The impact of lone-pair electrons on the lattice thermal conductivity of the thermoelectric compound CuSbS2

The discovery and design of compounds with intrinsically low thermal conductivity, especially compounds with a special bonding nature and stable crystal structure, is a new direction to broaden the scope of potential thermoelectric (TE) materials. This study revealed unambiguously the origin of the impact of the lone pair electrons on lattice thermal conductivity in Cu–Sb–S compounds by correlating the special bonding on the Sb site with the phonon dispersion spectrum and density of states. By substitution of Sb with the transition metal Fe and group IIIA element Ga without s2 electrons, lone-pair electrons on some of the Sb sites were removed, which created a scenario with opposite influences on lattice thermal conductivity from the loss of lone-pair electrons and gain of alloy scattering. We investigated the competition between the alloy phonon scattering and the extra phonon scattering mechanism linked to lone-pair electrons on trivalent Sb3+ sites in chalcostibite CuSbS2, which is a model system for benchmarking and quantifying the impact of lone-pair electrons on the lattice thermal conductivity of Cu–Sb–S compounds. A significant deviation from the classic alloy model was observed. Along with the impact of the lone-pair electrons on the bonding arrangement and crystal structure, the role of lone-pair electrons in the phonon transport of the TE compound CuSbS2 was well demonstrated and quantified. Two Sb-related quasi-single-frequency vibration modes behaving like localised Einstein harmonic oscillators were discovered and correlated with the bonding circumstance around Sb sites. These results give unequivocal evidence that the trivalent VA atom creates special bonding and vibration modes because of its nonbonding 5s lone-pair electrons.