Thermal and chemical expansion of layered oxygen-deficient double perovskites

Abstract

Layered oxygen-deficient double perovskites (ODP) based on the rare-earth elements (REE), barium and 3d-metals (Fe, Co, Cu etc.) are characterized by high values of electrical conductivity and high electrochemical activity in oxygen reduction reaction, and are considered as prospective cathode materials for intermediate-temperature solid oxide fuel cells (SOFC) on the base of proton- and oxygen-ion conducting solid electrolytes (SE). Effective cathode materials should be thermomechanically compatible with materials of SE, which tаkes place when the values of their thermal expansion coefficients (TEC) are close to each other. Due to this the study of thermal expansion of ODP as well as the isotation of different contributions in it (thermal, chemical, spin etc.), is of considerable interest. In this work using dilatometric method the thermal expansion of NdBa1–xSrxFeCo0,5Cu0,5O6−δ (0.0 ≤ х ≤ 1.0) (NBSFCC) ODP was studied using dilatometric method. It was established that the values of average linear thermal expansion coefficient (LTEC) (α) of the samples sharply increased from (15.1–16.2) · 10–6 K–1 at Т < 630–920 K to (18.9–23.5) 10–6 K–1 at Т > 630–920 K due to the evolution of weaklybonded oxygen from the samples. Values of α in the low-temperature region increase with increasing of values of their oxygen nonstoichiometry index (δ), and in the high-temperature one increase with the x increasing due to the increment of chemical contribution in the samples expansion. Based of the results of dilatometry, thermogravimetry, and iodometry, the thermal and chemical contributions in the expansion оn NBSFCC were isolated, and the effect of crystal structure, cationic and anionic composition of NBSFCC ODP on the values of their thermal and linear chemical expansion coefficient (LCEC, αδ ) was investigated. It was found, that LCEC values of the samples sharply increased from (8.6–11.8) · 10–3 at (х < 0.5) to (12.6–15.8) · 10–3 at (х > 0.5) when transition from ordered tetragonal (х < 0.5) to disordered cubic (х > 0.5) phase took place. It was shown, that dependences of LTEC and LCEC of NBSFCC phases on their crystal structure and chemical compositions obtained in this work are in good accordance with the analogous dependences determined earlier for the ODP of other types.