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Development of iron-based oxide cathodes using insertion/extraction reactions of excess fluoride-ions

Research Project

Project/Area Number 21H02048
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 36020:Energy-related chemistry
Research InstitutionNara Women's University (2022-2023)
Kyoto University (2021)

Principal Investigator

Yamamoto Kentaro  奈良女子大学, 工学系, 准教授 (90755456)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000)
Fiscal Year 2023: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2022: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Fiscal Year 2021: ¥13,260,000 (Direct Cost: ¥10,200,000、Indirect Cost: ¥3,060,000)
Keywords全固体フッ化物イオン二次電池 / 正極材料 / アニオンレドックス / 分子形成 / 全固体フッ化物電池 / インターカレーション正極 / フッ化物イオン二次電池
Outline of Research at the Start

フッ化物イオンをキャリアとするフッ化物イオン二次電池はリチウムイオン二次電池を超える蓄電デバイスとして期待されているものの、高容量・高出力・高寿命な正極材料が見つかっていないことが課題となっている。本研究では、規則的な酸素空孔を有する鉄系層状酸化物に着目し、酸化物アニオンの電荷補償を用いた過剰なフッ化物イオンの挿入・脱離反応、ならびにフッ化物イオンの拡散パスを制御することにより、超高容量・高出力・高寿命なフッ化物イオン二次電池用正極を創成する。

Outline of Final Research Achievements

In this study, Ca-substituted SrFeO2 (CaxSr1-xFeO2) and Ba-substituted SrFeO2 (BaxSr1-xFeO2) based on SrFeO2 with infinite layer structure were focused on, and evaluated their electrochemical properties and clarified their reaction mechanisms. It was clarified that SrFeO2 has Fe in the early stage of charge compensation and O in the late stage of charge compensation, and that more fluoride ions can be inserted than expected from the crystal structure due to the formation of molecular oxygen when O is responsible for charge compensation. Furthermore, it was found that doping Ca into SrFeO2 increased the capacity up to 580 mAhg-1, while doping Ba into SrFeO2 improved the power density by increasing the interlayer distance within the infinite layer structure.

Academic Significance and Societal Importance of the Research Achievements

本研究では、SrFeO2がFeの電荷補償とO2分子の形成を伴うOの電荷補償を利用することで、結晶構造から予想されるよりも多くのフッ化物イオンが挿入可能であり、高い可逆容量を発現することを示した。さらにSrFeO2にCaをドープすると容量は最大で580 mAhg-1まで増加すること、Baをドープするとinfinite layer構造内の層間距離が広がることで出力特性が向上することを示した。これらの成果は高容量、高出力な全固体フッ化物イオン二次電池の正極材料を開発する上で重要な知見であり、学術的・社会的意義は大きい。

Report

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

    (13 results)

All 2024 2023 2022 2021

All Journal Article (3 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 3 results) Presentation (10 results) (of which Int'l Joint Research: 4 results,  Invited: 2 results)

  • [Journal Article] Double-Layered Perovskite Oxyfluoride Cathodes with High Capacity Involving O-O Bond Formation for Fluoride-Ion Batteries2024

    • Author(s)
      Miki Hidenori、Yamamoto Kentaro、Nakaki Hiroyuki、Yoshinari Takahiro、Nakanishi Koji、Nakanishi Shinji、Iba Hideki、Miyawaki Jun、Harada Yoshihisa、Kuwabara Akihide、Wang Yanchang、Watanabe Toshiki、Matsunaga Toshiyuki、Maeda Kazuhiko、Kageyama Hiroshi、Uchimoto Yoshiharu
    • Journal Title

      Journal of the American Chemical Society

      Volume: 146 Issue: 6 Pages: 3844-3853

    • DOI

      10.1021/jacs.3c10871

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transient phase change of Ruddlesden-Popper type perovskite on fluoride-ion intercalation reaction2024

    • Author(s)
      Miki Hidenori、Yamamoto Kentaro、Matsunaga Toshiyuki、Watanabe Toshiki、Kumar Mukesh、Thakur Neha、Iba Hideki、Kageyama Hiroshi、Uchimoto Yoshiharu
    • Journal Title

      Solid State Ionics

      Volume: 406 Pages: 116481-116481

    • DOI

      10.1016/j.ssi.2024.116481

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Revealing the Unusual Mechanism of Mixed Cationic and Anionic Redox in Oxyfluorosulfide Cathode for All-Solid-State Fluoride-Ion Batteries2024

    • Author(s)
      Cao Zulai、Yamamoto Kentaro、Matsunaga Toshiyuki、Watanabe Toshiki、Kumar Mukesh、Thakur Neha、Ohashi Ryogo、Tachibana Shintaro、Miki Hidenori、Ide Kazuto、Iba Hideki、Kiuchi Hisao、Harada Yoshihisa、Orikasa Yuki、Uchimoto Yoshiharu
    • Journal Title

      Chemistry of Materials

      Volume: 36 Issue: 4 Pages: 1928-1940

    • DOI

      10.1021/acs.chemmater.3c02650

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] (Ca, Sr)FeO2 Cathodes with High Capacity using Anionic Redox for All-solid-state Fluoride-Ion Batteries2024

    • Author(s)
      Kentaro Yamamoto
    • Organizer
      48th International Conference and Expo on Advanced Ceramics and Composites (ICACC2024)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Intercalation Reaction Mechanism of Fluoride-Ions in (Ca, Sr)FeO2 Cathodes with Infinite Layer Structure for All-solid-state Fluoride-Ion Batteries2023

    • Author(s)
      Kentaro Yamamoto, Yanchang Wang, Hisao Kiuchi, Toshiyuki Matsunaga, Toshiki Watanabe, Hidenori Miki, Hideki Iba, Kazuhiko Maeda, Yoshihisa Harada, Hiroshi Kageyama, Yoshiharu Uchimoto
    • Organizer
      244th ECS Meeting
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 固体内アニオンの特異な電子状態制御に基づいた高容量正極材料の設計2023

    • Author(s)
      山本 健太郎
    • Organizer
      第61回セラミックス基礎科学討論会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] インターカレーション型フッ化物イオン電池用正極材料の開発11 Infinite layer構造を有する(Ba, Sr)FeO2正極の電気化学特性評価2022

    • Author(s)
      王彦昌, 山本健太郎, 松永利之, 中西康次, 内山智貴, 渡邊稔樹, 高見剛, 三木秀教, 射場英紀, 前田和彦, 陰山洋, 内本喜晴
    • Organizer
      第63回電池討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Infinite layer 構造を有する(Ba, Sr)FeO2 正極の電気化学特性評価2022

    • Author(s)
      王彦昌,山本健太郎,松永利之,中西康次,内山智貴, 渡邊稔樹, 高見剛, 三木秀教, 射場英紀, 前田和彦, 陰山洋, 内本喜晴
    • Organizer
      第48回固体イオニクス討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Electrochemical performance of (Ca, Sr)FeO2 cathode with infinite layer structure for all-solid-state fluoride ion battery2022

    • Author(s)
      Kentaro Yamamoto, Yanchang Wang, Yuki Sakaguchi, Hisao Kiuchi, Toshiyuki Matsunaga, Koji Nakanishi, Tomoki Uchiyama, Toshiki Watanabe, Tsuyoshi Takami, Hidenori Miki, Hideki Iba, Kazuhiko Maeda, Yoshihisa Harada, Hiroshi Kageyama, Yoshiharu Uchimoto
    • Organizer
      21th International Meeting on Lithium Batteries
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Infinite layer構造を有するSrFeO2正極のフッ化物イオン挿入脱離反応機構の解明2022

    • Author(s)
      王彦昌, 山本健太郎, 宮脇淳, 松永利之, 木内久雄, 中西康次, 壬生攻, 内山智貴, 渡邊稔樹, 高見剛, 三木秀教, 射場英紀, 前田和彦, 原田慈久, 陰山洋, 内本喜晴
    • Organizer
      電気化学会第89回大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] インターカレーション型フッ化物イオン電池用正極材料の開発9 Infinite layer構造を有する(Ca, Sr)FeO2正極の電気化学特性評価2021

    • Author(s)
      山本健太郎, 王彦昌, 阪口祐紀, 木内久雄, 松永利之, 中西康次, 内山智貴, 渡邊稔樹, 高見剛, 三木秀教, 射場英紀, 前田和彦, 原田慈久, 陰山洋, 内本喜晴
    • Organizer
      第62回電池討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Electrochemical characterization and charge compensation mechanism of (Ca, Sr)FeO2 cathode with infinite layer structure2021

    • Author(s)
      Kentaro Yamamoto, Yanchang Wang, Yuki Sakaguchi, Hisao Kiuchi, Toshiyuki Matsunaga, Koji Nakanishi, Tomoki Uchiyama, Toshiki Watanabe, Tsuyoshi Takami, Hidenori Miki, Hideki Iba, Kazuhiko Maeda, Yoshihisa Harada, Hiroshi Kageyama, Yoshiharu Uchimoto
    • Organizer
      International Conference on Mixed-Anion Compounds
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Infinite layer構造を有する全固体フッ化物電池(Ca, Sr)FeO2正極のフッ化物イオン挿入脱離反応機構2021

    • Author(s)
      山本健太郎, 王彦昌, 阪口祐紀, 木内久雄, 松永利之, 中西康次, 内山智貴, 渡邊稔樹, 高見剛, 三木秀教, 射場英紀, 前田和彦, 原田慈久, 陰山洋, 内本喜晴
    • Organizer
      第47回固体イオニクス討論会
    • Related Report
      2021 Annual Research Report

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

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