Perovskite-type oxides (ABO3) possess beneficial
cathode
characteristics for solid oxide fuel cells because of quick oxide
ion transport through the octahedral structures. However, mixed proton–electron
conducting Co-free perovskites, which extend the electrode reactions
from the electrolyte interface to the whole electrode, are still in
urgent need of development. Herein, the hydration and proton kinetics
in Ce-doped BaFeO3−δ
are
explored by using first-principles calculations. In our study, we
have defined two parameters to characterize the symmetry and investigate
the formation and motion of protons in cathode materials of perovskite
from the perspective of reaction thermodynamics and dynamics. The
results demonstrated that Ce exhibited the most favorable equilibrium
property at a low concentration of 12.5%, characterized by an oxygen
vacancy formation energy of 0.55 eV, hydration energy of −1.06
eV, and a migration energy barrier of 0.15 eV, thereby facilitating
the overall reaction process. The transition state calculation elucidates
the influence of lattice distortion and lattice oxidation environment
on proton migration. Specifically, a decrease in lattice distortion
facilitates proton hydration and reduces proton migration. As lattice
distortion increases, the energy barrier gradually rises from 0.076
to 0.4 eV. Moreover, in crystals with second-class symmetry, reducing
lattice distortion is more favorable for promoting proton migration
than increasing free volume. The reliability of the calculated parameters
is validated through comparison with experimental and computational
studies. This study provides a theoretical foundation for developing
Co-free perovskite cathodes with triple conductivity through doping.