High-Temperature Structural and Thermoelectric Study of Argyrodite Ag ₈ GeSe ₆

Argyrodites with a general chemical formula of A ₈ BX ₆ (A = Cu, Ag; B = Si, Ge, Sn; and X = S, Se, and Te) are known for the intimate interplay among mobile ions, electrons, and phonons, which yields rich material physics and materials chemistry phenomena. In particular, the coexistence of fast ionic conduction and promising thermoelectric performance in Ag ₈ GeTe ₆ , Ag ₈ SnSe ₆ , Ag ₈ SiTe ₆ , Ag ₈ SiSe ₆ , and Cu ₈ GeSe ₆ at high temperatures ushered us to their chemical neighbor Ag ₈ GeSe ₆ , whose high-temperature crystal structure and thermoelectric properties are not yet reported. In this work, we have employed a growth-from-the-melt technique followed by hot pressing to prepare polycrystalline Ag ₈ GeSe ₆ samples, on which the crystal structure, micro-morphology, compositional analysis, UV-vis absorption, specific heat, speed of sound, and thermoelectric properties were characterized as a function of the Se-deficiency ratio and temperature. We found that (i) the crystal structure of Ag ₈ GeSe ₆ evolved from orthorhombic at room temperature to face center cubic above 410 K, with a region of phase separations in between; (ii) like other argyrodite 816 phases, Ag ₈ GeSe ₆ exhibited ultralow thermal conductivities over a wide temperature range as the phonon mean free path was down to the order of interatomic spacing; and (iii) varying Se deficiency effectively optimized the carrier concentration and power factor, a figure of merit zT value ∼0.55 was achieved at 923 K in Ag ₈ GeSe _5.88 . These results not only fill a knowledge gap of Ag ₈ GeSe ₆ but also contribute to a comprehensive understanding of 816 phase argyrodites at large.