Y-doped BaZrO (BZY) is currently the most promising proton-conductive ceramic-type electrolyte for application in electrochemical devices, including fuel cells and electrolyzer cells. However, owing to its refractory nature, sintering additives, such as NiO, CuO, or ZnO are commonly added to reduce its high sintering temperature from 1600 °C to approximately 1400 °C. Even without deliberately adding a sintering additive, the NiO anode substrate provides another source of the sintering additive; during the co-sintering process, NiO diffuses from the anode into the BZY electrolyte layer. In this work, a systematic study of the effect of NiO, CuO, and ZnO on the electroconductive properties of BaZr Y O (BZY20) is conducted. The results revealed that the addition of NiO, CuO, or ZnO into BZY20 not only degraded the electrical conductivity but also resulted in enhancement of the hole conduction. Removal of these sintering additives can be realized by post-annealing in hydrogen at a mild temperature of 700 °C, but it is kinetically very slow. Therefore, the addition of NiO, CuO, and ZnO is detrimental to the electroconductive properties of BZY20, and significantly restrict its application as an electrolyte. The development of new sintering additives, new anode catalysts, or new methods for preparing BZY electrolyte-based cells is urgently needed.
Polarization tunability and analysis of X-rays is one of the most advancing features of thirdgeneration synchrotron radiation sources. In order to apply such developments to the observation of magnetic effects, a diffractometer for X-ray magnetic absorption and scattering experiments was constructed on BL39XU at SPring-8. The ef®ciency of the apparatus is clearly demonstrated by several observations of the magnetic effects. In particular, a diamond phase plate plays an essential role in regulating both circular and linear polarization states.
A novel high temperature reduction cleaning (HTRC) process to recover the electrical conductivity of Y-doped barium zirconate electrolytes from Ni contamination.
Mn 3 MC (M=Zn and Ga) perovskite has attracted interest because of a variety of magnetic phase transitions. In this work, we measure temperature and magnetic field dependence of X-ray magnetic circular dichroism (XMCD) at Mn K-edge and discuss effect of second constituent metal on the magnetic states of Mn atoms.The spectrum in Mn 3 ZnC is characterized by a dispersion-type profile. In Mn 3 GaC, intensity of the positive peak at the edge is drastically reduced. The difference originates in charge transfer from Zn or Ga to Mn atoms. Temperature and magnetic field variations of the Mn K-edge XMCD spectrum suggest that orbital magnetic moments are closely related to the magnetic phase transition.
Proton conductive BaZr0.8Y0.2O3−δ (BZY20) is a promising electrolyte candidate with perspective application in electrochemical devices, including fuel cells, electrolyzer cells. Mn, Fe, and Co are commonly incorporated into BZY20, to improve the sinterability (CoO), or due to possible inter‐diffusion by calcining with cathode materials (eg, La1−xSrxMnO3−δ, La1−xSrxCo1−yFeyO3−δ) for cell preparation. This work was performed to investigate the influence of Mn, Fe, and Co on the structural and electrochemical properties of BZY20. As reported in literature, the sinterability of BZY20 was improved by adding CoO. XANES analysis shows that Mn, Fe, and Co are possibly incorporated into the perovskite crystal structure of BZY20, and are partially reduced when the samples were exposed to hydrogen at 600°C for 24 hours. However, through electrochemical analysis, we found that all these three elements decrease both the proton conductivity and transport numbers of proton conduction of BZY20. Therefore, the BZY20 electrolyte should be carefully handled to avoid the incorporation of these transition metal elements, to fabricate the cells with high performance.
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