Development of Polymeric Electrode Materials on Proton Battery for Next Generation

下一代质子电池聚合物电极材料的开发

• 批准号: 13555261
• 负责人: YAMAMOTO Kimihisa
• 金额: $ 8万
• 依托单位: Keio University
• 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-13555261/
• 关键词: Proton Battery; Polymer Battery; Secondary Battery; Phenylazomethines; One-step Electron Transfer; 1段階2電子移動; アゾメチン; 2電子移動; 電池

Electron transfer is one of the most important reaction in a battery system. One-step two-electron transfer is very rare process in two-electron reaction, in which second electron transfer proceeds more easily than the first one due to the redox potential inversion. It is well-known that N,N'-diphenylphenylenediimine(PDI) is electrochemically activated in the presence of Lewis acid, that shows two-step two-electron reaction accompanied with proton transfer. We found that PDI derivatives introduced more bulky unit in the phenyl-ring at the center, such as N,N'-diphenylanthraquinonediimine (AQPDI), N,N-diphenyl-2,3,5,6-tetramethylphenylenediimine (TMPDI), NCCNtype-phenylazomethine, and their polymers show one-step two-electron transfer. Spectro- and electrochemical methods reveal that one-step two-electron transfer of AQPDI proceeds through coordination of two molecules of Lewis acids. New ploy(phenylazomethine)s are synthesized, which have high thermostability, high solubility, and redox activity bearing cooperative multi-electron transfer. Their polymers are applicable to the electrode materials for the poroton battery. The resulting battery shows high response during the charge and re-charging.

电子转移是电池系统中最重要的反应之一。一步双电子转移是双电子反应中非常罕见的过程，由于氧化还原电位反转，第二次电子转移比第一次更容易进行。众所周知，N,N'-二苯基亚苯基二亚胺（PDI）在路易斯酸存在下会发生电化学活化，表现为伴随质子转移的两步双电子反应。我们发现PDI衍生物在中心苯环上引入了更大的单元，如N,N'-二苯基蒽醌二亚胺(AQPDI)、N,N-二苯基-2,3,5,6-四甲基亚苯基二亚胺(TMPDI)、NCCN型-苯基偶氮甲碱及其聚合物表现出一步双电子转移。光谱和电化学方法揭示了 AQPDI 的一步双电子转移是通过两个路易斯酸分子的配位进行的。合成了新型聚合物（苯基偶氮甲碱），其具有高热稳定性、高溶解度和具有协同多电子转移的氧化还原活性。它们的聚合物适用于质子电池的电极材料。由此产生的电池在充电和再充电期间表现出高响应。

项目成果

K.Yamamoto et al.: "Metal Assembly in Novel Dendrimers with Porphyrin Cores"J.Am.Chem.Soc.. 125. 340-341 (2003)

K.Yamamoto 等人：“具有卟啉核心的新型树枝状聚合物中的金属组装”J.Am.Chem.Soc.. 125. 340-341 (2003)

K.Yamamoto et al.: "Novel Synthesis of Electroresponsive Poly(thiophenylene) through a Michael-Type Addtion"Organic Lett.. 3. 131-134 (2001)

K.Yamamoto 等人：“通过迈克尔型加成新合成电响应聚（噻吩）”Organic Lett.. 3. 131-134 (2001)

K.Yamamoto et al.: "First Synthesis of Phenylazomethine Dendrimer and Structural Studies"J.Am.Chem.Soc.. 122. 4414-4420 (2001)

K.Yamamoto 等：“首次合成苯甲亚碱树枝状聚合物和结构研究”J.Am.Chem.Soc.. 122. 4414-4420 (2001)

K.Yamamoto et al.: "Oligophenylazomethines : Synthesis, Structure, Electrochemical Property and Photo-cyclization"Polym.Adv.Technol.. 13. 765-770 (2002)

K.Yamamoto 等人：“低聚苯基偶氮甲碱：合成、结构、电化学性质和光环化”Polym.Adv.Technol.. 13. 765-770 (2002)

K.Yamamoto et al.: "A Novel oligothiophene Derivatives as a Hole Transport with Emitting Materials for OLED"Polym.Adv.Technol.. 14. 52-57 (2003)

K.Yamamoto 等人：“一种新型低聚噻吩衍生物作为 OLED 发光材料的空穴传输”Polym.Adv.Technol.. 14. 52-57 (2003)