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Preparation of High Lithium Ion Conducting Glass-Ceramics by Mechanical Milling

Research Project

Project/Area Number 13450359
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 無機工業化学
Research InstitutionOsaka Prefecture University

Principal Investigator

TATSUMISAGO Masahiro  Osaka Prefecture Univ., Prof., 工学研究科, 教授 (50137238)

Co-Investigator(Kenkyū-buntansha) MATSUDA Atsunori  Toyohashi Univ.Tech., Assoc.Prof., 物質工学系, 助教授 (70295723)
TADANAGA Kiyoharu  Osaka Prefecture Univ., Assoc.Prof., 工学研究科, 助教授 (90244657)
MINAMI Tsutomu  Osaka Prefecture Univ., President., 学長 (80081313)
Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥14,400,000 (Direct Cost: ¥14,400,000)
Fiscal Year 2002: ¥5,100,000 (Direct Cost: ¥5,100,000)
Fiscal Year 2001: ¥9,300,000 (Direct Cost: ¥9,300,000)
KeywordsMechanical milling / Amorphous / Ion conduction / Glass-ceramic / Ball milling / Conductivity / Solid electrolyte / Solid state battery / 非結晶
Research Abstract

1. Amorphous materials with various compositions in the systems Li_2S-P_2S_5, Li_2S-P_2S_5-SiS_2, and Li_2S-P_2S_5-GeS_2 were prepared by mechanical milling (MM) of crystalline starting materials in a dry N_2 atmosphere at room temperature. The pelletized samples of these glassy materials exhibited high conductivities in the order of 10^<-4> Scm^<-1> at 25℃. It was found that the transport number of lithium ions of the glassy materials was almost unity and the potential window as solid electrolytes was wider than 10 V.
2. Highly conductive glass-ceramics were obtained by the heat treatment under a variety of conditions of the above glassy materials prepared by MM. The glass-ceramics obtained after heating at around 230℃ showed the X-ray diffraction patterns very similar to those of highly conductive thio-LISICON II phases in Li_<4-x>Ge_<1-x>P_xS_4, suggesting that the thio-LISICON II analogue is formed in the glass-ceramics derived from the mechanically milled glassy powder in these systems.
3. The highly conductive glass-ceramics were also obtained by the MM of starting materials of elements. Glassy Li_2S-P_2S_5 samples were successfully prepared by the MM of Li_2S, P, and S. The properties and structure of the glassy samples are very similar those of the samples prepared using Li_2S and P_2S_5. The glass-ceramics obtained by the heating of such an element-derived sulfide glasses exhibited similar properties to the glass-ceramics from P_2S_5-derived glasses.
4. Electrochemical cells were constructed using glass-ceramics in the system Li_2S-P_2S_5 obtained by MM and heat treatment as an electrolyte, LiCoO_2, as a positive electrode and indium as a negative electrode. The all-solid-state cell exhibited excellent cycling performances with the reversible charge-discharge capacities of about 100mAhg^<-1> even after 200 cycles.

Report

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

    (64 results)

All Other

All Publications (64 results)

  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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 0btained by Mechanochemical Synthesis"Solid State Ionics. 140・[1-2]. 83-87 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Hayashi: "Preparation and Characterization of Lithium Ion Conducting Glass-Polymer Composites"Chem. Lett.. [8]. 814-815 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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・[1-3]. 1-7 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Hayashi: "High Lithium Ion Conductivity of Glass-Ceramics Derived from Mechanically Milled Glassy Powders"Chem. Lett.. [9]. 872-873 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tatsumisago: "Preparation and Characterization of Amorphous Based Solid Electrolytes (総説)"J. Ceram. Soc. Jpn.. 109・[10]. 809-814 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 辰巳砂昌弘: "リチウムイオン伝導体(総説)"Electrochemistry. 69・[10]. 793-797 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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・[111]. 37-43 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Morimoto: "Anode Properties of Amorphous 50SiO・50SnO Powders Synthesized by Mechanical Milling"Electrochem. Solid-State Lett.. 4・[2]. A16-18 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Hayashi: "Characterization of Li_2S-SiS_2-Li_3MO_3 (M=B, Al, Ga and In) Oxysulfide Glasses and Their Application to Solid State Lithium Secondary Batteries"Solid State Ionics. 152-153. 285-290 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Hayashi: "Structure and Properties of Glasses in the System Li_2O-SnO-B_2O_3"Comptes Rendus Chimie. 5. 751-757 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Hayashi: "Formation of Superionic Crystals from Mechanically Milled Li_2S-P_2S_5 Glasses"Electrochem. Comm.. 5. 111-114 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Tatsumisago: "Sulfide-Based Glass-Ceramic Electrolytes for All-Solid-State Lithium Secondary Batteries"Solid State Ionics. (in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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 Medianochemical Synthesis"Solid State Ionics. 140・[1-2]. 83-87 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "Preparation and Characterization of Lithium Ion Conducting Glass-Polymer Composites"Chem. Lett.. [8]. 814-815 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] R. Araki: "Efccteonic States Calculated by the DV-X α Cluster Method for Lithium Ion Conductive Li_2S-SiS_2-Li_4SiO_4 Oxysulfide Glasses"J. Non-Cryst. Solids.. 288・[1-3]. 1-7 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "High Lithium Ion Conductivity of Glass-Ceramics Derived from Mechanically Milled Glassy Powders"Chem. Lett.. [9]. 872-873 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Tatsumisago: "Preparation and Characterization of Amorphous Based Solid Electrolytes (Review)"J. Ceram. Soc. Jpn.. 109・[10]. 809-814 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Tatsumisago: "Lithium Ion Conductor (Review)"Electrochemistry. 69・[10]. 793-797 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Tatsumisago: "Ion Conduction in Glass (Review)"Materials Integration. 14・[11]. 37-43 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H. Morimoto: "Anode Properties of Amoiphous 50SiO ・ 50SnO Powders Synthesized by Mechanical Milling"Electrochem. Solid-State Lett.. 4・[2]. A16-A18 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Tatsumisago: "Development of Superionic Glasses (Review)"Kikaino Kenkyu. 54・[2]. 19-26 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "Structural Investigation of SnO-B_2O_3 Glasses by Solid-State NMR and X-ray Photoelectron Spectroscopy"J. Non-Crysl Solids. 306・[3]. 227-237 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "Characterization of Li_2S-SiS_2-Li_3MO_3 (M=B, Al, Ga and In) Oxysulfide Glasses and Their Application to Solid State Lithium Secondary Batteries"Solid State Ionics. 152-153. 285-290 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "Structure and Properties of Glasses in the System Li_2O-SnO-B_2O_3"Comptes Rendus Chimie. 5. 751-757 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Hayashi: "Formation of Superionic Crystals from Mechanically Milled Li_2S-P_2S_5 Glasses"Electrochem. Comm.. 5. 111-114 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M. Tatsumisago: "Sulfide-Based Glass-Ceramic Electrolytes for All-Solid-State Lithium Secondary Batteries"Solid State Ionics. in press.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [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)

    • Related Report
      2002 Annual Research Report
  • [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)

    • Related Report
      2002 Annual Research Report
  • [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)

    • Related Report
      2002 Annual Research Report
  • [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)

    • Related Report
      2002 Annual Research Report
  • [Publications] F.Mizuno: "All Solid-State Lithium Secondary Batteries Using High Lithium Ion Conducting Li_2S-P_2S_5 Glass-Ceramics"Chem.Lett.. [12]. 1244-1246 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Hayashi: "Characterization of Li_2S-SiS_2-Li_3MO_3 (M=B, Al, Ga and In) Oxysulfide Glasses and Their Application to Solid State Lithium Secondary Batteries"Solid State Ionics. 152-153. 285-290 (2002)

    • Related Report
      2002 Annual Research Report
  • [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)

    • Related Report
      2002 Annual Research Report
  • [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)

    • Related Report
      2002 Annual Research Report
  • [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 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Hayashi: "Formation of Superionic Crystals from Mechanically Milled Li_2S-P_2S_5 Glasses"Electrochem.Comm.. 5. 111-114 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Hayashi: "Structure and Properties of Glasses in the System Li_2O-SnO-B_2O_3"C.R.Chimie. (in press).

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Tatsumisago: "Sulfide-Based Glass-Ceramic Electrolytes for All-Solid-State Secondary Batteries"Solid State Ionics. (in press).

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Hayashi: "Preparation of Li2S-P2S5 Amorphous Solid Electrolytes by Mechanical Milling"J.Am.Ceram.Soc.. 84・[2]. 477-479 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] R.Komiya: "Solid State Lithium Secondary Batteries Using an Amorphous Solid Electrolyte in the System (100-x)(O.6Li_2S ・ 0.4SiS_2) ・ xLi_4SiO_4 Obtained by Mechanochemical Synthesis"Solid State Ionics. 140. 83-87 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] R.Araki: "Electronic States Calculated by the DV-X a Cluster Method for Lithium Ion Conductive Li_2S-SiS_2-Li_4SiO_4 Oxysulfide Glasses"J.Non-Cryst, Solids. 288. 1-7 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Hayashi: "High Lithium Ion Conductivity of Glass-Ceramics Derived from Mechanically Milled Glassy Powders"Chem.Lett.. [9]. 872-873 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.Tatsumisago: "Preparation and Characterization of Amorphous Based Solid Electrolytes (総説)"J.Ceram.Soc.Jpn.. 109・[10]. 809-814 (2001)

    • Related Report
      2001 Annual Research Report
  • [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)

    • Related Report
      2001 Annual Research Report

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

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