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メカノケミカル法による高イオン伝導性無機硫化物-ポリマーハイブリッドの創製

Research Project

Project/Area Number 16760549
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeSingle-year Grants
Research Field Inorganic materials/Physical properties
Research InstitutionOsaka Prefecture University

Principal Investigator

林 晃敏  大阪府立大学, 工学研究科, 助手 (10364027)

Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2005: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2004: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordsメカノケミカル法 / ハイブリッド / 固体電解質 / 全固体電池 / イオン伝導体 / 硫化物 / ガラス / リチウム電池
Research Abstract

本年度は、硫化物とオリゴマーのハイブリッド化における反応プロセスの解明を行い、得られたハイブリッド電解質のイオン伝導機構について検討した。ラマン分光測定の結果から、70Li_2S・30P_2S_5ガラスの局所構造は、PS_4^<3->やP_2S_7^<4->から構成されていることがわかった。このガラスとオリゴマーとして1,4-butanediolを反応させるとP_2S_7^<4->のピークの強度が減少していることから、硫化物ガラス中のP_2S_7^<4->とオリゴマー末端のヒドロキシル基が反応してハイブリッド化していることが示唆された。ガラス転移温度における導電率から、1,4-butanediolを2mol%添加して得たハイブリッド電解質のデカップリングインデックス(R_τ:伝導緩和時間に対する構造緩和時間の比)を求めるとR_τ=12.6となり、ガラスと同等の値を示すことがわかった。また直流分極測定により、ハイブリッド電解質のリチウムイオン輸率はほぼ1であることを確認した。以上の結果から、イオン伝導ガラスとオリゴマーのハイブリッド化を行っても、ガラスの高いデカップル性が維持され、ハイブリッド電解質はシングルイオン伝導性を示すことがわかった。作用極にステンレス板、対極にリチウムシートを用いた全固体二極式セルを用いてサイクリックボルタンメトリーを行った結果、ハイブリッド電解質はガラスと同等の電位窓を有しており、リチウムの溶解・析出が可逆的に生じることがわかった。負極に金属インジウム、固体電解質にハイブリッド材料、正極にLiCoO_2を用いた全固体電池を試作したところ、充放電が可能であり二次電池として作動することを確認した。

Report

(3 results)
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (31 results)

All 2006 2005 2004

All Journal Article (28 results) Book (3 results)

  • [Journal Article] All-Solid-State Lithium Secondary Batteries Using Sulfide-Based Glass-Ceramic Electrolytes2006

    • Author(s)
      M.Tatsumisago
    • Journal Title

      J. Power Sources 159

      Pages: 193-199

    • Related Report
      2006 Annual Research Report
  • [Journal Article] All-Solid-State Rechargeable Lithium Batteries Using SnX-P_2X_5 (X=S and O) Amorphous Negative Electrodes2006

    • Author(s)
      A.Hayashi
    • Journal Title

      Research on Chemical Intermediates 32 [5-6]

      Pages: 497-506

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Mechanochemical Synthesis of Hybrid Electrolytes from the Li_2S-P_2S_5 Glasses and Polyethers2006

    • Author(s)
      A.Hayashi
    • Journal Title

      J. Power Sources 163

      Pages: 289-293

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Recent Progress of Glass and Glass-Ceramics as Solid Electrolytes for Lithium Secondary Batteries2006

    • Author(s)
      T.Minami
    • Journal Title

      Solid State Ionics 177

      Pages: 2715-2720

    • Related Report
      2006 Annual Research Report
  • [Journal Article] High Lithium Ion Conducting Glass-Ceramics in the System Li_2S-P_2S_52006

    • Author(s)
      F.Mizuno
    • Journal Title

      Solid State Ionics 177

      Pages: 2721-2725

    • Related Report
      2006 Annual Research Report
  • [Journal Article] High Rate Performances of All-Solid-State In/LiCoO_2 Cells with the Li_2S-P_2S_5 Glass-Ceramics Electrolytes2006

    • Author(s)
      F.Mizuno
    • Journal Title

      Solid State Ionics 177

      Pages: 2731-2735

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Formation of Electrode-Electrolyte Interface by Lithium Insertion to SnS-P_2S_5 Negative Electrode Materials in All-Solid-State Cells2006

    • Author(s)
      A.Hayashi
    • Journal Title

      Solid State Ionics 177

      Pages: 2737-2740

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Lithium Ion Conducting Solid Electrolytes Prepared from Li_2S, Elemental P and S2006

    • Author(s)
      A.Hayashi
    • Journal Title

      Solid State Ionics 177

      Pages: 2753-2757

    • Related Report
      2006 Annual Research Report
  • [Journal Article] 超イオン伝導ガラス2006

    • Author(s)
      辰巳砂昌弘, 林 晃敏
    • Journal Title

      光学 35 [3]

      Pages: 139-144

    • NAID

      10017962535

    • Related Report
      2006 Annual Research Report
  • [Journal Article] 硫化物系固体電解質材料を用いた全固体リチウム二次電池2006

    • Author(s)
      辰巳砂昌弘, 林 晃敏
    • Journal Title

      電池技術 18

      Pages: 36-44

    • Related Report
      2006 Annual Research Report
  • [Journal Article] New, Highly Ion-Conductive Crystals Precipitated from Li_2S-P_2S_5 Glasses2005

    • Author(s)
      F.Mizuno
    • Journal Title

      Adv.Mater. 17 [7]

      Pages: 918-921

    • Related Report
      2005 Annual Research Report
  • [Journal Article] All-solid-state Lithium Secondary Batteries with SnS-P_2S_5 Negative Electrodes and Li_2S-P_2S_5 Solid Electrolytes2005

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Power Sources 146

      Pages: 496-500

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Design of Composite Positive Electrode in All-solid-state Secondary Batteries with Li_2S-P_2S_5 Glass-ceramic Electrolytes2005

    • Author(s)
      F.Mizuno
    • Journal Title

      J.Power Sources 146

      Pages: 711-714

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Electrical and Electrochemical Properties of Li_2S-P_2S_5-P_2O_5 Glass-ceramic Electrolytes2005

    • Author(s)
      T.Ohtomo
    • Journal Title

      Power Sources 146

      Pages: 715-718

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Mechanochemical Synthesis of Lithium Ion Conducting Glasses and Glass-Ceramics in the System Li_2S-P-S2005

    • Author(s)
      T.Ohtomo
    • Journal Title

      Solid State Ionics 176

      Pages: 2349-2353

    • Related Report
      2005 Annual Research Report
  • [Journal Article] 硫化物系ガラスセラミック固体電解質の高リチウムイオン伝導性2005

    • Author(s)
      林 晃敏
    • Journal Title

      金属 75[4]

      Pages: 351-354

    • NAID

      40006683793

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Effects of Conductive Additives in Composite Positive Electrodes on Charge-Discharge Behaviors of All-Solid-State Lithium Secondary Batteries2005

    • Author(s)
      F.Mizuno
    • Journal Title

      Electrochem.Soc. 152 [8]

    • Related Report
      2005 Annual Research Report
  • [Journal Article] New Lithium-Ion Conducting crystal Obtained by Crystallization of the Li_2S-P_2S_5 Glasses2005

    • Author(s)
      F.Mizuno
    • Journal Title

      Electrochem. Solid-State Lett. 8 [11]

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Lithium Ion Conducting Glasses and Glass-Ceramics in the Systems Li_2S-MxSy (M=Al,Si and P) Prepared by Mechanical Milling2004

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Ceram.Soc.Jpn. 112[5]

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Structure and Ion Conductivity of Li_2S-P_2S_5-P_2O_5 Glasses and Glass-Ceramics Prepared by Mechanical Milling2004

    • Author(s)
      F.Mizuno
    • Journal Title

      J.Ceram.Soc.Jpn. 112[5]

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Characterization of SnO-MxOy (M=B and P) Glassy Anode Materials for Lithium Secondary Batteries Prepared by Melt-Quenching and Mechanical Milling2004

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Ceram.Soc.Jpn. 112[5]

    • NAID

      130004610288

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Amorphous Solid Electrolytes in the System Li_2S-Al_2S_3-SiS_2 Prepared by Mechanical Milling2004

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Mater.Sci. 39

      Pages: 5125-5127

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Mechanochemical Synthesis of SnO-B_2O_3 Glassy Anode Materials for Rechargeable Lithium Batteries2004

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Mater.Sci. 39

      Pages: 5361-5364

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preparation and Characterization of SnO-P_2O_5 Glasses as Anode Materials for Lithium Secondary Batteries2004

    • Author(s)
      A.Hayashi
    • Journal Title

      J.Non-Cryst.Solids 345&346

      Pages: 478-483

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Mechanochemical Synthesis of Amorphous Solid Electrolytes Using SiS_2 and Various Lithium Compounds2004

    • Author(s)
      A.Hayashi
    • Journal Title

      Solid State Ionics 175

      Pages: 637-640

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Characterization of Li_2S-P_2S_5 Glass-Ceramics as a Solid Electrolyte for Lithium Secondary Batteries2004

    • Author(s)
      A.Hayashi
    • Journal Title

      Solid State Ionics 175

      Pages: 683-686

    • Related Report
      2004 Annual Research Report
  • [Journal Article] All-Solid-State Lithium Secondary Batteries Using Li_2S-SiS_2-Li_4SiO_4 Glasses and Li_2S-P_2S_5 Glass-Ceramics as Solid Electrolytes2004

    • Author(s)
      F.Mizuno
    • Journal Title

      Solid State Ionics 175

      Pages: 699-702

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Rechargeable Lithium Batteries, Using Sulfur-Based Cathode Materials and Li_2S-P_2S_5 Glass-Ceramic Electrolytes2004

    • Author(s)
      A.Hayashi
    • Journal Title

      Electrochim.Acta 50

      Pages: 893-897

    • Related Report
      2004 Annual Research Report
  • [Book] ユビキタスエネルギーの最新技術2006

    • Author(s)
      辰巳砂昌弘, 林 晃敏
    • Publisher
      シーエムシー出版
    • Related Report
      2006 Annual Research Report
  • [Book] ナノコンポジットマテリアル2005

    • Author(s)
      辰巳砂昌弘, 林 晃敏
    • Publisher
      フロンティア出版
    • Related Report
      2005 Annual Research Report
  • [Book] ナノマテリアル工学大系 第1巻ニューセラミックス・ガラス2005

    • Author(s)
      辰巳砂昌弘, 林 晃敏
    • Publisher
      フジ・テクノシステム
    • Related Report
      2005 Annual Research Report

URL: 

Published: 2004-04-01   Modified: 2016-04-21  

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