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Elucidation of the spatiotemporal flow of conductive ions in storage batteries during charging and discharging using neutron and synchrotron X-ray scattering

Research Project

Project/Area Number 20K05061
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 26010:Metallic material properties-related
Research InstitutionKyoto University

Principal Investigator

Fukunaga Toshiharu  京都大学, 複合原子力科学研究所, 名誉教授 (60142072)

Co-Investigator(Kenkyū-buntansha) 森 一広  大学共同利用機関法人高エネルギー加速器研究機構, 物質構造科学研究所, 教授 (40362412)
中村 秀仁  京都大学, 複合原子力科学研究所, 助教 (60443074)
Project Period (FY) 2020-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2023: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2022: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2021: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2020: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords中性子散乱 / X線回折 / 原子構造 / イオン伝導 / 電池材料 / MEM解析 / RMC解析 / 熱分析 / BVS解析 / X線回折
Outline of Research at the Start

本研究は、充放電下で全固体蓄電池の中性子散乱(回折)実験を行い、電池性能を高めるための「伝導イオンが高速で移動できる固体構造及び固ー固界面構造」を明らかにすることである。第4世代中性子回折装置SPICAや世界トップクラスの装置を活用し、充放電中の固体構造(原子配列)と固ー固界面構造を原子レベルで可視化するとともに、伝導イオンの動きも直接観察する。同時に、歪んだ結晶や非晶質でも伝導イオンの流れを可視化できるBVSイメージング法や、進化させた界面BVSイメージング法を活用し、充放電中の固体内のイオン伝導経路や固ー固界面内イオン伝導経路も可視化し、伝導イオンの時空間流れを明らかにする。

Outline of Final Research Achievements

Using the neutron scattering instruments at J-PARC/MLF, we aimed to visualize the atomic arrangement of the cathode, anode, and solid electrolyte during charging and discharging of all-solid-state batteries, as well as to elucidate the conduction ion pathways at the atomic level and directly observe the movement of the conduction ions. The results of the research are as follows: The fluorine ion conduction pathways in the solid electrolytes of BaF2-SnF2 and CaF2-BaF2 fluorides, which exhibit particularly high ionic conduction properties, were elucidated at the atomic level by MEM and RMC analysis of the crystal structures obtained from neutron diffraction.

Academic Significance and Societal Importance of the Research Achievements

次世代型蓄電池の研究の一環として、フッ化物系全固体電池の研究は社会的意義が大きい。特に、全固体電池に欠かせない固体電解質中のイオン伝導の知識は、新しい固体電解質を見出すための重要な情報であると考えている。高いイオン伝導特性を有する固体電解質の原子構造を解明し、その原子構造内をイオンがどのような経路で移動するかを解明することができれば、さらにイオン伝導特性を持つ固体電解質を開発する糸口が見出せると考えている。それ故、本研究の成果である原子レベルのイオン伝導経路の解明は学術的な意義ばかりでなく、革新的電池開発に向けた社会的意義が大きいものと考える。

Report

(5 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Research-status Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • Research Products

    (17 results)

All 2023 2022 2021 2020

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 5 results) Presentation (9 results)

  • [Journal Article] Practical Reversibility of CuF2 in a Bulk-Type All-Solid-State Fluoride-Ion Battery2023

    • Author(s)
      Keiji Shimoda, Yoshiyuki Morita, Kousuke Noi, Toshiharu Fukunaga, Zempachi Ogumi, and Takeshi Abe
    • Journal Title

      ACS Energy Lett.

      Volume: 8 Issue: 6 Pages: 2570-2575

    • DOI

      10.1021/acsenergylett.3c00459

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Effects of Mixed Phases on Electrical Conductivities for (CeF3)1-m(CaF2)m Fast-Fluoride-Ion-Conducting Solid Electrolytes2023

    • Author(s)
      Kazuhiro Mori, Shuki Torii, Kenji Iwase, Takeshi Abe, and Toshiharu Fukunaga
    • Journal Title

      J. Phys. Chem. C

      Volume: 127 Issue: 1 Pages: 59-68

    • DOI

      10.1021/acs.jpcc.2c06732

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Examination of Morphological Changes of Active Materials for Solution-Based Rechargeable Fluoride Shuttle Batteries Using In Situ Electrochemical Atomic Force Microscopy Measurements2022

    • Author(s)
      Ken-ichi Okazaki,* Hirofumi Nakamoto, Toshiro Yamanaka, Toshiharu Fukunaga, Zempachi Ogumi, and Takeshi Abe
    • Journal Title

      Chem. Mater.

      Volume: 34 Issue: 18 Pages: 8280-8288

    • DOI

      10.1021/acs.chemmater.2c01751

    • Related Report
      2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Commissioning of Versatile Compact Neutron Diffractometer (VCND) at the B-3 Beam Port of Kyoto University Research Reactor (KUR)2021

    • Author(s)
      Mori Kazuhiro、Okumura Ryo、Yoshino Hirofumi、Kanayama Masaya、Satoh Setsuo、Oba Yojiro、Iwase Kenji、Hiraka Haruhiro、Hino Masahiro、Sano Tadafumi、Kawabata Yuji、Kamiyama Takashi、Otomo Toshiya、Fukunaga Toshiharu
    • Journal Title

      JPS Conference Proceedings

      Volume: 33 Pages: 011093-011093

    • DOI

      10.7566/jpscp.33.011093

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electrochemical, Thermal, and Structural Features of BaF2-SnF2 Fluoride-Ion Electrolytes2021

    • Author(s)
      Kazuhiro Mori, Atsushi Mineshige, Takuro Emoto, Maiko Sugiura, Takashi Saito, Kaoru Namba, Toshiya Otomo, Takeshi Abe, and Toshiharu Fukunaga
    • Journal Title

      J. Phys. Chem. C

      Volume: 125 Issue: 23 Pages: 12568-12577

    • DOI

      10.1021/acs.jpcc.1c03326

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Hysteresis of the charge transfer resistance between the charge and discharge processes obtained from electrochemical impedance measurements using a thin-film cathode for a lithium-ion cell2021

    • Author(s)
      T. Ohashi, T. Hirano, K. Okazaki, T. Fukunaga, and T. Abe
    • Journal Title

      J. Electroanal. Chem

      Volume: 899 Pages: 115675-115675

    • DOI

      10.1016/j.jelechem.2021.115675

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] High fluoride-ion conductivity and fluoride-ion conductorinsulator transition in fluorinated hexagonal boron nitride2021

    • Author(s)
      Tsuyoshi Takami, Takashi Saito, Takashi Kamiyama, Katsumi Kawahara, Toshiharu Fukunaga, Takeshi Abe
    • Journal Title

      Materials Today Physics

      Volume: 21 Pages: 100523-100523

    • DOI

      10.1016/j.mtphys.2021.100523

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Structural and Electrochemical Properties of Tysonite Ce0.95A0.05F2.95 (A = Mg, Ca, Sr, and Ba): Fast-Fluoride-Ion-Conducting Solid Electrolytes2020

    • Author(s)
      Kazuhiro Mori, Yoshiyuki Morita, Takashi Saito, Takashi Kamiyama, Toshiya Otomo, Takeshi Abe, and Toshiharu Fukunaga
    • Journal Title

      J. Phys. Chem. C

      Volume: 124 Issue: 34 Pages: 18452-18461

    • DOI

      10.1021/acs.jpcc.0c05217

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Presentation] (CeF3)1-x(CaF2)xフッ化物イオン伝導体の電気伝導度と構造2023

    • Author(s)
      森 一広、鳥居周輝、安部武志、福永俊晴、安部武志
    • Organizer
      日本中性子科学会 第23回年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] (LaF3)1-x(SrF2)xフッ化物イオン伝導体のイオン結晶構造2023

    • Author(s)
      ソン スンヨブ、森一広、福永俊晴、安部武志
    • Organizer
      日本中性子科学会 第23回年会
    • Related Report
      2023 Annual Research Report
  • [Presentation] CaF2-BaF2フッ化物イオン伝導体の結晶構造とイオン拡散経路2023

    • Author(s)
      森 一広、佐藤和之、福永俊晴、小川貴史、桑原彰秀、安部武志
    • Organizer
      日本金属学会 2023年秋期(第173回)講演大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] SrドープLaF3フッ化物イオン伝導体の構造研究2023

    • Author(s)
      ソン スンヨブ、森一広、福永俊晴、安部武志
    • Organizer
      日本金属学会 2023年秋期(第173回)講演大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] CuF2を用いたバルク型全固体フッ化物イオン電池の充放電特性評価2023

    • Author(s)
      下田景士,森田善幸,野井浩祐,福永俊晴,小久見善八,安部武志
    • Organizer
      電気化学会第90回大会
    • Related Report
      2022 Research-status Report
  • [Presentation] CaドープCeF3フッ化物イオン伝導体の電気化学特性と構造2022

    • Author(s)
      森 一広、鳥居周輝、安部武志、福永俊晴
    • Organizer
      日本金属学会 秋期講演大会(171回)
    • Related Report
      2022 Research-status Report
  • [Presentation] BaF2-SnF2系フッ化物イオン伝導体のイオン伝導特性と構造2022

    • Author(s)
      森一広、嶺重温、斎藤高志、大友季哉、安部武志、福永俊晴
    • Organizer
      日本中性子科学会 第22回年会
    • Related Report
      2022 Research-status Report
  • [Presentation] Ba2SnF2 系フッ化物イオン導電性固体電解質の電気化学特性と構造2021

    • Author(s)
      森 一広、嶺重 温、斎藤高志、大友季哉、福永俊晴
    • Organizer
      日本金属学会
    • Related Report
      2021 Research-status Report
  • [Presentation] 電解液を用いたフッ化物シャトル型二次電池のモデル電極による反応機構解析2021

    • Author(s)
      岡崎 健一、福永俊晴、小久見善八、安部武志
    • Organizer
      電気化学秋季大会
    • Related Report
      2021 Research-status Report

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Published: 2020-04-28   Modified: 2025-01-30  

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