首页|Alleviated surface calcium segregation and improved electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ cathode: A demonstration of A-site deficiency effect

Alleviated surface calcium segregation and improved electrocatalytic properties of La0.3Ca0.7Fe0.7Cr0.3O3-δ cathode: A demonstration of A-site deficiency effect

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? 2022 Elsevier B.V.The crystal structure, electrical conductivity, thermal expansion behavior and electrocatalytic properties for oxygen reduction reaction of A-site deficient (La0.3Ca0.7)1?xFe0.7Cr0.3O3-δ (x = 0.01–0.05) perovskites were investigated in comparison with their stoichiometric counterpart (x = 0). The tolerance limit of the perovskite structure for A-site deficiency was x = 0.04 or so. The unit cell parameters decreased and oxygen nonstoichiometry (δ) increased with increasing A-site deficiency. The electrocatalytic activity was appreciably improved by introducing an A-site deficiency of x = 0.04, concomitant with a slight decrease of the electrical conductivity and thermal expansion coefficient. The porous electrode with x = 0.04 exhibited a polarization resistance of 0.044 Ω·cm2 at 800 °C, lowered by about 42% compared with the electrode with x = 0. Moreover, the introduction of the A-site deficiency enhanced the stability of the perovskite structure and electrocatalytic activity relative to cathodic polarization. The electrode with x = 0 showed segregation of calcium onto the surface and an increase of the polarization resistance by 0.106 Ω·cm2 after being cathodically polarized under 250 mA·cm-2 at 800 °C for 6 h. In contrast, surface calcium segregation was undetected for the electrode with x = 0.04 after being likewise polarized and the electrocatalytic activity of the polarized A-site deficient electrode was virtually undegraded. The improved stability of the structure and electrocatalytic activity of the A-site deficient electrode was tentatively explained with respect to its defect chemistry.

A-site deficiencyCathodeElectrocatalytic propertiesFerrite chromium perovskitesOxygen reduction reactionSurface calcium segregation

Zhang Z.-X.、Xie X.-B.、Xu Q.、Huang D.-P.、Zhang F.、Chen M.、Zhao K.、Chen D.-C.

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School of Materials Science and Engineering Wuhan University of Technology

School of Materials Science and Energy Engineering Foshan University

2022

Journal of Alloys and Compounds

Journal of Alloys and Compounds

EISCI
ISSN:0925-8388
年,卷(期):2022.924
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