TY - JOUR
T1 - Thermodynamic and kinetic considerations for Bi2O3-based electrolytes
AU - Fung, Kuan Zong
AU - Baek, Hyun Deok
AU - Virkar, Anil V.
N1 - Funding Information:
This work was supported by Gas Research Institute through a subcontract from Ceramatec, Inc. Dr. Daniel A. Scarpiello is the project monitor.
PY - 1992/5
Y1 - 1992/5
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0026865489&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0026865489&partnerID=8YFLogxK
U2 - 10.1016/0167-2738(92)90106-Y
DO - 10.1016/0167-2738(92)90106-Y
M3 - Article
AN - SCOPUS:0026865489
VL - 52
SP - 199
EP - 211
JO - Solid State Ionics
JF - Solid State Ionics
SN - 0167-2738
IS - 1-3
ER -