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Effect of Film Thickness of Layer-Structured Oxide Thin Films on Lithium Insertion/Extraction and Semiconductive Properties

Research Project

Project/Area Number 10650803
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 工業物理化学
Research InstitutionYAMAGATA UNIVERSITY

Principal Investigator

NISHINA Tatsuo  Faculty of Engineering, Yamagata University, Associate Professor, 工学部, 助教授 (60172673)

Co-Investigator(Kenkyū-buntansha) MATSUKI Kenzo  Faculty of Engineering, Yamagata University, Professor, 工学部, 教授 (70006998)
Project Period (FY) 1998 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1999: ¥1,100,000 (Direct Cost: ¥1,100,000)
Fiscal Year 1998: ¥2,900,000 (Direct Cost: ¥2,900,000)
KeywordsLayered-Structured Oxide / Lithium Batteries / Secondary Batteries / Intercalation / Passivated Films / Conductive Additives / Hetero-contacts / Optical Responses / 光電気化学 / 光充電
Research Abstract

LiMィイD2xィエD2OィイD2yィエD2 (M=Mn, Ni, Co) thin films were fabricated by dipping Au wire into the citric complex during the synthesis process (DICC method). Only the LiCoOィイD22ィエD2 thin film was obtained by the in situ oxidation in molten carbonate. However, DICC process enabled us to fabricate the LiCoOィイD22ィエD2, LiMnィイD22ィエD2OィイD24ィエD2 and LiNiOィイD22ィエD2 thin films onto the Au. In case of LiCoOィイD22ィエD2 and LiNiOィイD22ィエD2 thin films, lithium extraction was easy but hard to insert lithium it. On the other hand, lithium extraction/insertion was quite easy for LiMnィイD22ィエD2OィイD24ィエD2 thin film up to 1 V/s scan rate in cyclic voltammetry with excellent cyclability. This result is really amazing that the charging/discharging rate of theoretical capacity within 10 seconds is possible principally but the recent state-of-the-art battery technology needs an hour. However, similar reversible charging/discharging reaction was obtained at very slow scan rate (0.01 mV/s) when the composite electrode o … More f LiMnィイD22ィエD2OィイD24ィエD2 was applied. This difference is a clear indication that the carbon conductive additive in the composite electrode enhances the electronic conductivity of active materials and passivated film formed on the Al current collector. However, it makes no potential gradient inside the active material, and hence it reduces the lithium ion conduction inside the solid phase. In case of thin film electrode, potential difference between electrolyte solution and current collector exists at the active material, and this enhances the lithium ion conductivity inside the active material solid phase.
Optical current measurements were carried out using lock-in amplifier synchronized with the optical chopper. Unfortunately, we could not observe any traces of optical current. However, the formation of barrier type AlFィイD23ィエD2 passivation film was found at the Al current collector in the organic solution with LiPFィイD26ィエD2 and LiBFィイD24ィエD2 electrolyte by the high-potential field mechanism, which was similar to the anodic oxide film formation in aqueous solution. Less

Report

(3 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • Research Products

    (43 results)

All Other

All Publications (43 results)

  • [Publications] 立花和宏: "The Function of Carbon as Conductive Agent for Primary and Secondary Batteries"Progress in Batteries & Battery Materials. 17. 242-244 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Proposal for An Accurate and Rapid International Electrochemical Test for Various Battery Materials Using T-M Cell(Part 2), : Rechargeability of EMD Containing Bi_2O_3 in KOH"Progress in Batteries & Battery Materials. 17. 245-255 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Proposal for An Accurate and Rapid International Electrochemical Test for Various Battery Materials Using T-M Cell(Part 3) : The Charging/Discharging Characteristics of LiMn_2O_4 as The Cathode for Lithium Secondary Battery. -The Effect of Combination of Current Collector and Electrolyte"Progress in Batteries & Battery Materials. 17. 256-264 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Proposal for An Accurate and Rapid International Electrochemical Test for Various Battery Materials Using T-M Cell(Part 4), : SEM Observation of LiMn_2O_4 Positive Electrode (JEC N0.3), before and after The Charging/Discharging Test in Organic Electrolyte"Progress in Batteries & Battery Materials. 17. 265-272 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Charge-Discharge Characteristics of LiMn_2O_4 as The Cathode for Lithium Second Battery-Effect of Cathode Particle Size-"Progress in Batteries & Battery Materials. 17. 273-275 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Development of in situ a.c. Impedance Measurement System under Constant-Current Conditions and Its Application to Galvanostatic Discharge of Electrolytic Manganese Dioxide in Alkaline Solution"Journal of Power Sources. 74. 29-33 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Effect of Hetero-contacts at Active Material Conductive Additives on Lithium Intercalation/Deintercalation of LiCoO_2"Denki Kagaku. 66. 1248-1252 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 王献明: "マイクロ電極を用いる有機電解液と金属の安定性の評価"Electrochemistry. 67. 145-150 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 松木健三: "LiMn_2O_4系に対する導電付与材,集電体&電解液の効果"マテリアルインテグレーション. 12-3. 35-42 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "What Is the True Function of Carbon as a Conductive Additive for Primary and Second Batteries?"ITE Battery Letters. 1. 33-38 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell(Part 5): Discharging Kinetics of EMD in KOH Aqueous Solution"ITE Battery Letters. 1. 39-42 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "アルミニウム陽極酸化における定電圧印加時のリーク電流と定電流印加時の電位オーバーシュートの関係"Electrochemistry. 67. 774-779 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "アジピン酸アンモニウム水溶液中における微少電極を用いたアルミニウムの陽極酸化"Electrochemistry. 67. 780-783 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 仁科辰夫: "Conductivity Controlling of Oxide Scale on Corroded Metal Components by Applying Hetero-contact Technique"Proceedings of the Fifth International Symposium on Carbonate Fuel Cell Technology. ECS Proc.Vol.99-20. 142-149 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 松木健三: "リチウムニ次電池の性能評価の標準化"山形大学紀要(工学). 26-1. 25-32 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 立花和宏: "Impurity Effect in Aluminum Cathode Current Collector on Charging/Discharging Performance of Lithium Secondary Battery"Proceedings of the Symposium on Lithium Batteries. ECS Proc.Vol.99-25(in print). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "The Function of Carbon as Conductive Agent for Primary and Secondary Batteries"Progress in Batteries & Battery Material. 17. 242-244 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Proposal for An Accurate and Rapid International Electrochemical Test For Various Battery Materials using T-M Cell (Part 2), : Rechargeability of EMD Containing BiィイD22ィエD2OィイD23ィエD2 in KOH"Progress in Batteries & Battery Material. 17. 245-255 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Proposal for An Accurate and Rapid International Electrochemical Test for Various Battery Materials Using T-M Cell (Part 3) : The Charging/Discharging Characteristics of LiMnィイD22ィエD2OィイD24ィエD2 as The Cathode for Lithium Secondary Battery. -The Effect of Combination of Current Collector and Electrolyte"Progress in Batteries & Battery Material. 17. 256-264 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Proposal for An Accurate and Rapid International Electrochemical Test for Various Battery Materials Using T-M Cell (Part 4) : SEM Observation of LiMnィイD22ィエD2OィイD24ィエD2 Positive Electrode (JEC No.3), before and after The Charging/Discharging Test in Organic Electrolyte"Progress in Batteries & Battery Material. 17. 265-272 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Charge-Discharge Characteristics of LiMnィイD22ィエD2OィイD24ィエD2 as The Cathode for Lithium Secondary Battery -Effect of Cathode Particle Size-"Progress in Batteries & Battery Material. 17. 273-275 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Development of in situ a.c. Impedance Measurement System under Constant-Current Conditions and Its Application to Galvanostatic Discharge of Electrolytic Manganese Dioxide in Alkaline Solution"Journal of Power Sources. 74. 29-33 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Effect of Hetero-contacts at Active Material Conductive Additives on Lithium Intercalation/Deintercalation of LiCoOィイD22ィエD2"Denki Kagaku. 66. 1248-1252 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Xian-Ming Wang: "Evaluation of the Stability of Organic Solutions and Metals by Using Microelectrode Technique"Electrochemistry. 67. 145-150 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kenzo Matsuki: "The Effects of the Combinations of Conductive Additive, Current Collector and Their Functions in Lithium Secondary Battery Technology with LiMnィイD22ィエD2oィイD24ィエD2 Cathode"Materials Integration. 12. 35-42 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "What is the True Function of Carbon as a Conductive Additive for Primary and Secondary Batteries?"ITE Battery Letters. 1. 33-38 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Proposal for and accurate and rapid international electrochemical test for various battery using T-M cell (Part 5) : Discharging Kinetics of EMD in KOH Aqueous Solution"ITE Battery Letters. 1. 39-42 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Analysis of the Relationship between the Potential Overshoot under Constant Current Load and the Leakage Current under Constant Potential Load during Aluminum Anodic Oxide Formation"Electrochemistry. 67. 774-779 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Application of Microelectrode Technique to Aluminum anodic Oxide Film Formation in Ammonium Adipate Solution"Electrochemistry. 67. 780-783 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Tatsuo Nishina: "Conductivity Controlling of Oxide Scale on Corroded Metal Components by Applying Hetero-contact Technique"Proc. Of the 5th Internat. Symp. On Carbonate Fuel Cell Technology. 99-20. 142-149 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kenzo Matsuki: "An Accurate Electrochemical Test for Lithium-Ion Battery Materials"Bulletin of Yamagata University (Engineering). 26-1. 25-32 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Kazuhiro Tachibana: "Impurity Effect in Aluminum Cathode Current Collector on Charging/Discharging Performance of Lithium Secondary Battery"Proc. Of the Symp. On Lithium Batteries. 99-25 (in print). (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 王 献明: "マイクロ電極を用いる有機電解液と金属の安定性の評価"Electrochemistry. 67. 145-150 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 立花和宏: "アルミニウム陽極酸化における定電圧印加時のリーク電流と定電流印加時の電位オーバーシュートの関係"Electrochemistry. 67. 774-779 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 立花和宏: "アジピン酸アンモニウム水溶液中における微小電極を用いたアルミニウムの陽極酸化"Electrochemistry. 67. 780-783 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 立花和宏: "What Is the True Function of Carbon as a Conductive Additive for Primary and Secondary Batteries?"ITE Battery Letters. 1. 33-38 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 立花和宏: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell (Part 5): Discharging Kinetics of EMD in KOH Aqueous Soulution"ITE Battery Letters. 1. 39-42 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 立花 和宏: "Effect of Hetero-contacts at Active Matelial/Conductive Additives on Lithium Intercalation/Deintercalation of LiCoO_2" 電気化学. 66・12. 1248-1252 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 王 献明: "マイクロ電極を用いる有機電解液と金属の安定性の評価" 電気化学. 67・2. 145-150 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 立花和宏: "Development of In situ a.c. impedance measurement system under constant-Currentinditions and its application to galvanostatic discharge of electrclytic manganese dioxide in alkaline solution" Journal of Power Sources. 74. 29-33 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 松木健三: "LiMn_2O_4系に対する導電付与剤,集電体&電解液の効果" マテリアル インテグレーション. 12・3. 35-42 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] 立花和宏: "The Function of Carbon as Conductive Agent for Primary and Secondary Batteries" Progress in Batteries and Battery Materials. 17. 242-244 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 立花和宏: "Charge-discharge characteristic of LiMn_2O_4 as the Cathode for Lithium Secondary Battery-Effect of cathode Particle Size-" Progress in Batteries and Battery materials. 17. 273-275 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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