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A-site doping of cobalt-free Ba1-xAxFeO3-δ (A=Ca, Sr) as cathode for proton-conducting ceramic cells

Chenxiao Wang,Kui Liu,Yinghao Wu,Guangjun Zhang,Xuelian Li,Jiaxin Wu,Ruili Sun,Ting Chen,Lang Xu,Shaorong Wang

A-site doping with Ca 2+ , Sr 2+ for the cobalt-free BaFeO 3-δ -based cathode materials for proton-conducting ceramic fuel cells (PCFCs) is studied. The composite Ba 0·8 Ca 0·2 FeO 3-δ (BCF0.2)-BaZr 0.1 Ce 0·7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb) and Ba 0·8 Sr 0·2 FeO 3-δ (BSF0.2)-BZCYYb electrode show polarization resistance (R p ) of 0.156 Ω cm 2 and 0.308 Ω cm 2 at 700 °C, respectively. It is found that the Ca or Sr doping not only benefits oxygen vacancy formation and ion migration but also optimizes the surface oxygen reduction reaction (ORR) process. The density functional theory (DFT) calculations show that the Gibbs energies of *OOH and *OH intermediates are decreased, indicating an enhanced surface ORR. The PCFC with BCF0.2-BZCYYb composite cathode achieves the maximum power density of 299.75 mW cm −2 at 700 °C and shows good stability at 650 °C for 65 h under a constant voltage of 0.75 V. These findings suggest that the BCF0.2-BZCYYb has the potential to serve as cobalt-free cathode materials for PCFCs.