A series of silver
(Ag)-modified barium cobalt ferrous niobate (Ba1–x
Co0.7Fe0.2Nb0.1O3‑δ, BCFN) materials were fabricated using a solid-state
method by doping silver cations into the A-site of this perovskite
matrix (Ag-BCFN). The electrochemical analyses indicated that the
Ag-BCFN cathodic catalysts performed superior to the nonmodified catalysts
when applied in intermediate-temperature solid oxide fuel cells (IT-SOFCs).
These Ag-BCFN cathodic catalysts displayed a cubic perovskite structure
(PDF 75-0227, Pm3̅m, α
= 90°) with a high degree of crystallinity, as demonstrated by
X-ray powder diffraction analyses. It was also found that the in situ exsolution of the silver ion (Ag+) occurred,
where 57.9% of doped Ag+ was reduced into metallic Ag particles
with size ranging from 5 to 10 nm, as shown by electron microscopic
analyses. The cerium gadolinium oxide (Ce0.9Gd0.1O2−δ) electrolyte-supported symmetrical half
cell using different Ag-BCFN formulations of Ba1–x
Ag
x
Co0.7Fe0.2Nb0.1O3‑δ as electrodes
showed a polarization resistance as low as 0.233 Ω·cm2 and an exchange current density of 85.336 mA·cm–2 at 650 °C under ambient pressure. The improved
electrochemical kinetics is anticipated to be attributed to two reasons:
doping of ions (Ag+) in the A-site of perovskite and in situ exsolved silver nanoparticles (Ag NPs) along the
edge and on the surface of BCFNs improving the mobile charge and electrical
properties of the material. The remaining Ag+ in the A-site
induced the electron redistribution, whereas the Ag NPs were found
to increase the electrochemically active sites and enable the formation
of a triple-phase boundary. These explanations were confirmed by the
density functional theory study, indicating that Ag-doping processes
lead to a decrease in the formation energy of oxygen vacancies from
1.72 to 1.42 eV upon the partial substitution of Ba2+ by
Ag+ cations.