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6 Using Individual Carbon Fiber Electrodes to Quantify Effects of Thermal Activation Electrochemical measurements were also recorded in a 1 M KNO3 solution containing 1 mM K3Fe(CN)6 (Vickers Laboratories Ltd) and 1 mM K4Fe(CN)6 (BDH AnalaR). The diffusion coefficients were calculated from the limiting current reached during the recording of steady- state polarisation curves and is described further in our previous work [188]. The diffusion coefficients were found to be 8.6 × 10-6 cm2 s−1 for Fe(CN)4− and 8.37 × 10-6 cm2 s−1 for 6 Fe(CN)3−. In this chapter, simulations were carried out using the mean value of 8.50 ± 0.05 × 6 10-6 cm2 s−1. Cyclic voltammetry was again recorded at sweep rates of 0.05, 0.1, 0.2, 0.5 and 1 V s-1. Electrochemical impedance spectroscopy (EIS) was recorded at each fiber at open circuit potential, with a 5 mV rms AC perturbation, between 1 MHz and 0.1 Hz frequencies. Calculation of apparent rate constants was carried out using a one-dimensional numerical model for cylindrical electrodes solved using a method of lines approach. A more in depth discussion of the numerical model can be found in Chapter 5. Raman spectra of each carbon fiber surface was obtained and analysed to identify potential differences in the surface chemistry of the different carbon fibers, before and after thermal activation. Raman spectra measurements were performed using an alpha 300R+ confocal Raman microscope (WiTec, Ulm, Germany) equipped with a 532 nm excitation laser. Spectra acquisition were performed as maps scan across carbon fibers fastened onto a glass slide, over a spectral region of -52 to 3789 cm-1, using a 50x air objective and 15 mW laser power. 77PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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