Abstract: In the 21st century of rapid development of science, with the gradual depletion of fossil energy, discovery and application of new energy resources have been attracting lots of attention. Thermoelectric technology has become a promising choice. Thermoelectric conversion techno-logy based on thermoelectric materials can convert thermal energy into electrical energy directly. The related devices and systems have the advantages of small size, light weight, strong, non-transmission components, noise-free operation, safety, reliability and easy to control. Thermoelectric dimensionless figure of merit ZT is a parameter to evaluate the thermoelectric performance. ZT=S2σT/κ, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature, and κ is the thermal conductivity. It would have remarkable thermoelectric properties and can be considered for commercial applications if the ZT value is above 1. In recent years, various excellent thermoelectrical materials have been developed and applied. Since the concept of “Phonon liquid electron crystals (PLEC)” was brought up, more and more studies have been devoted to this novel kind of materials due to their feature of super-low thermal conductivity. Cu-S like materials (Cu2S and Cu2Se), as typical PLEC materials which are intrinsic p type semiconductors with very low thermal conductivity, have been taken more researches. As to their structures, both of them can undergo phase transition with increasing temperature. For instance, Cu2S would change to α-Cu2S in 723 K and Cu2Se would become β-Cu2Se in 400 K, both of which are cubic phase with lo-wer thermal conductivity. Especially, in the structure of α-Cu2S, a “liquid sub-lattice” is that S atoms form a rigid sublattice where Cu ions possess liquid-like migration behavior. Liquid sub-lattice disturbs the transverse propagation of lattice phonons strongly, such behavior reduces the number of transverse modes of heat conduction, leads to the decrease of specific heat at constant volume, average phonon velocity and average free path of phonons, and causes low thermal conductivity. Normally, hydrothermal method and precursor method are used to prepare most nanoscale materials with merits of simple operation, low cost, better appearance, and flexibility. In order to gather better thermal properties, we usually apply doping and composite to improve thermal conductivity or resistance further. For example, Te-doped Cu2S forms Cu2S0.52Te0.48 that is a nanoscale mosaic structure. Its ZT achieves 2.1 in 1 000 K. Similarly, S-doped Cu2Se to prepares Cu2Se0.8S0.2, not only can reduces the scattering speed of phonons, but also introduces additional point defect scattering phonons, further reducing the thermal conductivity with the result that ZT reaches 1.65 in 950 K. This paper mainly considers typical PLEC materials, that is, Cu2-xS and Cu2-xSe related thermoelectric materials. The structures and the cha-racteristics are briefly introduced. The progresses of the studies on the preparation methods and thermoelectric properties of these two kinds of materials are reviewed. And the development tendency is further discussed.
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2020, Vol. 34 
