2002 Fiscal Year Final Research Report Summary
Research on Redox Properties of Novel Electronically Conducting Materials and Their Application
| Project/Area Number |
13450350
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | Tokyo University of Agriculture and Technology |
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Principal Investigator |
HATOZAKI Osamu Tokyo University of Agriculture and Technology, Faculty of Technology, Research Associate, 工学部, 助手 (40313291)
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| Co-Investigator(Kenkyū-buntansha) |
IIHAMA Teruyuki Nippon Soda Co., Ltd., Fine Chemicals Development Department, Manager, 精密化学薬品事業部, 主査(研究職)
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| Project Period (FY) |
2001 – 2002
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| Keywords | Organosulfur Compound / Conducting Polymer / Disulfide / Electrocatalysis / Lithium Secondary Battery / Cathode Material / Polypyrrole / Polythiophene |
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| Research Abstract |
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 Monomers
Organosulfur 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
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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
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