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Synthesis of Metal-Substituted Manganese Dioxides by Soft-Chemistry Method and Application to Active Electrode Materials in secondary cells

Research Project

Project/Area Number 15350117
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic industrial materials
Research InstitutionIwate University

Principal Investigator

KUMAGAI Naoaki  Iwate University, Graduation School of Engineering, Professor, 工学研究科, 教授 (30003875)

Co-Investigator(Kenkyū-buntansha) NISHIDATE Kazume  Iwate University, Graduation School of Engineering, Associate Professor, 工学研究科, 助教授 (90250638)
KOMABA Shinichi  Iwate University, Graduation School of Engineering, Assistant Professor, 工学研究科, 助手 (20302052)
Project Period (FY) 2003 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥11,900,000 (Direct Cost: ¥11,900,000)
Fiscal Year 2006: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2005: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2004: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2003: ¥7,600,000 (Direct Cost: ¥7,600,000)
KeywordsSoft-Chemistry synthesis / metal-substituted Manganese Dioxide / Hollandite-type Manganese Oxide / Layered Manganese Oxide / Lithium-ion Battery / Lithium Intercalation / トドロカイト型二酸化マンガン / 異種金属置換二酸化マンガン / ホランダイト二酸化マンガン / トドロカイト二酸化マンガン
Research Abstract

The present research has aimed to synthesis several metal-substituted manganese dioxides by soft-chemistry routes, such as aqueous solution, hydrothermal, emulsion drying, and spray-drying methods. The chemical compositions and crystal structures of the prepared manganese dioxides were examined, and furthermore the electrochemical characteristics of the prepared manganese oxides were investigated as new cathode materials for secondary lithium batteries. The main results were as follows.
1.New hollandite-type Co-doped α-K_<0.12>(Mn_<1-x>Co_x)O_2 (x=0〜0.12) and orthorhombic LiMn_<1-x>M_x,O_2 (O<x≦0.14 in M=Co,O<x0.1.5 in M=Fe) have been synthesized by aqueous solution and hydrothermal methods, respectively. The crystal structure, surface fine structure, structural variation with lithium intercalation, and lithium diffusion behavior in the crystal lattice were examined.
2.The layered Li excess Li_<1+x>Ni_<0.5>Mn_<0.5>O_2 and its Ti-substituted LiNi_<0.5>Mn_<0.5-x>Ti_xO_2 (x=0〜0.3) have been synthesized by an emulsion-drying method. The structural analysis of the prepared layered materials was carried out by X-ray diffraction, newtron diffraction and X-ray absorption spectroscopic methods. These prepared materials showed a high discharge capacity of 170〜180 mAh/g oxide during 50 cyclings.
3.The layered Li_<1-x>(Ni_<1/3>Co_<1/3>Mn_<1/3>)_xO_2(0≦x≦0.17) has been prepared by a spray-drying method, and the electrochemical characteristics and structural stability have been investigated. The crystal lattice parameter decreased with increasing the amount of Li excess (x-value), and at x=0.17 the highest discharge capacity of 179 mAh/g was obtained during 50 cyclings, due to the enhanced structural stability

Report

(5 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (30 results)

All 2006 2005 2004 Other

All Journal Article (25 results) Book (1 results) Publications (4 results)

  • [Journal Article] Synthesis of Li [(Ni_<0.5>Mn_<0.5>)_<1-x>Li_x]O_2 by Entulsion Drying Method and Impact of Excess Li on Structural and Electrochemical Properties2006

    • Author(s)
      Seung-Taek Myungほか8
    • Journal Title

      Chemistry of Materials 18

      Pages: 1658-1666

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Hydrothermal phase formation of orthorhombic LiMnO_2 and its derivatives as lithium intercalation compounds2006

    • Author(s)
      Seung-Taek Myungほか3
    • Journal Title

      Solid State Ionics 177

      Pages: 733-739

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Improved electrochemical properties of Li_<1+x>(Ni_<0.3>Co_<0.4>Mn_<0.3>)_<2-δ> (x=0, 0.03 and 0.06) with lithium excess composition prepared by a spray drying method2006

    • Author(s)
      Jung-Min Kimほか2
    • Journal Title

      Electrochimica Acta 52

      Pages: 1483-1490

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Improved Electrochemical Properties and Structural Stability of Overlithiated Li_<1+x>(Ni_<1/3>Co_<1/3>Mn_<1/3>)_<1-x>O_2 Prepared by Spray-Drying Method2006

    • Author(s)
      Jung-Min Kimほか2
    • Journal Title

      Electrochemical and Solid-State Letters 9

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Characterization and Lithium Insertion Characteristics of Hollandite-type K_y (Mn_<1-x>M_x)O_2 for Rechargeable Lithium Battery Electrddes2006

    • Author(s)
      N.Kumagaiほか3
    • Journal Title

      Journal of New Materials for Electrochemical Systems 9

      Pages: 175-180

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Li[(Ni_<0.5>Mn_<0.5>)_<1-X>Lix]O_2 by Emulsion Drying Method and Impact of Excess Li on Structural and Electrochemical Properties2006

    • Author(s)
      Seung-Taek Myung, Shinichi Komaba, Koutarou Kurihara, Kiyoharu Hosoya, Naoaki Kumagai, Yang-Kook Sun, Izumi Nakai, Masao Yonemura, Takashi Kamiyama
    • Journal Title

      Chemistry of Materials 18

      Pages: 1658-1666

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Hydrothermal phase formation of orthorhombic LiMnO_2 and its derivatives as lithium intercalation compounds2006

    • Author(s)
      Seung-Taek Myung, Shinichi Komaba, Koutarou Kurihara, Naoaki Kumagai
    • Journal Title

      Solid State Ionics 177

      Pages: 733-739

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Improved electrochemical properties of Li_<1+X>(Ni_<0.3>Co_<0.4>Mn_<0.3>)_<2-δ>(x=0,0.03 and 0.06) with lithium excess composition prepared by a spray drying method2006

    • Author(s)
      Jung-Min Kim, Naoaki Kumagai, Shinichi Komaba
    • Journal Title

      Electrochimica Acta 52

      Pages: 1483-1490

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Improved Electrochemical Properties and Structural Stability of Overlithiated Li_<1+X>(Ni_<1/3>Co_<1/3>Mn_<1/3>)_<1-X>O_2 Prepared by Spray-Drying Method2006

    • Author(s)
      Jung-Min Kim, Naoaki Kumagai, Hoon-Taek Chung, Shinichi Komaba
    • Journal Title

      Electrochemical and Solid-State Letters 9

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Characterization and Lithium Insertion Characteristics of Hollandite-type K_y(Mn_<1-X>Mx)O_2 for Rechargeable Lithium Battery Electrodes2006

    • Author(s)
      Naoaki Kumagai, Teruhito Sasaki, Satoru Oshitari, S.Komaba
    • Journal Title

      Journal of New Materials for Electrochemical Systems 9

      Pages: 175-180

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Li [(Ni_<0.5>Mn_<0.5>)_<1-X>Li_X]O_2 by Emulsion Drying Method and Impact of Excess Li on Structural and Electrochemical Properties2006

    • Author(s)
      Seung-Taek Myung, ほか8
    • Journal Title

      Chemistry of Materials 18

      Pages: 1658-1666

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Hydrothermal phase formation of orthorhombic LiMnO_2 and its derivatives as lithium intercalation compounds2006

    • Author(s)
      Seung-Taek Myung, ほか3
    • Journal Title

      Solid State Ionics 177

      Pages: 733-739

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Improved electrochemical properties of Li_<1+X>(Ni_<0.3>Co_<0.4>Mn_<0.3>)_<2-δ>(x=0, 0.03 and 0.06) with lithium excess composition prepared by a spray drying method2006

    • Author(s)
      Jung-Min Kim, ほか2
    • Journal Title

      Electrochimica Acta 52

      Pages: 1483-1490

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Improved Electrochemical Properties and Structural Stability of Overlithiated Li_<1+X>(Ni_<1/3>Co_<1/3>Mn_<1/3>)_<1-X>O_2 Prepared by Spray-Drying Method2006

    • Author(s)
      Jung-Min Kim, ほか2
    • Journal Title

      Electrochemical and Solid-State Letters 9

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Characterization and Lithium Insertion Characteristics of Hollandite-type K_y(Mn_<1-X>M_X)O_2 for Rechargeable Lithium Battery Electrodes2006

    • Author(s)
      N.Kumagai, ほか3
    • Journal Title

      Journal of New Materials for Electrochemical Systems 9

      Pages: 175-180

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Hydrothermal systhesis of layered Li [Ni_<1/3>Co_<1/3>Mn_<1/3>]O_2 as positive electrode material for lithium secondary battery2005

    • Author(s)
      Seung-Taek Myungほか4
    • Journal Title

      Electrochimica Acta 50

      Pages: 4800-4806

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Hydrothermal systhesis of layered Li[Ni_<1/3>Co_<1/3>Mn_<1/3>]O_2 as positive electrode material for lithium secondary battery2005

    • Author(s)
      Seung-Taek Myung, Myung-Hun Lee, Shinichi Komaba, Naoaki Kumagai, Yang-Kook Sun
    • Journal Title

      Electrochimica Acta 50

      Pages: 4800-4806

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] コバルト含有バーネサイト型マンガン酸化物の熱的相転移とリチウム二次電池特性2005

    • Author(s)
      佐々木昭仁ほか5
    • Journal Title

      Electrochemistry 73・4

      Pages: 290-297

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Hydrothermal synthesis of layered Li[Ni_<1/3>Co_<1.3>Mn_<1/3>]O_2 as positive electrode material for lithium secondary battery2005

    • Author(s)
      Seung-Taek Myungほか4
    • Journal Title

      Electrochimica Acta 50

      Pages: 4800-4806

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Synthesis of LiNi_<0.5>Mn_<0.5-x>Ti_xO_2 by an Emulsion Drying Method and Effect of Ti on Structure and Electrochemical Properties2005

    • Author(s)
      Seung-Taek Myungほか5
    • Journal Title

      Chemistry of Materials 17

      Pages: 2427-2435

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Preparation and Electrochemical Performances of Composite Oxide of Alfa Manganese Oxide and Li-Mn-O Spinel2005

    • Author(s)
      S.Komabaら
    • Journal Title

      Electrochim.Acta (印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Effect of Excess Lithium on LiNi_<0.5>Mn_<0.5>O_<2+δ> and Its Electrochemistry as Lithium Insertion Material2004

    • Author(s)
      S.T.Myungら
    • Journal Title

      Solid State Ionics 170

      Pages: 139-144

    • Related Report
      2004 Annual Research Report
  • [Journal Article] バーネサイト型二酸化マンガンの焼成によるホランダイト型二酸化マンガンの合成およびリチウム二次電池用正極材料としての電気化学特性2004

    • Author(s)
      佐々木昭仁ら
    • Journal Title

      Electrochemistry 72・10

      Pages: 688-693

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Characterization of R.F.Magnetron Sputtered Vanadium Oxied Thin Films and Intercalation of Lithium in the Oxide Films2004

    • Author(s)
      Naoaki Kumagaiら
    • Journal Title

      Electrochemistry 72・4

      Pages: 261-265

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis of Hollandite-type Li_yMn_<1-X>Co_XO_2 (x=0-0.15) by Li^+ ion-exchange in molten salt and the electrochemical property for rechargeable Lithium battery electrodes

    • Author(s)
      N.Kumagai, ほか3
    • Journal Title

      Journal of Power Sources (in press)(印刷中)

    • Related Report
      2006 Annual Research Report
  • [Book] 第5版 実験化学講座27 機能性材料、2 電気的機能性材料2004

    • Author(s)
      熊谷直昭
    • Total Pages
      12
    • Publisher
      丸善株式会社
    • Related Report
      2004 Annual Research Report
  • [Publications] S.-T.Myung: "Structural Investigation of Layered Li_<1-s>Mn_xCr_<1-x>O_2 by XANES and In Situ XRD Measurements"Journal of the Electrochemical Society. 150・12. A1560-A1568 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.komaba: "Electrochemical Characteristics and Manganese Dissolution of Spinel Li_<1.05>M_<0.2>Mn_<1.75>O_4 (M=Al, Co and Cr) Cathode"Electrochemistry. 71・12. 1236-1239 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.-T.Myung: "Effects of Excess Lithium on LiNi_<0.5>Mn_<0.5>O_<2+s> and Its Electrochemistry Is Lithium Insertion Material"Solid State Ionics. (印刷中). (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 熊谷直昭: "地球環境シリーズ"自動車用大容量二次電池"第2章 高性能マンガン系正極材料の開発"シーエムシー出版. 11 (2003)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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