β-FeSi2 has long been investigated as a promising thermoelectric
(TE) material working at high temperatures due to its combining features
of environmental friendliness, good thermal stability, and strong
oxidation resistance. However, the real application of β-FeSi2 is still limited by its low TE figure of merit (zT). In this study, nearly doubled zT in p-type β-FeSi2 has been achieved via synergistically optimizing electrical
and thermal transports. Based on the first-principles calculations,
Al with shallow acceptor transition level and high carrier donation
efficiency is chosen to dope β-FeSi2. Significantly
improved electrical transport, particularly in the low temperature
range, has been obtained in the Al-doped β-FeSi2 system.
The power factor for FeSi1.96Al0.04 at 300 K
is even higher than that of p-type β-FeSi2-based
compounds reported previously at high temperatures. By alloying β-FeSi2 with Os at the Fe sites, we further lower the lattice thermal
conductivity. Fe0.80Os0.20Si1.96Al0.04 possesses the lowest lattice thermal conductivity among
the β-FeSi2 compounds prepared by the equilibrium
method. Finally, a record-high zT value of 0.35 is
obtained for p-type Fe0.80Os0.20Si1.96Al0.04. This study is expected to accelerate the application
of β-FeSi2.