Understanding the enhanced electrochemical performance of TEMPO derivatives in non-aqueous lithium ion redox flow batteries

Non-aqueous lithium-ion redox flow batteries (Li-RFBs) have recently garnered much interest because of their high operating voltage and energy density. Albeit these outstanding advantages, challenges, such as poor cyclability and efficiency, still remain in employing the practical application. In an attempt to address these problems, a series of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) and TEMPO derivatives catholytes were prepared and investigated as redox-active materials. Electrochemical evaluation exhibited that the introduction of polar and electron-withdrawing substituents to TEMPO was able to enhance the rate capability and cycling stability, when compared to those with the neat TEMPO. Extensive analysis of the electrochemical properties revealed that the electrophilic heteroatom stabilized the radical as well as alleviated the catholyte degradation. Overall, a careful selection of redox-active species demonstrates great promise in improving the current redox flow battery technology.