Enhanced Thermoelectric Properties of Cu₂SnSe₃-Based Materials with Ag₂Se Addition

In this work, (Ag, In)-co-doped Cu2SnSe3-based compounds are prepared using a self-propagating high-temperature synthesis process. Ag2Se and as-synthesized (Ag, In)-co-doped Cu2SnSe3-based powders are mixed in a proportion according to the formula of Cu1.85Ag0.15Sn0.91In0.09Se3/x Ag2Se (x = 0, 3, 4, and 5%), which is followed by a subsequent plasma-activated sintering (PAS) to obtain consolidated composite bulks. A sandwich experiment is designed to reveal the evolution of the microstructure and phase composition of the composite samples during the PAS process. We investigate the reaction mechanism between Ag2Se and Cu2SnSe3-based matrix as well as the influence of Ag2Se on the phase composition, microstructure, and thermoelectric transport properties of the composites. Ag2Se addition is proven to be effective to improve Ag solubility in the Cu1.85Ag0.15Sn0.91In0.09Se3 matrix and introduce a CuSe secondary phase and an Ag-rich phase at grain boundaries. The electrical conductivity of Cu1.85Ag0.15Sn0.91In0.09Se3/x Ag2Se (x = 0, 3, 4, and 5%) composites decreases while the Seebeck coefficient increases with increasing Ag2Se addition, resulting in an optimized power factor. Moreover, benefiting from the collective phonon scattering at various defects induced by Ag2Se addition, the composite samples exhibit significantly suppressed lattice thermal conductivity, which reaches as low as 0.11 W m-1 K-1 at 700 K for the x = 5% sample. A peak figure-of-merit (ZT) of 1.26 at 750 K and an average ZT of 0.75 at 300-800 K are obtained for Cu1.85Ag0.15Sn0.91In0.09Se3/5% Ag2Se. This work provides an efficient way to improve average ZT values of Cu2SnSe3-based compounds for promising power generation at intermediate temperatures.