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Mobile silver ions and glass formation in solid electrolytes

Nature volume 410, pages 1070–1073 (2001)Cite this article

Abstract

Solid electrolytes are a class of materials in which the cationic or anionic constituents are not confined to specific lattice sites, but are essentially free to move throughout the structure. The solid electrolytes AgI and Ag2Se (refs 1, 2, 3, 4, 5, 6, 7) are of interest for their use as additives in network glasses8,9,10,11,12, such as chalcogenides and oxides, because the resulting composite glasses can show high electrical conductivities with potential applications for batteries, sensors and displays. Here we show that these composite glasses can exhibit two distinct types of molecular structures—an intrinsic phase-separation that results in a bimodal distribution of glass transition temperatures, and a microscopically homogeneous network displaying a single glass transition temperature. For the first case, the two transition temperatures correspond to the solid-electrolyte glass phase and the main glass phase (the ‘base glass’), enabling us to show that the glass transition temperatures for the AgI and Ag2Se phases are respectively 75 and 230 °C. Furthermore, we show that the magnitude of the bimodal glass transition temperatures can be quantitatively understood in terms of network connectivity, provided that the Ag+ cations undergo fast-ion motion in the glasses. These results allow us to unambiguously distinguish base glasses in which these additives are homogeneously alloyed from those in which an intrinsic phase separation occurs, and to provide clues to understanding ion-transport behaviour in these superionic conductors.

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Figure 1: MDSC scans of AgI-based systems. A, the endothermic β→α transformation in β-AgI; B, two glass transitions in Ge0.22Se0.78 base glass containing 18.2 mol% AgI; C, two glass transitions in As2Se3 base glass containing 15 mol% AgI.
Figure 2: MDSC scans of Ag2Se-based systems. A, β-Ag2Se showing the β→α transition onset at 133 °C; B, GeSe4 base glass containing 10 mol% Ag2Se, showing two Tg values, one at 180 °C (ascribed to the base glass) and the other at 230 °C (ascribed to Ag2Se glass); C, As2Se3 base glass containing 10 mol% Ag2Se, showing one Tg at 160 °C ascribed to a homogeneously alloyed glass.
Figure 3: The crystal structure of α-Ag2Se and α-AgI.
Figure 4: Variations of the glass transition temperature (Tg) of binary GexSe1-x and SixSe1-x glasses.

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Acknowledgements

We thank D.H. McDaniel, M. Mitkova, D. Georgiev, B. Goodman and M. Micoulaut for discussions. This work was supported by the Solid State Physics Program of the National Science Foundation.

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  1. Department of Electrical & Computer Engineering and Computer Science, University of Cincinnati, Cincinnati, 45221-0030, Ohio, USA

    P. Boolchand & W. J. Bresser

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  1. P. Boolchand
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  2. W. J. Bresser
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Corresponding author

Correspondence to P. Boolchand.

Supplementary information

Figure 1a

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Figure 1b

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Figure shows MDSC scans of (a) (AgI) x(Ge0.22Se0.78)1-x glasses and (b) (Ag2Se)x(GeSe4)1-x glasses at indicated molar content x of respective electrolyte additives. In panel (a), one observes the AgI glass Tg endotherm fraction near 75°C and the transition endotherm fraction near 150°C (indicated by an asterisk) to progressively increase with x. In panel (b), one observes the Ag2Se glass Tg endotherm fraction near 230°C to monotonically increase with x. These results support the suggested Tg assignments made for respective solid-electrolyte glasses.

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Boolchand, P., Bresser, W. Mobile silver ions and glass formation in solid electrolytes. Nature 410, 1070–1073 (2001). https://doi.org/10.1038/35074049

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