Electrografting As a Versatile Approach to Engineer Porous Electrode Interfaces for Redox Flow Batteries

The intermittent nature of renewable sources can be alleviated by grid-scale energy storage technologies, such as redox flow batteries (RFBs). However, these systems are currently not cost-competitive for widespread deployment. The system costs are linked to stack performance that is limited by kinetic, ohmic and mass-transfer overpotentials as well as materials stability. Carbon fiber-based porous electrodes, ubiquitous in electrochemical reactors, strongly influence these limiting phenomena as they facilitate redox reactions on their surface, conduct electrons, and provide flow paths for reactant transport. Unfortunately, the inherently hydrophobic and inert carbon surface is not optimal for aqueous electrolytes with kinetically sluggish redox couples such as vanadium and iron 1 . In these systems, controlling the surface chemical state of the electrode is vital to attain significant performance gains. Popular strategies to modify surface chemistry are thermal and acid treatments with a general aim to increase the heteroatom content and number of functional groups of the carbon surface 2 . These functional groups increase the surface energy of inherently hydrophobic carbon electrode and can serve as active sites for redox-reactions 3 . However, these treatment strategies can cause embrittlement of the electrode 4 , mass-loss 5 , and the formed functional groups, especially in the case of oxygen, can manifest in multiple chemical forms, hindering proper structure-property relationships to be established. Thus, to correlate the surface chemical state to the battery performance, there is a need to develop methodologies to synthesize homogenous, conformal, and stable interfaces onto three-dimensional porous electrodes 6 . Here we propose electrografting as a surface modification strategy for carbon fiber-based RFB electrodes with a model molecule, taurine. Electrografting is the electrochemical analogue of chemical grafting where covalent bonds are formed between species and the conductive substrate 7 , with an added advantage that the charge transfer reactions responsible for bond formation can be controlled with applied voltage. We selected taurine as a model molecule to graft on carbon cloth electrodes as its amine group can undergo oxidative electrografting and we hypothesize its sulfonic acid group to be beneficial for electrode wetting, allowing coverage of the electrode surface with a thin layer of desired functional groups. We performed diagnostic st