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Quasi-ternary (AgI)x(HgS)0.5−x/2(GeS2)0.5−x/2 glasses, 10−4≤x≤0.6 were studied over a wide composition range covering nearly 4 orders of magnitude in the mobile cation content. The glasses show a remarkable increase of the ionic conductivity by 12 orders of magnitude and exhibit two drastically different ion transport regimes: (i) a power-law critical percolation at x≲0.04, and (ii) a modifier-controlled conductivity, exponentially dependent on x≳0.1. Using Raman spectroscopy and high-energy X-ray diffraction supported by DFT modelling of the Raman spectra we show that the glass network is essentially formed by corner-sharing CS-GeS4/2 tetrahedra. Mercury sulfide in glasses is dimorphic. The majority of Hg species (70% at x<0.2) exist as two-fold coordinated (HgS2/2)n chains. Silver species have mixed (2I+2S) tetrahedral environment forming either edge–sharing ES-Ag2I2S4/2 dimers or corner-sharing (CS-AgI2/2S2/2)n chains. The relationship between the ionic transport and atomic structure of the glasses is discussed.

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