Investigation of the stability of Co-doped apatite ionic conductors in NH3

Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 °C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH3 to the transition metal (Co) doped systems, La9.67Si5CoO26 and La10(Si/Ge)5CoO26.5. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH3 at high temperature and, consequentially, lower the interstitial oxide content. In La9.67Si5CoO26 and La10(Si/Ge)5CoO26.5 reduction of Co occurs as a competing process, favouring lower levels of nitride–oxide substitution.

Graphical AbstractIn reactions between the apatites La9.67Si5CoO26 and La10(Si/Ge)5CoO26.5 and NH3 (g) at temperatures T>500 °C, the partial substitution of the Si and Ge by Co seems to discourage O2−/N3− substitution in favour of the reduction of the metal.Figure optionsDownload as PowerPoint slide