Impact of Oxygen Deficiency on the Electrochemical Performance of K2 NiF4 -Type (La1-x Srx )2 NiO4-δ Oxygen Electrodes

ChemSusChem. 2017 Feb 8;10(3):600-611. doi: 10.1002/cssc.201601340. Epub 2016 Dec 28.

Abstract

Perovskite-related (La1-x Srx )2 NiO4-δ (x=0.5-0.8) phases were explored for possible use as oxygen electrodes in solid electrolyte cells with a main focus on the effect of oxygen deficiency on the electrocatalytic activity. (La1-x Srx )2 NiO4-δ solid solutions were demonstrated to preserve the K2 NiF4 -type tetragonal structure under oxidizing conditions. Acceptor-type substitution by Sr is compensated by the formation of oxygen vacancies and electron holes and progressively increases high-temperature oxygen nonstoichiometry, which reaches as high as δ=0.40 for x=0.8 at 950 °C in air. The electrical conductivity of (La1-x Srx )2 NiO4-δ ceramics at 500-1000 °C and p(O2 )≥10-3 atm is p-type metallic-like. The highest conductivity, 300 S cm-1 at 800 °C in air, is observed for x=0.6. The average thermal expansion coefficients, (14.0-15.4)×10-6 K-1 at 25-900 °C in air, are sufficiently low to ensure the thermomechanical compatibility with common solid electrolytes. The polarization resistance of porous (La1-x Srx )2 NiO4-δ electrodes applied on a Ce0.9 Gd0.1 O2-δ solid electrolyte decreases with increasing Sr concentration in correlation with the concentration of oxygen vacancies in the nickelate lattice and the anticipated level of mixed ionic-electronic conduction. However, this is accompanied by increasing reactivity between the cell components and necessitates the microstructural optimization of the electrode materials to reduce the electrode fabrication temperature.

Keywords: ceramics; electrochemistry; fuel cells; layered compounds; nonstoichiometric compounds.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Calcium Compounds / chemistry*
  • Electric Conductivity
  • Electrochemistry
  • Electrodes
  • Oxides / chemistry*
  • Oxygen / chemistry*
  • Temperature*
  • Titanium / chemistry*

Substances

  • Calcium Compounds
  • Oxides
  • perovskite
  • Titanium
  • Oxygen