Thermodynamic and kinetic considerations for Bi2O3-based electrolytes

Kuan Zong Fung, Hyun Deok Baek, Anil V. Virkar

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65 Citations (Scopus)


Development of bismuth oxide containing solid electrolytes for potential use in solid oxide fuel cells is the principal objective of this work. Bismuth-oxide-based solid electrolytes containing alkaline-earth or rare-earth oxides are known to exhibit high ionic conductivity. In the CaO-Bi2O3, SrO-Bi2O3, and BaO-Bi2O3 systems, there exist several compounds. A rhombohedral phase in these systems exhibits high ionic conductivity. Experiments were conducted to assess the thermodynamic stability of these materials in reducing environments. Galvanic cells with alkaline-earth fluorides as electrolytes were constructed for determining activity- composition diagrams in these three systems. Specifically, the activities of the alkaline-earth oxides were measured and those of Bi2O3 were determined by Gibbs-Dunhem intergration. The results indicate that the SrO-saturated rhombohedral phase in the SrO-Bi2O3 systems in more stable than the rhombohedral phase in the other two systems. The addition of Y2O3 or rare-earth oxides to Bi2O3 is known to stabilize the high-temperature CaF2-type phase to lower temperatures. However, annealing at ≈ 600°C for ≥200 h destabilizes the cubic phase. This destabilization can be suppressed by the addition of aliovalent dopants to suppress the cation interdiffusion. It has been observed that in Y2O3-Bi2O3 and Er2O3-Bi2O3 as well as other rare-earth oxide-Bi2O3 systems, the destabilization can be suppressed by adding ZrO2 as a dopant. This result is rationalized on the premise that cation interstitials are more mobile compared with cation vacancies in cubic Bi2O3. The potential use of Bi2O3-based electrolytes in solid oxide fuel cells is examined. It is shown that by a careful manipulation of conduction properties, the interface partial pressure of oxygen in two-layer electrolytes consisting of a thin layer of zirconia on Bi2O3-based materials can be maintained high enough to prevent electrolyte reduction. Fuel cells nade with such electrolytes should exhibit considerably higher power densities compared with all-zirconia electrolytes.

Original languageEnglish
Pages (from-to)199-211
Number of pages13
JournalSolid State Ionics
Issue number1-3
Publication statusPublished - 1992 May

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • General Materials Science
  • Condensed Matter Physics


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