High Thermoelectric Performance of CaMg2Bi2 Enabled by Dynamic Doping and Orbital Alignment

Abstract Substantial progress in improving the thermoelectric performance of CaMg 2 Bi 2 ‐based materials has been made, yet existing reports barely discuss the effect of intrinsic Bi impurity on the transport properties. In this study, the first‐principles calculation shows that the Bi‐rich environment associated with Bi impurities facilitates the reduction of cation vacancy formation energy and then increases the carrier concentration. In addition, in the samples containing Bi impurity, a dynamic doping behavior caused by the redissolving of Bi second phase into the matrix with increasing temperature is identified experimentally, which force the carrier concentration to approach the optimal carrier concentration n H,opt , leading to a more than a 5 times enhancement of the figure‐of‐merit (ZT) compared to the single‐phase CaMg 2 Bi 1.94 . Moreover, by doping Ba and Yb on the Ca Site, orbital alignment is realized and phonon scattering is also enhanced. The synergistical optimization of electrical and thermal transportation brings a peak ZT of 1.24 at 873 K and a record ZT ave of 0.86 (300–873 K) in (Ca 0.5 Yb 0.25 Ba 0.25 ) 0.995 Na 0.005 Mg 2 Bi 1.98 sample.