State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry & Chemical Engineering, Nanjing University of Technology, No. 5 Xin Mofan Road, Nanjing 210009, PR China.
ChemSusChem. 2012 Oct;5(10):2023-31. doi: 10.1002/cssc.201200264. Epub 2012 Aug 27.
It is generally recognized that the phase transition of a perovskite may be detrimental to the connection between cathode and electrolyte. Moreover, certain phase transitions may induce the formation of poor electronic and ionic conducting phase(s), thereby lowering the electrochemical performance of the cathode. Here, we present a study on the phase transition of a cobalt-free perovskite (SrNb(0.1)Fe(0.9)O(3-δ), SNF) and evaluate its effect on the electrochemical performance of the fuel cell. SNF exists as a primitive perovskite structure with space group P4mm (99) at room temperature. As evidenced by in situ high-temperature X-ray diffraction measurements over the temperature range of 600 to 1000 °C, SNF undergoes a transformation to a tetragonal structure with a space group I4/m (87). This phase transition is accompanied by a moderate change in the volume, allowing a good cathode/electrolyte interface on thermal cycling. According to the electrochemical impedance spectroscopy evaluation, the I4/m phase exhibits positive effects on the cathode's performance, showing the highest oxygen reduction reaction activity of cobalt-free cathodes reported so far. This activity improvement is attributed to enhanced oxygen surface processes.
人们普遍认为钙钛矿的相变可能会对阴极和电解质之间的连接造成损害。此外,某些相变可能会导致形成不良的电子和离子传导相,从而降低阴极的电化学性能。在这里,我们研究了一种无钴钙钛矿(SrNb(0.1)Fe(0.9)O(3-δ),SNF)的相变,并评估了其对燃料电池电化学性能的影响。SNF 在室温下以空间群 P4mm(99)存在于原始钙钛矿结构中。通过在 600 至 1000°C 的温度范围内进行原位高温 X 射线衍射测量,证明 SNF 经历了向具有空间群 I4/m(87)的四方结构的转变。这种相变伴随着体积的适度变化,使得在热循环时能够形成良好的阴极/电解质界面。根据电化学阻抗谱评估,I4/m 相对阴极性能有积极影响,表现出迄今为止报道的无钴阴极中最高的氧还原反应活性。这种活性的提高归因于增强的氧表面过程。