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Study on diffusion mechanism of all-solid-state battery materials by using isotope exchange SIMS analysis and application to operando measurements

Research Project

Project/Area Number 21H02033
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 36010:Inorganic compounds and inorganic materials chemistry-related
Research InstitutionNational Institute for Materials Science

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・環境材料研究センター, 主幹研究員 (00396459)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2023: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2022: ¥7,670,000 (Direct Cost: ¥5,900,000、Indirect Cost: ¥1,770,000)
Fiscal Year 2021: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Keywords拡散係数 / 同位体 / オペランド / SIMS / 固体電池 / 活物質 / 粒界 / ダイナミクス / 二次イオン質量分析 / トレーサー拡散係数 / 粒界拡散 / オペランド測定 / TOF-SIMS / リチウムイオン伝導体 / 固体イオニクス / イオン伝導 / その場測定 / 全固体電池 / 正極材料 / 単結晶 / 物理化学 / 電気化学 / イオニクス
Outline of Research at the Start

リチウムイオン電池の電解液を固体に置き換えた、全固体電池は次世代の充放電可能な電池として、高出力と安全性から期待されている。固体中のリチウムイオンの拡散を可視化するとはこれまで困難であった。申請者らはリチウムの同位体を拡散させて、その広がりを二次イオン質量分析(SIMS)測定により可視化する手法を開発してきた。本研究では、SIMS測定を全固体電池の充放電過程の観察に応用する。それにより、全固体電池の高性能化のために必要不可欠な界面でのイオンの移動を可視化して、拡散機構の解明および、全固体電池の高性能化に貢献する。

Outline of Final Research Achievements

Secondary ion mass spectrometry (SIMS) was used as a technique to elucidate the diffusion mechanism of battery materials and to visualize lithium diffusion. Perovskite-type LLTO polycrystals were used as model materials for isotope exchange SIMS. By quenching the lithium diffusion at low temperatures and performing SIMS measurements, we observed a significant change in isotope concentration at grain boundary portions. Analysis of lithium diffusion revealed that the diffusion coefficient was five orders of magnitude smaller at the grain boundaries compared to the diffusion coefficient within the crystal grains. Furthermore, it was demonstrated that changes in lithium distribution in solid battery cathodes can be observed in real time by operando SIMS.

Academic Significance and Societal Importance of the Research Achievements

本研究を実施することにより、電池材料におけるリチウムイオンの動きを可視化するための新しい手法を確立することができた。SIMSを用いた拡散解析手法は、固体電解質だけでなく、今後は正極・負極活物質や界面にも適用することができ、電池材料研究への貢献は大きい。また、SIMSによるリチウム拡散の解析は国内外を通して初めて得られたオリジナルな研究であり、学術的にも重要である。本研究を活用し、リチウム拡散をマクロな電池特性につなげることで、固体電池の性能向上に貢献できるだろう。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (24 results)

All 2024 2023 2022 2021

All Journal Article (12 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 11 results,  Open Access: 9 results) Presentation (12 results) (of which Int'l Joint Research: 2 results,  Invited: 3 results)

  • [Journal Article] Visualization and evaluation of lithium diffusion at grain boundaries in Li0.29La0.57TiO3 solid electrolytes using secondary ion mass spectrometry2024

    • Author(s)
      Hasegawa Gen、Kuwata Naoaki、Ohnishi Tsuyoshi、Takada Kazunori
    • Journal Title

      Journal of Materials Chemistry A

      Volume: 12 Issue: 2 Pages: 731-738

    • DOI

      10.1039/d3ta05012b

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Lithium-Ion Diffusion in Perovskite-Type Solid Electrolyte Lithium Lanthanum Titanate Revealed by Pulsed-Field Gradient Nuclear Magnetic Resonance2023

    • Author(s)
      Hasegawa Gen、Kuwata Naoaki、Hashi Kenjiro、Tanaka Yoshinori、Takada Kazunori
    • Journal Title

      Chemistry of Materials

      Volume: 35 Issue: 10 Pages: 3815-3824

    • DOI

      10.1021/acs.chemmater.2c03340

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] On the Origin of the Non‐Arrhenius Na‐ion Conductivity in Na3OBr2023

    • Author(s)
      Darminto Brigita、Rees Gregory J.、Cattermull John、Hashi Kenjiro、Diaz‐Lopez Maria、Kuwata Naoaki、Turrell Stephen J.、Milan Emily、Chart Yvonne、Di Mino Camilla、Jeong Lee Hyeon、Goodwin Andrew L.、Pasta Mauro
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 62 Issue: 51

    • DOI

      10.1002/anie.202314444

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Liquid phase penetration sintering of garnet-type solid electrolyte LLZTO2023

    • Author(s)
      Yoshida Naoki、Kuwata Naoaki、Hasegawa Gen、Takada Kazunori
    • Journal Title

      Solid State Ionics

      Volume: 403 Pages: 116408-116408

    • DOI

      10.1016/j.ssi.2023.116408

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Lithium Diffusion Analysis in All-Solid-State Battery Materials2022

    • Author(s)
      HASEGAWA Gen、KUWATA Naoaki
    • Journal Title

      Denki Kagaku

      Volume: 90 Issue: 4 Pages: 346-350

    • DOI

      10.5796/denkikagaku.22-FE0034

    • ISSN
      2433-3255, 2433-3263
    • Year and Date
      2022-12-05
    • Related Report
      2022 Annual Research Report
  • [Journal Article] Ion dynamics of the LiMn2O4 cathode in thin-film solid-state batteries revealed by in situ Raman spectroscopy2022

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

      Solid State Ionics

      Volume: 380 Pages: 115925-115925

    • DOI

      10.1016/j.ssi.2022.115925

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Effects of Halogen and Sulfur Mixing on Lithium-Ion Conductivity in Li7-x-y(PS4)(S2-x-yClxBry) Argyrodite and the Mechanism for Enhanced Lithium Conduction2022

    • Author(s)
      Masuda Naoya、Kobayashi Kiyoshi、Utsuno Futoshi、Uchikoshi Tetsuo、Kuwata Naoaki
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 126 Issue: 33 Pages: 14067-14074

    • DOI

      10.1021/acs.jpcc.2c03780

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Temperature Dependency of Ion Transport in Highly Concentrated Li Salt/Sulfolane Electrolyte Solutions2022

    • Author(s)
      Ugata Yosuke、Hasegawa Gen、Kuwata Naoaki、Ueno Kazuhide、Watanabe Masayoshi、Dokko Kaoru
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 126 Issue: 45 Pages: 19084-19090

    • DOI

      10.1021/acs.jpcc.2c06699

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fast fluoride ion conduction of NH4(Mg1-xLix)F3-x and (NH4)2(Mg1-xLix)F4-x assisted by molecular cations2022

    • Author(s)
      Motohashi Kota、Matsukawa Yosuke、Nakamura Takashi、Kimura Yuta、Kuwata Naoaki、Uchimoto Yoshiharu、Amezawa Koji
    • Journal Title

      Scientific Reports

      Volume: 12 Issue: 1 Pages: 5955-5955

    • DOI

      10.1038/s41598-022-09835-0

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Exploration of organic superionic glassy conductors by process and materials informatics with lossless graph database2022

    • Author(s)
      Hatakeyama-Sato Kan、Umeki Momoka、Adachi Hiroki、Kuwata Naoaki、Hasegawa Gen、Oyaizu Kenichi
    • Journal Title

      npj Computational Materials

      Volume: 8 Issue: 1 Pages: 170-170

    • DOI

      10.1038/s41524-022-00853-0

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Experimental Evaluation of Influence of Stress on Li Chemical Potential and Phase Equilibrium in Two-phase Battery Electrode Materials2021

    • Author(s)
      KIMURA Yuta、FUNAYAMA Keita、FAKKAO Mahunnop、NAKAMURA Takashi、KUWATA Naoaki、KAWADA Tatsuya、KAWAMURA Junichi、AMEZAWA Koji
    • Journal Title

      Electrochemistry

      Volume: 89 Issue: 4 Pages: 355-362

    • DOI

      10.5796/electrochemistry.21-00033

    • NAID

      130008062338

    • ISSN
      1344-3542, 2186-2451
    • Year and Date
      2021-07-05
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Tracer diffusion coefficients of Li+ ions in c-axis oriented LixCoO2 thin films measured by secondary ion mass spectrometry2021

    • Author(s)
      Hasegawa Gen、Kuwata Naoaki、Tanaka Yoshinori、Miyazaki Takamichi、Ishigaki Norikazu、Takada Kazunori、Kawamura Junichi
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 23 Issue: 3 Pages: 2438-2448

    • DOI

      10.1039/d0cp04598e

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Presentation] リチウム同位体拡散イメージングによる固体電解質内のバルク・粒界拡散の解析.2023

    • Author(s)
      長谷川 源, 桑田 直明
    • Organizer
      第64回電池討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] ペロブスカイト型単結晶LixLa(1-x)/3NbO3の高温イオンダイナミクス計測2023

    • Author(s)
      桑田 直明, 長谷川 源, 端 健二郎, 藤原靖幸, 射場英紀.
    • Organizer
      第49回固体イオニクス討論会
    • Related Report
      2023 Annual Research Report
  • [Presentation] SIMSを用いたLi0.29La0.57TiO3多結晶における 粒界でのリチウム拡散の可視化と評価2023

    • Author(s)
      長谷川 源, 桑田 直明
    • Organizer
      日本物理学会 第78回年次大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] パルス磁場勾配NMR法によるペロブスカイト型固体電解質Li0.29La0.57TiO3 におけるLiイオン拡散測定2022

    • Author(s)
      桑田 直明, 長谷川 源, 端 健二郎, 田中 喜典, 高田 和典
    • Organizer
      第63回電池討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 二次イオン質量分析法を用いたLi0.29La0.57TiO3固体電解質における粒界拡散の可視化と定量評価2022

    • Author(s)
      長谷川 源, 桑田 直明
    • Organizer
      第48回固体イオニクス討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] PFG-NMRによる固体電解質ニオブ酸ランタンリチウム単結晶の拡散係数測定2022

    • Author(s)
      桑田 直明, 長谷川 源, 藤原靖幸, 射場 英紀
    • Organizer
      第48回 固体イオニクス討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] K3H(SO4)2の前駆現象におけるプロトンの状態2022

    • Author(s)
      長谷川 佑介, 桑田 直明, 長谷川 源, 松井 広志
    • Organizer
      第48回固体イオニクス討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Lithium-Ion Diffusion in Solid Electrolytes Revealed by PFG-NMR and TOF-SIMS2021

    • Author(s)
      桑田 直明, 長谷川 源, 荒 宏子
    • Organizer
      MRM2021 (Materials Research Meeting 2021)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Direct Observation of Lithium Diffusion in Insertion Electrodes by Isotope Exchange and Secondary Ion Mass Spectrometry2021

    • Author(s)
      桑田 直明, 長谷川 源.
    • Organizer
      45th International Conference and Expo on Advanced Ceramics and Composites (ICACC2021)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 二次イオン質量分析法で計測するリチウムイオン電池材料のリチウム拡散2021

    • Author(s)
      桑田 直明
    • Organizer
      電気化学会北海道支部 学術講演会. 2021
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 多結晶Li0.29La0.57TiO3における粒界と粒内のLi拡散測定2021

    • Author(s)
      長谷川 源, 荒 宏子, 桑田 直明.
    • Organizer
      第47回固体イオニクス討論会. 2021
    • Related Report
      2021 Annual Research Report
  • [Presentation] 高温PFG-NMRによる固体電解質Li0.29La0.57TiO3のリチウム拡散係数測定2021

    • Author(s)
      桑田 直明, 長谷川 源, 端 健二郎
    • Organizer
      第47回固体イオニクス討論会. 2021
    • Related Report
      2021 Annual Research Report

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Published: 2021-04-28   Modified: 2025-01-30  

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