Strain-Induced Defect Evolution for the Construction of Porous Cu_2–xSe with Enhanced Thermoelectric Performance

Superionic Cu 2– x Se, with disordered and even liquid-like Cu ions, has been extensively studied as a high efficiency thermoelectric material. However, the relationship between lattice stability and microstructure evolution in Cu 2– x Se under strain, which is crucial for its application, has seldom been explored in previous research. In this study, we investigate the impacts of hydrostatic compression strain on the microstructural evolution and, consequently, its implications for thermoelectric performance. Molecular dynamics (MD) simulations show that high hydrostatic compression strain could induce local diffusion of Cu ions and Se twin evolution, resulting in the breaking and reforming of Cu–Se dynamic bonds and the unstable Se sublattice. The subsequent annealing process of the destabilized structure promoted Se evaporation from the sublattice and resulted in lotus-seedpod-like pores. The reduced sound velocity and intensified phonon scattering, due to pores, lead to a reduction in the lattice thermal conductivity from 0.44 W m –1 K –1 to 0.24 W m –1 K –1 at 800 K, a decrease of approximately 45%, in the porous Cu 1.92 Se sample. These findings reveal the relationship between stability and defect evolution in Cu 2– x Se under high hydrostatic compression, offering a straightforward strategy of defect engineering for designing unique microstructures by leveraging the instability in superionic conductor materials.