Regulating d-band center and d-p orbital alignment to enhance K 2 NiF 4 -type cathode performance for protonic ceramic fuel cells

Abstract Regulating the transition-metal d-band center and metal-oxygen orbital alignment represents a potentially useful approach to improve cathodic oxygen reduction reaction (ORR) kinetics in protonic ceramic fuel cells (PCFCs). Herein, K2NiF4-type La0.5Sr1.5MnO4+δ (LSMO) and Fe-based La0.5Sr1.5FeO4+δ (LSFO) cathodes were investigated to clarify how electronic-structure regulation affects oxygen-defect chemistry, oxygen/proton transport, and proton-involved ORR activity. Density functional theory (DFT) calculations reveal that the work-function difference between LSFO and LSMO is negligible, whereas LSFO possesses a more favorable Fe 3d-O 2p energy alignment. This electronic configuration lowers the energetic cost of oxygen-vacancy formation, improves hydration-related proton incorporation, reduces the proton-hopping barrier, and decreases the free-energy barrier for key ORR intermediates. Experimentally, LSFO exhibits enriched oxygen-vacancy-related surface oxygen species, much higher electronic conductivity, and accelerated oxygen/proton surface exchange and diffusion. PO2/PH2O-dependent electrochemical impedance spectra further confirm that LSFO promotes multiple p-ORR sub-processes, including interfacial charge/proton transfer, oxygen reduction, and surface oxygen transport. Consequently, the optimized LSFO cathode achieves a peak power density of 2.2 W cm-2 and a polarization resistance of 0.04 Ω cm2 at 700 °C, outperforming LSMO and many reported R-P cathodes. Moreover, the LSFO cell exhibits stable operation over 400 h. These results demonstrate that coordinated regulation of the d-band center and d-p orbital alignment is a viable way to design high-performance K2NiF4-type PCFC cathodes.