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The structure of samarium-doped ceria (CeO2-Sm2O3) transforms from fluorite to cubic and then monoclinic phases. Nanodomain growth, not phase separation, drives this transformation, impacting oxygen vacancy ordering.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Nanotechnology

Background:

  • Ceria (CeO2) is a key material for solid oxide fuel cell electrolytes.
  • Doping ceria with rare earth oxides like samarium oxide (Sm2O3) enhances ionic conductivity.
  • Understanding the structural evolution in doped ceria is crucial for optimizing its performance.

Purpose of the Study:

  • To investigate the structural transformations in the CeO2-Sm2O3 system.
  • To elucidate the local, mesoscopic, and average structure evolution with Sm doping.
  • To understand the mechanism of phase transitions and its impact on oxygen vacancy ordering.

Main Methods:

  • High-resolution synchrotron powder diffraction.
  • Pair distribution function (PDF) analysis.
  • Combined analysis of local and average structure.

Main Results:

  • CeO2 undergoes two phase transformations with Sm doping: fluorite to cubic (C-type) and then to monoclinic (B-type).
  • A miscibility gap exists between C-type and B-type phases, leading to long-range phase separation.
  • No miscibility gap was observed between fluorite and C-type phases; transformation occurs via C-type nanodomain growth within the fluorite matrix.
  • Oxygen vacancy ordering was observed as a consequence of this nanostructure formation, potentially hindering fuel cell applications.

Conclusions:

  • The structural evolution in CeO2-Sm2O3 is driven by nanodomain growth rather than long-range phase separation for the fluorite to C-type transition.
  • Oxygen vacancy ordering induced by nanostructuring can negatively affect the performance of doped ceria electrolytes.
  • These findings provide insights into structure-property relationships in doped ceria systems relevant to fuel cell technology.