Significant enhancement of figure-of-merit in carbon-reinforced Cu₂Se nanocrystalline solids

Liquid-like ionic conductors in the copper selenide family represent a promising class of thermoelectric materials capable of recycling waste heat into electrical energy with an exemplary figure-of-merit (zT > 1.4) above 800 K. Ion diffusion, however, is enhanced at such high temperatures and drives a non-reversible phase segregation that inhibits practical applications. In tandem, the thermoelectric performance at moderate temperatures (500–750 K) where ion diffusion is less problematic, is not optimal for real-world applications (zT < 1). In this work, we demonstrate that incorporating a small weight fraction of carbon using various carbon sources can significantly enhance the zT of Cu₂Se at both middle and high temperatures. All the carbon-doped Cu₂Se samples exhibit weak temperature dependent zT higher than 1.0 over a broad temperature range from 600 to 900 K, with the 0.6 wt% Super P doped Cu₂Se sample achieving a zT of 1.85 at 900 K. Furthermore, the 0.3 wt% carbon fiber doped Cu₂Se shows zT > 1 for T > 520 K and reaches a record level of zT of ~ 2.4 at 850 K. These values for the carbon doped Cu₂Se are comparable or superior to those for the current state-of-the-art thermoelectric materials. Microstructure studies on graphite incorporated Cu₂Se revealed that graphite nanostructures interspace between Cu₂Se nanoscale grains being responsible for the significantly enhanced zT. The low thermal conductivity in the nanostructured composite is attributed to the high density of interfaces caused by the small grain diameters (30–60 nm), along with the strong acoustic mismatch between Cu₂Se and carbon phonon states which enhances the thermal boundary resistance. This discovery indicates strong prospects for engineering carbon thermoelectric nanocomposites for a range of energy applications.