NbFeSb‐based half‐Heusler alloys have been recently identified as promising high‐temperature thermoelectric materials with a figure of merit zT > 1, but their thermal conductivity is still relatively high. Alloying Ta at the Nb site would be highly desirable because the large mass fluctuation between them could effectively scatter phonons and reduce the lattice thermal conductivity. However, practically it is a great challenge due to the high melting point of refractory Ta. Here, the successful synthesis of Ta‐alloyed (Nb1−xTax)0.8Ti0.2FeSb (x = 0 – 0.4) solid solutions with significantly reduced thermal conductivity by levitation melting is reported. Because of the similar atomic sizes and chemistry of Nb and Ta, the solid solutions exhibit almost unaltered electrical properties. As a result, an overall zT enhancement from 300 to 1200 K is realized in the single‐phase Ta‐alloyed solid solutions, and the compounds with x = 0.36 and 0.4 reach a maximum zT of 1.6 at 1200 K. This work also highlights that the isoelectronic substitution by atoms with similar size and chemical nature but large mass difference should reduce the lattice thermal conductivity but maintain good electrical properties in thermoelectric materials, which can be a guide for optimizing the figure of merit by alloying.

Typical 18-electron half-Heusler compounds, ZrNiSn and NbFeSb, have been identified as promising high temperature thermoelectric materials. NbCoSb with nominal 19 valence electrons, which is supposed to be metallic, has recently been reported to also exhibit thermoelectric properties of a heavily doped n-type semiconductor. Here we experimentally demonstrate, for the first time, that This article is protected by copyright. All rights reserved. 2 the nominal 19-electron NbCoSb is actually the composite of 18-electron Nb 0.8+ CoSb (0 ≤ < 0.05) and impurity phases. Single phase Nb 0.8+ CoSb with intrinsic Nb vacancies, following the 18-electron rule, possesses improved thermoelectric performance, and the slight change in the content of Nb vacancies has a profound effect on the thermoelectric properties. The carrier concentration can be controlled by varying the Nb deficiency, and the optimization of the thermoelectric properties can be realized within the narrow pure phase region. Benefiting from the elimination of impurity phases and the optimization of carrier concentration, thermoelectric performance is remarkably enhanced by ~100% and a maximum zT of 0.9 is achieved in Nb 0.83 CoSb at 1123 K. This work expands the family of half-Heusler thermoelectric materials and opens a new avenue for searching for nominal 19electron half-Heusler compounds with intrinsic vacancies as promising thermoelectric materials.

Bulk nanostructuring has been one of the leading strategies employed in the past decade for the optimization of thermoelectric properties by introducing strong grain boundary scattering of low-frequency phonons. However,...

Progress of utilizing conductive polymers and their composites to prepare flexible, smart and self-sustainable supercapacitors for portable/wearable electronics is reviewed.

Forming solid solutions, as an effective strategy to improve thermoelectric performance, has a dilemma that alloy scattering will reduce both the thermal conductivity and carrier mobility. Here, an intuitive way is proposed to decouple the opposite effects, that is, using lanthanide contraction as a design factor to select alloying atoms with large mass fluctuation but small radius difference from the host atoms. Typical half-Heusler alloys, n-type (Zr,Hf)NiSn and p-type (Nb,Ta)FeSb solid solutions, are taken as paradigms to attest the validity of this design strategy, which exhibit greatly suppressed lattice thermal conductivity and maintained carrier mobility. Furthermore, by considering lanthanide contraction, n-type (Zr,Hf)CoSb-based alloys with high zT of ≈1.0 are developed. These results highlight the significance of lanthanide contraction as a design factor in enhancing the thermoelectric performance and reveal the practical potential of (Zr,Hf)CoSb-based half-Heusler compounds due to the matched n-type and p-type thermoelectric performance.

Thermodynamically stable ground state half-Heusler structures are valence balanced irrespective of electron count or stoichiometry.

The discovery of short-range order, associated with diffuse bands in electron diffraction patterns, provides new insights into defective half-Heusler thermoelectric crystals.

Half‐Heusler (HH) compounds have shown great potential in waste heat recovery. Among them, p‐type NbFeSb and n‐type ZrNiSn based alloys have exhibited the best thermoelectric (TE) performance. However, TE devices based on NbFeSb‐based HH compounds are rarely studied. In this work, bulk volumes of p‐type (Nb0.8Ta0.2)0.8Ti0.2FeSb and n‐type Hf0.5Zr0.5NiSn0.98Sb0.02 compounds are successfully prepared with good phase purity, compositional homogeneity, and matchable TE performance. The peak zTs are higher than 1.0 at 973 K for Hf0.5Zr0.5NiSn0.98Sb0.02 and at 1200 K for (Nb0.8Ta0.2)0.8Ti0.2FeSb. Based on an optimal design by a full‐parameters 3D finite element model, a single stage TE module with 8 n‐p HH couples is assembled. A high conversion efficiency of 8.3% and high power density of 2.11 W cm−2 are obtained when hot and cold side temperatures are 997 and 342 K, respectively. Compared to the previous TE module assembled by the same materials, the conversion efficiency is enhanced by 33%, while the power density is almost the same. Given the excellent mechanical robustness and thermal stability, matchable thermal expansion coefficient and TE properties of NbFeSb and ZrNiSn based HH alloys, this work demonstrates their great promise for power generation with both high conversion efficiency and high power density.