Structural and microstructural characterization and properties of new phases in the Nd-Sr-Co-(Fe/Mn)-O system as air-electrodes in SOFCs.

New oxides of the (NdSr)n+1MO3n+1 (M = Co and Mn or Fe) series are reported. Compounds of composition NdSrCo0.75Fe0.25O4.10, NdSrCo0.75Mn0.25O4.08 and Nd0.5Sr1.5Co0.75Mn0.25O3.86 are the n = 1 members of the Ruddlesden-Popper homologous series (K2NiF4 structural type) as determined by X-ray diffraction and different transmission electron microscopy techniques. Their crystal structure consists of connected (Co-Fe/Mn)O6 octahedra blocks separated by (Nd/Sr)O rock-salt like layers along the c-axis. Interstitial oxygen atoms or anion vacancies are induced depending on composition. Oxides with interstitial oxygen show good performances as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. The area-specific resistance values of electrodes made of these oxides at 973 K in air are 0.18 Ω cm2 for NdSrCo0.75Fe0.25O4.10 and NdSrCo0.75Mn0.25O4.08 (comparable to the one of the state-of-the-art materials proposed as cathodes in IT-SOFC), and 1.38 Ω cm2 for Nd0.5Sr1.5Co0.75Mn0.25O3.86.

A-site sub-stoichiometry and oxygen vacancies as the origin of the electrical properties of Sr2-yLuNb1-xTixO6-δ perovskite-like materials.

Aliovalent substitution of Nb(5+) by Ti(4+) in Sr2LuNbO6 is limited to 10% of Nb atoms. A full structural determination by NPD confirms this and reveals that the structure is better described as a superstructure of the simple cubic perovskite (as previously reported) with the monoclinic cell 2(1/2)ap× 2(1/2)ap× 2ap and ß≈ 90° (S.G. P21/n). The substituted materials present both oxygen-vacancies induced by charge compensation and Sr-deficiency. Therefore, their formula should be given as Sr2-yLuNb1-xTixO6-δ. Electrical properties can be fully understood considering these compositional defects. The parent compound Sr2LuNbO6 presents low electrical conductivity in air, which improves by more than one order of magnitude upon Ti substitution. In any case, the title oxides show low electrical conductivity in a wide oxygen partial pressure (pO2) range (10(-25) atm ≤pO2≤ 10(-1) atm). At high pO2 the conductivity increases with pO2 due to oxygen-vacancy annihilation and hole creation, according to a general p-type semiconducting mechanism; A-site substoichiometry and Ti-substitution are the origin of this behaviour. In the low pO2 region, the conductivity increases as the oxygen partial pressure decreases. Reduction of cations, Nb(5+) or Ti(4+), supports n-type conduction by electrons and oxygen vacancy creation. For the intermediate pO2 range a low ionic conduction contribution is observed. Although the estimated ionic conductivity is not high in the substituted compounds, the strategy seems to be valid since a significant enhancement of ionic conduction is observed upon aliovalent substitution.

High-pressure investigation of Li2MnSiO4 and Li2CoSiO4 electrode materials for lithium-ion batteries.

In this work, the high-pressure behavior of Pmn2(1)-Li(2)MnSiO(4) and Pbn2(1)-Li(2)CoSiO(4) is followed by in situ X-ray diffraction at room temperature. Bulk moduli are 81 and 95 GPa for Pmn2(1)-Li(2)MnSiO(4) and Pbn2(1)-Li(2)CoSiO(4), respectively. Regardless of the moderate values of the bulk moduli, there is no evidence of any phase transformation up to a pressure of 15 GPa. Pmn2(1)-Li(2)MnSiO(4) shows an unusual expansion of the a lattice parameter upon compression. A density functional theory investigation yields lattice parameter variations and bulk moduli in good agreement with experiments. The calculated data indicate that expansion of the a lattice parameter is inherent to the crystal structure and independent of the nature of the transition-metal atom (M). The absence of pressure-driven phase transformation is likely associated with the incapability of the Li(2)MSiO(4) composition to adopt denser structures while avoiding large electrostatic repulsions.

Lattice dynamics of ß-V2O5: Raman spectroscopic insight into the atomistic structure of a high-pressure vanadium pentoxide polymorph.

We report here the Raman spectrum and lattice dynamics study of a well-crystallized ß-V(2)O(5) material prepared via a high-temperature/high-pressure (HT/HP) route, using α-V(2)O(5) as the precursor. Periodic quantum-chemical density functional theory calculations show good agreement with the experimental results and allow one to assign the observed spectral features to specific vibrational modes in the ß-V(2)O(5) polymorph. Key structure-spectrum relationships are extracted from comparative analysis of the vibrational states of the ß-V(2)O(5) and α-V(2)O(5) structures, and spectral patterns specific to the basic units of the two V(2)O(5) phases are proposed for the first time. Such results open the way for the use of Raman spectroscopy for the structural characterization of vanadium oxide-based host lattices of interest in the field of lithium batteries and help us to greatly understand the atomistic mechanism involved in the α-to-ß phase transition of vanadium pentoxide.