Macías Javier, Frade Jorge R, Yaremchenko Aleksey A
CICECO-Aveiro Institute of Materials, Department of Materials and Ceramic Engineering, University of Aveiro, 3810-193 Aveiro, Portugal.
Materials (Basel). 2023 Dec 14;16(24):7638. doi: 10.3390/ma16247638.
Perovskite-type Sr(Ti,V)O ceramics are promising anode materials for natural gas- and biogas-fueled solid oxide fuel cells, but the instability of these phases under oxidizing conditions complicates their practical application. The present work explores approaches to the fabrication of strontium titanate-vanadate electrodes from oxidized precursors. Porous ceramics with the nominal composition SrTiVO ( = 0.1-0.3) were prepared in air via a solid state reaction route. Thermal processing at temperatures not exceeding 1100 °C yielded composite ceramics comprising perovskite-type SrTiO, pyrovanadate SrVO and orthovanadate Sr(VO) phases, while increasing firing temperatures to 1250-1440 °C enabled the formation of SrTiVO perovskites. Vanadium was found to substitute into the titanium sublattice predominantly as V, even under oxidizing conditions at elevated temperatures. Both perovskite and composite oxidized ceramics exhibit moderate thermal expansion coefficients in air, 11.1-12.1 ppm/K at 30-1000 °C, and insignificant dimensional changes induced by reduction in a 10%H-N atmosphere. The electrical conductivity of reduced perovskite samples remains comparatively low, ~10 S/cm at 900 °C, whereas the transformation of oxidized vanadate phases into high-conducting SrVO perovskites upon reduction results in enhancement in conductivity, which reaches ~3 S/cm at 900 °C in porous composite ceramics with nominal composition SrTiVO. The electrical performance of the composite is expected to be further improved by optimization of the processing route and microstructure to facilitate the reduction of the oxidized precursor and attain better percolation of the SrVO phase.
钙钛矿型Sr(Ti,V)O陶瓷是用于天然气和沼气燃料固体氧化物燃料电池的有前景的阳极材料,但这些相在氧化条件下的不稳定性使其实际应用变得复杂。目前的工作探索了由氧化前驱体制备钛酸锶 - 钒酸盐电极的方法。通过固态反应路线在空气中制备了标称组成为SrTiVO(= 0.1 - 0.3)的多孔陶瓷。在不超过1100°C的温度下进行热处理得到了包含钙钛矿型SrTiO、焦钒酸盐SrVO和原钒酸盐Sr(VO)相的复合陶瓷,而将烧结温度提高到1250 - 1440°C能够形成SrTiVO钙钛矿。发现即使在高温氧化条件下,钒也主要以V的形式替代钛亚晶格。钙钛矿和复合氧化陶瓷在空气中均表现出适度的热膨胀系数,在30 - 1000°C时为11.1 - 12.1 ppm/K,并且在10%H - N气氛中还原引起的尺寸变化不明显。还原后的钙钛矿样品的电导率仍然相对较低,在900°C时约为10 S/cm,而氧化钒相在还原时转变为高导电的SrVO钙钛矿导致电导率提高,在标称组成为SrTiVO的多孔复合陶瓷中,在900°C时达到约3 S/cm。通过优化加工路线和微观结构以促进氧化前驱体的还原并实现SrVO相更好的渗流,预计复合材料的电性能将进一步提高。