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Thermoelectric properties, efficiency and thermal expansion of ZrNiSn half-Heusler by first-principles calculations

In this work, we try to understand the experimental thermoelectric (TE) properties of a ZrNiSn sample with DFT and semiclassical transport calculations using SCAN functional. SCAN and mBJ provide the same band gap $E_{g}$ of $\sim$0.54 eV. This $E_{g}$ is found to be inadequate to explain the experimental data. The better explanation of experimental Seebeck coefficient $S$ is done by considering $E_{g}$ of 0.18 eV which suggests the non-stoichiometry and/or disorder in the sample. Further improvement in the $S$ is done by the inclusion of temperature dependence on chemical potential. In order to look for the possible enhanced TE properties obtainable in ZrNiSn with $E_{g}$ of $\sim$0.54 eV, power factor and optimal carrier concentrations are calculated. The optimal electron and hole concentrations required to attain highest power factors are $\sim$7.6x10$^{19}$ cm$^{-3}$ and $\sim$1.5x10$^{21}$ cm$^{-3}$, respectively. The maximum figure of merit $ZT$ calculated at 1200 K for n-type and p-type ZrNiSn are $\sim$0.6 and $\sim$0.7, respectively. The % efficiency obtained for n-type ZrNiSn is $\sim$5.1 % while for p-type ZrNiSn is $\sim$6.1 %. The $ZT$ are expected to be further enhanced to $\sim$1.2 (n-type) and $\sim$1.4 (p-type) at 1200 K by doping with heavy elements for thermal conductivity reduction. The phonon properties are also studied by calculating dispersion, total and partial density of states. The calculated Debye temperature of 382 K is in good agreement with experimental value of 398 K. The thermal expansion behaviour in ZrNiSn is studied under quasi-harmonic approximation. The average linear thermal expansion coefficient $α_{ave}(T)$ of $\sim$7.8x10$^{-6}$ K$^{-1}$ calculated in our work is quite close to the experimental values.