Investigation into the effect of Si doping on the performance of Sr _(1-y)Ca_yMnO_(3-δ) SOFC cathode materials

摘要

In this paper we report the successful incorporation of silicon into Sr_(1-y)Ca_yMnO_(3-δ) perovskite materials for potential applications in cathodes for solid oxide fuel cells. The Si substitution onto the B site of a ~(29)Si enriched Sr _(1-y)Ca_yMn_(1-x)Si_xO_(3-δ) perovskite system is confirmed by ~(29)Si MAS NMR measurements at low B_0 field. The very large paramagnetic shift (～3000-3500 ppm) and anisotropy (span ～4000 ppm) suggests that the Si~(4+) species experiences both Fermi contact and electron-nuclear dipolar contributions to the paramagnetic interaction with the Mn~(3+/4+) centres. An improvement in the conductivity is observed for low level Si doping, which can be attributed to two factors. The first of these is attributed to the tetrahedral coordination preference of Si leading to the introduction of oxide ion vacancies, and hence a partial reduction of Mn~(4+) to give mixed valence Mn. Secondly, for samples with high Sr levels, the undoped systems adopt a hexagonal perovskite structure containing face sharing of MnO_6 octahedra, while Si doping is shown to help to stabilise the more highly conducting cubic perovskite containing corner linked octahedra. The level of Si, x, required to stabilise the cubic Sr_(1-y)Ca_yMn_(1-x)Si_xO _(3-δ) perovskite in these cases is shown to decrease with increasing Ca content; thus cubic symmetry is achieved at x = 0.05 for the Sr_(0.5)Ca_(0.5)Mn_(1-x)Si_xO _(3-δ) series; x = 0.075 for Sr_(0.7)Ca _(0.3)Mn_(1-x)Si_xO_(3-δ); x = 0.10 for Sr_(0.8)Ca_(0.2)Mn_(1-x)Si_xO _(3-δ); and x = 0.15 for SrMn_(1-x)Si_xO _(3-δ). Composites with 50% Ce_(0.9)Gd_(0.1)O _(1.95) were examined on dense Ce_(0.9)Gd_(0.1)O _91.95) pellets. For all series an improvement in the area specific resistances (ASR) values is observed for the Si-doped samples. Thus these preliminary results show that silicon can be incorporated into perovskite cathode materials and can have a beneficial effect on the performance.