アモルファス固体電解質材料の作製と特性評価

• Project/Area Number: 11229204
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Osaka Prefecture University
• Principal Investigator: 南 努 大阪府立大学, 学長 (80081313)
• Co-Investigator(Kenkyū-buntansha): 松田 厚範 豊橋技術科学大学, 物質工学系, 助教授 (70295723) ; 忠永 清治 大阪府立大学, 工学研究科, 助教授 (90244657) ; 辰巳砂 昌弘 大阪府立大学, 工学研究科, 教授 (50137238) ; 河村 純一 東北大学, 多元物質研究所, 助教授 (50142683) ; 町田 信也 甲南大学, 理工学部, 助教授 (10190381)
• Project Period (FY): 1999 – 2003
• Project Status: Completed (Fiscal Year 2003)
• Budget Amount: ¥64,600,000 (Direct Cost: ¥64,600,000); Fiscal Year 2003: ¥12,100,000 (Direct Cost: ¥12,100,000); Fiscal Year 2002: ¥13,500,000 (Direct Cost: ¥13,500,000); Fiscal Year 2001: ¥9,000,000 (Direct Cost: ¥9,000,000); Fiscal Year 2000: ¥14,800,000 (Direct Cost: ¥14,800,000); Fiscal Year 1999: ¥15,200,000 (Direct Cost: ¥15,200,000)
• Keywords: イオン伝導 / 固体電解質 / オキシスルフィドガラス / メカニカルミリング / プロトン伝導 / 非晶質 / 伝導度 / 無機ゲル / 導電率

Research Abstract

本年度得られた成果は以下の通りである。
1.リチウムイオン濃度を高めたLi_2S-SiS_2-P_2S_5-Al_2S_3多成分系ガラスを比較的低温で結晶化させることによって、固相反応では得られない高イオン伝導性チオリシコン結晶がガラスから初晶として析出し、室温で1.2x10^<-3>Scm^<-1>の極めて高い導電率を示すことが分った。
2.メカノケミカル法を用いてSnS-P_2S_5系負極材料やCu-S系正極材料を合成し、共通のガラスフォーマーを有するLi_2S-P_2S_5系固体電解質と組み合わせた全固体電池を試作した。いずれの場合もサイクル特性に優れた二次電池として作動し、従来のリチウムイオン二次電池と比べると大きな充放電容量の得られることが分かった。
3.Li_2S-P_2S_5系固体電解質を用いたIn/LiCoO_2系全固体電池において導電助剤の検討を行ったところ、アセチレンブラックは初期不可逆容量の一因となることが分かった。一方、気相成長炭素繊維を用いると不可逆容量を低減することができ、高電流密度での充放電が可能になることが明らかになった。
4.ゾル-ゲル法によってホスホシリケート系ハイブリッドおよびコンポジット系シートを作製した。γ-グリシドキシプロピルトリメトキシシランを用いたハイブリッド系シートやポリイミドを用いたコンポジットシートを電解質膜とした固体高分子形燃料電池は、130℃以上、相対湿度数%の中温低加湿条件下でOCVが0.7-0.85V、最大出力が20-50mWcm^<-2>を示し、連続発電できることが分かった。
5.レーザー蒸着(PLD)法によって、SnO/Li-V-Si-O系ガラス/LiCoO_2系全固体薄膜リチウム二次電池を試作した。200μAcm^<-2>までは二次電池として作動可能であり、容量は大きくないものの、100サイクル以上の充放電を確認した。動作可能な薄膜二次電池が全プロセスPLD法を用いて作製できたことにより、将来のマイクロエレクトロニクスの電源素子として、そのプロセスの確立が望まれる。

Research Products

• [Publications] 辰巳砂昌弘: "ガラスベース固体電解質(解説)"未来材料. 3[2]. 10-15 (2003)
• [Publications] A.Hayashi: "Formation of Superionic Crystals from Mechanically Milled Li_2S-P_2S_5 Glasses"Electrochem.Commun.. 5. 111-114 (2003)
• [Publications] A.Hayashi: "Fast Lithium-Ion Conducting Glass-Ceramics in the System Li_2S-SiS_2-P_2S_5"Electrochem.Solid-State Lett.. 6[3]. A47-A49 (2003)
• [Publications] K.Tadanaga: "Preparation of LiCoPO_4 for Lithium Battery Cathodes through Solution Process"Electrochemistry. 71[12]. 1192-1195 (2003)
• [Publications] 忠永清治: "中温作動燃料電池用プロトン伝導性無機-有機複合体電解質膜(解説)"工業材料. 51[4]. 35-38 (2003)
• [Publications] K.Tadanaga: "Preparation of Proton-Conductive Inorganic-Organic Hybrid Films from 3-Glycidoxypropyltrimethoxysilane and Orthophosphoric Acid"Chem.Mater.. 15[9]. 1910-1912 (2003)
• [Publications] C.Iwakura: "All Solid-State Nickel/Metal Hydride Battery with a Proton-Conductive Phosphoric Acid-Doped Silica Gel Electrolyte"Electrochimica Acta. 48[11]. 1499-1503 (2003)
• [Publications] F.Mizuno: "Cycle Performance of All-Solid-State In/LiCoO_2 Batteries with Li_2S-P_2S_5 Glass-Ceramic Electrolytes"Electrochemistry. 71[12]. 1196-1200 (2003)
• [Publications] A.Hayashi: "Structural Studies in Lithium Insertion into SnO-B_2O_3 Glasses and Their Applications for All-Solid-State Batteries"J.Electrochem.Soc.. 150[5]. A582-A587 (2003)
• [Publications] K.Tadanaga: "Inorganic-Organic Hybrid Films from 3-Glycidoxypropyltrimethoxysilane and Orthophosphoric Acid for Medium Temperature Fuel Cells"Electrochem.Commun.. 5. 644-646 (2003)
• [Publications] A.Hayashi: "All-Solid-State Li/S Batteries with Highly Conductive Glass-Ceramic Electrolytes"Electrochem.Commun.. 5. 701-705 (2003)
• [Publications] N.Kuwata: "Cation Dynamics of Stabilized α-AgI in AgI-Ag_2O-MoO_3 Glasses, Studied by Ag-109 NMR Spectroscopy"J.Non-Cryst.Solids. 324[1-2]. 79-91 (2003)
• [Publications] A.Hayashi: "High Conductivity of Superionic-Glass-in-Ionic-Liquid Solutions"Electrochem.Solid-State Lett.. 6[8]. E19-E22 (2003)
• [Publications] A.Matsuda: "Preparation and Characterization of Thermally Stable Proton-Conducting Composite Sheets Composed of Phosphosilicate Gel and Polyimide"Solid State Ionics. 162-163. 247-252 (2003)
• [Publications] A.Matsuda: "Proton Conductivity at Medium Temperature Range and Chemical Durability of Phosphosilicate Gels Added with a Third Component"Solid State Ionics. 162-163. 253-259 (2003)
• [Publications] F.Mizuno: "All-Solid-State Lithium Secondary Batteries Using a Layer-Structured LiNi0.5Mn0.5O2 Cathode Material"J.Power Sources. 124. 170-173 (2003)
• [Publications] H.Morimoto: "Cathode Properties of Amorphous 66.7V_2O_5・33.3FeOOH Powders Obtained by Mechanical Milling Technique"Electrochemistry. 71[12]. 1036-1038 (2003)
• [Publications] 辰巳砂昌弘: "先端化学シリーズII(著書、分担執筆)執筆項目「無機イオン伝導体」(日本化学会編)"丸善. 7 (2003)
• [Publications] 辰巳砂昌弘: "電子とイオンの機能化学シリーズVol.3(著書、分担執筆)執筆項目「リチウムイオン伝導性ガラス」"エヌ・ティー・エス. 15 (2003)
• [Publications] A.Matsuda: "Phosphosilicate Gels as a Solid State Proton Conductor at Medium Temperature and Low Humidity"J. Ceram. Soc. Jpn.. 110・[2]. 131-134 (2002)
• [Publications] 辰巳砂昌弘: "超イオン伝導ガラスの開発(総説)"機械の研究. 54・[2]. 19-26 (2002)
• [Publications] 松田厚範: "ホスホシリケートゲルおよび無機-有機ハイブリッド(解説)"工業材料. 50・[3]. 39-42 (2002)
• [Publications] K.I-io: "Mechanochemical Synthesis of High Lithium Ion Conducting Materials in the System Li_3N-SiS_2"Chem. Mater.. 14・[6]. 2444-2449 (2002)
• [Publications] A.Hayashi: "Characterization of Li_2S-SiS_2-LixMOy (M=Si, P, Ge) Amorphous Solid Electrolytes Prepared by Melt-Quenching and Mechanical Milling"Solid State Ionics. 148. 381-389 (2002)
• [Publications] K.Tadanaga: "Conductivity Enhancement and Thermal Properties of AgI-MO_2 (M=Zr, Si) Composites Using Sol-Gel Derived Aerogels"J. Electrochem. Soc.. 149・[6]. A773-A777 (2002)
• [Publications] 南 努: "超イオン伝導ガラスの開発-全固体二次電池の実現をめざして-(解説)"科学と工業. 76・[7]. 303-310 (2002)
• [Publications] A.Matsuda: "Sol-Gel Derived Porous Silica Gels Impregnated with Sulfuric Acid-Pore Structure and Proton Conductivities at Medium Temperatures-"J. Electrochem. Soc.. 149・[8]. E292-E297 (2002)
• [Publications] A.Hayashi: "Structural Investigation of SnO-B_2O_3 Glasses by Solid-State NMR and X-ray Photoelectron Spectroscopy"J. Non-Cryst. Solids. 306・[3]. 227-237 (2002)
• [Publications] F.Mizuno: "All Solid-State Lithium Secondary Batteries Using High Lithium Ion Conducting Li_2S-P_2S_5 Glass-Ceramics"Chem. Lett.. [12]. 1244-1245 (2002)
• [Publications] A.Hayashi: "Characterization of Li_2S-SiS_2-Li_3MO_3 (M=B, Al, Ga and In) Oxysuffide Glasses and Their Application to Solid State Lithium Secondary Batteries"Solid State Ionics. 152-153. 285-290 (2002)
• [Publications] S.Kohjiya: "Solid Electrolyte Composed of 95(0.6Li_2S・0.4SiS_2)・5Li_4SiO_4 Glass and High Molecular Weight Branched Poly(oxyethylene)"Solid State Ionics. 154-155. 1-6 (2002)
• [Publications] M.Tatsumisago: "New Lithium Ion Conducting Glass-Ceramics Prepared from Mechanochemical Li_2S-P_2S_5 Glasses"Solid State Ionics. 154-155. 635-640 (2002)
• [Publications] A.Matsuda: "Proton Conductivities of Sol-Gel Derived Phosphosilicate Gels in Medium Temperature Range with Low Humidity"Solid State Ionics. 154-155. 687-692 (2002)
• [Publications] K.Tadanaga: "Proton Conductive Inorganic-Organic Hybrid Membranes as an Electrolyte for Fuel Cells Prepared from 3-Glycidoxypropyltrimethoxysilane and Orthophosphoric Acid"Electrochemistry. 70・[12]. 998-1000 (2002)
• [Publications] N.Machida: "All-Solid-State Lithium Battery with LiCo_<0.3>Ni_<0.7>O_2 Fine Powder as Cathode Materials with an Amorphous Sulfide Electrolyte"J. Electrochem. Soc.. 149・[6]. A688-A693 (2002)
• [Publications] J.Kawamura: "Evidence of Multisite Exchange in AgI-AgPO_3 Glasses : ^<109>Ag NMR Hole-Burning Spectra"Solid State Ionics. 154. 183-188 (2002)
• [Publications] A.Hayashi: "Preparation of Li_2S-P_2S_5 Amorphous Solid Electrolytes by Mechanical Milling"J.Am.Ceram.Soc.. 84[2]. 477-479 (2001)
• [Publications] A.Matsuda: "Proton Conductivity and Structure of Phosphosilicate Gels Derived from Tetraethoxysilane and Phosphoric Acid or Triethylphosphate"Solid State Ionics. 139[1-2]. 113-119 (2001)
• [Publications] R.Komiya: "Solid State Lithium Secondary Batteries Using an Amorphous Solid Electrolyte in the System(100-x)(0.6Li_2S・0.4SiS_2)・xLi_4SiO_4 Obtained by Mechanochemical Synthesis"Solid State Ionics. 140. 83-87 (2001)
• [Publications] Y.Ikeda: "Ion Conducting Composite from Li_2S-SiS_2-Li_4SiO_4 Oxysulfide Glass and Poly(oxyethylene)s"Polymer. 42[16]. 7225-7228 (2001)
• [Publications] M.Tatsumisago: "Stabilization of Superionic α-AgI at Room Temperature by Heating of AgI-Ag_2O-MoO_3 Glasses"Chem.Lett.. [8]. 790-791 (2001)
• [Publications] A.Hayashi: "Preparation and Characterization of Lithium Ion Conducting Glass-Polymer Composites"Chem.Lett.. [8]. 814-815 (2001)
• [Publications] R.Araki: "Electronic States Calculated by the DV-Xα Cluster Method for Lithium Ion Conductive Li_2S-SiS_2-Li_4SiO_4 Oxysulfide Glasses"J.Non-Cryst.Solids. 288. 1-7 (2001)
• [Publications] T.Saito: "Crystallization of α-AgI from Melt and Glass in the Agl-Ag_2O-B_2O_3 System"J.Ceram.Soc.Jpn.. 109[9]. 757-760 (2001)
• [Publications] A.Hayashi: "High Lithium Ion Conductivity of Glass-Ceramics Derived from Mechanically Milled Glassy Powders"Chem.Lett.. [9]. 872-873 (2001)
• [Publications] M.Tatsumisago: "Formation of α-AgI Stabilized Composites from AgI-Ag_2O-B_2O_3 Melts and Glasses"J.Non-Cryst.Solids. 293-295. 10-18 (2001)
• [Publications] M.Tatsumisago: "Preparation of α-AgI Stabilized Composites from AgI-Ag_2O-MxOy(MxOy=B_2O_3,MoO_3)Melts and Glasses"Phys.Chem.Glasses. 42[3]. 215-219 (2001)
• [Publications] A.Matsuda: "Comparison of Structure and Proton Conductivity of Phosphosilicate Gels Derived from Several Kinds of Phosphorus-Containing Compounds"Solid State Ionics. 145. 161-166 (2001)
• [Publications] A.Matsuda: "Proton Conductivity of Acid-Impregnated Mesoporous Silica Gels Prepared Using Surfactants as a Template"Solid State Ionics. 145. 135-140 (2001)
• [Publications] A.Matsuda: "Medium Temperature Range Characterization as a Proton Conductor for Phosphosilicate Gels Containing Large Amounts of Phosphorus"Electrochim.Acta. 47[6]. 939-944 (2001)
• [Publications] M.Nakai: "Preparation and Characterization of SnO-Based Glasses as Anode Materials for Lithium Secondary Batteries"J.Ceram.Soc.Jpn. 109[12]. 1010-1016 (2001)
• [Publications] 南 努: "超イオン伝導ガラス-全固体二次電池用電解質-(解説)"未来材料. 1[1]. 80-81 (2001)
• [Publications] 松田厚範: "燃料電池用ホスホシリケートゲル固体電解質の開発-中温低湿度環境下で高いプロトン伝導性を示す(解説)"エコインダストリー. 6[6]. 5-10 (2001)
• [Publications] 松田厚範: "ゾル-ゲル法によるプロトン伝導性複合材料の開発(解説)"New Glass. 16[2]. 46-51 (2001)
• [Publications] M.Tatsumisago: "Preparation and Characterization of Amorphous Based Solid Electrolytes(総説)"J.Ceram.Soc.Jpn. 109[10]. 809-814 (2001)
• [Publications] 辰巳砂昌弘: "リチウムイオン伝導体(総説)"Electrochemistry. 69[10]. 793-797 (2001)
• [Publications] 松田厚範: "ゾル-ゲル法によるプロトン伝導性無機-有機複合体の作製と全固体型イオニクス素子への応用(解説)"日本ゴム協会誌. 74[11]. 50-55 (2001)
• [Publications] 辰巳砂昌弘: "ガラスのイオン伝導(総説)"マテリアルインテグレーション. 14[11]. 37-43 (2001)
• [Publications] J.Kawamura: "High temperature P-31 NMR study on Mg^<2+> ion conductors"Solid State Commun.. 120[7-8]. 295-298 (2001)
• [Publications] 辰巳砂昌弘: "化学総説(日本化学会編)「新型電池の材料化学」(分担執筆)"学会出版センター. 123-125 (2001)
• [Publications] K.Hirata: "Preparation and Characterization of Highly Proton-Conductive Composites Composed of Phosphoric Acid-Doped Silica Gel and Styrene-Ethylene-Butylene-Styrene Elastomer"J.Sol-Gel Sci.Tech. 17[1]. 61-69 (2000)
• [Publications] A.Matsuda: "Proton-Conductive Composites Composed of Phosphoric Acid-Doped Silica Gel and Organic Polymers with Sulfo Groups"J.Ceram.Soc.Jpn.. 108[1]. 45-50 (2000)
• [Publications] H.Morimoto: "Mechanochemical Synthesis of the High Lithium Ion Conductive Amorphous Materials in the Systems Li_2S-SiS_2 and Li_2S-SiS_2-Li_4Si0_4"J.Ceram.Soc.Jpn.. 108[2]. 128-132 (2000)
• [Publications] 林晃敏: "硫化物系リチウムイオン伝導ガラスの作製とキャラクタリゼーション(総説)"金属. 70[7]. 550-558 (2000)
• [Publications] M.Tatsumisago: "Preparation and Structure of Amorphous Solid Electrolytes Based on Lithium Sulfide"J.Non-Cryst.Solids. 274[1-3]. 30-38 (2000)
• [Publications] A.Hayashi: "Crystallization Process of Lithium Oxysulfide Glasses"J.Non-Cryst.Solids. 276[1-3]. 27-34 (2000)
• [Publications] T.Minami: "Superionic Borate Glasses : Microstructure and Fragility of AgI-Ag_2O-B_2O_3 Glasses"Phys.Chem.Galsses. 41[5]. 236-241 (2000)
• [Publications] A.Hayashi: "Development of Lithium Ion Conducting Oxysulfide Glasses"Proc.7th Asian Conf.on Solid State Ionics. 177-186 (2000)
• [Publications] H.Yamashita: "Formation Process of 60Li2S・40SiS2 Amorphous Materials with High Lithium Ion Conductivity Prepared by Mechanical Milling"J.Ceram.Soc.Jpn.. 108[11]. 973-978 (2000)
• [Publications] K.Tadanaga: "Preparation of AgI-Al_2O_3 Composites with High Ionic Conductivity Using Al_2O_3 Aerogel and Xerogel"J.Electrochem.Soc.. 147[11]. 4061-4064 (2000)
• [Publications] N.Machida: "Mechano Chemical Synthesis of a Silver Ion Conductor in the System AgI-Ag_3PO_4"Solid State Inoics. 136-137. 381-386 (2000)
• [Publications] M.Tatsumisago: "Preparation of Amorphous Solid Electrolytes in the System Li_2S-SiS_2-Li_4SiO_4 by Mechanical Milling"Solid State Ionics. 136-137. 483-488 (2000)
• [Publications] T.Minami: "Preparation and Characterization of Lithium Ion-Conducting Oxysulfide Glasses"Solid State Ionics. 136-137. 1015-1023 (2000)
• [Publications] N.Kuwata: "Ag-109 NMR Study of AgI-Based Glasses Containing Frozen α-AgI Nanocrystals"Solid Satate Ionics. 136-137. 1061-1066 (2000)
• [Publications] S.Nishiwaki: "Preparation and Proton Conductivity of Surfactant-Templated Mesoporous Silica Gels Impregnated with Protonic Acids"J.Am.Ceram.Soc.. 83[12]. 3004-3008 (2000)
• [Publications] A.Matsuda: "Application of Protonic Acid-Doped Silica Gels to Electric Double-Layer Capacitors"J.Sol-Gel Sci.Tech.. 19[1-3]. 581-584 (2000)
• [Publications] A. Matsuda: "Electric Double-Layer Capacitor Using Composites Composed of Phosphoric Acid-Doped Silica Gel and Styrene-Ethylene-Butylene-Styrene Elastomer as a Solid Electrolyte"J. Power Sources,. 77・[1]. 12-16 (1999)
• [Publications] R. Sakamoto: "Preparation of Fast Lithium Ion Conducting Glasses in the System Li_2S-SiS_2-Li_3N"J. Phys. Chem. B.,. 103・[20]. 4029-4031 (1999)
• [Publications] H. Morimoto: "Mechanochemical Synthesis of New Amorphous Materials of 60Li_2S・ 40SiS_2with High Lithium Ion Conductivity"J. Am. Ceram. Soc.,. 82・[5]. 1352-1354 (1999)
• [Publications] A. Hayashi: "Structural Change Accompanying Crystallization in the Lithium Ion Conductive Li_2S-SiS_2-Li_3PO_4Oxysulfide Glasses"J. Am. Ceram. Soc.,. 107・[6]. 510-516 (1999)
• [Publications] M. Tatsumisago: "Crystallization of α-AgI from AgI-Ag_2O-MxOy(MxOy=B_2O_3, GeO_2, WO_3, )Melts and Glasses"Solid State Ionics. 121・[1-4]. 193-200 (1999)
• [Publications] A. Hayashi: "Higt-Resolution Solid-State NMR Studies of Ionically Conductive Li_2S-SiS_2-Li_2O-P_2O_5 Oxysulfide Glasses"Phys. Chem. Glasses. 40・[3]. 140-145 (1999)
• [Publications] 南 努: "超イオン伝導ガラス(総説)"電池技術. 11. 131-138 (1999)
• [Publications] A. Hayashi: "Electrochemical Properties for the Lithium Ion Conductive (100-x)(0.6Li_2S・ 0.4SiS_2)・ xLi_4SiO_4 Oxysulfide Glasses"J. Electrochem. Soc.,. 146・[9]. 3472-3475 (1999)
• [Publications] K. Hasegawa: "Preparation of Novel Lithium Ion Conductors Composed of LiSCN-AlCl_3and Silica Particles"J. Electrochem. Soc.,. 146・[10]. 3539-3542 (1999)
• [Publications] H. Morimoto: "Mechanical Synthesis and Anode Properties of SnO-Based Amorphous Materials"J. Electrochem. Soc.,. 146・[11]. 3970-3973 (1999)
• [Publications] A. Hayashi: "Cystallization of Li_2S-SiS_2 Based Lithium Ion Conducting Glasses"Phys. Chem. Glasses.,. 40・[6]. 333-338 (1999)
• [Publications] A. Matsuda: "Application of Composites Composed of Phosphoric Acid-Doped Silica Gel and Styrene-Ethylene-Buthylene-Styrene Elastomer to Electric Double-Layer Capacitors"Korean J. Ceramics,. 5・[4]. 353-356 (1999)