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The SOEC basically can be thought as a SOFC, working in reverse mode [5]. Therefore, many materials currently studied as potential candidates for SOFC cathode can also be used as anodes in the SOEC.While the solid oxide cell are efficient systems for energy conversion and production of [H.sub.2], the oxygen separation membranes are oxides ceramics with selectivity for the oxygen diffusion allowing the control of oxygen partial pressure in reactivity chambers for selective oxidation of hydrocarbons [3]. Particularly, mixed conductors with high oxide-ion conductivity can be used as oxygen separation membranes without the use of electrodes and external circuit required for a traditional ceramic oxygen pump.Materials selection for these high temperature electrochemical devices involves an iterative design process that eventually becomes specific to the technical requirements and economic considerations. By one hand, in SOCs the critical parameters to the efficiency and operation are the voltages loss associated to ohmic drop in electrolyte and overpotentials on electrodes. By other hand, in oxygen separation membranes the critical issue is the stability of the ceramic membranes in both oxidant and reducing atmospheres. Besides, long term stability is required for both electrochemical devices due to the high working temperature. Therefore, thermodynamic and structural stability, along with chemical compatibility and zero thermal stress should be assured for the materials.Most of the mixed conductors to be used as potential candidates for oxygen electrodes of intermediate temperature SOCs and oxygen separation membranes are transition metal oxides with perovskite or perovskite-related crystal structures exhibiting oxygen non-stoichiometry. The electronic conductivity of mixed conductors is mainly related to the mixed valence of the transition metals whereas the ionic conductivity is due to the presence of mobile oxygen vacancies at high temperatures.It seems evident that the electrode reaction in oxygen electrodes and the oxygen transport in ceramic membranes should be related to the defect structure of the transition metal oxides.The thermal analysis involves powerful techniques allowing the evaluation of the defect structure [10-14] and structural transformations [15, 16] of non-stoichiometric oxides used in combination with data obtained from high temperature XRD. Also it is possible to study, trough thermal analysis, the thermodynamic properties, and the chemical stability of diverse systems [17, 18].
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