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Nonstoichiometric La(2 - x)GeO(5 - delta) monoclinic oxide as a new fast oxide ion conductor.
Authors:T Ishihara  H Arikawa  T Akbay  H Nishiguchi  Y Takita
Affiliation:Contribution from the Department of Applied Chemistry, Faculty of Engineering, Oita University, Dannoharu 700, Oita 870-1192, Japan.
Abstract:Oxide ion conductivity in La(2)GeO(5)-based oxide was investigated and it was found that La-deficient La(2)GeO(5) exhibits oxide ion conductivity over a wide range of oxygen partial pressure. The crystal structure of La(2)GeO(5) was estimated to be monoclinic with P2(1)/c space group. Conductivity increased with increasing the amount of La deficiency and the maximum value was attained at x = 0.39 in La(2 - x)GeO(5 - delta). The oxide ion transport number in La(2)GeO(5)-based oxide was estimated to be unity by the electromotive force measurement in H(2)-O(2) and N(2)-O(2) gas concentration cells. At a temperature higher than 1000 K, the oxide ion conductivity of La(1.61)GeO(5 - delta) was almost the same as that of La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3 - delta) or Ce(0.85)Gd(0.15)O(2 - delta), which are well-known fast oxide ion conductors. On the other hand, a change in the activation energy for oxide ion conductivity was observed at 973 K, and at intermediate temperature, the oxide ion conductivity of La(1.61)GeO(5 - delta) became much smaller than that of these well-known fast oxide ion conductors. The change in the activation energy of the oxide ion conductivity seems to be caused by a change in the local oxygen vacancy structure. However, doping a small amount of Sr for La in La(2)GeO(5) was effective to stabilize the high-temperature crystal structure to low temperature. Consequently, doping a small amount of Sr increases the oxide ion conductivity of La(2)GeO(5)-based oxide at low temperature.
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