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6 Using Individual Carbon Fiber Electrodes to Quantify Effects of Thermal Activation Unlike analysis of cyclic voltammetry, EIS enables the apparent rate constant to be calculated from a composite parameter 𝛹, without prior knowledge of the fiber diameter. However, similarly to the numerical cyclic voltammetry model the electrochemically active surface area of the electrode is unknown. Therefore, the geometric area is assumed and the resulting values should be considered as apparent, not inherent rate constants. The apparent rate constant can also be calculated from the fitted 𝑅𝑐𝑡 parameter, with the electrode geometric area calculated from the measured length and by assuming the diameter of each fiber electrode is the same as the mean value found for that fiber type from SEM analysis, (Table 6.4). Table 6.4: Rate constant values calculated from EIS measurements. Fiber Type GFE Thermal G100 Thermal C100 Thermal Toray Thermal Rate constant (composite parameter) (cm s-1) 0.12 ± 0.05 0.04 ± 0.01 0.01 ± 0.01 0.004 ± 0.002 Rate constant (charge transfer resistance) (cm s-1) 0.09 ± 0.05 0.02 ± 0.01 0.012 ± 0.008 0.003 ± 0.002 The rate constants calculated from 𝛹 and 𝑅𝑐𝑡 are in good agreement, implying that there are only minor differences between the diameter of the tested fibers and the mean diameter of each fiber type. The average apparent rate constant values for GFE and G100, as calculated by EIS are in very close agreement with those calculated from CVs, Figure 6.4. 86PDF Image | Electron Transfer Kinetics in Redox Flow Batteries
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