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essential electrochemical kinetics parameters for this ROM were also extracted (Figure 2d). Using the Randles–Sevcik equation (Equation S1), an experimental diffusion coefficient (D) of 2.10(5) × 10-5 cm2 s-1 and 2.09(4) × 10-5 cm2 s-1 were determined for the C+/C● and C●++/C+ couples, respectively. These values are higher than other known anolytes,29,42,43 and about four times higher than recent catholytes studied, which is an advantage for our DMQA+.28–30,43,44 The electron transfer rate constants (k0) were determined using the Nicholson method (Equation S2, Figures S5-6),45 where the k0 = 2.5(5) × 10-3 cm s-1 for C+/C● redox couple is almost similar to that of the C●++/C+ redox pair k0 = 2.3(1) × 10-3 cm s-1 and both are comparable to recent electrolytes developed for RFB.28,30 The persistent oxidized and reduced species of C+, and their fast and identical electronic kinetics, suggest that this electrolyte is suitable for ORFB application. We then investigated the use of this [4]helicenium ion as electrolyte for symmetric ORFB application. The electrochemical stability of the electrolyte C+ was evaluated by bulk electrolysis charge/discharge cycling using a three-electrode cell modelling a redox flow cell setup. Sanford et al. have shown that similar electrochemical cell designs with organic ROMs have been acceptable test beds for RFBs performance.28 Charge-discharge experiments were performed inside a nitrogen-filled glovebox with a setup inspired by Hansmann et al.31 using a custom-made H-cell with a porous glass frit to separate both compartments. The reference electrode (0.01 M AgNO3/Ag in 0.1 M TBAPF6/ACN solution) with two reticulated vitreous carbon (RVC) electrodes (Duocel®, 100 ppi) were added to complete our test cell (Figure S7). Both sides of the cell were equally filled with a 1.2 mM solution of C+ (0.1 M TBAPF6/ACN) (Figure 3a, “Init.”). In the first instance, mono-electron transfer at 100% capacity charge and discharge cycles (Figure 3a, blue arrows I and II) were performed with a galvanostatic charging of |5| mA with cutoff potentials at -1.64 V and 0.5 V vs Eref. A complete cycle corresponds to a charge step 7PDF Image | Organic Redox Flow Battery Helical Carbeniun Ion
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