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Molecular design based on controlled ion-ordered structure in highly concentrated battery electrolytes

Research Project

Project/Area Number 20H02823
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 36010:Inorganic compounds and inorganic materials chemistry-related
Research InstitutionYamaguchi University

Principal Investigator

Fujii Kenta  山口大学, 大学院創成科学研究科, 教授 (20432883)

Co-Investigator(Kenkyū-buntansha) 松上 優  熊本高等専門学校, リベラルアーツ系理数グループ, 准教授 (50455177)
片山 祐  大阪大学, 産業科学研究所, 准教授 (70819284)
Project Period (FY) 2020-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2022: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Fiscal Year 2021: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2020: ¥10,920,000 (Direct Cost: ¥8,400,000、Indirect Cost: ¥2,520,000)
KeywordsLiイオン電池 / 電解質溶液 / 超濃厚電解液 / 溶液構造解析 / イオン秩序構造 / イオン溶媒和 / 構造解析 / 電池電極反応 / 構造秩序化 / 濃厚電解液 / リチウムイオン電池 / 放射光散乱実験 / MDシミュレーション / 電極/電解液界面
Outline of Research at the Start

Liイオン電池用超濃厚電解液を「Liイオン・対アニオン・溶媒分子」からなる3成分溶液として捉え、3成分間の相互作用により規定される「Liイオンの集合様態」を制御することで電解液の機能を高度に設計する。まず、バルクで形成するLiイオンのナノスケール集合体を構造と自由エネルギーの二軸で定量化し、集合様態を制御するための支配因子を特定する。次に、電位を制御しながら電極/電解液界面をその場分光観測することで、界面に特有のLiイオン集合様態を解明する。各種電気化学測定により電池特性を調べ、電極反応に及ぼす集合様態制御の効果を明らかにする。

Outline of Final Research Achievements

We investigated structural and electrochemical properties of highly concentrated Li-ion battery (LIB) electrolytes via both experimental and theoretical techniques. Major topics were shown below.
(1) Structural and thermodynamic properties of Li ion-ordered complexes in highly concentrated electrolytes were investigated by experimental (mainly, X-ray scattering and vibrational spectroscopy) and all-atom molecular dynamics (MD) simulations. (2) in-situ SEIRA spectra were measured for highly concentrated electrolyte to elucidate the electrode/electrolyte interface structure, and the results were compared with those from MD simulations. (3) LIB performance of the highly concentrated electrolytes was evaluated via systematic electrochemical measurements for commonly used LIB electrode materials to optimize electrolyte composition.

Academic Significance and Societal Importance of the Research Achievements

高濃度のLi塩を溶解した超濃厚電解液の構造およびエネルギー的特性を分子レベルで解明し、Liイオン電池電解液の性能を分子レベルで設計することを目的とした基礎研究を遂行した。超濃厚電解液のバルク構造および電極界面構造を実験・理論の両面から調べた結果、超濃厚化に伴うLiイオンの秩序構造形成が電気化学特性と密接に関係しており、その構造秩序性は塩濃度に加えて、溶媒分子の特徴(主に、分子サイズと電子対供与性)に強く依存することを見出した。これらの結果に基づき、溶液化学的観点で超濃厚電解液の特性を制御することが電池電極反応のメカニズム解明、引いては、電池特性の向上に有効であることを指摘した。

Report

(4 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • Research Products

    (45 results)

All 2023 2022 2021 2020

All Journal Article (16 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 16 results,  Open Access: 4 results) Presentation (29 results) (of which Int'l Joint Research: 2 results,  Invited: 1 results)

  • [Journal Article] Effect of a Weak Coordination Solvent on a Kinetically Favorable Electrode Reaction in Concentrated Lithium-Ion Battery Electrolytes2023

    • Author(s)
      Sawayama Saki、Ochi Riko、Kawaguchi Tsubasa、Katayama Yu、Morita Masayuki、Fujii Kenta
    • Journal Title

      ACS Applied Energy Materials

      Volume: 6 Issue: 2 Pages: 989-996

    • DOI

      10.1021/acsaem.2c03446

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A structural and electrochemical study of lithium-ion battery electrolytes using an ethylene sulfite solvent: from dilute to concentrated solutions2022

    • Author(s)
      Suzuki Kenzo、Sawayama Saki、Deguchi Yuna、Sai Ryansu、Han Jihae、Fujii Kenta
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 44 Pages: 27321-27327

    • DOI

      10.1039/d2cp03616a

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Lithium salt-concentrated organogels prepared via one-step polymer network formation in acetonitrile-based solutions2022

    • Author(s)
      Han Jihae、Osugi Mayu、Ikeda Namie、Fujii Kenta
    • Journal Title

      Polymer

      Volume: 262 Pages: 125426-125426

    • DOI

      10.1016/j.polymer.2022.125426

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structural aspect on “Salting-in” mechanism of PEG chains into a phosphonium-based ionic liquid using lithium salt2022

    • Author(s)
      Shibata Masayuki、Sawayama Saki、Osugi Mayu、Fujii Kenta
    • Journal Title

      Journal of Molecular Liquids

      Volume: 366 Pages: 120255-120255

    • DOI

      10.1016/j.molliq.2022.120255

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Controlling the Phase Separation of Dimethyl Carbonate Solvents Using a Dual-Cation System: Applications in High-Power Lithium Ion-Based Hybrid Capacitors2022

    • Author(s)
      Chikaoka Yu、Ochi Riko、Fujii Kenta、Ariga Takaaki、Sakurai Masato、Matsumoto Ayuna、Ueda Tsukasa、Iwama Etsuro、Naoi Katsuhiko
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 126 Issue: 34 Pages: 14389-14398

    • DOI

      10.1021/acs.jpcc.2c03004

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polyether-based solid electrolytes with a homogeneous polymer network: effect of the salt concentration on the Li-ion coordination structure2022

    • Author(s)
      Ikeda Namie、Ishikawa Asumi、Fujii Kenta
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 16 Pages: 9626-9633

    • DOI

      10.1039/d1cp05351e

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Homogeneous Polymer Network Organogel Prepared in Concentrated Lithium-ion Battery Electrolytes Using a Nonflammable Fluorinated Solvent2022

    • Author(s)
      Takano Saori、Sawayama Saki、Han Jihae、Fujii Kenta
    • Journal Title

      Chemistry Letters

      Volume: 51 Issue: 4 Pages: 412-415

    • DOI

      10.1246/cl.210815

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] 2,2,2-Trifluoroethyl Acetate as an Electrolyte Solvent for Lithium-Ion Batteries: Effect of Weak Solvation on Electrochemical and Structural Characteristics2021

    • Author(s)
      Sawayama Saki、Ochi Riko、Mimura Hideyuki、Morita Masayuki、Fujii Kenta
    • Journal Title

      The Journal of Physical Chemistry C

      Volume: 125 Issue: 49 Pages: 27098-27105

    • DOI

      10.1021/acs.jpcc.1c07312

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Local Structure of Li+ in Superconcentrated Aqueous LiTFSA Solutions2021

    • Author(s)
      Watanabe Hikari, Arai Nana, Nozaki Erika, Han Jihae, Fujii Kenta, Ikeda Kazutaka, Otomo Toshiya, Ueno Kazuhide, Dokko Kaoru, Watanabe Masayoshi, Kameda Yasuo, Umebayashi Yasuhiro
    • Journal Title

      The Journal of Physical Chemistry B

      Volume: 125 Issue: 27 Pages: 7477-7484

    • DOI

      10.1021/acs.jpcb.1c04693

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Tetra-arm Poly(ethylene glycol)-based Ion Gels with Controlled Polymer Network Defects: Application to Lithium-ion Battery Gel Electrolytes2021

    • Author(s)
      Han Jihae、Takano Saori、Fujii Kenta
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 8 Pages: 1508-1511

    • DOI

      10.1246/cl.210235

    • NAID

      130008072836

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Fluorophosphate-Based Nonflammable Concentrated Electrolytes with a Designed Lithium-Ion-Ordered Structure: Relationship between the Bulk Electrolyte and Electrode Interface Structures2021

    • Author(s)
      Sawayama Saki、Morinaga Asuka、Mimura Hideyuki、Morita Masayuki、Katayama Yu、Fujii Kenta
    • Journal Title

      ACS Applied Materials & Interfaces

      Volume: 13 Issue: 5 Pages: 6201-6207

    • DOI

      10.1021/acsami.0c19293

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Anion effects on Li ion transference number and dynamic ion correlations in glyme?Li salt equimolar mixtures2021

    • Author(s)
      Shigenobu Keisuke、Shibata Masayuki、Dokko Kaoru、Watanabe Masayoshi、Fujii Kenta、Ueno Kazuhide
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 23 Issue: 4 Pages: 2622-2629

    • DOI

      10.1039/d0cp06381a

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Solvation Structure of Li+ in Concentrated Acetonitrile and N,N-Dimethylformamide Solutions Studied by Neutron Diffraction with 6Li/7Li Isotopic Substitution Methods2020

    • Author(s)
      Kameda Yasuo, Saito Shu, Saji Aoi, Amo Yuko, Usuki Takeshi, Watanabe Hikari, Arai Nana, Umebayashi Yasuhiro, Fujii Kenta, Ueno Kazuhide, Ikeda Kazutaka, Otomo Toshiya
    • Journal Title

      The Journal of Physical Chemistry B

      Volume: 124 Issue: 46 Pages: 10456-10464

    • DOI

      10.1021/acs.jpcb.0c08021

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Local structure of a highly concentrated NaClO4 aqueous solution-type electrolyte for sodium ion batteries2020

    • Author(s)
      Sakamoto Ryo、Yamashita Maho、Nakamoto Kosuke、Zhou Yongquan、Yoshimoto Nobuko、Fujii Kenta、Yamaguchi Toshio、Kitajou Ayuko、Okada Shigeto
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 22 Issue: 45 Pages: 26452-26458

    • DOI

      10.1039/d0cp04376a

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Importance of Lithium Coordination Structure to Lithium-Ion Transport in Polyether Electrolytes with Cyanoethoxy Side Chains: An Experimental and Theoretical Approach2020

    • Author(s)
      Matsuoka Riho、Shibata Masayuki、Matsuo Kousuke、Sai Ryansu、Tsutsumi Hiromori、Fujii Kenta、Katayama Yu
    • Journal Title

      Macromolecules

      Volume: 53 Issue: 21 Pages: 9480-9490

    • DOI

      10.1021/acs.macromol.0c01634

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Physicochemical and Structural Properties of a Hydrophobicity/ Hydrophilicity Switchable Ionic Liquid2020

    • Author(s)
      Kota Ohkubo, Keiya Yanagisawa, Akio Kamimura, and Kenta Fujii
    • Journal Title

      J. Phys. Chem. B

      Volume: 124 Issue: 18 Pages: 3784-3790

    • DOI

      10.1021/acs.jpcb.0c02067

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Presentation] 超濃厚LiFSA/アセトニトリル電解液を反応場とした均一高分子網目ゲルの架橋反応メカニズムと電極反応特性2023

    • Author(s)
      出口由菜, 藤井健太
    • Organizer
      電気化学会第90回大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 超濃厚 LiFSA 電解液を反応場とする金属イオン架橋型均一網目ゲルの電解質特性2023

    • Author(s)
      田窪 樹, 藤田小雪, 藤井健太
    • Organizer
      電気化学会第90回大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Ethylene sulfiteを溶媒とする希薄~超濃厚電解液の溶媒和構造と電気化学特性2023

    • Author(s)
      澤山沙希, 韓 智海, 藤井健太
    • Organizer
      電気化学会第90回大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] Fluorophosphate-Based Nonflammable Concentrated Electrolytes with a Controlled Lithium-ion Ordered Structure2022

    • Author(s)
      Kenta Fujii
    • Organizer
      Asian Conference on Electrochemical Power Sources 11 (ACEPS'11)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Electrode Reaction Mechanism in Highly Concentrated Fluoroacetate-Based Electrolytes for Lithium-Ion Batteries2022

    • Author(s)
      Saki Sawayama, Kenta Fujii
    • Organizer
      Asian Conference on Electrochemical Power Sources 11 (ACEPS'11)
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Liイオン電池用超濃厚水系電解液の分子レベル構造解析2022

    • Author(s)
      大杉茉由, 藤井健太
    • Organizer
      2022年日本化学会中四国支部大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 超濃厚フッ素化アセテート電解液中のイオン秩序構造と電極反応メカニズム2022

    • Author(s)
      澤山沙希, 藤井健太
    • Organizer
      第63回電池討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 超濃厚電解液中におけるLiイオン脱溶媒和プロセスと電極反応速度論2022

    • Author(s)
      澤山沙希, 藤井健太
    • Organizer
      日本分析化学会第71年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 高濃度LiFSA/イオン液体電解液の溶液構造解析と電極反応メカニズム2022

    • Author(s)
      川口 翼, 藤井健太
    • Organizer
      日本分析化学会第71年会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 2,2,2-Trifluoroethyl Acetateを用いたLiTFSA電解液のイオン溶媒和および電気化学特性2022

    • Author(s)
      澤山沙希, 藤井健太
    • Organizer
      2022年電気化学秋季大会
    • Related Report
      2022 Annual Research Report
  • [Presentation] FSA型超濃厚イオン液体電解液に特有なPEG鎖の可溶化メカニズムとこれを利用した新規イオンゲル電解質の創成2022

    • Author(s)
      池田奈美恵, 藤井健太
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 金属イオン錯形成を駆動力とする4分岐高分子の均一網目形成とLiイオン電池用ゲル電解質への応用2022

    • Author(s)
      藤田小雪, 藤井健太
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 優れた力学特性を有する全固体高分子電解質の物性-構造相関:金属イオン種依存性2022

    • Author(s)
      加藤亜蘭, 藤井健太
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 低配位性溶媒・フッ素化アセテートを用いたLiイオン電池用電解液中のLiイオン溶媒和構造と電極反応特性2022

    • Author(s)
      澤山沙希, 藤井健太
    • Organizer
      第82回分析化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 理想的な均一高分子網目を有する全固体高分子電解質の物性-構造相関2022

    • Author(s)
      池田奈美恵, 藤井健太
    • Organizer
      第82回分析化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 有機電解液中における多分岐高分子の網目形成メカニズムと全固体高分子電解質への応用2022

    • Author(s)
      加藤亜蘭, 藤井健太
    • Organizer
      第82回分析化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] 超濃厚電解液中で特有なLiイオン錯形成型ゲル電解質の架橋反応メカニズム2022

    • Author(s)
      藤田小雪, 藤井健太
    • Organizer
      第82回分析化学討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] FSA型イオン液体を溶媒とする超濃厚LiFSA電解液の溶液構造解析および電極反応特性2022

    • Author(s)
      川口 翼, 大杉茉由, 藤井健太
    • Organizer
      電気化学会第89回大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 金属イオン錯形成により架橋する四分岐高分子を用いた超濃厚電解液のゲル化メカニズムと電解質特性2022

    • Author(s)
      藤田小雪, 藤井健太
    • Organizer
      電気化学会第89回大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ケトエステル系超濃厚電解液の溶液構造解析:分子コンフォメーション変化とイオン秩序構造形成2021

    • Author(s)
      江原寧々, 上野和英, 藤井健太
    • Organizer
      日本分析化学会第70年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] フッ素化アセテート溶媒を用いた超濃厚電解液の精密溶液構造解析と電気化学的特性2021

    • Author(s)
      越智梨瑚, 三村英之, 藤井健太
    • Organizer
      第81回分析化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 低配位性溶媒を用いた超濃厚電解液のバルクおよび電極界面構造2021

    • Author(s)
      越智梨瑚, 三村英之, 片山 祐, 藤井健太
    • Organizer
      第58回化学関連支部合同九州大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 2,2,2-trifluoroethyl acetate を溶媒とする超濃厚電解液の溶液構造と電気化学特性2021

    • Author(s)
      越智梨瑚, 三村英之, 藤井健太
    • Organizer
      電気化学会第88回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ケトエステル系溶媒を用いた超濃厚LiFSA電解液の分子レベル構造解析2021

    • Author(s)
      江原寧々, 上野和英, 藤井健太
    • Organizer
      電気化学会第88回大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] ホスホニウム型イオン液体を溶媒とする均一網目ゲル電解質の物性および電気化学特性2020

    • Author(s)
      松浦沙樹, 柴田雅之, 韓 智海, 藤井健太
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Liイオン電池用イオン液体ゲル電解質の網目構造制御とイオン輸送特性2020

    • Author(s)
      石川明日美, 藤井健太
    • Organizer
      第69回高分子学会年次大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Liイオン電池用不燃性超濃厚電解液のバルク構造と電極/電解液界面構造への影響2020

    • Author(s)
      澤山沙希, 森永明日香, 片山 祐, 三村英之, 藤井健太
    • Organizer
      日本分析化学会第69年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] フッ素化リン酸エステル溶媒を用いた不燃性ゲル電解質のゲル化反応メカニズムと電気化学特性2020

    • Author(s)
      髙野沙織, 松浦沙樹, 韓 智海, 藤井健太
    • Organizer
      日本分析化学会第69年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 低配位性溶媒を用いたLiイオン電池用超濃厚電解液のバルク構造と電極/電解液界面構造への影響2020

    • Author(s)
      澤山沙希, 森永明日香, 片山 祐, 三村英之, 森田昌行, 藤井健太
    • Organizer
      第61回電池討論会
    • Related Report
      2020 Annual Research Report

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Published: 2020-04-28   Modified: 2024-01-30  

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