DOE OSTI2022
Next generation of fuel cells, electrolyzers, and batteries requires higher power, faster kinetics, and larger energy density, which necessitate the use of compositionally complex oxides to achieve multifunctionalities and activity. These compositionally complex oxides may change their phases and structures during an electrochemical process – a so-called “electrochemically driven phase transformation”. The origin for such a phase change has remained obscure. More importantly, there is a need to develop high performance solid oxide fuel cells with an enhanced stability. In this work, the La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) cathode surface is modified by infiltration of Pr 6 O 11 and the power density at 0.8V and 750 °C is improved by 21%. In addition, by replacing the traditional barrier layer Gd 0.2 Ce 0.8 O 1.9 with mixed conducting Pr 0.1 Gd 0.1 Ce 0.8 O 1.9 , the power density increases by 38%. The different mechanism of promotions was investigated by electrochemical impedance spectroscopy. The ohmic resistance is dramatically reduced by applying the PGCO interlayer, and the distribution of relaxation time was used to analyze the mechanism for which the polarization resistance was decreased attributing to the mixed conduction nature in PrO x . An increase of power density at 0.8 V of 0.358 W/cm 2 (71%) is achieved with the implementation of both surface modification and buffer layer engineering. An experimental study and a theoretical analysis were then carried out on phase evolution in praseodymium nickelates. Nickelate-based electrodes show up to 60× greater phase transformation during operation when compared to thermally annealed ones. Theoretical analysis suggests that the presence of a reduced oxygen partial pressure at the interface between the oxygen electrode and the electrolyte is the origin for the phase change in an oxygen electrode. Guided by the theory, an addition of the electronic conduction in the interface layer leads to the significant suppression of phase change, while improving cell performance and performance stability. When an oxygen electrode is under polarization, the oxygen partial pressure at the interface between the oxygen electrode and the electrolyte is lower than that of incoming oxidant. Under a high polarization, the environment at the aforementioned interface may lead to phase transformation of the oxygen electrode. The local oxygen partial pressure is determined by the transport properties at the interfaces. An addition of the electronic conduction in the interface layer, for instance using (Pr,Gd)-doped ceria to replace Gd-doped ceria, results in improved cell performance and performance stability, while the phase transformation is significantly suppressed. This work provides a fundamental understanding of the origin for phase transformation in oxygen electrodes during operation and use this knowledge to develop a high-performance electrode that exhibits improved performance stability.
30 DIRECT ENERGY CONVERSION↗