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Mixed ionic-electronic conducting (MIEC) ceramics as oxygen transport membranes (OTMs) can provide high oxygen permeation rates at comparably low energy demands. For this purpose, Ba_._Sr_._Co_._Fe_._O___ (BSCF) shows the best performance under ideal operating conditions. Thermal and chemical stability investigations, electrical behavior _(T,pO_,t), and oxygen exchange parameter extraction by means of electrical conductivity relaxation resulted in a far better understanding of the BSCF system.