Etude des propriétés d'oxydo-réduction de LSCF par spectroscopie d'impédance électrochimique et voltammétrie cyclique

Abstract : Among perovskite-type oxide materials (ABO3), rare earth doped cobalt ferrites (LSCFs) aroused a lot of interest because of their mixed ionic and electronic conductivity (MIEC) and their high catalytic activity. The objective of this fundamental study was to understand the influence of the microstructure, the LSCF composition and the oxygen partial pressure on the voltammogram shape and on the variation of the series resistance, Rs, as a function of continuous polarization. Thus, the redox properties of LSCF deposited on CGO were studied by cyclic voltammetry and by DC impedance measurements in the temperature range of 300-700 °C and under oxygen partial pressure equal to 0.21 and 1.8 × 10-4 atm. First, we demonstrated the significant effects of the microstructure on the voltammogram shape of the LSCF / CGO electrode. In the case of a dense layer, the voltammograms exhibit symmetrical cathodic and anodic peaks characteristic of an intercalation compound and Rs increases with cathodic polarization. For a porous layer in air, the voltammograms are identical to the polarization curve and Rs do not vary. Then, we have shown that the oxygen partial pressure strongly influences the voltammetric response of the porous material with appearance of cathodic and anodic peaks. The nature of the peaks and their attribution to the change of concentration in vacancies in LSCF were confirmed by a study of simulation of the voltammograms according to microstructural parameters and the oxygen partial pressure. Finally, the study of five LSCF compositions with porous microstructure showed under low p(O2) that cyclic voltammograms are more complex for cobalt-rich LSCF compounds than for iron-rich ones.
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Submitted on : Wednesday, June 5, 2019 - 12:19:20 PM
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Vladyslav Tezyk. Etude des propriétés d'oxydo-réduction de LSCF par spectroscopie d'impédance électrochimique et voltammétrie cyclique. Génie des procédés. Université Grenoble Alpes, 2019. Français. ⟨NNT : 2019GREAI005⟩. ⟨tel-02148206⟩



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