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Enhanced ionic conductivity in $Ce_{0.8}Sm_{0.2}O_{1.9}$: Unique effect of calcium co-doping

Banerjee, Suparna and Devi, Parukuttyamma Sujatha and Topwal, Dinesh and Mandal, Suman and Menon, K (2007) Enhanced ionic conductivity in $Ce_{0.8}Sm_{0.2}O_{1.9}$: Unique effect of calcium co-doping. In: Advanced Functional Materials, 17 (15). pp. 2847-2854.

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Abstract

In order to identify new oxide ion-conducting materials in the ceria family of oxides, the unique effect of co-doping is explored and a novel series of $Ce_{0.8}Sm_{0.2}_xCa_xO_{2-\delta}$ compositions is identified that have enhanced properties compared to the singledoped $Ce_{0.8}Sm_{0.2}O_{1.9}$ and $Ce_{0.8}Ca_{0.2}O_{1.9}$ compositions. Moreover, the superior characteristics of the co-doped $Ce_{0.8}Sm_{0.2-x}-Ca_xO_{2-\delta}$ powders prepared by the mixed-fuel process aid in obtaining 98% dense ceramics upon sintering at $1200^o$C for 6 h.Though a linear increase in conductivity is observed by replacing Sm with Ca, the composition with the maximum amount of Ca and the minimum amount of Sm exhibits a significant improvement in properties compared to the rest in the series. The composition $Ce_{0.80}Sm_{0.05}Ca_{0.15}O_{2-\delta}$ exhibits a conductivity as high as 1.22 \times $10^{-1} Scm^{-1}$ at $700^o$ C with minimum activation energy (0.56 eV) and a superior chemical stability to reduction compared to any of the hitherto known (CaSm) compositions. The absence of $Ce^{III}$, confirmed both from X-ray photoelectron spectroscopy and X-ray absorption spectroscopy, strongly suggests that the observed increase in conductivity is solely due to the oxide ion conductivity and not due to the partial electronic contribution arising from the presence of $Ce^{III}$ and $Ce^{IV}$. To conclude, the experimental results on the $Ce_{0.8}Sm_{0.2-x}Ca_xO_{2-\delta}$ series underscore the unique effect of calcium co-doping in identifying a cost-effective new composition, with a remarkably high conductivity and enhanced chemical stability to reduction, for technological applications.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to John Wiley & Sons, Inc.
Keywords: Calcium; Ceria;Co-doping;Conductivity;ionic;Electrolytes;solid oxide;Nanocrystalline materials;Oxygen vacancies;Samaria.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 25 Nov 2008 07:35
Last Modified: 19 Sep 2010 04:52
URI: http://eprints.iisc.ernet.in/id/eprint/16492

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