4.6 Article

Sillen-Aurivillius phase bismuth niobium oxychloride, Bi4NbO8Cl, as a new oxide-ion conductor

期刊

JOURNAL OF MATERIALS CHEMISTRY A
卷 10, 期 5, 页码 2550-2558

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta07335d

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资金

  1. Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, through the Japan Society for the Promotion of Science (JSPS) [19H00821]
  2. Grants-in-Aid for Scientific Research [19H00821] Funding Source: KAKEN

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This study investigates the influence of partial substitutions of Bi with Ca2+, Sr2+, Ba2+, La3+, Ga3+ and Sn4+ on the electrical properties of Sillen-Aurivillius phase Bi4NbO8Cl, finding that low valence cations substitutions are effective for increasing electrical conductivity, with Sr2+ substitution being the most effective. The oxygen-ion conductivity in Sr-doped Bi4NbO8Cl mainly occurs along the Bi2O22+ layer, indicating that it is a new family of fast oxide-ion conductors with optimized Sr doping at x = 0.1.
Sillen-Aurivillius phase Bi4NbO8Cl consists of Bi2O2+/NbO3-/Bi2O2+/Cl- layers and oxide-ion conduction is expected to occur in its Bi2O2+ layer. Here, we report the influence of partial substitutions of Bi with Ca2+, Sr2+, Ba2+, La3+, Ga3+ and Sn4+ on the electrical properties. It was found that substitution with low valence cations is effective for increasing electrical conductivity, and in particular, Sr2+ substitution is the most effective for this purpose. The dependence of electrical conductivity on the oxygen partial pressure of a Sr-doped sample is quite low (PO2-0.015) and the optimized amount of Sr doping is x = 0.1 in Bi4-xSrxNbO8-deltaCl. The electromotive force of N2/O2 gas concentration cell is 90% of the theoretical value and the tracer diffusion constant (D) estimated by 18O2 diffusion almost corresponds with that estimated from conductivity. Considering the activation energy of the D value, oxide-ion conductivity in Sillen-Aurivillius phase Bi4NbO8Cl mainly occurs along the Bi2O22+ layer, which indicates that Bi4NbO8Cl is a new family of fast oxide-ion conductors.

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