• Journal of Electrochemical Science and Technology
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• v.8 no.4
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• pp.344-355
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• 2017

In this study, a numerical approach is adopted to investigate the effectiveness factors for distributed electrochemical reactions in thin active reaction layers of solid oxide fuel cells (SOFCs), taking into account the Butler-Volmer reaction kinetics. The mathematical equations for the electrochemical reaction and charge conduction process were formulated by assuming that the active reaction layer has a small thickness, homogeneous microstructure, and high effective electronic conductivity. The effectiveness factor is defined as the ratio of the actual reaction rate (or equivalently, current generation rate) in the active reaction layer to the nominal reaction rate. From extensive numerical calculations, the effectiveness factors were obtained for various charge transfer coefficients of 0.3-0.8. These effectiveness data were then fitted to simple correlation equations, and the resulting correlation coefficients are presented along with estimated magnitude of error.

• Bulletin of the Korean Chemical Society
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• v.19 no.6
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• pp.661-666
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• 1998

Active reaction sites and electrochemical O2 reduction kinetics on La_{1-x}Sr_xMnO_{3+{\delta}} (x=0.1-0.4)/YSZ (yttria-stabilized zirconia) electrodes are investigated in the temperature range of 700-900 ℃ at $Po_2=10^{-3}$-0.21 atm. Results of the steady-state polarization measurements, which are formulated into the Butler-Volmer formalism to extract transfer coefficient values, lead us to conclude that the two-electron charge transfer step to atomically adsorbed oxygen is rate-limiting. The same conclusion is drawn from the $Po_2$-dependent ac impedance measurements, where the exponent m in the relationship of $I_o$ (exchange current density) ∝ $P_{o_{2}}^m$ is analyzed. Chemical analysis is performed on the quenched Mn perovskites to estimate their oxygen stoichiometry factors (δ) at the operating temperature (700-900 ℃). Here, the observed δ turns out to become smaller as both the Sr-doping contents (x) and the measured temperature increase. A comparison between the 8 values and cathodic activity of Mn perovskites reveals that the cathodic transfer coefficients $({\alpha}_c)$ for oxygen reduction reaction are inversely proportional to δ whereas the anodic ones $({\alpha}_a)$ show the opposite trend, reflecting that the surface oxygen vacancies on Mn perovskites actively participate in the $O_2$ reduction reaction. Among the samples of x= 0.1-0.4, the manganite with x=0.4 exhibits the smallest 8 value (even negative), and consistently this electrode shows the highest ${\alpha}_c$ and the best cathodic activity for the oxygen reduction reaction.