Bi2Te3 thermoelectric materials are utilized for refrigeration for decades, while their application of energy harvesting requires stable thermoelectric and mechanical performances at elevated temperatures. This work reveals that a steady zT of ≈0.85 at 200 to 300 °C can be achieved by doping small amounts of copper iodide (CuI) in Bi2Te2.2Se0.8-silicon carbide (SiC) composites, where SiC nanodispersion enhances the flexural strength. It is found that CuI plays two important roles with atomic Cu/I dopants and CuI precipitates. The Cu/I dopants show a self-tuning behavior due to increasing solubility with increasing temperatures. The increased doping concentration increases electrical conductivity at high temperatures and effectively suppresses the intrinsic excitation. In addition, a large reduction of lattice thermal conductivity is achieved due to the "in situ" CuI nanoprecipitates acting as phonon-scattering centers. Over 60% reduction of bipolar thermal conductivity is achieved, raising the maximum useful temperature of Bi2Te3 for substantially higher efficiency. For module applications, the reported materials are suitable for segmentation with a conventional ingot. This leads to high device ZT values of ≈0.9-1.0 and high efficiency up to 9.2% from 300 to 573 K, which can be of great significance for power generation from waste heat.
Keywords: bismuth‐telluride‐selenide; device figure of merit; self‐tuning; thermoelectrics.