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A kind of composite cathode, La
0.58Sr
0.4Co
0.2Fe
0.8O
3−
δ
–Ce
0.8Sm
0.2O
2−
δ
(LSCF–SDC), was presented in this paper. The electrochemical performance of the cathode on the electrolyte of SDC and YSZ coated with a thin SDC (YSZ/SDC) layer was studied by electrochemical impedance spectroscopy (EIS) and cathodic polarization techniques for their potential utilization in the intermediate temperature solid oxide fuel cell (IT-SOFC). Also studied was the relationship between the electro-catalytic characteristics and the electrode microstructure. Results showed that the LSCF–SDC composite electrode performed better on the SDC electrolyte than on the electrolyte of YSZ/SDC. The polarization resistance,
R
p, of the cathode on the SDC electrolyte was 0.23
Ω
cm
2 at 700
°C and 0.067
Ω
cm
2 at 750
°C, much lower than the corresponding
R
p of the same cathode on the YSZ/SDC electrolyte. At 750
°C, the cathodic overpotential of the composite cathode on the SDC electrolyte was 99.7
mV at the current density of 1.0
A
cm
−2.