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Simultaneously optimizing electrical and thermal transport properties of bulk thermoelectric materials remains a key challenge due to the conflicting combination of material traits. Here, we have explored the electrical and thermal transport features of In-filled CoSb 3  through X-ray absorption fine structure, X-ray photoemission spectra, transport measurement and theoretical calculation. The results provide evidence of three types of coexisting multi-localization transport behaviours in the material; these are heat-carrying phonon-localized resonant scattering, accelerated electron movement and increase in density of states near the Fermi level. The 5 p -orbital hybridization between In and Sb is discovered in the In-filled CoSb 3  compound, which results in a charge transfer from Sb to In and the enhancement of  p–d  orbital hybridization between Co and Sb. Our work demonstrates that the electrical and thermal properties of filled skutterudite bulk thermoelectric materials can be simultaneously optimized through the three types of coexisting multi-localization transport behaviours in an independent way.

Multi-localization transport behaviour in bulk thermoelectric materials