Ion Conductivity in All-Solid-State Thin-Film Lithium Batteries

• Project/Area Number: 16H03864
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Thin film/Surface and interfacial physical properties
• Research Institution: Nippon Institute of Technology (2017-2018); Tohoku University (2016)
• Principal Investigator: Shiraki Susumu 日本工業大学, 基幹工学部, 教授 (80342799)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥16,770,000 (Direct Cost: ¥12,900,000、Indirect Cost: ¥3,870,000); Fiscal Year 2018: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2017: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2016: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000)
• Keywords: 界面 / 表面 / 薄膜 / 全固体電池 / リチウム２次電池 / エピタキシャル薄膜 / パルスレーザー堆積法 / 表面界面物性 / リチウム電池 / 表面・界面物性

Outline of Final Research Achievements

All-solid-state Li batteries show great promise as a next-generation energy-storage devices because of their high energy density and good safety. However, practical applications of such batteries are hampered by the high resistance at their solid electrolyte/electrode interfaces. In this study, we fabricaｔeｔd all-solid-state thin-film batteries, and achieved an extremely low electrolyte/electrode interface resistance. Using synchrotron surface X-ray diffraction, we found the low-resistance interface exhibited a flat and well-ordered atomic arrangement at the electrode surface, whereas the high resistance interface showed a disordered interface.

Academic Significance and Societal Importance of the Research Achievements

今回の成果により、全固体電池を実用化するための道筋が見えてきました。高出力型全固体電池における界面抵抗の低減や高速充放電の実証は、全固体リチウム電池の実用化の鍵であり、実用化を目指す上で、大きな一歩です。今回の研究で得られた知見が全固体電池の作製プロセスの改良に活用され、高性能全固体電池の開発につながることが期待されます。

Research Products

• [Journal Article] Atomically Well-Ordered Structure at Solid Electrolyte and Electrode Interface Reduces the Interfacial Resistance (2018)
  • Author(s): Shiraki Susumu、Shirasawa Tetsuroh、Suzuki Tohru、Kawasoko Hideyuki、Shimizu Ryota、Hitosugi Taro
  • Journal Title: ACS Applied Materials & Interfaces Volume: 10 Issue: 48 Pages: 41732-41737
  • DOI: 10.1021/acsami.8b08926
  • Peer Reviewed
• [Journal Article] Impact of a surface TiO2 atomic sheet on the electronic transport properties of LaAlO3/SrTiO3 heterointerfaces (2018)
  • Author(s): T. Ohsawa, M. Saito, R. Shimizu, K. Iwaya, S. Shiraki, Y. Ikuhara, and T. Hitosugi
  • Journal Title: Applied Physics Letters Volume: 113 Issue: 14 Pages: 141602-141602
  • DOI: 10.1063/1.5046876
  • Peer Reviewed
• [Journal Article] Extremely low resistance of Li3PO4 electrolyte/Li(Ni0.5Mn1.5)O4 electrode interfaces (2018)
  • Author(s): Hideyuki Kawasoko, Susumu Shiraki, Toru Suzuki, Ryota Shimizu, and Taro Hitosugi
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 10 (32) Issue: 32 Pages: 27498-27502
  • DOI: 10.1021/acsami.8b08506
  • Peer Reviewed
• [Journal Article] On the Use of 31Mg for b-Detected NMR Studies of Solids (2018)
  • Author(s): R. M. L. McFadden, A. Chatzichristos, M. H. Dehn, D. Fujimoto, H. Funakubo, A. Gottberg, T. Hitosugi, V. L. Karner, R. F. Kiefl, M. Kurokawa, J. Lassen, C. D. Philip Levy, R. Li, G. D. Morris, M. R. Pearson, S. Shiraki, M. Stachura, J. Sugiyama, D. M. Szunyogh, W. A. MacFarlane
  • Journal Title: JPS Conference Proceedings Volume: 21
  • DOI: 10.7566/jpscp.21.011047
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Challenge for Detecting the Interface between Electrode and Electrolyte with β-NMR (2018)
  • Author(s): Sugiyama Jun、Umegaki Izumi、Shiraki Susumu、Hitosugi Taro、McFadden Ryan M. L.、Wang Dongsheng、Karner Victoria、Morris Gerald D.、MacFarlane W. Andrew、Kiefl Robert F.
  • Journal Title: JPS Conference Proceedings Volume: 21 Pages: 011021-011021
  • DOI: 10.7566/jpscp.21.011021
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] LE-μ+SR Study of Superconductivity in the Thin Film Battery Material LiTi2O4 (2018)
  • Author(s): Mansson M.、Forslund O. K.、Nozaki H.、Umegaki I.、Shiraki S.、Hitosugi T.、Prokscha T.、Salman Z.、Suter A.、Sassa Y.、Sugiyama J.
  • Journal Title: JPS Conference Proceedings Volume: 21 Pages: 011025-011025
  • DOI: 10.7566/jpscp.21.011025
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Li-Diffusion in Spinel Li[Ni1/2Mn3/2]O4 Powder and Film Studied with μ+SR (2018)
  • Author(s): Sugiyama Jun、Nozaki Hiroshi、Umegaki Izumi、Mukai Kazuhiko、Cottrell Stephen P.、Shiraki Susumu、Hitosugi Taro、Sassa Yasmine、Suter Andreas、Salman Zaher、Prokscha Thomas、Mansson Martin
  • Journal Title: JPS Conference Proceedings Volume: 21 Pages: 011015-011015
  • DOI: 10.7566/jpscp.21.011015
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Lithium diffusion in spinel Li4Ti5O12 and LiTi2O4 films detected with Li8β-NMR (2017)
  • Author(s): Sugiyama Jun、Umegaki Izumi、Uyama Takeshi、McFadden Ryan M. L.、Shiraki Susumu、Hitosugi Taro、Salman Zaher、Saadaoui Hassan、Morris Gerald D.、MacFarlane W. Andrew、Kiefl Robert F.
  • Journal Title: Physical Review B Volume: 96 Issue: 9 Pages: 094402-094402
  • DOI: 10.1103/physrevb.96.094402
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Fabrication of atomically abrupt interfaces of single-phase TiH2 and Al2O3 (2017)
  • Author(s): Ryota Shimizu, Yuki Sasahara, Hiroyuki Oguchi, Kuniko Yamamoto, Issei Sugiyama, Susumu Shiraki, Shin-ichi Orimo, and Taro Hitosugi
  • Journal Title: APL Materials Volume: ５ Issue: 8 Pages: 086102-086102
  • DOI: 10.1063/1.4996984
  • Peer Reviewed / Open Access
• [Journal Article] Scanning tunneling spectroscopy of superconductivity on surfaces of LiTi2O4(111) thin films (2017)
  • Author(s): Yoshinori Okada, Yasunobu Ando, Ryota Shimizu, Emi Minamitani, Susumu Shiraki, Satoshi Watanabe, and Taro Hitosugi
  • Journal Title: Nature Communications Volume: ８ Issue: 1 Pages: 15975-15975
  • DOI: 10.1038/ncomms15975
  • Peer Reviewed / Open Access
• [Journal Article] Quasiparticle interference on cubic perovskite oxide surfaces (2017)
  • Author(s): Y. Okada, S.-Y. Shiau, T.-R. Chang, G. Chang, M. Kobayashi, R. Shimizu, H.-T. Jeng, S. Shiraki, H. Kumigashira, A. Bansil, H. Lin, T. Hitosugi
  • Journal Title: Phys. Rev. Lett. Volume: VOL. 119 Issue: 8 Pages: 086801-086801
  • DOI: 10.1103/physrevlett.119.086801
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Nonvolatile Memory Device with Very Low Power Consumption Based on the Switching of a Standard Electrode Potential (2017)
  • Author(s): Issei Sugiyama, Ryota Shimizu, Tohru Suzuki, Kuniko Yamamoto, Hideyuki Kawasoko, Susumu Shiraki, and Taro Hitosugi
  • Journal Title: APL Materials Volume: 5 Issue: 4 Pages: 046105-046105
  • DOI: 10.1063/1.4980031
  • Peer Reviewed / Open Access
• [Journal Article] Self-assembly of very-low height/width aspect-ratio Li3Ni2NbO6 disks embedded in Li3NbO4 epitaxial films. (2017)
  • Author(s): H. Kawasoko, R. Shimizu, Y. Takagi, K. Yamamoto, I. Sugiyama, S. Shiraki, T. Hitosugi
  • Journal Title: Thin Solid Films Volume: 621 Pages: 202-206
  • DOI: 10.1016/j.tsf.2016.12.006
  • Peer Reviewed
• [Journal Article] Transparent conducting properties of Re-doped β-MoO3 films (2016)
  • Author(s): Kuniko Yamamoto, Ryota Shimizu, Susumu Shiraki, and Taro Hitosugi
  • Journal Title: APL Materials Volume: 4 Issue: 9 Pages: 096104-096104
  • DOI: 10.1063/1.4963154
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Li diffusion in (110)-oriented LiCoO2 thin films grown on Au and Pt (110) substrates (2016)
  • Author(s): S. Shiraki, H. Oki, T. Hitosugi
  • Journal Title: Surface and Interface Analysis Volume: 48 Issue: 11 Pages: 1240-1243
  • DOI: 10.1002/sia.6108
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Negligible Sr segregation on SrTiO3 (001) √13 x √13 reconstructed surfaces (2016)
  • Author(s): Takeo Ohsawa, Ryota Shimizu, Katsuya Iwaya, Susumu Shiraki and Taro Hitosugi
  • Journal Title: Appl. Phys. Lett. Volume: 108 Issue: 16 Pages: 161603-161603
  • DOI: 10.1063/1.4947441
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Preparation and in-situ characterization of well-defined solid electrolyte/electrode interfaces in thin-film lithium batteries (2016)
  • Author(s): Masakazu Haruta, Susumu Shiraki, Takeo Ohsawa, Tohru Suzuki, Akichika Kumatani, Yoshitaka Takagi, Ryota Shimizu, and Taro Hitosugi
  • Journal Title: Solid State Ionics Volume: 285 Pages: 118-121
  • DOI: 10.1016/j.ssi.2015.06.007
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 全固体電池実用化に向けた大学での取組み (2018)
  • Author(s): 白木将
  • Organizer: とちぎ環境産業振興協議会・環境負荷低減技術研究部会
  • Invited
• [Presentation] 薄膜型全固体電池の作製とそのin-situ電気化学特性評価 (2018)
  • Author(s): 白木将
  • Organizer: 2018年日本表面真空学会学術講演会
• [Presentation] Fabrication and In-Situ Characterization of All-Solid-State Thin-Film Batteries (2018)
  • Author(s): S. Shiraki
  • Organizer: 14th International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures (ACSIN-14)
  • Int'l Joint Research
• [Presentation] 全固体薄膜電池作製・in-situ評価装置の構築 (2018)
  • Author(s): 白木将
  • Organizer: 第79回応用物理学会秋季学術講演会
• [Presentation] Electrochemical Properties of Li4Ti5O12 and LiTi2O4 Epitaxial Thin Films (2018)
  • Author(s): S. Shiraki, Y. Takagi, R. Shimizu, T. Hitosugi
  • Organizer: 2018 International Conference on Solid State Devices and Materials (SSDM2018)
  • Int'l Joint Research
• [Presentation] 真空・薄膜技術を活用した全固体リチウム電池研究 (2018)
  • Author(s): 白木将
  • Organizer: 表面技術協会・表面技術とものづくり研究部会例会
  • Invited
• [Presentation] Fabrication and in-situ characterization of well-defined solid electrolyte/electrode interfaces in thin-film lithium batteries (2018)
  • Author(s): S. Shiraki
  • Organizer: The 3rd International Symposium on "Recent Trends in the Elucidation and Function Discovery of Next Generation Functional Materials of Surface / Interface Properties"
  • Int'l Joint Research
• [Presentation] 薄膜型全固体電池作製・in-situ評価装置の構築 (2018)
  • Author(s): 白木将
  • Organizer: 平成30年度日本表面真空学会 九州支部学術講演会
• [Presentation] 薄膜型全固体リチウム電池の作製と表面界面研究 (2017)
  • Author(s): 白木将
  • Organizer: 表面技術協会第135回講演大会
  • Place of Presentation: 東洋大学（埼玉）
  • Year and Date: 2017-03-09
  • Invited
• [Presentation] Ion conductivity at solid-electrolyte/electrode interface in all-solid-state Li batteries (2017)
  • Author(s): S. Shiraki
  • Organizer: The 2nd international symposium on “Recent Trends in Analysis Techniques for Functional Materials and Devices
  • Place of Presentation: Osaka, Japan
  • Year and Date: 2017-01-17
  • Int'l Joint Research / Invited
• [Presentation] 5V級正極LiNi0.5Mn1.5O4を用いた全固体薄膜電池の作製とその高速充放電特性 (2017)
  • Author(s): 白木将
  • Organizer: 第6回酸化物研究の新機軸に向けた学際討論会
  • Invited
• [Presentation] 5V級正極Li(Ni0.5Mn1.5)O4と固体電解質Li3PO4界面におけるイオン伝導特性 (2017)
  • Author(s): 白木将、河底秀幸、鈴木竜、清水亮太、一杉太郎
  • Organizer: 九州表面・真空研究会2017
• [Presentation] 5V級正極LiNi0.5Mn1.5O4と固体電解質Li3PO4が形成する超低抵抗界面 (2017)
  • Author(s): 白木将、河底秀幸、鈴木竜、清水亮太、一杉太郎
  • Organizer: 第58回電池討論会
• [Presentation] Very-Low Solid-Electrolyte/Electrode Interface Resistance in Li(Ni0.5Mn1.5)O4-Based Thin-Film Battery (2017)
  • Author(s): Susumu Shiraki, Hideyuki Kawasoko, Toru Suzuki, Ryota Shimizu, and Taro Hitosugi
  • Organizer: The 5th Ito International Research Conference
  • Int'l Joint Research
• [Presentation] Electrochemical Properties of Li4Ti5O12 and LiTi2O4 epitaxial thin films synthesized with pulsed laser deposition (2017)
  • Author(s): Susumu Shiraki, Yoshitaka Takagi, Ryota Shimizu, Taro Hitosugi
  • Organizer: 11th International Symposium on Atomic Level Characterizations for New Materials and Devices ’17 (ALC'17)
  • Int'l Joint Research
• [Presentation] 固体電解質/電極界面の界面抵抗発生起源の解明 (2016)
  • Author(s): 白木将、白澤徹郎、鈴木竜、河底秀幸、清水亮太、一杉太郎
  • Organizer: 第42回固体イオニクス討論会
  • Place of Presentation: 名古屋国際会議場（愛知）
  • Year and Date: 2016-12-05
• [Presentation] Very-low solid-electrolyte/electrode interface resistance in Li(Ni0.5Mn1.5)O4-based thin-film Lithium Battery (2016)
  • Author(s): S. Shiraki, H. Kawasoko, T. Suzuki, R. Shimizu, T. Hitosugi
  • Organizer: Prime2016
  • Place of Presentation: Hawaii, USA
  • Year and Date: 2016-10-02
  • Int'l Joint Research
• [Presentation] 固体電解質/電極界面の界面抵抗発生起源の解明 (2016)
  • Author(s): 白木将、白澤徹郎、鈴木竜、河底秀幸、清水亮太、一杉太郎
  • Organizer: 第77回応用物理学会秋季学術講演会
  • Place of Presentation: 朱鷺メッセ（新潟）
  • Year and Date: 2016-09-13
• [Presentation] PLDで成膜したLi3PO4固体電解質/LiCoO2電極界面のイオン伝導 (2016)
  • Author(s): 白木将、鈴木竜、河底秀幸，一杉太郎
  • Organizer: 学術振興会マイクロビームアナリシス第141委員会第164回研究会
  • Place of Presentation: 堀場製作所（東京）
  • Year and Date: 2016-05-24
• [Presentation] PLDで成膜したLi3PO4固体電解質/LiCoO2電極界面のイオン伝導 (2016)
  • Author(s): (5)白木将、鈴木竜、河底秀幸、清水亮太、白澤徹郎、一杉太郎
  • Organizer: 九州薄膜表面研究会
  • Place of Presentation: 九州大学（福岡）
• [Book] 全固体電池の基礎理論と開発最前線 (2018)
  • Author(s): 白木将、一杉太郎
  • Total Pages: 271
  • Publisher: シーエムシー・リサーチ
  • ISBN: 9784904482513
• [Book] 全固体電池のイオン伝導性向上技術と材料、製造プロセスの開発 (2017)
  • Author(s): 白木将、白澤徹郎、河底秀幸、一杉太郎
  • Total Pages: 475
  • Publisher: 技術情報協会
  • ISBN: 9784861046476
• [Remarks] 日本工業大学応用化学科固体電気化学研究室
  • URL: http://enjoy1.bb-east.ne.jp/~shiraki/
• [Remarks] 日本工業大学ブランディング事業「次世代動力源としての全固体電池技術の開発と応用」
  • URL: https://www.nit.ac.jp/education-research/branding.html
• [Remarks] 東工大、産業技術総合研究所、科学技術振興機構との共同研究により、全固体電池実現のネックを解明
  • URL: https://www.nit.ac.jp/topics/link/pdf_452.pdf
• [Remarks] 東工大、東北大との共同研究により、全固体電池で超高速充放電を実現
  • URL: https://www.nit.ac.jp/topics/link/pdf_407.pdf