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Study of diffusion mechanism in lithium-ion battery materials by SIMS with isotope ion-exchange method

Research Project

Project/Area Number 17K19134
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Research Field Inorganic/Coordination chemistry, Analytical chemistry, and related fields
Research InstitutionNational Institute for Materials Science (2019)
Tohoku University (2017-2018)

Principal Investigator

KUWATA Naoaki  国立研究開発法人物質・材料研究機構, エネルギー・環境材料研究拠点, 主幹研究員 (00396459)

Project Period (FY) 2017-06-30 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2018: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywordsリチウムイオン電池 / 拡散係数 / 表面交換 / SIMS / 固体イオニクス / 混合伝導体 / 空孔拡散 / 粒界 / リチウムマンガン酸化物 / 表面交換速度 / 正極材料 / 同位体 / 混合導電体 / 二次イオン質量分析 / 正極 / 拡散機構 / スピネル / 同位体交換 / フィックの法則 / インターカレーション / 化学ポテンシャル / 二次電池 / 物性実験 / 拡散 / 薄膜
Outline of Final Research Achievements

We clarified the tracer diffusion coefficient of Li-ion battery cathode materials by using isotope ion exchange methods and SIMS analysis. These methods were applied to LiCoO2 and LiMn2O4 thin films. The compositional dependence of the diffusion coefficients indicates that the vacancy diffusion mechanism is dominant in these cathode materials. The LiCoO2 films exhibited Li diffusion along the c-axis, which suggest diffusion kinetics through the grain boundaries and the antiphase boundaries. The isotope profiles provided information on diffusion coefficients and surface exchange rates. An analysis based on the theory of mixed conductors was performed to compare the electrochemical measurements. The thermodynamic factor strongly amplified the chemical diffusion coefficients.

Academic Significance and Societal Importance of the Research Achievements

正極材料中のリチウム拡散はLiイオン電池の出力を決める重要な因子である。しかし、従来の電気化学測定法では、界面交換と拡散の問題が分離できず、バラバラの値が報告されていた。本研究で開発したトレーサー拡散測定法では、界面交換と拡散を分離して計測することができ、正確で信頼性の高い拡散係数を決定することができる。これらの研究は高速で充放電可能なLiイオン電池の開発につながり、エネルギー資源の高効率な利用に貢献するものである。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (25 results)

All 2020 2019 2018 2017

All Journal Article (7 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 7 results,  Open Access: 4 results) Presentation (14 results) (of which Int'l Joint Research: 2 results,  Invited: 5 results) Book (4 results)

  • [Journal Article] Effect of post-deposition annealing in oxygen atmosphere on LiCoMnO4 thin films for 5 V lithium batteries2019

    • Author(s)
      Ishigaki Norikazu、Kuwata Naoaki、Dorai Arunkumar、Nakamura Takashi、Amezawa Koji、Kawamura Junichi
    • Journal Title

      Thin Solid Films

      Volume: 686 Pages: 137433-137433

    • DOI

      10.1016/j.tsf.2019.137433

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ionic conduction in Li3Na(NH2)4: Study of the material design for the enhancement of ion conductivity in double-cation complex hydrides2019

    • Author(s)
      B. Paik, H. Oguchi, T. Sato, S. Takagi, A. Dorai, N. Kuwata, J. Kawamura, S. Orimo
    • Journal Title

      AIP Advances

      Volume: 9 Issue: 5 Pages: 055109-055109

    • DOI

      10.1063/1.5093580

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries2019

    • Author(s)
      Kim Sangryun、Oguchi Hiroyuki、Toyama Naoki、Sato Toyoto、Takagi Shigeyuki、Otomo Toshiya、Arunkumar Dorai、Kuwata Naoaki、Kawamura Junichi、Orimo Shin-ichi
    • Journal Title

      Nature Communications

      Volume: 10 Issue: 1 Pages: 1081-1081

    • DOI

      10.1038/s41467-019-09061-9

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] In situ Raman spectroscopy of Li CoO2 cathode in Li/Li3PO4/LiCoO2 all-solid-state thin-film lithium battery2019

    • Author(s)
      Matsuda Yasutaka、Kuwata Naoaki、Okawa Tatsunori、Dorai Arunkumar、Kamishima Osamu、Kawamura Junichi
    • Journal Title

      Solid State Ionics

      Volume: 335 Pages: 7-14

    • DOI

      10.1016/j.ssi.2019.02.010

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Diffusion coefficient of lithium ions in garnet-type Li6.5La3Zr1.5Ta0.5O12 single crystal probed by 7Li pulsed field gradient-NMR spectroscopy2018

    • Author(s)
      Dorai Arunkumar、Kuwata Naoaki、Takekawa Reiji、Kawamura Junichi、Kataoka Kunimitsu、Akimoto Junji
    • Journal Title

      Solid State Ionics

      Volume: 327 Pages: 18-26

    • DOI

      10.1016/j.ssi.2018.10.016

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electrochemically Synthesized Tin/Lithium Alloy To Convert Laser Light to Extreme Ultraviolet Light2018

    • Author(s)
      Nagai Keiji、Musgrave Christopher S. A.、Kuwata Naoaki、Kawamura Junichi
    • Journal Title

      ACS Omega

      Volume: 3 Issue: 10 Pages: 12422-12427

    • DOI

      10.1021/acsomega.8b01220

    • NAID

      120006602757

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Lithium diffusion coefficient in LiMn 2 O 4 thin films measured by secondary ion mass spectrometry with ion-exchange method2018

    • Author(s)
      Kuwata Naoaki、Nakane Masakatsu、Miyazaki Takamichi、Mitsuishi Kazutaka、Kawamura Junichi
    • Journal Title

      Solid State Ionics

      Volume: 320 Pages: 266-271

    • DOI

      10.1016/j.ssi.2018.03.012

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 電池材料のLiイオン拡散:NMRおよびSIMSによる自己拡散係数測定2019

    • Author(s)
      桑田 直明
    • Organizer
      日本物理学会 2019年秋季大会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Lithium Diffusion Coefficient in Solid State Battery Materials: SIMS and NMR analysis2019

    • Author(s)
      Naoaki Kuwata
    • Organizer
      IUMRS-ICA 2019, 20th International Union of Materials Research Societies Conference
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] イオニクス材料の拡散係数の基礎2019

    • Author(s)
      桑田 直明
    • Organizer
      蓄電固体界面科学 第1回若手勉強会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 二次イオン質量分析法によるLixCoO2単結晶のリチウム拡散機構の解析2019

    • Author(s)
      桑田 直明、長谷川源、秋本順二、宮崎孝道、河村純一
    • Organizer
      第22回超イオン導電体物性研究会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 単結晶LixCoO2におけるLi自己拡散係数の異方性2019

    • Author(s)
      長谷川源、桑田 直明、秋本順二、宮崎孝道、河村純一
    • Organizer
      固体イオニクス討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] LiCoO2単結晶のLi自己拡散係数測定2019

    • Author(s)
      長谷川源、桑田 直明、秋本順二、宮崎孝道、河村純一
    • Organizer
      日本物理学会 2019年秋季大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 高速製膜LixCoO2正極の薄膜電池特性と化学拡散係数2018

    • Author(s)
      桑田直明,松田康孝,長谷川源,河村純一
    • Organizer
      第21回 超イオン導電体物性研究会 (第70回 固体イオニクス研究会)
    • Related Report
      2018 Research-status Report
  • [Presentation] PLD法を用いた電池材料の薄膜作製と基礎物性,および全固体薄膜電池への応用2018

    • Author(s)
      桑田 直明
    • Organizer
      「全固体薄膜電池の製造プロセスと積層、量産技術」セミナー
    • Related Report
      2018 Research-status Report
    • Invited
  • [Presentation] Thin-film solid-state batteries prepared by high-rate PLD and diffusion coefficient in the battery materials2018

    • Author(s)
      Naoaki Kuwata, Yasutaka Matsuda, Gen Hasegawa, Norikazu Ishigaki, Takamichi Miyazaki and Junichi Kawamura
    • Organizer
      16th Asian Conference on Solid State Ionics (ACSSI-2018),
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 高速PLD製膜したLixCoO2正極の薄膜電池特性と化学拡散係数2018

    • Author(s)
      桑田直明, 松田康孝, 長谷川源, 河村純一
    • Organizer
      日本物理学会 2018年秋季大会
    • Related Report
      2018 Research-status Report
  • [Presentation] ガーネット型 LLZTO 単結晶の Li 自己拡散係数:パルス磁場勾配 NMR による測定2018

    • Author(s)
      桑田 直明, Dorai Arunkumar, 武川 玲治, 河村 純一, 片岡 邦光, 秋本 順二
    • Organizer
      第59回 電池討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] SIMSを用いたLixMn2O4薄膜におけるLi自己拡散係数測定2018

    • Author(s)
      前田大輝,中根正勝,宮崎孝道,長谷川源,石垣範和,桑田直明,河村純一
    • Organizer
      日本物理学会 第73回年次大会
    • Related Report
      2017 Research-status Report
  • [Presentation] LixCoO2薄膜におけるLi自己拡散係数の組成依存性2017

    • Author(s)
      長谷川源、桑田直明、宮崎孝道、石垣範和、河村純一
    • Organizer
      第43回 固体イオニクス討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] LixMn2O4薄膜におけるリチウム拡散係数の組成依存性2017

    • Author(s)
      前田大輝、中根正勝、長谷川源、宮崎孝道、石垣範和、桑田直明、河村純一
    • Organizer
      第43回 固体イオニクス討論会
    • Related Report
      2017 Research-status Report
  • [Book] 全固体電池の界面抵抗低減と作製プロセス、評価技術2020

    • Author(s)
      桑田直明、河村純一
    • Total Pages
      9
    • Publisher
      技術情報協会
    • ISBN
      9784861047800
    • Related Report
      2019 Annual Research Report
  • [Book] 2020版 薄膜作製応用ハンドブック2019

    • Author(s)
      桑田直明
    • Total Pages
      7
    • Publisher
      (株)エヌ・ティー・エス
    • ISBN
      9784860436315
    • Related Report
      2019 Annual Research Report
  • [Book] リチウムイオン電池における 高容量化・高電圧化技術と安全対策2018

    • Author(s)
      桑田直明
    • Total Pages
      707
    • Publisher
      技術情報協会
    • ISBN
      9784861047282
    • Related Report
      2018 Research-status Report
  • [Book] 全固体電池開発の現状と産業化へのアプローチ2018

    • Author(s)
      桑田直明
    • Total Pages
      178
    • Publisher
      情報機構
    • ISBN
      9784865021615
    • Related Report
      2018 Research-status Report

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Published: 2017-07-21   Modified: 2021-02-19  

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