Herein, highly stable and exceptionally high oxide-ion conducting vanadium- and strontium/calcium-codoped bismuth oxides of Bi_0.893Sr_0.02V_0.087O_1.577 (BSV_0.087O) and Bi_0.893Ca_0.02V_0.087O_1.577 (BCV_0.087O) have been reported. Both materials exhibit conductivity values of ∼10^–3 S/cm at 300 °C, ∼10^–2 S/cm at 400 °C, and ∼10^–1 S/cm at 500 °C. Analysis of X-ray and neutron diffraction data revealed that the materials possess a major rhombohedral (R3m) and a minor cubic (I23) phase. The R3m phase is similar to a fluorite-type superstructure with 3 × 3 × 3 subcells, and the I23 phase is equivalent to the known γ-Bi₂O₃ phase. The results of the Bi L₃-edge X-ray absorption fine structure study show that the Bi local structure is heavily disordered, favoring oxide-ion conduction in both materials. Soft bond valence sum analysis of neutron powder diffraction data uncovers the pathways of the ionic conduction of the R3m and I23 phases. Our results of as-sintered (unaged), 400 °C/100 h, and 600 °C/100 h annealed (aged) samples of BSV_0.087O and BCV_0.087O demonstrate the long-term stability of phase, structure, and conduction properties. High conductivity at low temperatures and long-term stability of both materials make them potential candidates for low-temperature solid oxide fuel cells, oxygen pumps and sensors, and gas separation membrane applications.

中文翻译：

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增强 V-和 Sr/Ca 共掺杂 Bi2O3 陶瓷的相稳定性和氧化物-离子电导率


在此，已经报道了 Bi_0.893Sr_0.02V_0.087O_1.577 （BSV_0.087O） 和 Bi_0.893Ca_0.02V_0.087O_1.577 （BCV_0.087O） 的高度稳定和极高的氧化钒和锶/钙共掺杂氧化铋。两种材料的电导率值在 300 °C 时分别为 ∼^10-3 S/cm、400 °C 时 ∼^10-2 S/cm、500 °C 时 ∼^10-1 S/cm。 对 X 射线和中子衍射数据的分析表明，这些材料具有一个大菱面体 （R3m） 和一个小立方 （I23） 相。R3m 相类似于具有 3 × 3 × 3 个子胞的萤石型上层结构，而 I23 相相当于已知的 γ-Bi₂O₃ 相。Bi L₃ 边缘 X 射线吸收精细结构研究的结果表明，Bi 局部结构严重无序，有利于两种材料中的氧化物离子传导。中子粉衍射数据的软键价和分析揭示了 R3m 和 I23 相的离子传导途径。我们对 BSV_0.087O 和 BCV_0.087O 的烧结（未老化）、400 °C/100 小时和 600 °C/100 小时退火（时效）样品的结果表明，相、结构和传导性能的长期稳定性。这两种材料在低温下的高导电性和长期稳定性使其成为低温固体氧化物燃料电池、氧气泵和传感器以及气体分离膜应用的潜在候选者。