Theoretical Understanding of thermoelectric energy conversion efficiency in Lead-Free halide double perovskites showing intrinsic defect tolerance

Abstract

Thermoelectric devices based on the Seebeck effect can directly convert waste heat to electricity, but the demand for better thermoelectric materials remains unfulfilled. The lead-free halide double perovskites have recently shown promises for their stability and environment-friendly nature, but impacts from intrinsic defects (vacancies and anti-sites) on their thermoelectric performance remains elusive. Combing first-principle calculations, the Boltzmann transport theory, and the defect formation theory, we investigate the thermoelectric properties of lead-free double perovskite Cs2NaInCl6, taking the intrinsic defects into consideration. Our results demonstrate that the pristine Cs2NaInCl6 presents thermodynamic, mechanical, and dynamic stability. The band edges are mainly comprised of the electrons from In and Cl atoms. Furthermore, the double perovskite has an ultra-low lattice thermal conductivity and a high Seebeck coefficient, while showing a small charge carrier relaxation time and electric conductivity. Promisingly, the maximum ZT values can reach as high as ∼ 1.36 and ∼ 1.44 at 800 K temperature, respectively, with optimal extrinsic carrier concentrations of ∼ 1.9 × 1019 and 5.8 × 1020 cm−3 for N- and P-type carriers (holes and electrons), and the maximum power generation efficiency can reach ∼ 14% (for P-type) when the hot-side temperature is 800 K. Among various intrinsic defect types, we determine the preferable defect types in Cs2NaInCl6 based on the minimal defect formation energy criteria. The free carriers can be switched from N- to P-type under these two preferable defects, respectively, with Cl and Na vacancies. Even under a very high defect concentration of 2.1 × 1019/cm3 considered here, the extra carrier concentrations induced by the defects are only ∼ 1017 cm−3 at 800 K, showing strong defect tolerance in carrier concentration. This work suggests that lead-free halide double perovskites are promising thermoelectric materials, and they show strong intrinsic defect tolerance that prevents a negative impact on the extrinsic doping-controlled carrier concentrations.