Studies on Effect of Ca-Doping on Structure and Electrochemical Properties of Garnet-type Y3-xCaxFe5O12-δ

Abstract

In this study, effect of Ca-doping on electrical and electrochemical properties of garnet structure Y3-xCaxFe5O12-δ (x ​= ​0, 0.05, 0.1, 0.3, 0.5 and 0.7) was investigated. Cubic-phase (Ia-3d) garnet was prepared through sol-gel method and sintered at 1100 ​°C for 2 ​h in air. Highest oxygen non-stoichiometry (δ ​= ​0.19) was found in x ​= ​0.3 member. X-ray absorption spectroscopy (XAS) confirmed the formation of hole carriers () due to Ca-substitution for Y in Y3Fe5O12. 4-Probe DC measurements showed that electrical conductivity increased with an increase in Ca amount until x ​= ​0.1 (1.58 ​S/cm at 750 ​°C) and then decreased due to decrease in the concentration of the charge carriers. Lowest area specific resistance (ASR) of 1 Ωcm2 was seen at 750 ​°C in air for the symmetrical cell with x ​= ​0.3 garnet-LSGM composite electrode. Studies on pO2 dependent ASR and impedance spectroscopy genetic programming (ISGP) analysis revealed that oxygen dissociation and partial reduction of adsorbed oxygen molecule co-limit the electrochemical performance for oxygen reduction reaction (ORR).

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