RESUMEN
Half-Heusler alloys are leading contenders for application in thermoelectric generators. However, reproducible synthesis of these materials remains challenging. Here, we have used in situ neutron powder diffraction to monitor the synthesis of TiNiSn from elemental powders, including the impact of intentional excess Ni. This reveals a complex sequence of reactions with an important role for molten phases. The first reaction occurs upon melting of Sn (232 °C), when Ni3Sn4, Ni3Sn2, and Ni3Sn phases form upon heating. Ti remains inert with formation of Ti2Ni and small amounts of half-Heusler TiNi1+ySn only occurring near 600 °C, followed by the emergence of TiNi and full-Heusler TiNi2y'Sn phases. Heusler phase formation is greatly accelerated by a second melting event near 750-800 °C. During annealing at 900 °C, full-Heusler TiNi2y'Sn reacts with TiNi and molten Ti2Sn3 and Sn to form half-Heusler TiNi1+ySn on a timescale of 3-5 h. Increasing the nominal Ni excess leads to increased concentrations of Ni interstitials in the half-Heusler phase and an increased fraction of full-Heusler. The final amount of interstitial Ni is controlled by defect chemistry thermodynamics. In contrast to melt processing, no crystalline Ti-Sn binaries are observed, confirming that the powder route proceeds via a different pathway. This work provides important new fundamental insights in the complex formation mechanism of TiNiSn that can be used for future targeted synthetic design. Analysis of the impact of interstitial Ni on the thermoelectric transport data is also presented.
RESUMEN
TiNiSn is an intensively studied half-Heusler alloy that shows great potential for waste heat recovery. Here, we report on the structures and thermoelectric properties of a series of metal-rich TiNi1+ySn compositions prepared via solid-state reactions and hot pressing. A general relation between the amount of interstitial Ni and lattice parameter is determined from neutron powder diffraction. High-resolution synchrotron X-ray powder diffraction reveals the occurrence of strain broadening upon hot pressing, which is attributed to the metastable arrangement of interstitial Ni. Hall measurements confirm that interstitial Ni causes weak n-type doping and a reduction in carrier mobility, which limits the power factor to 2.5-3 mW m-1 K-2 for these samples. The thermal conductivity was modelled within the Callaway approximation and is quantitively linked to the amount of interstitial Ni, resulting in a predicted value of 12.7 W m-1 K-1 at 323 K for stoichiometric TiNiSn. Interstitial Ni leads to a reduction of the thermal band gap and moves the peak ZT = 0.4 to lower temperatures, thus offering the possibility to engineer a broad ZT plateau. This work adds further insight into the impact of small amounts of interstitial Ni on the thermal and electrical transport of TiNiSn.
RESUMEN
Half-Heusler alloys based on TiNiSn are promising thermoelectric materials characterized by large power factors and good mechanical and thermal stabilities, but they are limited by large thermal conductivities. A variety of strategies have been used to disrupt their thermal transport, including alloying with heavy, generally expensive, elements and nanostructuring, enabling figures of merit, ZT ≥ 1 at elevated temperatures (>773 K). Here, we demonstrate an alternative strategy that is based around the partial segregation of excess Cu leading to grain-by-grain compositional variations, the formation of extruded Cu "wetting layers" between grains, and-most importantly-the presence of statistically distributed interstitials that reduce the thermal conductivity effectively through point-defect scattering. Our best TiNiCuySn (y ≤ 0.1) compositions have a temperature-averaged ZTdevice = 0.3-0.4 and estimated leg power outputs of 6-7 W cm-2 in the 323-773 K temperature range. This is a significant development as these materials were prepared using a straightforward processing method, do not contain any toxic, expensive, or scarce elements, and are therefore promising candidates for large-scale production.