TY - JOUR
T1 - All-halide superionic glasses
AU - Liu, Changle
AU - Sundar, H. G.K.
AU - Angell, C. A.
N1 - Funding Information:
This work has been supported primarily by the Office of Naval Research under Contract No. N84K0289. The work on PbC12-containing systems was performed under the auspices of the Department of Energy under Grant No. DE-FG02-84ER45102.
PY - 1986/1
Y1 - 1986/1
N2 - To date all the highest-conducting Ag+ and alkali cation glasses have involved admixture of a halide, usually the iodide, with some oxyanion salt of the same cation. In this paper we report cases where the oxyanion can be omitted. Instead, a second cation (Cs+ or Rb+) is introduced to provide, together with a mixture of anions, the inmobile quasi-lattice through which the mobile cations, Ag+ or Cu+, can migrate. The materials are evidently vitreous state analogs of the well-known superionic crystals CsAg4I5 and RbCu4I5. In these new systems, conductivities at 25°C can reach record values. Glass transition temperatures, however, are lower than for oxyanion- containing glasses of the same conductivity. Since they contain only heavy monovalent ions, the far IR transparency of the new glasses is unprecedented. The characteristics of stress relaxation for both electrical and mechanical stresses are studied and are compared with those of the oxyanion + halide glasses. The all-halide glasses show less exponential relaxation (broader distributions of relaxation times) despite equivalence of all Ag+. They nevertheless show smaller deviations from the Arrhenius law in their temperature dependences.
AB - To date all the highest-conducting Ag+ and alkali cation glasses have involved admixture of a halide, usually the iodide, with some oxyanion salt of the same cation. In this paper we report cases where the oxyanion can be omitted. Instead, a second cation (Cs+ or Rb+) is introduced to provide, together with a mixture of anions, the inmobile quasi-lattice through which the mobile cations, Ag+ or Cu+, can migrate. The materials are evidently vitreous state analogs of the well-known superionic crystals CsAg4I5 and RbCu4I5. In these new systems, conductivities at 25°C can reach record values. Glass transition temperatures, however, are lower than for oxyanion- containing glasses of the same conductivity. Since they contain only heavy monovalent ions, the far IR transparency of the new glasses is unprecedented. The characteristics of stress relaxation for both electrical and mechanical stresses are studied and are compared with those of the oxyanion + halide glasses. The all-halide glasses show less exponential relaxation (broader distributions of relaxation times) despite equivalence of all Ag+. They nevertheless show smaller deviations from the Arrhenius law in their temperature dependences.
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U2 - 10.1016/0167-2738(86)90157-8
DO - 10.1016/0167-2738(86)90157-8
M3 - Article
AN - SCOPUS:0021896459
SN - 0167-2738
VL - 18-19
SP - 442
EP - 448
JO - Solid State Ionics
JF - Solid State Ionics
IS - PART 1
ER -