Phase stability and lattice thermal conductivity reduction in CoSb3 skutterudites, doped with chalcogen atoms

摘要

We report a significant reduction in the lattice thermal conductivity of the CoSb3 skuttertudites, doped with chalcogen atoms. Te/Se chalcogen atoms doped CoSb3 skutterudite samples (Te0.1Co4Sb12, Se0.1Co4Sb12, Te0.05Se0.05Co4Sb12) are processed by ball milling and spark plasma sintering. X-ray diffraction data combined with energy dispersive X-ray spectra indicate the doping of Te/Se chalcogen atoms in the skutterudite. The temperature dependent X-ray diffraction confirms the stability of the Te/Se doped CoSb3 skutterudite phase and absence of any secondary phase in the temperature range starting from 300 K to 773 K. The Raman spectroscopy reveals that different chalcogen dopant atoms cause different resonant optical vibrational modes between the dopant atom and the host CoSb3 skutterudite lattice. These optical vibrational modes do scatter heat carrying acoustic phonons in a different spectral range. It was found that among the Te/Se chalcogen atoms, Te atoms alter the host CoSb3 skutterudite lattice vibrations to a larger extent than Se atoms, and can potentially scatter more Sb related acoustic phonons. The Debye model of lattice thermal conductivity confirms that the resonant phonon scattering has important contributions to the reduction of lattice thermal conductivity in CoSb3 skutterudites doped with Te/Se chalcogen atoms. Lattice thermal conductivity ～ 0.9 W/mK at 773 K is achieved in Te0.1Co4Sb12 skutterudites, which is the lowest value reported so far in CoSb3 skutterudites, doped with single Te chalcogen atom.