High pressure phase transitions in proton-conductor SrZrO3–based perovskites

Aneta Slodczyk 1,2Marie-Helene Limage 1Philippe Colomban 1Stephanie Willemin 2,3Beatrice Sala 2,3

1. Lab Dynamique Interaction et Reactivite, CNRS and Univ Paris VI (LADIR), 2 rue Henry Dunant, Thiais 94320, France
2. AREVA NP, Centre Technique, Chalon sur Saone 71328, France
3. Institut Européen des Membranes, Montpellier 34095, France

Abstract

The water electrolysis operating at temperature below 700°C is recently considered as one of the most efficient and economical methods to obtain the hydrogen – future energetic carrier1,2. Prior to the better industrial application it is crucial to well understand the modifications of the host perovskite behaviour induced by the protonic species3. Therefore, the high pressure Raman study of pure, Ln-modified protonated and non-protonated SrZrO3 dense ceramics were performed between 0.1 and 40 GPa using a Diamond Anvil Cell (DAC). The comparison of the Raman spectra shows important differences in the pressure behaviour between the pure and Ln-modified SrZrO3 ceramics. Simultaneously, rather similar sequence of phase transition (orthorhombic Pnma –10 GPa– > pseudo-tetragonal Imma –20 GPa– > tetragonal I4/mcm -35 GPa- > cubic Pm3m) was revealed in the case of Ln-modified samples, both protonated and non-protonated. Note that the lack of abrupt structural differences between protonated and non-protonated samples is very important from the application point of view because preserves the mechanical strength and the long life time. The main differences between the protonated and non-protonated ceramics concern the behaviour of Zr-O stretching mode of the Zr-O6-x octahedron perturbated by neighbouring oxygen vacancies and Ln ions. The high pressure Raman results are compared with the Raman data as the function of high temperature as well as the diffraction and the thermal expansion ones.

1. S. Willemin, O. Lacroix, B. Sala, Ph. Colomban, A. Julbe, A. Ayral, H. Takenouti, J.P. Py, Desalination 200[1-3] (2006) 92.

2. PCT patent WO 2008/152317 A2 (18-12-2008).

3. A. Slodczyk, Ph. Colomban,  D. Lamago, MH. Limage, F. Romain, S. Willemin, B. Sala     Phase transitions in the H+ -conducting perovskite ceramics by the quasi-elastic neutron and high-pressure Raman scattering,  Ionics 14  (2008)  215.

 

Related papers
  1. Proton diffusion in perovskites by Elastic and Quasi-Elastic Neutron Scattering measurement
  2. Raman evaluation of the proton diffusion coefficient in the pressure protonated perovskite electrolytes
  3. Raman intensity : an important tool in the study of nanomaterials and nanostructures

Presentation: Oral at E-MRS Fall Meeting 2009, Symposium G, by Aneta Slodczyk
See On-line Journal of E-MRS Fall Meeting 2009

Submitted: 2009-05-11 11:38
Revised:   2009-06-07 00:48