Mechanism of Thermoelectric Performance Enhancement in CaMg₂Bi₂-Based Materials with Different Cation Site Doping

Chemical bonds determine electron and phonon transport in solids. Tailoring chemical bonding in thermoelectric materials causes desirable or compromise thermoelectric transport properties. In this work, taking an example of CaMg₂Bi₂ with covalent and ionic bonds, density functional theory calculations uncover that element Zn, respectively, replacing Ca and Mg sites cause the weakness of ionic and covalent bonding. Electrically, Zn doping at both Ca and Mg sites increases carrier concentration, while the former leads to higher carrier concentration than that of the latter because of its lower vacancy formation energy. Both doping types increase density-of-state effective mass but their mechanisms are different. The Zn doping Ca site induces resonance level in valence band and Zn doping Mg site promotes orbital alignment. Thermally, point defect and the change of phonon dispersion introduced by doping result in pronounced reduction of lattice thermal conductivity. Finally, combining with the further increase of carrier concentration caused by Na doping and the modulation of band structure and the decrease of lattice thermal conductivity caused by Ba doping, a high figure-of-merit ZT of 1.1 at 823 K in Zn doping Ca sample is realized, which is competitive in 1–2–2 Zintl phase thermoelectric systems.