Kinetics of oxygen reduction at composite electrodes with controlled three-phase boundaries by patterning YSZ column

The oxygen reduction mechanism was investigated at the porous LSM-patterned YSZ composite electrode by employing the ac-impedance spectroscopy and the potentiostatic current transient (PCT) technique. For this purpose, the dense YSZ pellet was patterned by a laser beam, and was then coated with the LSM slurry. The length of three-phase boundaries (TPBs) per unit area l_TPB was effectively controlled by varying the width of the YSZ column. From analyses of the ac-impedance spectra and the cathodic PCTs obtained from the electrodes based upon the modified transmission line model (TLM), it was first experimentally confirmed that the effective migration length l_m decreased with increasing l_TPB under the mixed migration and charge-transfer control. Secondly, as the value of l_TPB increases, the charge-transfer resistance R_ct is decreased to a more extent but the ion migration resistance R_i is reduced to a less extent. Finally, from a comparison of the cathodic PCTs measured on the porous LSM-YSZ composite electrode to those measured on the porous LSM-patterned YSZ composite electrode, the oxygen reduction kinetics at that porous composite electrode was discussed in terms of the steady-state current density i_st and the time to reach the steady-state current density t_st.