of Layered Rock-Salt LiCoO_2 and Its Electrochemical Lithium Deintercalation" J.Raman Spectrosc.28. 613-617 (1997)

[Publications] T.Ioroi: "Preparation of Perovskite-Type La_<1-x> Sr_x MnO_3 Films by Vapor-Phase Processes and Their Electrochemical Proper" J.Electrochem.Soc.144. 1362-1370 (1997)

[Publications] 岸本昭: "「工業材料大事典」" 産業調査会, (1997)

[Publications] 岸本昭: "「セラミックス用語辞典」" 日刊工業新聞, (1997)

小久見善八京都大学, 工学研究科, 教授 (60110764)