Synthesis of Hyperbranched Polyether Macromonomers and Ion-conducting Behavior of Their Polymer Electrolytes

超支化聚醚大单体的合成及其聚合物电解质的离子传导行为

• 批准号: 10650878
• 负责人: WATANABE Masayoshi
• 金额: $ 2.37万
• 依托单位: Yokohama National University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10650878/
• 关键词: Hyperbranched Polymer; Polyther; Ion Conducting Polymer; Polymer Electrolyte; Dendrimer; Macromonomer; Lithium Polymer Battery; Electron Transfer Reaction; リチウム電池; 多分岐ポリマー; 270モノマー; イオン伝導; デンドリュー

Progress of the study of ion-conducting polymers stimulates to alter conventional electrochemical systems, which consist of electrolytes and liquid electrolytes, to solid electrochemical systems. Polymer electrolytes have, thus, occupied an important position in solid state electrochemistry, because of their unique properties, such as thin film forming property, good processability, flexibility, light weight, elasticity (plasticity), and transparency as well as relatively high ionic conductivity and wide potential window in the solid states. Especially, it has been considered to be important and promising to apply polymer electrolytes to solid-state lithium/polymer batteries, which ensure safety, high energy density, freedom in shape geometry, and processability in large-scale-production. The development of large-scale high-energy-density rechargeable lithium/polymer electrolyte batteries, applicable to electric vehicles, is one of the most challenging science and technology in solid s … More tate electrochemistry.Polymer electrolytes are solid solutions of electrolyte salts in ion-conducting polymers and exhibit relatively high ionic conductivity at ambient temperatures. Ion transport in the polymer electrolytes is considered to be cooperative with local segmental motion of the polymers. In this study, polyether-based ion-conducting polymers having free chain ends in high densities have been prepared as matrixes for electrolyte salts. Our working concept of this study to achieve highly conducting polymer electrolytes is that fast molecular motion of short and flexible ether side chains in the matrix polymers would contribute to fast ion transport. 2-(2-Methoxyethoxy)ethyl glycidyl ether (MEEGE) has been copolymefized with ethylene oxide (EO) to obtain P(EO/MEEGE) as the matrix polymers. EO and MEEGE were copolymerized by KOH-catalyzed ring-opening anionic polymerization in the presence of 2-(2-methoxyethoxy)ethanol to give OH-terminated oligomers, followed by esterification reaction of the OH groups by acrylic acid to give P(EO/MEEGE) macromonomers. The macromonomer/salt solutions containing a photo-initiator were cast on glass plates and irradiated with UV light, resulting to from network polymer electrolytes. The conductivity for the network polymer electrolytes, which give the best conductivity in this study, reaches 10ィイD1-4ィエD1 ScmィイD1-1ィエD1 and 10ィイD1-3ィエD1 ScmィイD1-1ィエD1 at 30℃ and at 80℃, respectively, and even at 0℃ it is close to 10ィイD1-5ィエD1 ScmィイD1-1ィエD1. Although LiィイD1+ィエD1 transport number of the polymer electrolytes is lower than 0.5, as is generally seen polyether based polymer electrolytes, the electrochemically stable domain is wider than 4 V vs. Li/LiィイD1+ィエD1. The presence of the conductivity maximum as a function of the macromonomer molecular weight, irrespective of the constant Tg, indicates that the dendritie-side-chain motion that can not be scaled by Tg and mainly affects the fast ion transport. The introduction of hyper-branched structure is quite effective to achieve fast ion transport in polymer electrolytes. Less

因此，离子传导聚合物的研究的进展会刺激改变电化学系统的rolytes，因此，耐受器电解质在其独特特性的固态Elochemistry中占据了重要位置（塑料）y高离子电导率和固体状态的广泛窗口。大规模生产中的Proc essabelity。 - 聚合物和聚合物电解质中的离子离子转运相对较高，被认为与具有高密度的高密度末端的局部节段性相关。是在基质聚合物中的短而柔性的乙醚链在快速离子转运中的分子运动。 ）作为基质聚合物。 （EO/MEEGE）在玻璃A上施放含有照相剂的宏观分子/盐溶液。达到10 I D1-4 Yi D1-SCM I D1-1 YIER D1-3 Yi D1-3 Yi D1-1在30°C和80°C下，尊重器，甚至在0°C下，它接近10 II D1-5 Yi D1-1-SCM II D1。无论TG，电导率最大值作为宏观分子量的函数，表明无法通过TG缩放的树突链运动，并且主要影响Fasto RT的引入。聚合物电解质中的快速离子传输较少

项目成果

A.Uedono,S.Tanigawa A.Nishimoto,M.Watanabe: "Open Spaces and Molecular Motions of Polyether-Based Network Polymers Probed by Positron Annihilation" J.Polym.Sci.,Part B,Polym.Phys.36. 1919-1925 (1998)

A.Uedono,S.Tanikawa A.Nishimoto,M.Watanabe：“通过正电子湮灭探测聚醚基网络聚合物的开放空间和分子运动”J.Polym.Sci.，B 部分，Polym.Phys.36。

T.Endo,A.Nishimoto M.Watanabe,et al.: "High Ionic Conductivity and Electrode Interface Properties of Polymer Electrlytes Based on High Molecular Weight Branched Polyether" J.Power Sources. (in press). (1999)

T.Endo、A.Nishimoto M.Watanabe 等人：“基于高分子量支化聚醚的聚合物电解质的高离子电导率和电极界面性能”J.Power Sources。

J. Amanokura, Y. Suzuki, S. Imabayashi, M. Watanabe: "Preparation of Polypyrrole/Polymer Electrolytes Composites with Concentration Gradient of Polyprrole as Cathode/Electrolyte Material for Lithium Secondary Battery"Electrochemistry. 67. 1159-1161 (1999)

J. Amanokura、Y. Suzuki、S. Imabayashi、M. Watanabe：“以聚吡咯浓度梯度作为锂二次电池正极/电解质材料的聚吡咯/聚合物电解质复合材料的制备”电化学。

M. Watanabe, Y. Suzuki, A. Nishimoto: "Single Ion Conduction in Polyether Electrolytes Alloyed with Lithium Salt of A Perfluorinated Polymide"Electrochem. Acta.. 45. 1187-1192 (2000)

M. Watanabe、Y. Suzuki、A. Nishimoto：“与全氟化聚酰亚胺的锂盐合金的聚醚电解质中的单离子传导”Electrochem。

A.Nishimoto,M.Watanabe Y.Ikeda,S.Kohjiya: "High Ionic Conductivity of New Polymer Electrolytes based on High Molecular Weight Polyether Comb Polymers" Electrochem.Acta. 43. 1177-1184 (1998)

A.Nishimoto,M.Watanabe Y.Ikeda,S.Kohjiya：“基于高分子量聚醚梳状聚合物的新型聚合物电解质的高离子电导率”Electrochem.Acta。