西湖大学王盼团队开发了一种在近中性pH值下具有长寿命的仿生氨基酸功能化吩嗪液流电池。 该研究成果于2020年11月28日发表在国际知名学术期刊《德国应用化学》。

水系有机氧化还原液流电池（AORFBs）是一种很有前途的大型储能电化学技术。

研究人员利用溴化吩嗪与氨基酸的简单一步偶联反应，合成并了一系列氨基酸功能化的吩嗪类化合物（AFPs），并对其进行了研究。相比 2,7‐ and 1,8-AFPs，1,6-氨基酸取代的吩嗪在循环过程中表现出更高的稳定性。

机理研究表明，还原的2,7-和1,8-AFPs倾向于互变异构并失去其可逆的氧化还原活性，而1,6-AFPs在氧化态和还原态都具有超高的稳定性。通过将3,3'-（吩嗪-1,6-二基双（氮杂二酰））二丙酸（1,6-DPAP）与亚铁氰化物在pH值为8、电子浓度为1.0 M的条件下配对，这种流电池的OCV为1.15 V，容量衰减率极低，每年为0.5%。

该结果表明了氧化还原活性有机物分子工程对于脱氧化还原流电池的重要性。

附：英文原文

Title: Biomimetic Amino Acid Functionalized Phenazine Flow Batteries with Long Lifetime at Near‐Neutral pH

Author: Shuai Pang, Xinyi Wang, Pan Wang, Yunlong Ji

Issue&Volume: 28 November 2020

Abstract: Aqueous organic redox flow battery is a promising electrochemical technology for large‐scale energy storage. Here we report a biomimetic, ultra‐stable AORFB utilizing an amino acid functionalized phenazine (AFP). A series of AFPs with various commercial amino acids at different substituted positions were synthesized and studied. 1,6‐amino acid substituted phenazines display much higher stability during cycling when compared to 2,7‐ and 1,8‐substituted AFPs. Mechanism investigations reveal that the reduced 2,7‐ and 1,8‐AFPs tend to tautomerize and lose their reversible redox activities, while 1,6‐AFPs possess ultra‐high stability both in their oxidized and reduced states. By pairing 3,3'‐(phenazine‐1,6‐diylbis(azanediyl))dipropionic acid (  1,6‐DPAP  ) with ferrocyanide at pH 8 with 1.0 M electron concentration, this flow battery exhibits an OCV of 1.15 V and an extremely low capacity fade rate of 0.5% per year. These results show the importance of molecular engineering of redox‐active organics for robust redox‐flow batteries.

DOI: 10.1002/anie.202014610

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202014610