A-site doping enabled higher-oxygen-vacancy cobalt-free layered perovskite cathode for higher-performing protonic ceramic fuel cells

Abstract

Cobalt-free layered perovskite as a promising mixed ionic electronic conductor cathode has shown outstanding performance in conventional oxygen-ion conducting solid oxide fuel cells (O–SOFCs), but not in next-generation proton-conducting solid oxide fuel cells (H–SOFCs) due to insufficient oxygen vacancy so far. We propose a facile A-site doping strategy to enable higher-oxygen-vacancy cobalt-free layered perovskite cathode for higher-performing protonic ceramic fuel cells at reduced temperatures. As proof of concept, two different typical A-site doping of mixed-rare-earth Nd and alkali-metal K in PrBaFe1.9Zn0.1O5+δ are chosen as potential H–SOFC cathode materials. Pr0.8Nd0.2BaFe1.9Zn0.1O5+δ (PNBFZ) and PrBa0.9K0.1Fe1.9Zn0.1O5+δ (PBKFZ) layered perovskite cathodes were synthesized using a nitrate-gel combustion method. Both PNBFZ and PBKFZ have a layered perovskite structure and are chemically compatible with protonic BaZr0.1Ce0.7Y0.2O3−δ (BZCY) electrolyte. Both Nd and K doping dramatically improve the electrical conductivities under operation temperatures. Compared with PBKFZ, PNBFZ shows a lower average thermal expansion coefficient (TEC) of 13.9✕10−6 K−1, being thermally compatible with the BZCY electrolyte without cracks. A-site doping in Fe-based layered perovskite cathodes promotes the single-cell output performance by around 100-26% at 550–700 °C, especially for the mixed-rare-earth doped PNBFZ with high peak power densities of 401–650 mW cm−2.