The long-standing popularity of thermoelectric materials has contributed to the creation of various thermoelectric devices and stimulated the development of strategies to improve their thermoelectric performance. In this review, we aim to comprehensively summarize the state-of-the-art strategies for the realization of high-performance thermoelectric materials and devices by establishing the links between synthesis, structural characteristics, properties, underlying chemistry and physics, including structural design (point defects, dislocations, interfaces, inclusions, and pores), multidimensional design (quantum dots/wires, nanoparticles, nanowires, nano- or microbelts, few-layered nanosheets, nano- or microplates, thin films, single crystals, and polycrystalline bulks), and advanced device design (thermoelectric modules, miniature generators and coolers, and flexible thermoelectric generators). The outline of each strategy starts with a concise presentation of their fundamentals and carefully selected examples. In the end, we point out the controversies, challenges, and outlooks toward the future development of thermoelectric materials and devices. Overall, this review will serve to help materials scientists, chemists, and physicists, particularly students and young researchers, in selecting suitable strategies for the improvement of thermoelectrics and potentially other relevant energy conversion technologies.

Advanced Thermoelectric Design: From Materials and Structures to Devices

Thermoelectric generators, capable of directly converting heat into electricity, hold great promise for tackling the ever-increasing energy sustainability issue. The thermoelectric energy conversio...

Advances in thermoelectrics

Routes for high-performance thermoelectric materials

Discovery of thermoelectric materials has long been realized by the Edisonian trial and error approach. However, recent progress in theoretical calculations, including the ability to predict structures of unknown phases along with their thermodynamic stability and functional properties, has enabled the so-called inverse design approach. Compared to the traditional materials discovery, the inverse design approach has the potential to substantially reduce the experimental efforts needed to identify promising compounds with target functionalities. By adopting this approach, here we have discovered several unreported half-Heusler compounds. Among them, the p-type TaFeSb-based half-Heusler demonstrates a record high ZT of ~1.52 at 973 K. Additionally, an ultrahigh average ZT of ~0.93 between 300 and 973 K is achieved. Such an extraordinary thermoelectric performance is further verified by the heat-to-electricity conversion efficiency measurement and a high efficiency of ~11.4% is obtained. Our work demonstrates that the TaFeSb-based half-Heuslers are highly promising for thermoelectric power generation. The discovery of thermodynamically stable thermoelectric materials for power generation has relied on empirical methods that were not effective. Here, the authors apply the inverse design approach to identify and experimentally realize TaFeSb-based half Heuslers with high thermoelectric performance.

Discovery of TaFeSb-based half-Heuslers with high thermoelectric performance

Thermoelectrics (TE), the direct solid-state conversion of waste heat to electricity, is a promising field with potential wide-scale application for power generation. Intrinsic conflicts in the requirements for high electrical conductivity but (a) low thermal conductivity and (b) a large Seebeck coefficient have made enhancing TE performance difficult. Several recent striking advances in the field are reviewed. In regard to the former conflict, notable bottom-up nanostructuring methods for phonon-selective scattering are discovered, namely using nanosheets, dislocations, and most strikingly a process to fabricate nano-micropores leading to a 100% enhancement in the figure of merit (ZT ≈ 1.6) for rare-earth-free skutterudites. Porous materials are hitherto considered as having poor TE performance, so this is a new paradigm. In regard to the latter conflict, nanocomposite materials with hybrid effects and use of magnetism are emerging as novel bottom-up methods to enhance TE. Material informatics efforts to identify high-ZT materials are also reviewed.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/smll.201702013

Novel Principles and Nanostructuring Methods for Enhanced Thermoelectrics.

Recent progress in half-Heusler thermoelectric materials

The 18-electron rule is a widely used criterion in the search for new half-Heusler thermoelectric materials. However, several 19-electron compounds such as NbCoSb have been found to be stable and exhibit thermoelectric properties rivaling state-of-the art materials. Using synchrotron X-ray diffraction and density functional theory calculations, we show that samples with nominal (19-electron) composition NbCoSb actually contain a half-Heusler phase with composition Nb0.84CoSb. The large amount of stable Nb vacancies reduces the overall electron count, which brings the stoichiometry of the compound close to an 18-electron count, and stabilizes the material. Excess electrons beyond 18 electrons provide heavy doping needed to make these good thermoelectric materials. This work demonstrates that considering possible defect chemistry and allowing small variation of electron counting leads to extra degrees of freedom for tailoring thermoelectric properties and exploring new compounds. Here we discuss the 18-elec...

Using the 18-Electron Rule To Understand the Nominal 19-Electron Half-Heusler NbCoSb with Nb Vacancies

A new n-type half-Heusler thermoelectric material NbCoSb

Here we report the thermoelectric properties of NbCoSn-based n-type half-Heuslers (HHs) that were obtained through arc melting, ball milling, and hot pressing process. With 10% Sb substitution at the Sn site, we obtained enhanced n-type properties with a maximum power factor reaching ∼35 μW cm−1 K−2 and figure of merit (ZT) value ∼0.6 in NbCoSn0.9Sb0.1. The ZT is doubled compared to the previous report. In addition, the specific power cost ($ W−1) is decreased by ∼68% comparing to HfNiSn-based n-type HH because of the elimination of Hf.

Lihong Huang

Papers

Recent progress in half-Heusler thermoelectric materials

Using the 18-Electron Rule To Understand the Nominal 19-Electron Half-Heusler NbCoSb with Nb Vacancies

A new n-type half-Heusler thermoelectric material NbCoSb

Enhanced thermoelectric properties of n-type NbCoSn half-Heusler by improving phase purity

Synthesis and thermoelectric properties of n-type half-Heusler compound VCoSb with valence electron count of 19