A Stability Study of [Cu(I)(dmby)₂]TFSI in Biopolymer-Based Aqueous Quasi-Solid Electrolytes

In the field of advanced electrical energy conversion and storage, remarkable attention has been given to the development of new, more sustainable electrolytes. In this regard, the combination of redox shuttles with aqueous bio-polymer gels seems to be a valid alternative via which to overcome the typical drawbacks of common liquid electrolytes such as corrosion, volatility or leakage. Despite the promising results obtained so far, redox-active species such as bis(6,6'-dimethyl-2,2'-bipyridine)copper(I) trifluoromethanesulfonylimide, ([Cu(I)(dmby)₂]TFSI), still present inherent challenges associated with their poor water solubility and oxidative lability, which prevents their employment in cheap and sustainable aqueous electrolytes. The present study investigates the stabilization of the Cu(I) complex ([Cu(I)(dmby)₂]TFSI) within two natural hydrogels based on the biopolymers κ-carrageenan and galactomannan, using ZnO nanoparticles as gelling agents. These eco-friendly and biocompatible systems are proposed as potential matrices for quasi-solid electrolytes (QSEs), offering a promising platform for advanced electrolyte design in electrochemical applications. Both hydrogels effectively stabilized and retained the redox species within their networks. In order to shed light on distinct stabilization mechanisms, complementary FTIR and SEM analyses were relevant to reveal the structural rearrangements, specific to each matrix, upon complex incorporation. Furthermore, thermogravimetric analysis confirmed notable thermal resilience in both systems, with the galactomannan-based gel demonstrating enhanced performance. Altogether, this work introduces a novel strategy for embedding copper-based redox couples into gelled electrolytes, paving the way toward their integration in real electrochemical devices, where long-term stability, redox retention, and energy conversion efficiency are critical evaluation criteria.