1999 年度実績報告書

リチウムイオン脱挿入化合物のミクロ構造制御と単一粒子レベルの電池特性評価

研究課題

研究課題/領域番号	10555297
研究機関	東北大学
研究代表者	内田勇東北大学, 未来科学技術共同研究センター, 教授 (50005302)
研究分担者	松木健三山形大学, 工学部, 教授 (70006998) 伊藤隆東北大学, 大学院・工学研究科, 助手 (40302187) 西澤松彦東北大学, 大学院・工学研究科, 講師 (20273592) 漆畑広明三菱電機株式会社, 先端技術総合研究所・エネルギー変換技術部, 電気化学グループマネージャー(研究職) 仁科辰夫山形大学, 工学部, 助教授 (60172673)
キーワード	リチウムイオン電池 / 電池活物質 / 層状化合物 / リチウム脱挿入反応 / インターカレーション反応 / マイクロ電極 / クエン酸錯体 / in-situ測定
研究概要	本研究は二つの大学がそれぞれ異なる手法を用いて協力し,電気自動車等への応用が期待される高性能2次電池,いわゆるリチウムイオン電池の材料開発と評価法の確立に取り組んだものである。 1.山形大では,各構成原子を原子レベルで均一に混合でき,且つ多成分の層状化学物を簡便かつ系統的に合成できるクエン酸錯体法を改良・駆使してミクロ構造制御合成を行った。特に,今後の材料展開を予想してニッケル系およびマンガンスピネル系材料で焼成条件の最適化を進め,サイクル安定性に優れた材料を得ている。(1)LiNiO_2系ではLiやNiに対するクエン酸のモル比を量論比で1.5以上とし,分散仮焼することにより反応を抑制し,最終的に酸素中720℃,15時間以上の焼成で安定な材料を得た。(2)LiCoO_2やLiMn_2O_4の場合はクエン酸錯体生成後,空気中300℃以下の低温仮焼段階で既にサブミクロンサイズの微粒子の基本骨格が生成し,空気中700℃、4時間の本焼成により,結晶構造が十分に発達した粒径10μmの酸化物が合成できた。 2.東北大では,微量の電池材料で迅速に電気化学特性を評価し,電池材料としての1次スクリーニングを速度論的評価を交えて行うマイクロ電極法を確立し,それらの結果を実電池用試料に反映させるべく山形大及び三菱電機側に流すと共に,ここからフィードバックされる試料を測定に供した。成果を羅列すると,単一の電池活物質粒子(〜10μm)について、(1)分極化での粒子の機械的安定性のin-situ観察、(2)高電圧(〜5V)ボルタンメトリーによる電気化学的安定性評価(3)ACインピーダンス測定を含む過渡応答測定による拡散係数の決定と単一粒子の等価回路解析,(4)in-situラマン及び導電率測定、さらに上記の測定を(5)室温から高温(50度C)に拡張し、温度特性の評価も行っている。

研究成果

(34件)

すべてその他

すべて文献書誌 (34件)

[文献書誌] M.Nishizawa: "Measurements of chemical Diffusion Coefficient of Lithium Ion in a Graphitized Mesocarbon Microbeads Using a Microelectrode"Electrochem.Solid State Lett. 1. 10-12 (1998)
[文献書誌] S.Yamamura: "Photo-Assisted Lithium Insertion to Li_<1-X>Mn_2O_4 Film Electrodes"Chem.Lett. 7. 495-496 (1998)
[文献書誌] M.Nishizawa: "Electrochemical Studies of Spinel LiMn_2O_4 Films Prepared by Electrostatic Spray Deposition"Bull.Chem.Soc.Jpn.. 8. 2011-2015 (1998)
[文献書誌] 山田耕太: "静電噴霧法(ESD)を用いた複含酸化物薄膜の作製とリチウムイオンニ次電池用電極材料への応用"表面技術. 49. 1631-1632 (1998)
[文献書誌] M.Nishizawa: "Desirable Hysteresis on Electrical Conductivity of Li1-xCoO2 during Lithium Insertion/Extraction"Chem.Commun. 16. 991-995 (1998)
[文献書誌] 西澤松彦: "リチウムニ次電池におけるin situ XRD及び導電率測定"電気化学. 66. 991-995 (1998)
[文献書誌] Kazuhiro Tachibana: "The Function of Carbon as Conductive Agent for Primary and Secondary Batteries"Progress in Batteries & Battery Materials. 17. 242-244 (1998)
[文献書誌] K.Tachibana: "Proposal for an accurate and rapid international Electrochemical test for various battery materials using T-M cell (Part2): Rechargeability of EMD containing Bi203 in KOH"Progress in Batteries & Battery Materials. 17. 245-248 (1998)
[文献書誌] K.Tachibana: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell (Part 3): The charging/discharging characteristics of LiMn204 as the cathode for Lithium secondary battery.-The effect of combination of Current collector and electolyte -"Progress in Batteries & Battery Materials. 17. 256-264 (1998)
[文献書誌] K.Tachibana: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell (Part 4) :SEM observation of LiMn204 positive electrode (JEC No.3) before and after the charging/discharging test in organic electrolyte"Progress in Batteries & Battery Materials. 17. 265-272 (1998)
[文献書誌] Kazuhiro Tachibana: "Charge-discharge Characteristics of LiMn204 as The Cathode for Lithium Secondary Battery-Effect of Cathode Particle.Size-"Progress in Batteries & Battery Materials. 17. 273-275 (1998)
[文献書誌] Kazuhiro Tachibana: "Effect of Hetero-contacts at Active Material Conductive Additives on Lithium ntercalation/Deintervalation of LiCo02"Denki Kagaku. 66. 1248-1252 (1998)
[文献書誌] K.Tachibana: "Development of in situ AC impedance Measurement System under Constant-current Conditions and Its Application to Galvanostatic Discharge of Electrolytic Manganese Dioxide in Alkaline Solution"J.Power Sources. 74. 29-33 (1998)
[文献書誌] K.Dokko: "High Resolution Cyclic Voltammograms of LiMn_<2-x>Ni_xO_4 with a Microelectrode Technique"Denki Kagaku. 66. 1188-1193 (1998)
[文献書誌] S.-J.Lee: "Electrochemical Insertion Behavior of Lithium Ions into Mesophase Pitch Carbon Films Prepared by Electrostatic Spray Deposition"Denki Kagaku. 66. 1276-1280 (1998)
[文献書誌] M.Nishizawa: "Microelectrode Techniques for In Situ Studies on Electrical Conductance of a Carbon Particle and its Composite Film during Electrochemical Lithium Intercalation/Extraction"J.Phys.Chem. 103. 192-196 (1999)
[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems: Application to Lithium Ion Battery Materials"Electrochemistry. 67. 420-426 (1999)
[文献書誌] S.-J.Lee: "Fabrication of Mesophase Pitch Carbon Thin Film Electrodes and the Effect of Heat Treatment on Electrochemical Lithium Insertion and Extraction"Electrochim.Acta. 44. 2379-2383 (1999)
[文献書誌] 王献明: "マイクロ電極を用いる有機電解液と金属の安定性の評価"Electrochemistry. 67. 145-150 (1999)
[文献書誌] 松木健三: "LiMn_2O_4系に対する導電付与材、集電体&電解液の効果"マテリアルインテグレーション. 12. 35 (1999)
[文献書誌] Kazuhiro Tachibana: "What Is the True Function of Carbon as a Conductive Additive for Primary and Secondary Batteries?"ITE Battery Letters. 1. 33-38 (1999)
[文献書誌] Kazuhiro Tachibana: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell (Part5): Discharging Kinetics of EMD in KOH Aqueous Solution"ITE Battery Letters. 1. 39-42 (1999)
[文献書誌] H.-S.Kim: "Microvoltammetric Study of Electrochemical Hydrogenation of a Surface-Treated Mg_2Ni Alloy Single Particle"Bullitun of Chemical Society of Japan. 72. 1643-1646 (1999)
[文献書誌] H.-S.Kim: "Single Particle Electrochemistry for Hydrogen Storage Alloys, MmNi_<3.55>Co_<0.75>Mn_<0.4>Al_<0.3>"Electrochimica Acta. 45. 483-488 (1999)
[文献書誌] M.Nishizawa: "Microelectrode Techniques for in situ Measurements on Electrical Conductance of a Carbon Particle and Its Composite Film during Electrochemical Insertion /Extraction"Journal of Physical Chemistry B. 103. 192-196 (1999)
[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems for Advanced Materials in Battery and Sensor Applications"Electrochimica Acta. 44. 3629-3637 (1999)
[文献書誌] M.Nishizawa: "Ion-and Electron-Transport Properties of a Single Particle of Disordered Carbon during Lithium Insertion Reaction"J.Phys.Chem.B. 103. 4933-4936 (1999)
[文献書誌] 立花和宏: "アルミニウム陽極酸化における定電圧印加時のリーク電流と帝電流印加時の電位オーバーシュートの関係"Electrochemistry. 67. 774-779 (1999)
[文献書誌] 立花和宏: "アジピン酸アンモニウム水溶液中における微少電極を用いたアルミニウムの陽極酸化"Electrochemistry. 67. 780-783 (1999)
[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems for Advanced Materials in Battery and Sensor Technologies"Electrochim.Acta. 44. 3629-3637 (1999)
[文献書誌] M.Nishizawa: "Electrochemical Quartz Crystal Microbalance for Insertion/Extraction of Lithium in Spinel LiMn_2O_4 Thin Films"Langmuir. 15. 4949-4951 (1999)
[文献書誌] M.Nishizawa: "In Situ Conductance Measurement to Investigate Ro1es of Conductive Additives in Lithium Ion Battery Electrodes"Electrochem.Commun.. 1. 375-378 (1999)
[文献書誌] Takashi Itoh: "High Temperature in situ Raman Spectroscopy of Oxide Species in Molten(Li+K) Carbonate Eutectic"Chemistry Letters. 1115-1116 (1999)
[文献書誌] Takashi Itoh: "In Situ Raman Spectroscopic Investigations of Oxide Chemistry in Molten Carbonates"Proc. Of The Fifth Int. Symp. On Molten Carbonate Fuel Ce1l Technology. 990-20. 242-248 (1999)

1999 年度 実績報告書

リチウムイオン脱挿入化合物のミクロ構造制御と単一粒子レベルの電池特性評価

研究代表者

内田 勇 東北大学, 未来科学技術共同研究センター, 教授 (50005302)

研究成果

[文献書誌] M.Nishizawa: "Measurements of chemical Diffusion Coefficient of Lithium Ion in a Graphitized Mesocarbon Microbeads Using a Microelectrode"Electrochem.Solid State Lett. 1. 10-12 (1998)

[文献書誌] S.Yamamura: "Photo-Assisted Lithium Insertion to Li_<1-X>Mn_2O_4 Film Electrodes"Chem.Lett. 7. 495-496 (1998)

[文献書誌] M.Nishizawa: "Electrochemical Studies of Spinel LiMn_2O_4 Films Prepared by Electrostatic Spray Deposition"Bull.Chem.Soc.Jpn.. 8. 2011-2015 (1998)

[文献書誌] 山田耕太: "静電噴霧法(ESD)を用いた複含酸化物薄膜の作製とリチウムイオンニ次電池用電極材料への応用"表面技術. 49. 1631-1632 (1998)

[文献書誌] M.Nishizawa: "Desirable Hysteresis on Electrical Conductivity of Li1-xCoO2 during Lithium Insertion/Extraction"Chem.Commun. 16. 991-995 (1998)

[文献書誌] 西澤松彦: "リチウムニ次電池におけるin situ XRD及び導電率測定"電気化学. 66. 991-995 (1998)

[文献書誌] Kazuhiro Tachibana: "The Function of Carbon as Conductive Agent for Primary and Secondary Batteries"Progress in Batteries & Battery Materials. 17. 242-244 (1998)

[文献書誌] K.Tachibana: "Proposal for an accurate and rapid international Electrochemical test for various battery materials using T-M cell (Part2): Rechargeability of EMD containing Bi203 in KOH"Progress in Batteries & Battery Materials. 17. 245-248 (1998)

[文献書誌] Kazuhiro Tachibana: "Charge-discharge Characteristics of LiMn204 as The Cathode for Lithium Secondary Battery-Effect of Cathode Particle.Size-"Progress in Batteries & Battery Materials. 17. 273-275 (1998)

[文献書誌] Kazuhiro Tachibana: "Effect of Hetero-contacts at Active Material Conductive Additives on Lithium ntercalation/Deintervalation of LiCo02"Denki Kagaku. 66. 1248-1252 (1998)

[文献書誌] K.Tachibana: "Development of in situ AC impedance Measurement System under Constant-current Conditions and Its Application to Galvanostatic Discharge of Electrolytic Manganese Dioxide in Alkaline Solution"J.Power Sources. 74. 29-33 (1998)

[文献書誌] K.Dokko: "High Resolution Cyclic Voltammograms of LiMn_<2-x>Ni_xO_4 with a Microelectrode Technique"Denki Kagaku. 66. 1188-1193 (1998)

[文献書誌] S.-J.Lee: "Electrochemical Insertion Behavior of Lithium Ions into Mesophase Pitch Carbon Films Prepared by Electrostatic Spray Deposition"Denki Kagaku. 66. 1276-1280 (1998)

[文献書誌] M.Nishizawa: "Microelectrode Techniques for In Situ Studies on Electrical Conductance of a Carbon Particle and its Composite Film during Electrochemical Lithium Intercalation/Extraction"J.Phys.Chem. 103. 192-196 (1999)

[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems: Application to Lithium Ion Battery Materials"Electrochemistry. 67. 420-426 (1999)

[文献書誌] S.-J.Lee: "Fabrication of Mesophase Pitch Carbon Thin Film Electrodes and the Effect of Heat Treatment on Electrochemical Lithium Insertion and Extraction"Electrochim.Acta. 44. 2379-2383 (1999)

[文献書誌] 王献明: "マイクロ電極を用いる有機電解液と金属の安定性の評価"Electrochemistry. 67. 145-150 (1999)

[文献書誌] 松木健三: "LiMn_2O_4系に対する導電付与材、集電体&電解液の効果"マテリアルインテグレーション. 12. 35 (1999)

[文献書誌] Kazuhiro Tachibana: "What Is the True Function of Carbon as a Conductive Additive for Primary and Secondary Batteries?"ITE Battery Letters. 1. 33-38 (1999)

[文献書誌] Kazuhiro Tachibana: "Proposal for an accurate and rapid international electrochemical test for various battery materials using T-M cell (Part5): Discharging Kinetics of EMD in KOH Aqueous Solution"ITE Battery Letters. 1. 39-42 (1999)

[文献書誌] H.-S.Kim: "Microvoltammetric Study of Electrochemical Hydrogenation of a Surface-Treated Mg_2Ni Alloy Single Particle"Bullitun of Chemical Society of Japan. 72. 1643-1646 (1999)

[文献書誌] H.-S.Kim: "Single Particle Electrochemistry for Hydrogen Storage Alloys, MmNi_<3.55>Co_<0.75>Mn_<0.4>Al_<0.3>"Electrochimica Acta. 45. 483-488 (1999)

[文献書誌] M.Nishizawa: "Microelectrode Techniques for in situ Measurements on Electrical Conductance of a Carbon Particle and Its Composite Film during Electrochemical Insertion /Extraction"Journal of Physical Chemistry B. 103. 192-196 (1999)

[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems for Advanced Materials in Battery and Sensor Applications"Electrochimica Acta. 44. 3629-3637 (1999)

[文献書誌] M.Nishizawa: "Ion-and Electron-Transport Properties of a Single Particle of Disordered Carbon during Lithium Insertion Reaction"J.Phys.Chem.B. 103. 4933-4936 (1999)

[文献書誌] 立花和宏: "アルミニウム陽極酸化における定電圧印加時のリーク電流と帝電流印加時の電位オーバーシュートの関係"Electrochemistry. 67. 774-779 (1999)

[文献書誌] 立花和宏: "アジピン酸アンモニウム水溶液中における微少電極を用いたアルミニウムの陽極酸化"Electrochemistry. 67. 780-783 (1999)

[文献書誌] M.Nishizawa: "Microelectrode-Based Characterization Systems for Advanced Materials in Battery and Sensor Technologies"Electrochim.Acta. 44. 3629-3637 (1999)

[文献書誌] M.Nishizawa: "Electrochemical Quartz Crystal Microbalance for Insertion/Extraction of Lithium in Spinel LiMn_2O_4 Thin Films"Langmuir. 15. 4949-4951 (1999)

[文献書誌] M.Nishizawa: "In Situ Conductance Measurement to Investigate Ro1es of Conductive Additives in Lithium Ion Battery Electrodes"Electrochem.Commun.. 1. 375-378 (1999)

[文献書誌] Takashi Itoh: "High Temperature in situ Raman Spectroscopy of Oxide Species in Molten(Li+K) Carbonate Eutectic"Chemistry Letters. 1115-1116 (1999)

[文献書誌] Takashi Itoh: "In Situ Raman Spectroscopic Investigations of Oxide Chemistry in Molten Carbonates"Proc. Of The Fifth Int. Symp. On Molten Carbonate Fuel Ce1l Technology. 990-20. 242-248 (1999)

1999 年度実績報告書

内田勇東北大学, 未来科学技術共同研究センター, 教授 (50005302)