Development of Polymeric Electrode Materials on Proton Battery for Next Generation

电子传递是电池系统中最重要的反应之一。在两电子反应中，一步两电子转移是非常罕见的过程，由于氧化还原电势的反转，第二电子转移比第一电子转移更容易进行。众所周知，N，N‘-二苯基苯二亚胺(PDI)在Lewis酸存在下被电化学活化，表现为伴随质子转移的两步两电子反应。我们发现，PDI类化合物在中心苯环上引入了更多的大分子单元，如N，N‘-二苯基并喹二亚胺(AQPDI)、N，N-diphenyl-2，3，5，6-tetramethylphenylenediimine(TMPDI)、NCN型苯偶氮亚胺等，它们的聚合物表现出一步两电子转移。光谱和电化学方法表明，AQPDI的一步两电子转移是通过两个Lewis酸分子的配位进行的。合成了具有高热稳定性、高溶解度和具有协同多电子转移氧化还原活性的新型多(苯基偶氮甲亚胺)S。它们的聚合物适用于作为锂离子电池的电极材料。由此产生的电池在充电和再充电过程中表现出高响应。

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.