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電子活性部位を有する新規硫黄共重合体の創製に基づいた高性能硫黄二次電池の開発

Research Project

Project/Area Number 19K22222
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 35:Polymers, organic materials, and related fields
Research InstitutionKwansei Gakuin University

Principal Investigator

吉川 浩史  関西学院大学, 工学部, 教授 (60397453)

Co-Investigator(Kenkyū-buntansha) 谷藤 尚貴  米子工業高等専門学校, その他部局等, 教授 (80423549)
Project Period (FY) 2019-06-28 – 2025-03-31
Project Status Granted (Fiscal Year 2023)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2020: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Fiscal Year 2019: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords硫黄共重合体 / 二次電池 / 正極材料 / 硫黄 / 共重合 / 正極 / 共重合体 / 加硫 / XAFS / 逆加硫 / リチウム硫黄電池
Outline of Research at the Start

本研究では、酸化還元活性かつ高伝導性を有する小分子により硫黄鎖を架橋するという応募者独自の発想に基づき、機能性と安定性を兼ね備えた新規硫黄系高分子材料(硫黄共重合体)の創製を行い、これを正極に用いることで、硫黄単体の理論容量に迫る実容量と高いサイクル安定性を有する二次電池を実現する。さらに、各種物理化学計測法を用いて、その電気化学反応挙動を明らかにし、硫黄共重合体のサイエンスを深化させる。

Outline of Annual Research Achievements

リチウム硫黄(Li-S)電池は、その理論容量が従来のリチウムイオン電池の約10倍(約1670 mAh/g)であり、硫黄が安価な材料であることから、次世代二次電池の正極材料として期待されている。しかし、電気化学反応における硫黄の電解質溶液への溶出により、サイクル安定性が低いという問題がある。本研究課題では、この問題を解決するため、電気化学反応による硫黄の溶出が抑制される材料の創製と電極特性の検討研究を行った。今年度は、硫黄と様々なアルコールからなる複合体(SAC)の作製を行った。
具体的には、炭素鎖長や級数の異なるアルコールと硫黄を重量比1:5で混合し、窒素雰囲気下、400 ℃で2 時間還流を行った。その後、未反応の硫黄を除くため、窒素雰囲気下300 ℃で加熱した。得られたSACを 30 wt%、トーカブラックを50 wt%、PVDF を20 wt%とする合材電極を作製し、Al 箔に塗工し、薄膜正極を作製した。これを用いて、LiTFSI、LiNO3、DOL、DME からなる電解液、カーボンコートセパレーター、およびLi 箔負極から成るLi-S電池を作成し、その電池特性を計測した。
その結果、各種SACを正極とするLi-S電池の放電容量のサイクル特性が得られ、それより、1-オクタノールと硫黄から作製したSACの電池特性が良好であり、電流密度200mAh/gで初期容量は約1660mAh/g、100サイクル後でも約800mAh/gを維持した。また、級数を変えたヘキサノールを用いたSACでは第2級が最も良好で、1-オクタノールと同等の電池特性を示した。これらより、炭素鎖長とOH基の位置が電池特性に影響することが示唆された。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

本課題は、有機小分子により、硫黄を固定化し、電気化学反応による硫黄の溶出を抑えて、リチウム硫黄電池を高性能化することを目的としている。現在、小分子であるアルコールを用いて、ある程度、その高性能化には成功していると言うことができる。よって、研究はおおむね順調に進展している。

Strategy for Future Research Activity

今後であるが、なぜ、アルコールと硫黄を反応させた材料にて、高性能化が実現できるのかが分かっておらず、その機構解明を行う必要があると考えている。例えば、SのX線吸収分光などを行うことで、その詳細に迫り、より高性能な硫黄共重合材料の創製へとつなげる予定である。

Report

(5 results)
  • 2023 Research-status Report
  • 2022 Research-status Report
  • 2021 Research-status Report
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (39 results)

All 2024 2023 2022 2021 2020 2019 Other

All Int'l Joint Research (7 results) Journal Article (19 results) (of which Int'l Joint Research: 8 results,  Peer Reviewed: 19 results,  Open Access: 6 results) Presentation (10 results) (of which Int'l Joint Research: 6 results,  Invited: 9 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] CSIR(インド)

    • Related Report
      2023 Research-status Report
  • [Int'l Joint Research] インド科学技術庁・機械工学中央研究所(インド)

    • Related Report
      2022 Research-status Report
  • [Int'l Joint Research] Zhengzhou University of Light Industry(オーストラリア)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] University of Wollongong(中国)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] Uni-versita di Trieste(イタリア)

    • Related Report
      2020 Research-status Report
  • [Int'l Joint Research] 鄭州軽工業学院(中国)

    • Related Report
      2019 Research-status Report
  • [Int'l Joint Research] トリエステ大学(イタリア)

    • Related Report
      2019 Research-status Report
  • [Journal Article] Inorganic-Organic Framework Constructed by the Intercalation of a Double-Decker Porphyrin Metal Complex into Clay Nanosheets and Its Efficient Dye Adsorption Ability2024

    • Author(s)
      Yasuyuki Yamada*, Toshio Nishino, Ayako Hashimoto, Yuka Toyoda, Hirofumi Yoshikawa, Kentaro Tanaka
    • Journal Title

      ACS Applied Optical Materials

      Volume: 2 Issue: 3 Pages: 405-413

    • DOI

      10.1021/acsaom.3c00444

    • Related Report
      2023 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electron Storage Performance of Metal-Organic Frameworks Based on Tetrathiafulvalene-Tetrabenzoate as Cathode Active Materials in Lithium and Sodium-ion Batteries2023

    • Author(s)
      Katsuhiro Wakamatsu, Soichiro Furuno, Yoshihiko Yamaguchi, Ryo Matsushima, Takeshi Shimizu, Naoki Tanifuji, Hirofumi Yoshikawa
    • Journal Title

      ACS Appl. Energy Mater.

      Volume: 6 Issue: 18 Pages: 9124-9135

    • DOI

      10.1021/acsaem.2c03537

    • Related Report
      2023 Research-status Report 2022 Research-status Report
    • Peer Reviewed
  • [Journal Article] Selective synthesis of two-dimensional semiconductive coordination polymers with silver-sulfur network2023

    • Author(s)
      Akiyoshi Ryohei、Saeki Akinori、Ogasawara Kazuyoshi、Yoshikawa Hirofumi、Nakamura Yuiga、Tanaka Daisuke
    • Journal Title

      CrystEngComm

      Volume: - Issue: 20 Pages: 2990-2994

    • DOI

      10.1039/d3ce00106g

    • Related Report
      2023 Research-status Report
    • Peer Reviewed
  • [Journal Article] High-density cathode structure of independently acting Prussian-blue-analog nanoparticles: a high power Zn-Na-ion battery discharging ~200 mA cm-2 at 1000C2023

    • Author(s)
      Yuta Asahina, Ryo Terashima, Manabu Ishizaki, Hideo Ando, Jun Matsui, Hirofumi Yoshikawa and Masato Kurihara
    • Journal Title

      J. Mater. Chem. A

      Volume: 11 Issue: 48 Pages: 26452-26464

    • DOI

      10.1039/d3ta05143a

    • Related Report
      2023 Research-status Report
    • Peer Reviewed
  • [Journal Article] Electron Storage Performance of Hybrid Materials Comprising Polyoxometalates and Carbon Nanohorns as Cathode-Active Materials2023

    • Author(s)
      Katsuhiro Wakamatsu, Akinori Sekihara, Yoshihiko Yamaguchi, Ryo Matsushima, Daiju Matsumura, Tapas Kuila, Hirofumi Yoshikawa
    • Journal Title

      Batteries&Supercaps

      Volume: 6

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Application of Porous Coordination Polymer Containing Aromatic Azo Linkers as Cathode Active Materials in Sodium-Ion Batteries Application of Porous Coordination Polymer Containing Aromatic Azo Linkers as Cathode Active Materials in Sodium-Ion Batteries2022

    • Author(s)
      Takeshi Shimizu, Takumi Mameuda, Hiroki Toshima, Ryohei Akiyoshi, Yoshinobu Kamakura, Katsuhiro Wakamatsu, Daisuke Tanaka, and Hirofumi Yoshikawa
    • Journal Title

      ACS Appl. Energy Mater

      Volume: 5 Issue: 4 Pages: 5191-5198

    • DOI

      10.1021/acsaem.2c00537

    • Related Report
      2022 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Application of μ-Nitrido- and μ-Carbido-Bridged Iron Phthalocyanine Dimers as Cathode-Active Materials for Rechargeable Batteries2021

    • Author(s)
      Takeshi Shimizu, Katsuhiro Wakamatsu, Yasuyuki Yamada, Yuka Toyoda, Shigehisa Akine, Kenji Yoza, and Hirofumi Yoshikawa
    • Journal Title

      ACS Appl. Mater. Interfaces

      Volume: 60 Issue: 34 Pages: 40612-40617

    • DOI

      10.1021/acsami.1c10540

    • Related Report
      2021 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of Hexaazatriphenylene Charge-Transfer Complexes and Their Application in Cathode Active Materials for Lithium-Ion Batteries2021

    • Author(s)
      Nakao Keisuke、Kamakura Yoshinobu、Fujiwara Makoto、Shimizu Takeshi、Yoshida Yukihiro、Kitagawa Hiroshi、Yoshikawa Hirofumi、Kitagawa Yasutaka、Tanaka Daisuke
    • Journal Title

      Crystal Growth & Design

      Volume: 22 Issue: 1 Pages: 26-31

    • DOI

      10.1021/acs.cgd.1c00793

    • Related Report
      2021 Research-status Report
    • Peer Reviewed
  • [Journal Article] Selective Phosphorization Boosting High-performance NiO/Ni2Co4P3 Microspheres as Anode Materials for Lithium Ion Batteries2021

    • Author(s)
      Ji Yan *, Xin-Bo Chang, Xiao-Kai Ma, Heng Wang, Yong Zhang, Ke-Zheng Gao, Hirofumi Yoshikawa *, Li-Zhen Wang
    • Journal Title

      Materials

      Volume: 134 Issue: 1 Pages: 21-21

    • DOI

      10.3390/ma14010024

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] TTF-Annulated Silicon Phthalocyanine Oligomers and Their External-Stimuli-Responsive Orientational Ordering2020

    • Author(s)
      Y. Shiina, Y. Kage, K. Furukawa, H. Wang, H. Yoshikawa, H. Furuta, N. Kobayashi, and S. Shimizu
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Issue: 50 Pages: 22721-22730

    • DOI

      10.1002/anie.202011025

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] General synthesis of single-atom catalysts for hydrogen evolution reactions and room-temperature Na-S batteries2020

    • Author(s)
      Wei-Hong Lai, Heng Wang, Lirong Zheng, Quan Jiang, Zi-Chao Yan, Lei Wang,* Hirofumi Yoshikawa, Daiju Matsumura, Qiao Sun, Yun-Xiao Wang,* Qinfen Gu, Jia-Zhao Wang, Hua-Kun Liu, Shu-Lei Chou,* Shi-Xue Dou
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 59 Issue: 49 Pages: 22171-22178

    • DOI

      10.1002/anie.202009400

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Coordination Distortion Induced Water Adsorption in Hydrophobic Flexible Metal Organic Frameworks2020

    • Author(s)
      Yoshinobu Kamakura, Arata Hikawa, Hirofumi Yoshikawa, Wataru Kosaka, Hitoshi Miyasaka, and Daisuke Tanaka
    • Journal Title

      Chem. Commun.

      Volume: 59 Issue: 64 Pages: 9106-9109

    • DOI

      10.1039/d0cc03772a

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Reversible Control of Ionic Conductivity and Viscoelasticity of Organometallic Ionic Liquids by Application of Light and Heat2020

    • Author(s)
      Ryo Sumitani, Hirofumi Yoshikawa and Tomoyuki Mochida
    • Journal Title

      Chem. Commun.

      Volume: 56 Issue: 46 Pages: 6189-6192

    • DOI

      10.1039/d0cc02786c

    • NAID

      120006867368

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Competing Roles of Two Kinds of Ligand during Nonclassical Crystallization of Pillared-Layer Metal-Organic Frameworks Elucidated Using Microfluidic Systems2020

    • Author(s)
      Yoko Tanaka, Yu Kitamura, Ryuji Kawano,* Kan Shoji, Moe Hiratani, Tetsuo Honma, Hikaru Takaya, Hirofumi Yoshikawa, Takaaki Tsuruoka, Daisuke Tanaka*
    • Journal Title

      Chem. Eur. J.

      Volume: 26 Issue: 41 Pages: 8889-8896

    • DOI

      10.1002/chem.202001438

    • Related Report
      2020 Research-status Report
    • Peer Reviewed
  • [Journal Article] Porous Metal?Organic Frameworks Containing Reversible Disulfide Linkages as Cathode Materials for Lithium‐Ion Batteries2020

    • Author(s)
      Shimizu Takeshi、Wang Heng、Matsumura Daiju、Mitsuhara Kei、Ohta Toshiaki、Yoshikawa Hirofumi
    • Journal Title

      ChemSusChem

      Volume: - Issue: 9 Pages: 2256-2263

    • DOI

      10.1002/cssc.201903471

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Concise, Single-step Synthesis of Sulfur-enriched Graphene: Immobilization of Molecular Clusters and Battery Applications2020

    • Author(s)
      Haruka Omachi, Tsukasa Inoue, Shuya Hatao, Hisanori Shinohara, Alejandro Criado, Hirofumi Yoshikawa, Zois Syrgiannis, Maurizio Prato
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: - Issue: 20 Pages: 7836-7841

    • DOI

      10.1002/anie.201913578

    • Related Report
      2020 Research-status Report 2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Zeolitic vanadomolybdates as high performance cathode-active materials for sodium ion battery2020

    • Author(s)
      Zhenxin Zhang*, Heng Wang, Hirofumi Yoshikawa*, Daiju Matsumura, Syuya Hatao, Satoshi Ishikawa, Wataru Ueda*
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 12 Issue: 5 Pages: 6056-6063

    • DOI

      10.1021/acsami.9b19808

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A new design strategy for redox-active molecular assemblies with crystalline porous structures for lithium-ion batteries2020

    • Author(s)
      Nakashima Kensuke、Shimizu Takeshi、Kamakura Yoshinobu、Hinokimoto Akira、Kitagawa Yasutaka、Yoshikawa Hirofumi、Tanaka Daisuke
    • Journal Title

      Chemical Science

      Volume: 11 Issue: 1 Pages: 37-43

    • DOI

      10.1039/c9sc04175c

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Semiconductive Nature of Lead-Based Metal?Organic Frameworks with Three-Dimensionally Extended Sulfur Secondary Building Units2019

    • Author(s)
      Kamakura Yoshinobu、Chinapang Pondchanok、Masaoka Shigeyuki、Saeki Akinori、Ogasawara Kazuyoshi、Nishitani Shigeto R.、Yoshikawa Hirofumi、Katayama Tetsuro、Tamai Naoto、Sugimoto Kunihisa、Tanaka Daisuke
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 1 Pages: 27-32

    • DOI

      10.1021/jacs.9b10436

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] Battery Performances of Polyoxometalates/Nanocarbon Nanohybrid Materials2023

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC) Bali 2023
    • Related Report
      2023 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Application of Porous Coordination Polymer Containing Aromatic Azo Linkers as Cathode Active Materials in Sodium-Ion Batteries2022

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      8th Asian Conference on Coordination Chemistry (ACCC8)
    • Related Report
      2022 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Li-ion battery cathode performances of metal-organic frameworks containing reversible disulfide linkages2021

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      The 2021 International Chemical Congress of Pacific Basin Societies
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Development of Functional Materials Based on MOF Topology2021

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      The 21st International Conference on Discrete Geometric Analysis for Materials Design
    • Related Report
      2021 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 分子ナノ材料の特異な蓄電機能2020

    • Author(s)
      吉川浩史
    • Organizer
      ナノ学会主催 ナノ構造・物性-ナノ機能・応用部会 合同シンポジウム
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] 分子および分子集積体の蓄電機能2020

    • Author(s)
      吉川浩史
    • Organizer
      錯体化学会若手の会 第7回ウェブ勉強会
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] Potentiality of Polyoxometalate Materials as Battery Electrodes2020

    • Author(s)
      吉川浩史
    • Organizer
      錯体化学会第70回討論会
    • Related Report
      2020 Research-status Report
    • Invited
  • [Presentation] 分子および分子集積体の蓄電機能開拓2020

    • Author(s)
      吉川浩史
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] Rechargeable Batteries Using Redox-Active MOFs as Cathode Active Materials2019

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      7th Asian Conference on Coordination Chemistry (ACCC7)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Cathode performances of porous organic crystals formed by charge-transfer interactions2019

    • Author(s)
      Hirofumi Yoshikawa
    • Organizer
      The 3rd Organic Battery Days
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Remarks] 吉川研究室

    • URL

      https://www.kg-nanotech.jp/yoshikawa/

    • Related Report
      2021 Research-status Report
  • [Remarks] 吉川研究室

    • URL

      http://www.kg-nanotech.jp/yoshikawa/

    • Related Report
      2020 Research-status Report 2019 Research-status Report
  • [Patent(Industrial Property Rights)] 正極合材及び全固体電池2023

    • Inventor(s)
      谷藤尚貴、吉川浩史、加藤敦隆、高橋雅也、山本真理
    • Industrial Property Rights Holder
      学校法人 関西学院
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2023-223748
    • Filing Date
      2023
    • Related Report
      2023 Research-status Report

URL: 

Published: 2019-07-04   Modified: 2024-12-25  

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