Nouveaux conducteurs ioniques caracterises par une structure a tunnels entrecroises

The ionic conductivity of pyrochlores A_1+α(Ta_1+αW_1?α)O₆ was investigated for A = Na and T1. The thallium compounds are rather good conductors (0.34 ≤ ΔE ≤ 0.40 eV and $\text{5 10}{}^{\mathrm{?8}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}\text{≤}{}^{\mathrm{\sigma }}\text{25°}\text{C}\text{≤ 5.5 10}{}^{\mathrm{?5}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}$); the sodium oxides are poor conductors (0.76 eV ≤ ΔE ≤ 1.48 eV and $\text{10}{}^{\mathrm{?7}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}\text{≤}{}^{\mathrm{\sigma }}\text{500}\text{K}\text{≤ 10}{}^{\mathrm{?5}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}$). The differences between these two classes of pyrochlores are explained in terms of structure. New non-stoechiometric oxides T1_12+x(M_30+xW_3?x)O₉₀, with M = Ta, Nb, and 0 ≤ x ≤ 3, were isolated. They are, like pyrochlores, characterized by an intersecting tunnel structure, which is an intergrowth of pyrochlore and A₂M₇O₁₈ structures. These oxides show ionic conduction properties which are very close to those of pyrochlores: the tantalum oxides are better conductors (0.30 eV ≤ ΔE ≤ 0.37 eV ; $\text{3.6 10}{}^{\mathrm{?7}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}\text{≤}{}^{\mathrm{\sigma }}\text{25°}\text{C}\text{≤ 1.4 10}{}^{\mathrm{?6}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}$) than the niobium oxides (0.36 eV ≤ ΔE ≤ 0.42 eV ; $\text{10}{}^{\mathrm{?7}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}\text{≤}{}^{\mathrm{\sigma }}\text{25°}\text{C}\text{≤ 3.8 10}{}^{\mathrm{?7}}\text{(Θ}\text{cm}\text{)}{}^{\mathrm{?1}}$). The evolution ofionic conduction properties of all these compounds is discussed.