Research on Redox Properties of Novel Electronically Conducting Materials and Their Application

新型导电材料氧化还原性能研究及其应用

• 批准号: 13450350
• 负责人: HATOZAKI Osamu
• 金额: $ 10.88万
• 依托单位: Tokyo University of Agriculture and Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450350/
• 关键词: Organosulfur Compound; Conducting Polymer; Disulfide; Electrocatalysis; Lithium Secondary Battery; Cathode Material; Polypyrrole; Polythiophene; レドックス特性; 分子内一体化; エネルギー貯蔵; ピロール

The subject of this research project is to develop electroactive materials with novel or improved functionality by molecularly coupling organosulfur compounds and conducting polymers. The promise of these composite materials was examined in the application to a cathode material for lithium secondary batteries with high energy density.1.Synthesis and Electropolymerization of Organosulfur-Functionalized Pyrrole MonomersOrganosulfur functional groups such as thiols and disulfides were covalently introduced to a pyrrole monomer in an attempt to enhance electrocatalytic activity of conducting polymers toward organosulfur redox reactions. Pyrrole monomer, to which disulfide group was attached, was successfully synthesized and further electropolymerized at electrode surfaces. A polypyrrole derivative thus obtained showed higher electroactivity compared to that of unmodified, pristine polypyrrole prepared under the same condition, which suggested that the redox reaction of the disulfide group … More was activated due to electrocatalysis of polypyrrole chain. However, clear evidences for the redox transformation between disulfide and thiol have not so far obtained from Raman spectroscopy and electrochemical quartz crystal microbalance. Further characterization of the polymer is currently under way.2.Electrocatalytic Redox Reactions of Organosulfur Compounds on Poly(3,4-ethylenedioxythiophene) (PEDOT)In this study, high electrocatalytic activity of poly(3,4-ethylenedioxythiophene) (PEDOT) toward organosulfur redox reactions was confirmed for the first time. It was observed that redox reactions of an organosulfur compound such as 2,5-dimercapto-1,3,4-thiadiazole (DMcT) was efficiently activated at a PEDOT-modified carbon electrodes. PEDOT also electrocatalyzed the redox reactions of DMcT dimer and oligomers. Such acceleration of the DMcT redox reactions, which is essential to practical application of organosulfur compounds to batteries, was ascribed to electronic properties of PEDOT matrix, into which DMcT was incorporated. Chronopotentiometric results indicated that the redox reactions of DMcT were enough fast at PEDOT modified electrodes to sustain an electrolysis current even at 1.0 mA/cm^2 and coulombic efficiency for DMcT was virtually 100%. Less

本研究计画之主题为将有机硫化合物与导电高分子偶联，以开发具有新颖或改良功能之电活性材料。这些复合材料的应用前景进行了检查，在高能量密度的锂二次电池的阴极材料。1.合成和电聚合的有机硫功能化吡咯单体的有机硫官能团，如硫醇和二硫化物共价引入到吡咯单体，试图提高导电聚合物对有机硫氧化还原反应的电催化活性。成功地合成了吡咯单体，并在其上连接了二硫键，进一步在电极表面电聚合。与在相同条件下制备的未修饰的原始聚吡咯相比，由此获得的聚吡咯衍生物显示出更高的电活性，这表明二硫键基团的氧化还原反应 ...更多信息 由于聚吡咯链的电催化作用而被活化。然而，二硫化物和硫醇之间的氧化还原转化的拉曼光谱和电化学石英晶体微天平迄今没有得到明确的证据。2.有机硫化合物在聚（3，4-乙撑二氧噻吩）（PEDOT）上的电催化氧化还原反应本研究首次证实了聚（3，4-乙撑二氧噻吩）（PEDOT）对有机硫氧化还原反应的高电催化活性。观察到有机硫化合物如2，5-二巯基-1，3，4-噻二唑（DMcT）的氧化还原反应在PEDOT修饰的碳电极上被有效地活化。PEDOT还电催化DMcT二聚体和低聚体的氧化还原反应。DMcT氧化还原反应的这种加速，这是必不可少的有机硫化合物的电池的实际应用，归因于PEDOT矩阵，其中DMcT被纳入电子性能。计时电位结果表明，DMcT在PEDOT修饰电极上的氧化还原反应足够快，即使在1.0 mA/cm^2的电解电流下，DMcT的库仑效率几乎为100%。少

项目成果

Jong Eun Park: "Roles of Metal Nanoparticles on Organosulfur-Conducting Polymer Composites for Lithium Buttery with High Energy Density"Macromolecular Symposium. 186. 35-40 (2002)

Jong Eun Park：“金属纳米粒子对高能量密度锂电池有机硫导电聚合物复合材料的作用”高分子研讨会。

N.Oyama, Y.Kiya, O.Hatozaki, S.Morioka, H.D.Abruna: "Dramatic Acceleration of Organosulfur redox Behavior by Poly(3,4-ethylenedioxythiophene)"Electrochemical and Solid-State Letters. 6(12). A286-A289 (2003)

N.Oyama、Y.Kiya、O.Hatozaki、S.Morioka、H.D.Abruna：“聚（3,4-乙撑二氧噻吩）显着加速有机硫氧化还原行为”电化学和固态快报。

Jong Eun Park: "Chemical Reactions of Pd Nanoparticles with Organosulfur Compound and N, N'-Diphenyl-p-phenylenediamine as a Model Compound of Polyaniline"Journal of New Materials for Electrochemical System. (in press). (2003)

Jong Eun Park：“Pd纳米颗粒与有机硫化合物和N,N-二苯基对苯二胺作为聚苯胺模型化合物的化学反应”电化学系统新材料杂志。

J.E.Park, O.Hatozaki, N.Oyama: "Electrocatalytic Activation of Organosulfur Redox Reactions by Metal Nanoparticles"Chemistry Letters. 32. 138-139 (2003)

J.E.Park、O.Hatozaki、N.Oyama：“金属纳米粒子对有机硫氧化还原反应的电催化活化”化学快报。

Satoru Mihashi: "Electrocatalytic Oxidation of 2, 5-Dimercapto-1, 3, 4-thiadiazole by Polyaniline. 1 Use of N, N'-Diphenyl-p-phenylenediamine as a Model Compound of Polyaniline"Electrochemistry. 69. 991-993 (2001)

Satoru Mihashi：“聚苯胺对 2, 5-二巯基-1, 3, 4-噻二唑的电催化氧化。1 使用 N,N-二苯基对苯二胺作为聚苯胺的模型化合物”电化学。