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Impedance spectroscopic investigations of Ag 5 Te 2 Cl 0.8 Br 0.2 , a selected representative of the solid solutions Ag 5 Te 2 Cl 1−x Br x  with x = 0 - 1, proved the mixed-conducting property of this class of materials. Two polymorphs are realized in the temperature range of 309 to 410 K, the monoclinic β - phase (space group P2 1 /n) and the tetragonal α-phase (space group I4/mcm) with an order-disorder phase transition temperature of 336 K (DSC). A sharp increase of the total and ionic conductivity can be observed at 337 K, in good accordance with the phase transition temperature. The electronic conductivity exceeds the ionic conductivity by approximately one order of magnitude over a wide range of temperature. Conductivities are σ ion  = 6.9×10 −5  (309 K) and σ tot  = 4.80×10 −4  Ω −1  cm −1  (310 K) for β -Ag 5 Te 2 Cl 0.8 Br 0.2  and σ ion  = 1.6×10 −2  (395 K) and σ tot  = 1.73×10 −1  Ω −1  cm −1  (394 K) for α-Ag 5 Te 2 Cl 0.8 Br 0.2 .

Electrochemical Properties of Ag 5 Te 2 Cl 0.8 Br 0.2 , a Representative of the Solid Solutions Ag 5 Te 2 Cl 1–x Br x