ABSTRACT
As a crucial component responsible for the oxygen reduction reaction (ORR), cobalt-rich perovskite-type cathode materials have been extensively investigated in protonic ceramic fuel cell (PCFC). However, their widespread application at a commercial scale is considerably hindered by the high cost and inadequate stability. In response to these weaknesses, the study presents a novel cobalt-free perovskite oxide, Ba0.95La0.05(Fe0.8Zn0.2)0.95O3-δ (BLFZ0.95), with the triple-conducting (H+|O2-|e-) property as an active and robust air electrode for PCFC. The B-site deficiency state contributes significantly to the optimization of crystal and electronic structure, as well as the increase in oxygen vacancy concentration, thus in turn favoring the catalytic capacity. As a result, the as-obtained BLFZ0.95 electrode demonstrates exceptional electrochemical performance at 700 °C, representing extremely low area-specific resistance of 0.04 Ω cm2 in humid air (3 vol.% H2O), extraordinarily high peak power density of 1114 mW cm-2, and improved resistance against CO2 poisoning. Furthermore, the outstanding long-term durability is achieved without visible deterioration in both symmetrical and single cell modes. This study presents a simple but crucial case for rational design of cobalt-free perovskite cathode materials with appreciable performance via B-site deficiency regulation.
ABSTRACT
Developing high-performance and cost-effective cathodes is ever-increasingly vital for the advancement of intermediate-temperature solid oxide fuel cells (IT-SOFCs). To facilitate the popularization of nonprecious metallic and cobalt-free oxygen reduction electrodes, herein, we propose a novel perovskite-based BaFeO3-δ (BF) matrix, Ba0.75Sr0.25Fe0.875Y0.125O3-δ (BSFY), as a highly active cathode for IT-SOFCs. To our satisfaction, the BSFY electrode showcases a low area-specific resistance of 0.063 Ω cm2, as well as a high peak power density of 1288 mW cm-2 at 600 °C, yielding a more than threefold improvement compared to that of its BF counterpart (371 mW cm-2). The long-term durability test highlights its practicability under the IT operating condition. When tested in 10 vol % CO2-containing air, the BSFY electrode exhibits impressive resistance against contaminants within 50 h (<0.4 Ω cm2 with a deterioration rate of â¼0.00011 Ω cm2 min-1). Coupled with its reversible response between pure air and the contaminant, the BSFY cathode is expected to be a promising cobalt-free alternative with high CO2 resistance for IT-SOFCs.
ABSTRACT
Developing low-cost, efficient, and durable cobalt-free perovskite oxides for oxygen reduction reaction at intermediate-to-low temperatures is crucial to enhance the viability of solid oxide fuel cells (SOFCs), a promising ingredient for establishing a more sustainable future. Herein, a highly active and robust cobalt-free perovskite Ba0.75 Sr0.25 Fe0.95 P0.05 O3-δ (BSFP) oxygen electrode via a facile co-doping strategy for intermediate-to-low temperature SOFCs (ILT-SOFCs) is reported by a combined experimental and theoretical approach. Attributed to stable and oxygen defect-rich structure, and remarkable intrinsic oxygen transport kinetics, the BSFP cathode shows exceptional catalytic performance, including record-level power output among iron-based perovskite cathodes (1464 mW cm-2 at 600 °C), low area-specific resistance (≈0.1 Ω cm2 at 600 °C), robust stability both in symmetrical and single cell configurations, and outstanding CO2 tolerance/reversibility. The first-principle calculations validate the role of co-doping of strontium and phosphorus for the high activity and durability. Central to this work is the combined experiment-calculation approach to point to an effective strategy in the development of highly active and stable perovskite-type cathodes for ILT-SOFCs and related applications.
