Triiodide-in-Iodine Networks Stabilized by Quaternary Ammonium Cations as Accelerants for Electrode Kinetics of...

The Zn-polyiodide redox flow battery is considered to be a promising aqueous energy storage system. However, in its charging process, the electrode kinetics of I^- oxidation often suffer from an intrinsically generated iodine film (I₂-F) on the cathode of the battery. Therefore, it is critical to both understand and enhance the observed slow electrode kinetics of I^- oxidation by an electrochemically generated I₂-F. In this article, we introduced an electrogenerated N-methyl-N-ethyl pyrrolidinium iodide (MEPI)-iodine (I₂) solution, designated as MEPIS, and demonstrated that the electrode kinetics of I^- oxidation were dramatically enhanced compared to an I₂-F under conventional electrolyte conditions, such as NaI. We showed that this result mainly contributed to the fast electro-oxidation of triiodide (I₃^-), which exists in the shape of a I₃^--in-I₂ network, [I₃^-·(I₂)]. Raman spectroscopic and electrochemical analyses showed that the composition of electrogenerated MEPIS changed from I₃^- to [I₃^-·(I₂)] via I₅^- as the anodic overpotential increased. We also confirmed that I^- was electrochemically oxidized on a MEPIS-modified Pt electrode with fast electrode kinetics, which is clearly contrary to the nature of an I₂-F derived from a NaI solution as a kinetic barrier of I^- oxidation. Through stochastic MEPIS-particle impact electrochemistry and electrochemical impedance spectroscopy, we revealed that the enhanced electrode kinetics of I^- oxidation in MEPIS can be attributed to the facilitated charge transfer of I₃^- oxidation in [I₃^-·(I₂)]. In addition, we found that the degree of freedom of I₃^- in a quaternary ammonium-based I₂-F can also be critical to determine the kinetics of the electro-oxidation of I^-, which is that MEPIS showed more enhanced charge-transfer kinetics of I^- oxidation compared to tetrabutylammonium I₃^- due to the higher degree of freedom of I₃^-.