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Investigation of interface between complex hydride solid electrolyte and sulfur/carbon composite electrode

Research Project

Project/Area Number 19K15305
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 26040:Structural materials and functional materials-related
Research InstitutionTohoku University

Principal Investigator

Kisu Kazuaki  東北大学, 金属材料研究所, 助教 (80755645)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2021: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywordsイオン伝導 / 錯体水素化物 / 二次電池 / 全固体電池 / リチウム硫黄電池
Outline of Research at the Start

錯体水素化物固体電解質は高いイオン伝導性や高い耐還元性を有しており、高エネルギー密度化が実現可能なリチウム硫黄電池の電解質として期待されている。本研究では、錯体水素化物固体電解質と電極材料間において生成される界面に着目し、界面挙動が電池特性に与える影響を明らかにすることで、サイクル寿命向上や充放電速度向上への新たな指針を得ることを目的としている。

Outline of Final Research Achievements

Complex hydride materials have been widely investigated as potential solid electrolytes because they have good compatibility with the lithium metal anodes used in all-solid-state batteries. However, the de- velopment of all-solid-state batteries utilizing complex hydrides has been difficult as these cells tend to have short cycle lives. This study investigated the capacity fading mechanism of all-solid-state lithium-sulfur (Li-S) batteries using Li4(BH4)3I solid electrolytes by analyzing the cathode microstructure. Cross- sectional scanning electron microscopy observations after 100 discharge-charge cycles revealed crack formation in the Li4(BH4)3 I electrolyte and an increased cathode thickness. Raman spectroscopy indicated that decomposition of the Li4(BH4)3 I solid electrolyte occurred at a constant rate during the cycling tests. To combat these effects, the cycle life of Li-S batteries was improved by increasing the amount of solid electrolyte in the cathode.

Academic Significance and Societal Importance of the Research Achievements

本研究は、錯体水素化物を全固体電池用途としての固体電解質として捉え、電池材料としての安定性評価を本格的に行うという研究であった。研究対象とする錯体水素化物は最もシンプルな構造でかつ代表的な水素化物であるLiBH4を用いて評価を行うことで、水素化物としての共通的な界面安定性を明らかにした。近年、申請者のグループでは、LiBH4を超える高いイオン伝導特性を有する多種多様な錯体水素化物を生み出しており、本研究で得られた基盤的な知見を活かすことで、今後幅広い錯体水素化物固体電解質へと展開が可能となった。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (35 results)

All 2022 2021 2020 2019 Other

All Int'l Joint Research (3 results) Journal Article (10 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 8 results,  Open Access: 4 results) Presentation (17 results) (of which Int'l Joint Research: 8 results,  Invited: 1 results) Book (5 results)

  • [Int'l Joint Research] スイス連邦工科大学ローザンヌ校(スイス)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] EPFL(スイス)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] University of Turin(イタリア)

    • Related Report
      2020 Research-status Report
  • [Journal Article] Monocarborane cluster as a stable fluorine‐free calcium battery electrolyte2021

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Takara Shinohara, Kun Zhao, Andreas Zuttel, Shin‐ichi Orimo
    • Journal Title

      Scientific Report

      Volume: 11 Issue: 1 Pages: 7563-7563

    • DOI

      10.1038/s41598-021-86938-0

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Stabilization of Superionic-Conducting High-Temperature Phase of Li(CB9H10) via Solid Solution Formation with Li2(B12H12)2021

    • Author(s)
      Sangryun Kim, Kazuaki Kisu, Shin-ichi Orimo
    • Journal Title

      Crystals

      Volume: 11 Issue: 4 Pages: 330-330

    • DOI

      10.3390/cryst11040330

    • Related Report
      2021 Annual Research Report 2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] 錯体水素化物系マグネシウムイオン伝導体の開発2021

    • Author(s)
      木須一彰、金相侖、折茂慎一
    • Journal Title

      セラミックス

      Volume: 56(2) Pages: 72-75

    • Related Report
      2020 Research-status Report
    • Open Access
  • [Journal Article] Microstructural analyses of all-solid-state Li-S batteries using LiBH4-based solid electrolyte for prolonged cycle performance2020

    • Author(s)
      Kazuaki Kisu、Sangryun Kim、Ryuga Yoshida、Hiroyuki Oguchi、Naoki Toyama、Shin-ichi Orimo
    • Journal Title

      Journal of Energy Chemistry

      Volume: - Pages: 424-429

    • DOI

      10.1016/j.jechem.2020.03.069

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Magnesium Borohydride Ammonia Borane as a Magnesium Ionic Conductor2020

    • Author(s)
      Kisu Kazuaki、Kim Sangryun、Inukai Munehiro、Oguchi Hiroyuki、Takagi Shigeyuki、Orimo Shin-ichi
    • Journal Title

      ACS Applied Energy Materials

      Volume: 3 Issue: 4 Pages: 3174-3179

    • DOI

      10.1021/acsaem.0c00113

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Complex Hydride Solid Electrolytes of the Li(CB9H10)?Li(CB11H12) Quasi-Binary System: Relationship between the Solid Solution and Phase Transition, and the Electrochemical Properties2020

    • Author(s)
      Kim Sangryun、Kisu Kazuaki、Takagi Shigeyuki、Oguchi Hiroyuki、Orimo Shin-ichi
    • Journal Title

      ACS Applied Energy Materials

      Volume: 3 Issue: 5 Pages: 4831-4839

    • DOI

      10.1021/acsaem.0c00433

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Room temperature operation of all-solid-state battery using a closo-type complex hydride solid electrolyte and a LiCoO2 cathode by interfacial modification2020

    • Author(s)
      Kim Sangryun、Harada Kentaro、Toyama Naoki、Oguchi Hiroyuki、Kisu Kazuaki、Orimo Shin-ichi
    • Journal Title

      Journal of Energy Chemistry

      Volume: 43 Pages: 47-51

    • DOI

      10.1016/j.jechem.2019.08.007

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Noncrystalline Nanocomposites as a Remedy for the Low Diffusivity of Multivalent Ions in Battery Cathodes2020

    • Author(s)
      Orikasa Yuki、Kisu Kazuaki、Iwama Etsuro、Naoi Wako、Yamaguchi Yusuke、Yamaguchi Yoshitomo、Okita Naohisa、Ohara Koji、Munesada Toshiyuki、Hattori Masashi、Yamamoto Kentaro、Rozier Patrick、Simon Patrice、Naoi Katsuhiko
    • Journal Title

      Chemistry of Materials

      Volume: 32 Issue: 3 Pages: 1011-1021

    • DOI

      10.1021/acs.chemmater.9b03665

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Interfacial stability between LiBH4-based complex hydride solid electrolytes and Li metal anode for all-solid-state Li batteries2019

    • Author(s)
      Kisu Kazuaki、Kim Sangryun、Oguchi Hiroyuki、Toyama Naoki、Orimo Shin-ichi
    • Journal Title

      Journal of Power Sources

      Volume: 436 Pages: 226821-226821

    • DOI

      10.1016/j.jpowsour.2019.226821

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] 錯体水素化物リチウムイオン伝導体を用いた全固体電池2019

    • Author(s)
      金相侖, 木須一彰, 折茂慎一
    • Journal Title

      電気評論

      Volume: 104 Pages: 20-29

    • Related Report
      2019 Research-status Report
  • [Presentation] 錯体水素化物マグネシウムイオン伝導体Mg(BH4)2(NH3BH3)2の電気化学特性2021

    • Author(s)
      木須一彰, 金相侖, 犬飼宗弘, 大口裕之, 高木成幸, 折茂慎一
    • Organizer
      日本金属学会 第168回春期講演大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Energy Related Application of Hydrides2021

    • Author(s)
      Kazuaki Kisu
    • Organizer
      Joint Workshop AIMR-Fraunhofer ENAS
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] カルシウムイオン電池用電解質 Ca(CB11H12)2の合成と特性評価2021

    • Author(s)
      木須一彰, 金相侖, 折茂慎一
    • Organizer
      第140回東北大学金属材料研究所講演会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 錯体水素化物系電解質 Ca[CB11H12]2 の合成と電気化学評価2021

    • Author(s)
      木須一彰, 金相侖, 折茂慎一
    • Organizer
      日本金属学会 第169回秋期講演大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 次世代エネルギーデバイスに向けた錯体水素化物の開発2021

    • Author(s)
      木須一彰
    • Organizer
      第10回 MaSC 技術交流会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Hydride-based Monocarborane Cluster for Calcium Battery Electrolyte2021

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Shin-ichi Orimo
    • Organizer
      5th Symposium for the Core Research Clusters for Materials Science and Spintronics
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] カルシウム蓄電池用電解質 Ca[CB11H12]2 の合成と電気化学評価2021

    • Author(s)
      木須一彰, 金相侖, 折茂慎一
    • Organizer
      第62回 電池討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Calcium Battery Electrolyte with Hydride-based Monocarborane Cluster2021

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Kun Zhao, Andreas Zuttel, Shin‐ichi Orimo
    • Organizer
      Material Research Meeting 2021 (MRM2021)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Electrochemical characterization of Magnesium Borohydride Ammonia Borane Mg(BH4)2(NH3BH3)2 as a Magnesium Ionic Conductor2020

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Munehiro Inukai, Hiroyuki Oguchi, Shigeyuki Takagi, and Shin-ichi Orimo
    • Organizer
      The 4th Symposium for The Core Research Cluster for Materials Science
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Microstructural analyses of all-solid-state Li-S battery using LiBH4-based solid electrolyte for prolonged cycle performance2020

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, and Shin-ichi Orimo
    • Organizer
      The 3rd Symposium for The Core Research Clusters for Materials Science and Spintronics
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] ALL SOLID-STATE BATTERIES USING LIBH4-BASED SOLID ELECTROLYTE AND LITHIUM METAL ELECTRODE2020

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, and Shin-ichi Orimo
    • Organizer
      1st International Symposium “Hydrogenomics” combined with 14th International Symposium Hydrogen & Energy
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] 錯体水素化物マグネシウムイオン伝導体Mg(BH4)2(NH3BH3)2の電気化学特性2020

    • Author(s)
      木須一彰, 金相侖, 犬飼宗弘, 大口裕之, 高木成幸, 折茂慎一
    • Organizer
      日本金属学会 第168回春期講演大会
    • Related Report
      2020 Research-status Report
  • [Presentation] マグネシウムイオン伝導体Mg(BH4)2(NH3BH3)2の電気化学特性2020

    • Author(s)
      木須一彰, 金相侖, 犬飼宗弘, 大口裕之, 高木成幸, 折茂慎一
    • Organizer
      第61回電池討論会
    • Related Report
      2020 Research-status Report
  • [Presentation] LiBH4系錯体水素化物固体電解質を用いたリチウム-硫黄全固体電池の電極/電解質界面安定性2020

    • Author(s)
      木須一彰, 金相侖, 大口裕之, 折茂慎一
    • Organizer
      電気化学会第87回大会
    • Related Report
      2020 Research-status Report
  • [Presentation] 水素化物系全固体電池の開発動向 -高速陽イオン伝導と電極界面安定性-2019

    • Author(s)
      木須一彰, 金相侖, 折茂 慎一
    • Organizer
      第107回 新電池構想部会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] All solid-state batteries using complex hydrides solid electrolyte and lithium metal electrode2019

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Hiroyuki Oguchi, Naoki Toyama, Shin-ichi Orimo
    • Organizer
      Gordon Research Conference Hydrogen-Metal Systems
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Interfacial stability between lithium metal anode and LiBH4-based complex hydride solid electrolytes for all-solid-state lithium battery2019

    • Author(s)
      Kazuaki Kisu, Sangryun Kim, Hiroyuki Oguchi, Naoki Toyama, Shin-ichi Orimo
    • Organizer
      22nd International Conference on Solid State Ionics
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Book] “水素”を使いこなすためのサイエンス ハイドロジェノミクス2022

    • Author(s)
      折茂 慎一、福谷 克之、藤田 健一
    • Total Pages
      216
    • Publisher
      共立出版
    • ISBN
      4320044983
    • Related Report
      2021 Annual Research Report
  • [Book] 錯体水素化物系マグネシウムイオン伝導体の開発2021

    • Author(s)
      木須一彰、金相侖、折茂慎一
    • Total Pages
      4
    • Publisher
      セラミックス
    • Related Report
      2021 Annual Research Report
  • [Book] 電池技術2020

    • Author(s)
      木須一彰, 金相侖, 折茂慎一
    • Total Pages
      7
    • Publisher
      水素化物系全固体電池の開発動向, 高速陽イオン伝導と電極界面安定性
    • Related Report
      2020 Research-status Report
  • [Book] 技術情報協会2020

    • Author(s)
      金相侖, 木須一彰, 折茂慎一
    • Total Pages
      8
    • Publisher
      全固体電池の界面抵抗低減と作製プロセス、評価技術
    • Related Report
      2020 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:錯体水素化物固体電解質を用いた高エネルギー密度型全固体電池の開発2019

    • Author(s)
      金相侖, 木須一彰, 折茂慎一
    • Total Pages
      8
    • Publisher
      技術情報協会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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