Redox flow batteries (RFBs) possess a longer cycle life than other secondary batteries owing to their limited electrode deterioration upon charge/discharge cycling. Commercial RFBs use vanadium ions as active materials, resulting in a high cost. Therefore, more abundant and less expensive iron-based complexes are desirable as catholyte active materials for RFBs. However, to develop stable iron-based aqueous electrolytes, precipitation of ferric hydroxides under a mild alkaline condition should be suppressed. One potential strategy is to use polydentate ligands that stabilizes the iron coordination structure owing to a chelating effect. For example, a heptadentated [Fe(DTPA)]2 − (DTPA: diethylenetriaminepentaacetate) shows an excellent cycle stability of 0.029% per cycle as an RFB posolyte.[2] In this study, we further improve the cycle stability of iron-based complexes using an octadentate tetraazacyclododecatetraacetate (DOTA) ligand.The target complex, K[Fe(DOTA)], was prepared by adding FeCl3•6H2O to an aqueous solution of deprotonated DOTA. Single-crystal X-ray structural analysis reveals an eight-coordinated structure of the iron complex. Cyclic voltammetry shows a redox peak at 0.37 V (vs. SHE) for K[Fe(DOTA)], which is higher by 0.088 V than that for K2[Fe(DTPA)] and by 0.12 V than that for K[Fe(EDTA)] (Figure 1). Levich plots obtained by rotating desk electrode measurements reveal the diffusion coefficient of 9.9×10−7 cm2 s−1 and the electron transfer rate constant of 5.0×10−3 cm s−1 for K[Fe(DOTA)] , which are comparable to those of K2[Fe(DTPA)]. UV-Vis spectroscopy shows the aqueous solubility of 0.57 mol L−1 for K[Fe(DOTA)], which is lower than that of K2[Fe(DTPA)] (1.3 mol L−1). The low solubility of K[Fe(DOTA)] should arise from large lattice energy owing to its symmetric structure. Charge/discharge measurements using an H-type cell with 0.10 mol L−1 KCl aqueous solution reveal that K[Fe(DOTA)] exhibits a greater capacity retention rate of 99.973% per cycle than K2[Fe(DTPA)] (99.333%/cycle) (Figure 2). Reference: [1] H. J. Schugar, C. Walling, R. B. Jones, H. B. Gray, J. Am. Chem. Soc. 1967, 89, 3712.[2] S. E. Waters, B. H. Robb, M. P. Marshak, ACS Energy Lett. 2020, 5, 1758. Figure 1
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