(Invited) Charge Propagation in Highly Concentrated Iodine/Iodide Solutions as Potential Redox Electrolytes and Mediators for Redox Flow Batteries and Solar Cells
Authors: Kulesza Pawel J. , Rutkowska Iwona A. , Lubera Justyna , Di Noto Vito , Negro Enrico , Vezzu Keti 
Published: September 2023

The technology of Redox Flow Batteries is an important option to store energy from the operating irregularly renewable energy sources. The perspectives concern stationary energy storage, including grid-scale energy storage, thanks to their high power performance, flexible design, and ease of scaling-up. The flow-based electrochemical energy storage systems utilize the appropriate electroactive species dissolved in externally flowing electrolytes which are ready to accumulate all (or part) of the charge. Among important issues is the search for highly efficient (i.e., capable of fast electron transfers) electroactive systems that would yield high power and energy densities during the systems’ operation. Highly concentrated iodine/iodide system can act as redox conducting electrolyte. Furthermore its charge mediating capabilities has been recognized in the Dye Sensitized Solar Cell technology due to the feasibilioty of fast charge propagation accompanied by efficient electron self-exchange or diffusional-type electron hopping.
In the present work, we concentrate on utilization of highly concentrated iodine/iodide redox systems and their possibility to exhibit high rates of charge propagation. In practical terms, it can be combined with ZnI2, or other zinc salt, containing electrolyte. Reactions in the zinc/iodine (polyiodide) redox flow battery are as follows: Zn → Zn2+ + 2e- (E = −0.76 V vs SHE) at the negative electrode (anode), and 3I- → I3
− + 2e− (E = 0.54 V vs SHE) at the positive electrode (cathode) thus yielding a total theoretical potential output as high as ∼1.3 V. The increase of current density could be achieved not only by reducing the viscosity of the electrolyte, thus accelerating charge-carrier transport, but also – by referencing to my experience with the iodine/iodide couple as charge relay for dye-sensitized solar cells – through improvement of the dynamics of charge propagation in highly concentrated iodine/iodide solution via the catalyzed enhancement of rates of electron self-exchange (hopping) between iodine/iodide (polyiodide) redox species as well as by accelerating the interfacial kinetics at electrodes. This can be realized by choosing appropriate electrode materials and through their activation or modification. The electrochemical activities of the redox couples are usually significantly increased through application of nanostructured functionalized carbons. While dispersed in solutions they can improve electron transfers to the redox sites. The proposed chemistry has been first tested using the microelectrode methodology to determine mass-transport (effectively diffusional) coefficients for charge propagation, heterogeneous and homogeneous (electron self-exchange) rates of electron transfers. Unless catalyzed, both interfacial and bulk (self-exchange) electron transfers involving the iodine/iodide redox system are somewhat complicated; there is a need to break the I-I bond in the I3
-or I2 molecule; it has also been well-established that platinum (e.g. when deposited on the counter electrode) induces electron transfers within the iodine/iodide redox system [1]. In the presentation, we are going to explore the respective interfacial (electrocatalytic) phenomena on nanostructured metal oxides (e.g. zirconia), in addition to traces of expensive platinum or palladium nanoparticles (provided that catalytic centers are three-dimensionally distributed in the electrolyte phase), and we will utilize them to enhance iodine/iodide electron transfers to develop a new generation of redox mediators or ultra-fast components of redox electrolytes. Our results show that the catalyzed iodine/iodide system can reach extremely high electron self-exchange rates, namely on the level of
109 – 1010 mol-1 dm3 s-1
.

[1] I.A. Rutkowska I.A., M. Marszalek, J. Orlowska, W. Ozimek, S.M. Zakeeruddin, P.J. Kulesza, M. Grätzel, ChemSusChem 8 (2015) 2560-2568.