Design of solid interface for all-solid-state sodium batteries with oxide solid electrolytes

• Project/Area Number: 18H01713
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 26020:Inorganic materials and properties-related
• Research Institution: Osaka Prefecture University
• Principal Investigator: Hayashi Akitoshi 大阪府立大学, 工学(系)研究科(研究院), 教授 (10364027)
• Project Period (FY): 2018-04-01 – 2021-03-31
• Project Status: Completed (Fiscal Year 2020)
• Budget Amount: ¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000); Fiscal Year 2020: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2019: ¥6,370,000 (Direct Cost: ¥4,900,000、Indirect Cost: ¥1,470,000); Fiscal Year 2018: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
• Keywords: 固体電解質 / 酸化物電解質 / 硫化物電解質 / 複合電解質 / 全固体ナトリウム電池 / 酸化物 / 界面制御

Outline of Final Research Achievements

Composite solid electrolytes consisting of NASICON and Na3SbS4 are prepared by ball-milling without high-temperature sintering. The electrolyte with 70 vol.% NASICON shows the conductivity of 2.7×10-4 S cm-1 and it is used for all-solid-state sodium batteries operating at room temperature. The Na2.88Sb0.88W0.12S4 electrolyte exhibits the highest conductivity of 3.2×10-2 S cm-1 and it is synthesized by not only conventional solid-state reaction, but also a liquid-phase process. Na3BO3-based oxide glasses are Na+ ion conductors with good formability.

Academic Significance and Societal Importance of the Research Achievements

化学安定性に優れるNASICON粒子間に成形性に優れるNa3SbS4を介在させることによって、高温焼結なしで導電率と成形性を兼ね備えた電解質複合体が得られており、酸化物を主成分とする固体電解質を用いた全固体ナトリウム電池の室温作動を実証した。安全性、経済性、高エネルギー密度を兼ね備えた全固体ナトリウム電池の実現に寄与する研究成果であり、社会的波及効果は大きいと考えられる。

Research Products

• [Journal Article] Preparation and characterization of sodium-ion conductive Na3BS3 glass and glass?ceramic electrolytes (2021)
  • Author(s): Tsuji Fumika、Nasu Akira、Hotehama Chie、Sakuda Atsushi、Tatsumisago Masahiro、Hayashi Akitoshi
  • Journal Title: Materials Advances Volume: 2 Issue: 5 Pages: 1676-1682
  • DOI: 10.1039/d0ma00777c
  • Peer Reviewed / Open Access
• [Journal Article] All-solid-state sodium-sulfur battery showing full capacity with activated carbon MSP20-sulfur-Na3SbS4 composite (2020)
  • Author(s): Ando Taka、Sakuda Atsushi、Tatsumisago Masahiro、Hayashi Akitoshi
  • Journal Title: Electrochemistry Communications Volume: 116 Pages: 106741-106741
  • DOI: 10.1016/j.elecom.2020.106741
  • Peer Reviewed / Open Access
• [Journal Article] Preparation of sodium-ion-conductive Na3-xSbS4-xClx solid electrolytes (2020)
  • Author(s): Tsuji Fumika、Yubuchi So、Sakuda Atsushi、Tatsumisago Masahiro、Hayashi Akitoshi
  • Journal Title: Journal of the Ceramic Society of Japan Volume: 128 Issue: 9 Pages: 641-647
  • DOI: 10.2109/jcersj2.20089
  • NAID: 130007895341
  • Peer Reviewed / Open Access
• [Journal Article] Preparation and Characterization of Cation-Substituted Na3SbS4 Solid Electrolytes (2020)
  • Author(s): Tsuji Fumika、Masuzawa Naoki、Sakuda Atsushi、Tatsumisago Masahiro、Hayashi Akitoshi
  • Journal Title: ACS Applied Energy Materials Volume: 3 Issue: 12 Pages: 11706-11712
  • DOI: 10.1021/acsaem.0c01823
  • Peer Reviewed
• [Journal Article] Aqueous solution synthesis of Na3SbS4-Na2WS4 superionic conductors (2020)
  • Author(s): Yubuchi So、Ito Akane、Masuzawa Naoki、Sakuda Atsushi、Hayashi Akitoshi、Tatsumisago Masahiro
  • Journal Title: Journal of Materials Chemistry A Volume: 8 Issue: 4 Pages: 1947-1954
  • DOI: 10.1039/c9ta02246e
  • Peer Reviewed
• [Journal Article] Mechanochemical Synthesis of Na-Sb Alloy Negative Electrodes and Their Application to All-solid-state Sodium Batteries (2019)
  • Author(s): ANDO Taka、YUBUCHI So、SAKUDA Atsushi、HAYASHI Akitoshi、TATSUMISAGO Masahiro
  • Journal Title: Electrochemistry Volume: 87 Issue: 5 Pages: 289-293
  • DOI: 10.5796/electrochemistry.19-00014
  • NAID: 130007702959
  • ISSN: 1344-3542, 2186-2451
  • Year and Date: 2019-09-05
  • Peer Reviewed / Open Access
• [Journal Article] Suspension synthesis of Na3-xPS4-xClx solid electrolytes (2019)
  • Author(s): Uematsu Miwa、Yubuchi So、Tsuji Fumika、Sakuda Atsushi、Hayashi Akitoshi、Tatsumisago Masahiro
  • Journal Title: Journal of Power Sources Volume: 428 Pages: 131-135
  • DOI: 10.1016/j.jpowsour.2019.04.069
  • Peer Reviewed
• [Journal Article] A sodium-ion sulfide solid electrolyte with unprecedented conductivity at room temperature (2019)
  • Author(s): Hayashi A.、Masuzawa N.、Yubuchi S.、Tsuji F.、Hotehama C.、Sakuda A.、Tatsumisago M.
  • Journal Title: Nature Communications Volume: 10 Issue: 1 Pages: 5266-5266
  • DOI: 10.1038/s41467-019-13178-2
  • Peer Reviewed / Open Access
• [Journal Article] 全固体電池への応用に向けた固体電解質の進展 (2019)
  • Author(s): 林 晃敏、作田 敦、辰巳砂昌弘
  • Journal Title: 日本ゴム協会誌 Volume: 92 Pages: 430-434
  • NAID: 130007844490
  • Peer Reviewed
• [Journal Article] 全固体における界面形成とキャラクタリゼーション (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Journal Title: セラミックス Volume: 54 Pages: 250-253
• [Presentation] Mechanochemical Synthesis of Na3BS3 Glass Electrolyte (2020)
  • Author(s): 辻 史香・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: Pacific Rim Meeting on Electrochemical and Solid-State Science (PRiME2020)
  • Int'l Joint Research
• [Presentation] 固体電解質が次世代電池を制する (2020)
  • Author(s): 林 晃敏
  • Organizer: 日本化学会秋季事業第10回CSJ化学フェスタ2020
  • Invited
• [Presentation] ナトリウムイオン伝導性Na3BS3ガラス電解質の作製と評価 (2020)
  • Author(s): 辻 史香・奈須 滉・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 第61回電池討論会
• [Presentation] ナトリウムイオン伝導性Na2.88Sb0.88S4-xOx固体電解質の作製と評価 (2020)
  • Author(s): 高柳拓真・奈須 滉・辻 史香・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 2020年度第3回関西電気化学研究会
• [Presentation] 固体電解質創製にむけた無機化学プロセスと全固体電池への応用 (2020)
  • Author(s): 林 晃敏
  • Organizer: 日本化学会第101春季年会
  • Invited
• [Presentation] 種々のナトリウム塩を添加したNa3BO3ガラス電解質のメカノケミカル合成 (2020)
  • Author(s): 林 晃敏・奥島千尋・日下部史也・奈須 滉・木村拓哉・作田 敦・辰巳砂昌弘
  • Organizer: 日本化学会第101春季年会
• [Presentation] 硫化物固体電解質を用いた全固体電池の開発 (2020)
  • Author(s): 林 晃敏
  • Organizer: 電気化学会第88回大会
  • Invited
• [Presentation] 無機アモルファス材料を用いる全固体電池 (2020)
  • Author(s): 林 晃敏
  • Organizer: 第175回電子セラミック・プロセス研究会
  • Invited
• [Presentation] ナトリウムイオン伝導性Na2S-B2S3系ガラス固体電解質の作製 (2020)
  • Author(s): 辻 史香・井上文音・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 電気化学会第87回大会
• [Presentation] メカノケミカル法を用いて作製したNa3-xP1-xWxS4固体電解質の特性評価 (2020)
  • Author(s): 辻 史香・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 電気化学会第87回大会
• [Presentation] 大気フロー下におけるNa3PS4固体電解質のin-situX線回折 (2020)
  • Author(s): 林 晃敏・中野 匠・木村拓哉・作田 敦・辰巳砂昌弘
  • Organizer: 日本化学会第100春季年会
• [Presentation] メカノケミカル法を用いたナトリウムイオン伝導性Na3SbS4-xOx固体電解質の作製と評価 (2020)
  • Author(s): 林 晃敏・高柳拓真・辻 史香・作田 敦・辰巳砂昌弘
  • Organizer: 日本化学会第100春季年会
• [Presentation] 全固体電池実現に資するアルカリイオン伝導体に関する研究 (2019)
  • Author(s): 林 晃敏
  • Organizer: 日本セラミックス協会関西支部2019年度支部大会
  • Invited
• [Presentation] 全固体電池の構築に向けた非晶質ベース電解質および電極材料の創出 (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: 第38回無機高分子シンポジウム
  • Invited
• [Presentation] Sulfide Na+ Ion Conductors for All-Solid-State Batteries (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: 10th International Conference on Materials for Advanced Technologies (ICMAT2019)
  • Int'l Joint Research / Invited
• [Presentation] Characterization of Na3Zr2Si2PO12-Na3SbS4 Composite Electrolytes with Sodium Ion Conductivity (2019)
  • Author(s): 矢野綾子・由淵 想・長尾賢治・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 10th International Conference on Materials for Advanced Technologies (ICMAT2019)
  • Int'l Joint Research
• [Presentation] Mechanochemical Preparation of Sodium Ion Conductive Na10+xSn1+xP2-xS12 Glass-Ceramic Electrolytes (2019)
  • Author(s): 辻 史香・Kah Loong HOH・Steve W. Martin・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 10th International Conference on Materials for Advanced Technologies (ICMAT2019)
  • Int'l Joint Research
• [Presentation] ナトリウムイオン伝導性NASICON-Na3SbS4複合電解質の作製と評価 (2019)
  • Author(s): 矢野綾子・由淵 想・長尾賢治・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 第14回日本セラミックス協会関西支部学術講演会
• [Presentation] Na欠損を導入したNa3SbS4固体電解質の作製と評価 (2019)
  • Author(s): 辻 史香・増澤直貴・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 2019年度電気化学会関西支部・東海支部合同シンポジウム
• [Presentation] Sulfide and Oxide Glassy Electrolytes for All-Solid-State Batteries (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: 2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors
  • Int'l Joint Research / Invited
• [Presentation] Sodium Ion Conducting Cl-Doped Na3SbS4 Solid Electrolytes (2019)
  • Author(s): 辻 史香・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: 2nd World Conference on Solid Electrolytes for Advanced Applications: Garnets and Competitors
  • Int'l Joint Research
• [Presentation] Na+ Conducting Sulfide Electrolytes for All-Solid-State Batteries (2019)
  • Author(s): 林 晃敏
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)
  • Int'l Joint Research / Invited
• [Presentation] Development of All-Solid-State Rechargeable Batteries with Ductile Amorphous Materials (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)
  • Int'l Joint Research / Invited
• [Presentation] Reaction Mechanism in Liquid-phase Synthesis Using Acetonitrile for Na3-xPS4-xCLx Solid Electrolytes (2019)
  • Author(s): 伊藤 茜・増澤直貴・由淵 想・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)
  • Int'l Joint Research
• [Presentation] 全固体電池実現に資するアルカリイオン伝導体に関する研究 (2019)
  • Author(s): 林 晃敏
  • Organizer: 2019年度日本セラミックス協会東海支部学術研究発表会
  • Invited
• [Presentation] 液相法を用いたNa3-xPS4-xClx固体電解質合成における反応機構 (2019)
  • Author(s): 伊藤 茜・増澤直貴・由淵 想・作田 敦・辰巳砂昌弘・林 晃敏
  • Organizer: ニューセラミックス懇話会第240回特別研究会
• [Presentation] Na+ Conducting Na3SbS4-Based Solid Electrolytes (2019)
  • Author(s): 林 晃敏・辻 史香・増澤直貴・由淵 想・保手浜千絵・作田 敦・辰巳砂昌弘
  • Organizer: Materials Research Meeting 2019 (MRM2019)
  • Int'l Joint Research
• [Presentation] Development of Glass-Based Solid Electrolyte for All-Solid-State Lithium and Sodium Batteries (2019)
  • Author(s): 林 晃敏
  • Organizer: 43rd International Conference and Exposition on Advanced Ceramics and Composites (ICACC2019)
  • Int'l Joint Research / Invited
• [Presentation] Preparation and Characterization of Cation-Substituted Na3SbS4 Electrolyte with Na+ Ion Conductivity (2019)
  • Author(s): 増澤直貴・由淵 想・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 43rd International Conference and Exposition on Advanced Ceramics and Composites (ICACC2019)
• [Presentation] アセトニトリルを用いたNa3-xPS4-xClx固体電解質の液相合成と特性評価 (2019)
  • Author(s): 林 晃敏・伊藤 茜・増澤 直貴・由淵 想・作田 敦・辰巳砂昌弘
  • Organizer: 日本化学会第99春季年会
• [Presentation] 全固体電池にむけたガラス系アルカリイオン伝導体の開発 (2019)
  • Author(s): 林 晃敏
  • Organizer: 日本セラミックス協会2019年年会
  • Invited
• [Presentation] ガラス電解質を用いた固体界面構築と全固体エネルギー貯蔵デバイスへの応用 (2019)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: 電気化学会第86回大会
  • Invited
• [Presentation] メカニカルミリングにより複合化したNa3Zr2Si2PO12-Na3SbS4電解質のイオン伝導性 (2019)
  • Author(s): 矢野綾子・由淵 想・長尾賢治・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 電気化学会第86回大会
• [Presentation] Glass-Ceramic Solid Electrolytes for All-Solid-State Rechargeable Batteries (2018)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: The 19th International Meeting on Lithium Batteries (IMLB2018)
  • Int'l Joint Research / Invited
• [Presentation] Preparation of Sodium Ion Conductive Na3-xSbS4-xClx Glass-Ceramic Electrolytes (2018)
  • Author(s): 辻 史香・増澤直貴・由淵 想・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: The 19th International Meeting on Lithium Batteries (IMLB2018)
• [Presentation] 全固体ナトリウム電池用NaCrO2-NASICON-Na3BO3正極の共焼結と評価 (2018)
  • Author(s): 矢野綾子・浅野能正・鈴木健治・野井浩祐・西村政輝・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 第13回日本セラミックス協会関西支部学術講演会
• [Presentation] Glass-based Solid Electrolytes for Interface Formation in All-Solid-State Batteries (2018)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: The 12th Japan-France Joint Seminar on Battery
  • Int'l Joint Research / Invited
• [Presentation] All-Solid-State Rechargeable Batteries with Ductile Glass Electrolytes (2018)
  • Author(s): 林 晃敏・作田 敦・辰巳砂昌弘
  • Organizer: The 5th International Conference on Electronic Materials and Nanotechnology for Green Environment (ENGE2018)
  • Int'l Joint Research / Invited
• [Presentation] Na3SbS4をベースとしたカチオン置換型固体電解質の作製とキャラクタリゼーション (2018)
  • Author(s): 増澤直貴・由淵 想・作田 敦・林 晃敏・辰巳砂昌弘
  • Organizer: 第59回電池討論会
• [Presentation] 硫化物系アルカリイオン伝導体を用いた全固体電池の開発 (2018)
  • Author(s): 林 晃敏
  • Organizer: 第44回固体イオニクス討論会
  • Invited
• [Remarks] 大阪府立大学大学院工学研究科応用化学分野無機化学研究グループ
  • URL: http://www2.chem.osakafu-u.ac.jp/ohka/ohka2/index.html