Enhancing thermoelectric performance of n-type AgBi3S5 through synergistically optimizing the effective mass and carrier mobility

AgBi3S5 is a new n-type thermoelectric material that is environmentally friendly and composed of elements of earth-abundant, non-toxic and high performance-cost ratio. This compound features an intrinsically low thermal conductivity derived from its complex monoclinic structure. However, the terrible electrical transport properties greatly limited the improvement of thermoelectric performance. Most previous studies considered that carrier concentration is the main reason for low electrical conductivity and focused on improving carrier concentration by aliovalent ion doping. In this work, we found that the critical parameter that restricts the electric transport performance of AgBi3S5 was the extremely low carrier mobility instead of the carrier concentration. According to the Pisarenko relationships and density functional theory calculations, Nb doping can sharpen the conduction band of AgBi3S5, which contributes to reducing the effective mass and improving the carrier mobility. With a further increase of the Nb doping content, the conduction band convergence can enlarge the effective mass and preserve the carrier mobility. Combined with the decrease in lattice thermal conductivity due to the intensive phone scattering, a maximum ZT value of ∼0.50 at 773 K was achieved in Ag0.97Nb0.03Bi3S5, which was ∼109.6% higher than that of pure AgBi3S5. This work will stimulate the new exploration of high-performance thermoelectric materials in ternary metal sulfides.