New two-dimensional quantum magnets by creating superoxyhalides

• Project/Area Number: 19K22056
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 26:Materials engineering and related fields
• Research Institution: Kyoto University
• Principal Investigator: Kitada Atsushi 京都大学, 工学研究科, 助教 (30636254)
• Project Period (FY): 2019-06-28 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000); Fiscal Year 2020: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2019: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
• Keywords: 電解液材料 / 超酸化物 / ポリエーテル / イオン液体 / 濃厚電解質溶液 / 超酸化物イオン / スーパーオキシハライド / 複合アニオン / 磁性体

Outline of Research at the Start

超酸化物イオン（スーパーオキサイドイオン、[O2]-：酸素分子の１電子還元体）は、2
価の銅イオンと同じくスピン1/2の磁気モーメントを担う。一般的な磁性イオンが金属カチオンであるのに対して、[O2]-イオンは非金属のアニオンである。本研究では、[O2]-アニオンとハロゲン化物アニオンの複合アニオン化合物、すなわち「スーパーオキシハライド」という未開拓の物質群の創製に挑む。超酸化物イオンが二次元に配置された新物質を合成できれば、同じスピン1/2の磁気モーメントを担う銅酸化物が、なぜ高温で超伝導状態になるのか、どうすればより高温で超伝導にできるかを考える上で役に立つ。

Outline of Final Research Achievements

New material synthesis by low-temperature mixing under anaerobic condition has been studied. Equimolar potassium superoxide (KO2), metal halides, and polyether solvents were mixed. However, solvents and KO2 seems decomposed even at room temperature. Solventless reactions seem to work, which we will continue studying after ending this funding.
From our findings mentioned above, polyether-based concentrated electrolyte solutions were examined without using KO2. Our achievements are as follows: (I)We realized flat aluminum electrodeposition with good corrosion resistance and hardness. (II)We synthesized new materials named protic solvate ionic liquids and found the expression conditions of fast proton conduction. (III)We noticed expression of lithium ion hopping, as the first example for short-chain polyether system.

Academic Significance and Societal Importance of the Research Achievements

超酸化物という耳慣れない物質についての理解を深めた。特にポリエーテル溶媒との反応性についての知見が得られた。ポリエーテル溶媒を用いるイオン性溶液についての理解も深まった。結果として本研究は当初予期していなかった展開を見せた。具体的な成果として、室温アルミニウムめっき液、高速プロトン伝導体、高速リチウムイオン伝導体の３つの新材料の発見に至った。これらは次世代めっき材料や次世代エネルギー材料として期待される。

Research Products

• [Int'l Joint Research] 南京航空航天大学(中国)
• [Journal Article] Proton Conduction in Hydronium Solvate Ionic Liquids Affected by Ligand Shape (2021)
  • Author(s): Kio KAWATA, Atsushi KITADA, Naoki TSUCHIDA, Masayuki SAIMURA, Takashi NAGATA, Masato KATAHIRA, Kazuhiro FUKAMI, Kuniaki MURASE
  • Journal Title: Physical Chemistry Chemical Physics Volume: 23 Pages: 449-456
  • DOI: 10.1039/d0cp05025c
  • NAID: 120006950365
  • Peer Reviewed / Open Access
• [Journal Article] Ligand Exchange Conduction of Lithium Ion in a Pentaglyme-Lithium Bis(trifluoromethylsulfonyl)amide Super-Concentrated Electrolyte (2021)
  • Author(s): Atsushi KITADA, Kio KAWATA, Masahiro SHIMIZU, Masayuki SAIMURA, Takashi NAGATA, Masato KATAHIRA, Kazuhiro FUKAMI, Kuniaki MURASE
  • Journal Title: Journal of The Electrochemical Society Volume: 168 Pages: 016506-016506
  • DOI: 10.1149/1945-7111/abda03
  • Peer Reviewed / Open Access
• [Journal Article] An Ammonium Solvate Ionic Liquid (2021)
  • Author(s): Kio KAWATA, Atsushi KITADA, Kazuhiro FUKAMI, Masayuki SAIMURA, Takashi NAGATA, Masato KATAHIRA, Kuniaki MURASE
  • Journal Title: Journal of The Electrochemical Society Volume: 168 Pages: 026515-026515
  • DOI: 10.1149/1945-7111/abe512
  • Peer Reviewed / Open Access
• [Journal Article] A Concentrated AlCl3?Diglyme Electrolyte for Hard and Corrosion-Resistant Aluminum Electrodeposits (2020)
  • Author(s): Zhang Zelei、Kitada Atsushi、Gao Si、Fukami Kazuhiro、Tsuji Nobuhiro、Yao Zhengjun、Murase Kuniaki
  • Journal Title: ACS Applied Materials & Interfaces Volume: 12 Pages: 43289-43298
  • DOI: 10.1021/acsami.0c12602
  • NAID: 120007002691
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Ammonium・18-crown-6 bis(trifluoromethylsulfonyl)amide (2020)
  • Author(s): Kawata Kio、Kitada Atsushi、Fukami Kazuhiro、Murase Kuniaki
  • Journal Title: ECS Transactions Volume: 98 Pages: 471-475
  • DOI: 10.1149/09810.0471ecst
  • NAID: 120007006208
• [Presentation] グライム系銀溶媒和イオン液体からの銀電析 (2020)
  • Author(s): 森 崇裕、北田 敦、土田直輝、深見一弘、邑瀬邦明
  • Organizer: イオン液体ワークショップ2020
• [Presentation] Ammonium・18-crown-6 bis(trifluoromethylsulfonyl)amide (2020)
  • Author(s): 川田稀士、北田 敦、深見一弘、才村正幸、永田 崇、片平正人、邑瀬邦明
  • Organizer: イオン液体ワークショップ2020
• [Presentation] Electrodeposition of Void-free Nanostructured Aluminum from AlCl3-diglyme Electrolyte (2020)
  • Author(s): Zelei Zhang, Atsushi Kitada, Kazuhiro Fukami, Kuniaki Murase
  • Organizer: PRiME2020
  • Int'l Joint Research
• [Presentation] Ag Electrodeposition from Silver Solvate Ionic Liquid (2020)
  • Author(s): Takahiro Mori, Atsushi Kitada, Naoki Tsuchida, Kazuhiro Fukami, Kuniaki Murase
  • Organizer: PRiME2020
  • Int'l Joint Research
• [Presentation] Ammonium・18-crown-6 bis(trifluoromethylsulfonyl)amide (2020)
  • Author(s): Kio Kawata, Atsushi Kitada, Kazuhiro Fukami, Kuniaki Murase
  • Organizer: PRiME2020
  • Int'l Joint Research
• [Remarks] 京都大学／材質制御学研究室
  • URL: http://www.echem.mtl.kyoto-u.ac.jp/index.html