幾何学構造に基づいた多孔性炭素材料の開発

• Project Area: Discrete Geometric Analysis for Materials Design
• Project/Area Number: 18H04491
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Kwansei Gakuin University
• Principal Investigator: 吉川 浩史 関西学院大学, 理工学部, 准教授 (60397453)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000); Fiscal Year 2019: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000); Fiscal Year 2018: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 金属有機構造体 / 多孔性炭素 / 電極 / 極小曲面 / カーボンナノチューブ / グラフェン / 多孔質炭素

Outline of Annual Research Achievements

本研究では、金属有機構造体(MOF)の有する離散幾何学的な三次元極小曲面構造の違いが、得られる多孔性炭素の構造および電極特性にどう影響を与えるかを調べるため、3種類の極小曲面構造(SchwarzのP曲面およびD曲面、SchoenのG曲面)を対象に、それらの曲面構造に対応するMOF（それぞれcubic構造、diamond構造、gyroid構造を取るMOF）を鋳型とする多孔性炭素を作成し、その負極特性を検討した。
これまでに、P曲面を有するMOFとしてZIF-8を、D曲面を有するMOFとして[1-ethyl-3-methylimidazolium][In(4,4’-(diazene-1,2-diyl)dibenzoate)2])2を、G曲面を有するMOFとしてSTU-1(Zn(1,2-bis((5H-imidazol-4-yl)methylene)hydrazine))3を用いた。これらは購入、もしくは文献に従い合成した。これらを鋳型に、多孔性炭素を作製し、その負極特性評価を行った。
Cubic MOFおよびgyroid MOFを鋳型に作成した炭素の放電容量のサイクル特性を検討したところ、gyroid炭素は初期容量963mAh/gを示し、2サイクル目以降600mAh/gで安定化した。一方で、cubic炭素の方は、1サイクル目に683mAh/gの容量を示し、2サイクル目は422mAh/gに減衰したが、それ以降の容量は徐々に上昇し、80サイクル目の容量は507mAh/gとなった。炭素負極材料の容量は、グラファイトの場合、6つの炭素当たり一つのリチウムイオンが挿入されることで計算されることから、表面積との相関関係が考えられる。今回、cubicとgyroid構造炭素の容量の違いが、焼成する前のMOFの極小曲面構造に基づいた表面積の差に由来する可能性を示す結果を得た。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] 鄭州軽工業学院(中国)
• [Int'l Joint Research] トリエステ大学(イタリア)
• [Int'l Joint Research] 鄭州軽工業学院(中国)
• [Journal Article] Porous Metal?Organic Frameworks Containing Reversible Disulfide Linkages as Cathode Materials for Lithium‐Ion Batteries (2020)
  • 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
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Concise, Single-step Synthesis of Sulfur-enriched Graphene: Immobilization of Molecular Clusters and Battery Applications (2020)
  • 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
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Zeolitic vanadomolybdates as high performance cathode-active materials for sodium ion battery (2020)
  • 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
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A new design strategy for redox-active molecular assemblies with crystalline porous structures for lithium-ion batteries (2020)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Semiconductive Nature of Lead-Based Metal?Organic Frameworks with Three-Dimensionally Extended Sulfur Secondary Building Units (2019)
  • 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
  • Peer Reviewed
• [Journal Article] Tetracoordinate Boron-Fused Double [5]Helicenes as Cathode Active Materials for Lithium Batteries (2019)
  • Author(s): Oda Susumu、Shimizu Takeshi、Katayama Takazumi、Yoshikawa Hirofumi、Hatakeyama Takuji
  • Journal Title: Organic Letters Volume: 21 Issue: 6 Pages: 1770-1773
  • DOI: 10.1021/acs.orglett.9b00337
  • Peer Reviewed
• [Journal Article] In situ X-ray Absorption Fine Structure studies of amorphous and crystalline polyoxovanadate cluster cathodes for lithium batteries (2018)
  • Author(s): H. Wang, J. Isobe, D. Matsumura, H. Yoshikawa
  • Journal Title: Journal of Solid State Electrochemistry Volume: 7 Issue: 7 Pages: 2067-2071
  • DOI: 10.1007/s10008-018-3920-4
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Reversible Batteries Based on Stable Redox Reactions of Disulfide Included in a Metal-Organic Framework as Ligands (2018)
  • Author(s): Takeshi Shimizu, Heng Wang, Naoki Tanifuji, Daiju Matsumura, Masashi Yoshimura, Koji Nakanishi, Toshiaki Ohta, Hirofumi Yoshikawa
  • Journal Title: Chem. Lett. Volume: 印刷中 Issue: 5 Pages: 678-681
  • DOI: 10.1246/cl.180121
  • NAID: 130006732216
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Atomic Force Microscopy Study of the Influence of the Synthesis Conditions on the Single-Crystal Surface of Interdigitated Metal-Organic Frameworks (2018)
  • Author(s): Y. Kamakura, N. Hosono, A. Terashima, S. Kitagawa, H. Yoshikawa, D. Tanaka
  • Journal Title: ChemPhysChem Volume: 19 Issue: 17 Pages: 2134-2138
  • DOI: 10.1002/cphc.201800439
  • Peer Reviewed
• [Presentation] Rechargeable Batteries Using Redox-Active MOFs as Cathode Active Materials (2019)
  • Author(s): Hirofumi Yoshikawa
  • Organizer: 7th Asian Conference on Coordination Chemistry (ACCC7)
  • Int'l Joint Research / Invited
• [Presentation] Cathode performances of porous organic crystals formed by charge-transfer interactions (2019)
  • Author(s): Hirofumi Yoshikawa
  • Organizer: The 3rd Organic Battery Days
  • Int'l Joint Research
• [Presentation] 分子および分子集積体の蓄電機能開拓 (2019)
  • Author(s): 吉川 浩史
  • Organizer: 日本化学会第100春季年会
  • Invited
• [Presentation] Rechargeable Batteries of MOFs Including Disulfide Ligand (2018)
  • Author(s): Hirofumi Yoshikawa
  • Organizer: The 2nd Organic Battery Days
  • Int'l Joint Research / Invited
• [Presentation] Electrochemical Performances of Polyoxometalate-based Nanomaterials (2018)
  • Author(s): Hirofumi Yoshikawa
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC2018)
  • Int'l Joint Research / Invited
• [Presentation] Battery Performances of Molecule-Integrated Systems (2018)
  • Author(s): Hirofumi Yoshikawa
  • Organizer: 2018 Nankai International Symposium on Advanced Materials
  • Int'l Joint Research / Invited
• [Presentation] 金属錯体マテリアルが示す蓄電機能 (2018)
  • Author(s): 吉川 浩史
  • Organizer: 錯体化学若手の会 第 58 回近畿支部勉強会
  • Invited
• [Presentation] 分子および分子集積体の蓄電機能開拓 (2018)
  • Author(s): 吉川 浩史
  • Organizer: 統合物質化学研究推進機構 第4回国内シンポジウム「物質創製化学の多様化と深化」
  • Invited
• [Remarks] 吉川研究室
  • URL: http://www.kg-nanotech.jp/yoshikawa/
• [Remarks] http://www.kg-nanotech.jp/yoshikawa/