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Considering nitrogen functionalities, the binding energies around 399 eV, 401 eV and 403 eV correspond to pyridinic, pyrrolic and graphitic or quaternary, respectively. Before treatment with dPEI-containg electrolyte, increases the contribution of C-N functionalities (i.e. 285eV in C1s spectra), also the C-O-C groups and chemisorbed oxygen (i.e. 532 and 533 eV) and an additional peak appears (i.e. 403 eV in N1s spectra) corresponding to quaternary nitrogen. As consequences, the additive introduces functional groups, (i.e. quaternary nitrogen functionalities) into surface electrode. 5.1.1.1 Electrochemical characterization Table 5.3- Electrochemical parameters obtained from cyclic voltammetry (Figure 5.5). 0.15 4.35 3.43 1.27 0.30 0.60 6.01 4.91 1.26 0.29 Firstly, the electrochemical properties of the dPEI additive as well as their dose effect in a positive electrolyte were evaluated using graphite felt. The cyclic voltammetry (CV) is displayed in Figure 5.5 and the related data based on CV analysis is summarized in Table 5.3. As it can be seen, well-defined peaks for anodic and cathodic peak associated with the V(IV)/V(V) redox couple are obtained for all electrolytes tested. Comparing the CV associated with fresh and 0.15, 0.30, and 0.60 % w/v dPEI-containing electrolytes (Figure 5.5a), the current density increase with the increment of the dose additive. This positive effect on the electrochemical properties towards positive reaction is due to the increment of functionalized groups introduced in the surface of the graphite felt electrode. These extra groups introduced in situ for the additive improve the electron transfer process for the oxidation and reduction process of the V(V)/V(IV) redox couple165. Increments up to 33% and 34% of the anodic and cathodic peak current were observed for 0.60% w/v dPEI containing electrolyte, indicating the improvement of the dPEI on the positive reaction kinetics. Moreover, the ratios of anodic peak current to cathodic peak current (Ipa/Ipc) and the peak potential separation for V(IV)/V(V) redox reaction are decreased, implying the dPEI improves the reversibility of positive reaction. dPEI conc. / %w/v Ipa / g A-1 Ipc / g A-1 Ipa/Ipc ΔE / V 0 4.11 3.14 1.31 0.31 0.30 5.06 3.74 1.35 0.29 1.20-2.5 5.21 4.12 1.26 0.30 73PDF Image | Redox Flow Batteries Vanadium to Earth Quinones
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