Elucidation of the structure of carbon electrodes for high-capacity/high-rate sodium ion battery

• Project/Area Number: 17K06017
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic industrial materials
• Research Institution: Okayama University
• Principal Investigator: Gotoh Kazuma 岡山大学, 自然科学研究科, 准教授 (20385975)
• Project Period (FY): 2017-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2020: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2019: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2018: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: ナトリウムイオン電池 / 炭素 / ハードカーボン / 黒鉛層間化合物 / 固体NMR / 炭素材料 / 固体核磁気共鳴 / 負極 / グライム / クラウンエーテル / 核磁気共鳴 / 無機工業化学

Outline of Final Research Achievements

Analyses of the state of sodium ions in closed-pore of carbon electrode for sodium ion batteries (NIBs) using solid state nuclear magnetic resonance (NMR) were performed. Dynamic behavior of organic molecules and cations in graphite intercalation compounds for an electrode of high-rate NIBs was also investigated. The fully sodiated sample prepared at higher carbonization temperature shows a higher 23Na NMR shift associated with Na clusters. The active motion of sodium－diglyme complexes is favorable for Na diffusion between graphene layers in the graphite intercalation compound. The deposition mechanism of Na metal on carbon electrode was also revealed.

Academic Significance and Societal Importance of the Research Achievements

ナトリウムイオン電池炭素負極の高容量化には擬金属Naとして吸蔵されるナトリウムを増やすことが有効と考えられる。本研究では擬金属Naの生成と細孔サイズの関係を明らかにした。過充電時においても、ナトリウムはある程度までは炭素内部細孔に擬金属として貯蔵され、デンドライト析出を抑制するバッファーとして作用することを解明した。これらの結果は、炭素負極の高容量化や安全性評価に不可欠な情報であり、ナトリウムイオン電池実用化において学術的・社会的意義のある成果と考えられる。

Research Products

• [Int'l Joint Research] Oregon State University(米国)
• [Int'l Joint Research] Oregon State Ujniversity(米国)
• [Int'l Joint Research] Oregon State University(米国)
• [Int'l Joint Research] Dongguk University(韓国)
• [Int'l Joint Research] Institute of High Performance Computing(シンガポール)
• [Int'l Joint Research] Oregon State University(米国)
• [Int'l Joint Research] Dongguk University-Seoul(韓国)
• [Journal Article] MgO‐Template Synthesis of Extremely High Capacity Hard Carbon for Na‐Ion Battery (2021)
  • Author(s): Azusa Kamiyama, Kei Kubota, Daisuke Igarashi, Yong Youn, Yoshitaka Tateyama, Hideka Ando, Kazuma Gotoh, Shinichi Komaba
  • Journal Title: Angew. Chem. Int. Ed. Volume: 60 Issue: 10 Pages: 5114-5120
  • DOI: 10.1002/anie.202013951
  • Peer Reviewed / Open Access
• [Journal Article] Vanadium diphosphide as a negative electrode material for sodium secondary batteries (2021)
  • Author(s): Shubham Kaushik, Kazuhiko Matsumoto, Yuki Orikasa, Misaki Katayama, Yasuhiro Inada, Yuta Sato, Kazuma Gotoh, Hideka Ando, Rika Hagiwara
  • Journal Title: J. Power Sources Volume: 483 Pages: 229182-229182
  • DOI: 10.1016/j.jpowsour.2020.229182
  • Peer Reviewed
• [Journal Article] Na3V2O2(PO4)2F3-2 as a stable positive electrode for potassium-ion batteries (2021)
  • Author(s): Kumar P. Ramesh、Kubota Kei、Miura Yusuke、Ohara Mirai、Gotoh Kazuma、Komaba Shinichi
  • Journal Title: Journal of Power Sources Volume: 493 Pages: 229676-229676
  • DOI: 10.1016/j.jpowsour.2021.229676
  • Peer Reviewed
• [Journal Article] 23Na solid-state NMR analyses for Na-ion batteries and materials (2021)
  • Author(s): Kazuma Gotoh
  • Journal Title: Batter. Supercaps Volume: in press Issue: 8 Pages: 1267-1278
  • DOI: 10.1002/batt.202000295
  • Peer Reviewed
• [Journal Article] Mechanisms for overcharging of carbon electrodes in lithium-ion/sodium-ion batteries analysed by operando solid-state NMR (2020)
  • Author(s): Kazuma Gotoh, Tomu Yamakami, Ishin Nishimura, Hina Kometani, Hideka Ando, Kenjiro Hashi, Tadashi Shimizu, and Hiroyuki Ishida
  • Journal Title: J. Mater. Chem. A Volume: 8 Issue: 29 Pages: 14472-14481
  • DOI: 10.1039/d0ta04005c
  • NAID: 120007039932
  • Peer Reviewed
• [Journal Article] Structural Analysis of Sucrose-Derived Hard Carbon and Correlation with the Electrochemical Properties for Lithium, Sodium, and Potassium Insertion (2020)
  • Author(s): Kei Kubota, Saori Shimadzu, Naoaki Yabuuchi, Satoshi Tominaka, Soshi Shiraishi, Maria Abreu-Sepulveda, Ayyakkannu Manivannan, Kazuma Gotoh, Mika Fukunishi, Mouad Dahbi and Shinichi Komaba
  • Journal Title: Chemistry of Materials Volume: 32 Issue: 7 Pages: 2961-2977
  • DOI: 10.1021/acs.chemmater.9b05235
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] States of thermochemically or electrochemically synthesized NaxPy compounds analyzed by solid state 23Na and 31P nuclear magnetic resonance with theoretical calculation (2019)
  • Author(s): Ryohei Morita, Kazuma Gotoh, Mouad Dahbi, Kei Kubota, Shinichi, Komaba, Kazuyasu Tokiwa, Saeid Arabnejad, Koichi Yamashita, Kenzo Deguchi, Shinobu Ohki, Tadashi Shimizu, Robert Laskowski, Hiroyuki Ishida
  • Journal Title: J. Power Sources Volume: 413 Pages: 418-424
  • DOI: 10.1016/j.jpowsour.2018.12.070
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Correlation of carbonization condition with metallic property of sodium clusters formed in hard carbon studied using 23Na nuclear magnetic resonance (2019)
  • Author(s): Ryohei Morita, Kazuma Gotoh, Kei Kubota, Shinichi Komaba, Kenjiro Hashi, Tadashi Shimizu, Hiroyuki Ishida
  • Journal Title: Carbon Volume: 145 Pages: 712-715
  • DOI: 10.1016/j.carbon.2019.01.080
  • Peer Reviewed / Open Access
• [Journal Article] Negative dielectric constant of water confined in nanosheets (2019)
  • Author(s): Akira Sugahara, Yasunobu Ando, Satoshi Kajiyama, Koji Yazawa, Kazuma Gotoh, Minoru Otani, Masashi Okubo, Atsuo Yamada
  • Journal Title: Nature Commun. Volume: 10 Pages: 850-850
  • Peer Reviewed / Open Access
• [Journal Article] Structure and dynamic behavior of Na-crown ether complex in the graphite layers studied by DFT and 1H NMR (2018)
  • Author(s): Kazuma Gotoh, Shinya Kunimitsu, Hanyang Zhang, Michael M. Lerner, Keisuke Miyakubo, Takahiro Ueda, Hyung-Jin Kim, Young-Kyu Han, Hiroyuki Ishida
  • Journal Title: J. Phys. Chem. C Volume: 122 Issue: 20 Pages: 10963-10970
  • DOI: 10.1021/acs.jpcc.8b02965
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Surface modification effects on the tensile properties of functionalised graphene oxide epoxy films (2018)
  • Author(s): Matsuura Koji、Umahara Yuki、Gotoh Kazuma、Hoshijima Yuko、Ishida Hiroyuki
  • Journal Title: RSC Advances Volume: 8 Issue: 18 Pages: 9677-9684
  • DOI: 10.1039/c8ra00252e
  • Peer Reviewed / Open Access
• [Journal Article] Production of a porous carbon material and a carbon-iron oxide hybrid using tubular iron oxide of bacterial origin (2017)
  • Author(s): Nishimura Ishin、Gotoh Kazuma、Hiura Towa、Kawamura Hitomi、Hashimoto Hideki、Matsumoto Syuji、Takada Jun、Kasukabe Takatoshi、Nishihara Hirotomo、Goto Hidenori、Ohkubo Takahiro、Ishida Hiroyuki
  • Journal Title: TANSO Volume: 2017 Issue: 280 Pages: 188-197
  • DOI: 10.7209/tanso.2017.188
  • NAID: 130006284850
  • ISSN: 0371-5345, 1884-5495
  • Peer Reviewed / Open Access
• [Presentation] Analysis of Overcharged Carbon Electrodes in Lithium ion / Sodium ion Batteries Using Solid State NMR (2021)
  • Author(s): Kazuma Gotoh
  • Organizer: ICEAST 2021
  • Int'l Joint Research / Invited
• [Presentation] operando NMR を用いた二次電池の金属析出メカニズムの解析 (2020)
  • Author(s): 後藤和馬
  • Organizer: 第68回固体NMR・材料フォーラム
  • Invited
• [Presentation] オペランドNMRによるNaイオン／Liイオン電池炭素電極の過充電挙動の解析 (2020)
  • Author(s): 後藤和馬, 山上登夢, 端健二郎, 石田祐之
  • Organizer: 第47回炭素材料学会年会
• [Presentation] Analysis of overcharged carbon electrodes in lithium ion / sodium ion batteries using solid state NMR (2019)
  • Author(s): Kazuma Gotoh
  • Organizer: 7th Japanese‐German Workshop on Carbon Materials
  • Int'l Joint Research / Invited
• [Presentation] 固体NMRを用いたナトリウムイオン電池負極材料の状態分析 (2019)
  • Author(s): 後藤和馬
  • Organizer: ESICB電子論検討会
• [Presentation] Operando NMR Analysis of Li Plating on Graphite and Hard Carbon Electrodes (2019)
  • Author(s): Kazuma Gotoh, Ishin Nishimura, Tomu Yamakami, Hina Kometani, Hiroyuki Ishida
  • Organizer: Carbon2019
  • Int'l Joint Research
• [Presentation] in situ NMR法を用いたBC2N負極における充放電および過充電挙動の解析 (2019)
  • Author(s): 山上登夢, 後藤和馬, 端健二郎, 清水禎, 高田光基, 横山隆司, 大山貴志, 川口雅之, 石田祐之
  • Organizer: 第57回炭素材料夏季セミナー
• [Presentation] 23Na MAS NMRによるスクロース由来難黒鉛化性炭素負極の吸蔵Naの状態解析 (2019)
  • Author(s): 鹿島小弥太，後藤和馬，豊田昌宏，石田祐之
  • Organizer: 第57回炭素材料夏季セミナー
• [Presentation] in situ NMR法によるリチウムイオン電池炭素負極の過充電挙動の解析 (2019)
  • Author(s): 山上登夢, 米谷雛, 後藤和馬, 端健二郎, 清水禎, 大山貴志, 石田祐之
  • Organizer: 第58回NMR討論会
• [Presentation] 1Hおよび2H NMRによるMg共挿入エチレンジアミンの黒鉛層間での運動状態解析 (2019)
  • Author(s): 橋本一樹, 後藤和馬, 水野元博, 堂ノ下将希, 北川宏, 石田祐之
  • Organizer: 第58回NMR討論会
• [Presentation] 固体NMRによるナトリウムイオン電池の解析 (2018)
  • Author(s): 後藤和馬
  • Organizer: 2018年度第4回CPC研究会
  • Invited
• [Presentation] in situ NMR 測定を用いた黒鉛負極上におけるデンドライト状リチウムの析出過程の観測 (2018)
  • Author(s): 西村維心，後藤和馬，品川秀行，端健二郎，清水禎，高田光基，横山隆司，石田祐之
  • Organizer: 第63回固体NMR・材料フォーラム
• [Presentation] in situ NMR 測定を用いた黒鉛負極上におけるデンドライト状リチウムの析出過程の観測 (2018)
  • Author(s): 西村維心，後藤和馬，品川秀行，端健二郎，清水禎，高田光基，横山隆司，石田祐之
  • Organizer: 第56回炭素材料夏季セミナー
• [Presentation] in situ NMR 測定を用いた難黒鉛化性炭素負極上におけるデンドライト状リチウムの析出過程の観測 (2018)
  • Author(s): 西村維心，後藤和馬，品川秀行，端健二郎，清水禎，高田光基，横山隆司，石田祐之
  • Organizer: 第64回固体NMR・材料フォーラム
• [Presentation] ジグライム/エチレンジアミンを含むピラー化黒鉛層間化合物の内部分子の運動解析 (2018)
  • Author(s): 国光真弥，後藤和馬，水野元博，石田祐之
  • Organizer: 第64回固体NMR・材料フォーラム
• [Presentation] in situ NMR 測定を用いた炭素負極におけるデンドライト状リチウム挿入過程と過充電状態解析 (2018)
  • Author(s): 西村維心，後藤和馬，品川秀行，端健二郎，清水禎，川口雅之，高田光基，横山隆司，石田祐之
  • Organizer: 第45回炭素材料学会年会
• [Presentation] ジグライム/エチレンジアミンを含むピラー化黒鉛層間化合物の内部分子の運動解析 (2018)
  • Author(s): 国光真弥，後藤和馬，水野元博，石田祐之
  • Organizer: 第45回炭素材料学会年会
• [Presentation] 23Naおよび31P NMRを用いたナトリウムイオン二次電池リン負極の状態分析 (2018)
  • Author(s): 森田凌平
  • Organizer: 分子研研究会
  • Invited
• [Presentation] インターカレーション化合物のNMR解析 (2017)
  • Author(s): 後藤和馬
  • Organizer: 第27回吸着シンポジウム
  • Invited
• [Presentation] The use of solid state NMR for analyses of carbon and battery materials (2017)
  • Author(s): Kazuma Gotoh
  • Organizer: Fall Meeting of Korean Carbon Society
  • Int'l Joint Research / Invited
• [Presentation] The use of solid state NMR for analyses of negative electrode materials in NIB (2017)
  • Author(s): Kazuma Gotoh
  • Organizer: 4th International Conference on Sodium Batteries
  • Int'l Joint Research / Invited
• [Presentation] 23Na solid state NMR analysis of sodium inserted in nanopore of hard carbon anode for sodium ion battery (2017)
  • Author(s): Ryohei Morita, Kazuma Gotoh, Mika Fukunishi, Mouad Dahbi, Kei Kubota, Shinichi Komaba, Kenzo Deguchi, Shinobu Ohki, Tadashi Shimizu, Katsuyuki Kawamura, and Hiroyuki Ishidaa
  • Organizer: ISMAR2017
  • Int'l Joint Research
• [Presentation] 2H and 1H NMR study for dynamics of glyme and crown ethers co-intercalated with alkali metals in graphite layers (2017)
  • Author(s): Kazuma Gotoh, Shinya Kunimitsu, Motohiro Mizuno, Tatsuya Miyatou, Michael M. Lerner, Hanyang Zhang, Keisuke Miyakubo, Takahiro Ueda, and Hiroyuki Ishida
  • Organizer: ISMAR2017
  • Int'l Joint Research
• [Presentation] 黒鉛層間にナトリウムと共挿入されたクラウンエーテルの運動解析 (2017)
  • Author(s): 国光真弥，後藤和馬，石田祐之，Michael M. Lerner
  • Organizer: 第55回炭素材料夏季セミナー
• [Presentation] 23Naおよび31P NMRを用いたナトリウムイオン二次電池リン負極の状態分析 (2017)
  • Author(s): 森田凌平，後藤和馬，Mouad Dahbi，久保田圭，駒場慎一，Saeid Arabnejad，山下晃一，石田祐之
  • Organizer: 第62回固体NMR・材料フォーラム
• [Presentation] 還元型酸化グラフェンベース材料のナトリウムイオン電池の負極特性 (2017)
  • Author(s): 楊智光，後藤和馬，石田祐之，陳 望，仁科勇太
  • Organizer: 日本化学会中国四国支部大会
• [Remarks] 蓄電池過充電時の金属析出メカニズムを解明 ～発火事故を防ぐための安全性評価に貢献～
  • URL: https://www.okayama-u.ac.jp/tp/release/release_id749.html
• [Remarks] 超高容量を示すナトリウムイオン電池用炭素負極材料
  • URL: https://www.okayama-u.ac.jp/tp/release/release_id791.html