Thermoelectric properties of Co doped TiNiCo_<i>x</i>Sn alloys fabricated by melt spinning

Abstract

Although TiNiSn-based half-Heusler thermoelectric materials obtain high power factors, their high lattice thermal conductivity greatly hinders the improvement of thermoelectric properties. In this work, TiNiCo_<i>x</i>Sn (<i>x</i> = 0–0.05) samples are prepared by melt spinning combined with spark plasma sintering method, and their phase, microstructure and thermoelectric properties are studied. The XRD results show that the main phase of all samples is TiNiSn phase, and no any other impurity phases are found, indicating that the high purity single phase can be prepared by rapid quenching process combined with SPS process. In the solidification process, the large cooling rate (10⁵–10⁶ K/s) is conducive to obtaining the uniform nanocrystalline structure. The grains are closely packed, with grain sizes in a range of 200–600 nm. The grain sizes decrease to 50–400 nm for the Co-doping samples, which indicates that Co doping can reduce the grain size. For the <i>x</i> = 0 sample, the thermal conductivity of the rapid quenching sample is significantly lower than that of bulk sample, with an average decrease of about 17.8%. Compared with the TiNiSn matrix, the Co-doping sample has the thermal conductivity that decreases significantly, and the maximum decrease can reach about 38.9%. The minimum value of lattice thermal conductivity of TiNiCo_<i>x</i>Sn samples is 3.19 W/(m·K). Therefore, Co doping can significantly reduce the <i>κ</i>_l values of TiNiCo_<i>x</i>Sn (<i>x</i> = 0.01–0.05) samples. With the increase of Co doping amount <i>x</i>, n/p transition is observed in the TiNiCo_<i>x</i>Sn samples, resulting in gradually reducing the conductivity and the power factor, and finally deteriorating the electrical transport performance, of which, the TiNiSn sample obtains the highest power factor of 29.56 W/(m·K²) at 700 K. The <i>ZT</i> value decreases with the Co doping amount <i>x</i> increasing, and the maximum <i>ZT</i> value of TiNiSn sample at 900 K is 0.48. This work shows that the thermal conductivity of TiNiSn can be effectively reduced by using the melt spinning process and magnetic Co doping.