Abstract

In this paper we report the successful incorporation of silicon into SrFeO3−δ perovskite materials for potential applications as electrode materials for solid oxide fuel cells. It is observed that Si doping leads to a change from a tetragonal cell (with partial ordering of oxygen vacancies) to a cubic one (with the oxygen vacancies disordered). Annealing experiments in 5% H2/95% N2 (up to 800 °C) also showed the stabilization of the cubic form for the Si-doped samples under reducing conditions, suggesting that they may be suitable for both cathode and anode applications. In contrast to the cubic cell of the reduced Si doped system, reduction of undoped SrFeO3−δ leads to the formation of a brownmillerite structure with ordered oxide ion vacancies. SrFe0.90Si0.10O3−δ and SrFe0.85Si0.15O3−δ were analysed by neutron powder diffraction, and the data confirmed the cubic cell, with no long range oxygen vacancy ordering. Mossbauer spectroscopy data were also recorded for SrFe0.90Si0.10O3−δ, and indicated the presence of only Fe3+ and Fe5+ (i.e. disproportionation of Fe4+ to Fe3+ and Fe5+) for such doped samples. Conductivity measurements showed an improvement in the conductivity on Si doping. Composite electrodes with 50% Ce0.9Gd0.1O1.95 were therefore examined on dense Ce0.9Gd0.1O1.95 pellets in two different atmospheres: air and 5% H2/95% N2. In both atmospheres an improvement in the area specific resistance (ASR) values is observed for the Si-doped samples. Thus the results show that silicon can be incorporated into SrFeO3−δ-based materials and can have a beneficial effect on the performance, making them potentially suitable for use as cathode and anode materials in symmetrical SOFCs.

Highlights

  • Perovskite transition metal containing oxides have attracted considerable interest due to potential applications as cathode materials in the eld of Solid Oxide Fuel Cells (SOFCs)

  • The change in cell parameters for these oxyanion doped perovskite materials is a balance between the effect of the smaller size of Si4+ ions, which would be expected to lead to a reduction in cell volume, and the associated reduction of Fe4+ to give a higher concentration of Fe3+, which would be expected to lead to an increase in cell volume

  • Annealing experiments in 5% H2/95% N2 showed the stabilization of the cubic form for the Si-doped samples under reducing conditions, making them potentially suitable for anode applications

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Summary

Introduction

Perovskite transition metal containing oxides have attracted considerable interest due to potential applications as cathode materials in the eld of Solid Oxide Fuel Cells (SOFCs). The approach employed stems from prior observations on the successful incorporation of oxyanions into perovskite-type cuprate superconductors and related phases.[20,21,22,23,24,25,26,27,28] This work demonstrated that the perovskite structure can incorporate signi cant levels of oxyanions (carbonate, borate, nitrate, sulfate, and phosphate) In such samples, C, B, N, P, and S of the oxyanion group were shown to reside on the perovskite B cation site, with the oxide ions of this group lling 3 (C, B, N) – 4 (P, S) of the available 6 oxide ion positions around this site. In addition Si and Fe containing perovskites are of interest in Earth Science, where (Mg, Fe)SiO3, (Ca, Fe)SiO3 and Ca(Si, Fe)O3Àx phases have attracted substantial interest due to their accepted presence in the Earth's interior.[45,46,47,48] Such phases have been traditionally thought to require very high pressure synthesis conditions, and so the work here, showing for the rst time synthesis of an Fe and Si containing perovskite at ambient pressure, is of signi cant relevance to a perovskite chemistry eld in general

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