Design of High‐Performance Disordered Half‐Heusler Thermoelectric Materials Using 18‐Electron Rule

Ternary half‐Heusler (HH) alloys display intriguing functionalities ranging from thermoelectric to magnetic and topological properties. For thermoelectric applications, stable HH alloys with a nominal valence electron count (VEC) of 18 per formula or defective HH alloys with a VEC of 17 or 19 are assumed to be promising candidates. Inspired by the pioneering efforts to design a TiFe_0.5Ni_0.5Sb double HH alloy by combining 17‐electron TiFeSb and 19‐electron TiNiSb HH alloys, both high‐performance n‐type and p‐type materials based on the same parent TiFe_0.5Ni_0.5Sb are developed. First‐principles calculation results demonstrate their beneficial band structure having a high band degeneracy that contributes to their large effective mass and thereby maintains their high Seebeck coefficient values. Due to the strong Fe/Ni disorder effect, TiFe_0.5Ni_0.5Sb exhibits a much lower lattice thermal conductivity than does TiCoSb, consistent with very recently reported results. Furthermore, tuning the ratio of Fe and Ni leads to achieving both p‐ and n‐types, and alloying Ti by Hf further enhances the thermoelectric performance significantly. A peak ZT of ≈1 and ≈0.7 at 973 K are achieved in the p‐type and n‐type based on the same parent, respectively, which are beneficial and promising for real applications.     

Nanograined Half‐Heusler Semiconductors as Advanced Thermoelectrics: An Ab Initio High‐Throughput Statistical Study

Nanostructuring has spurred a revival in the field of direct thermoelectric energy conversion. Nanograined materials can now be synthesized with higher figures of merit (ZT) than the bulk counterparts. This leads to increased conversion efficiencies. Despite considerable effort in optimizing the known and discovering the unknown, technology still relies upon a few limited solutions. Here ab initio modeling of ZT is performed for 75 nanograined compounds—the result of accurate distillation with electronic and thermodynamic filtering techniques from the 79 057 half‐Heusler entries available in the AFLOWLIB.org repository. For many of the compounds, the ZTs are markedly above those attainable with nanograined IV and III‐V semiconductors. About 15% of them may even outperform ZT ≈ 2 at high temperatures. This analysis elucidates the origin of the advantageous thermoelectric properties found within this broad material class. Machine learning techniques are used to unveil simple rules determining if a nanograined half‐Heusler compound is likely to be a good thermoelectric given its chemical composition.     

Large Nonclassical Electrostriction in (Y,Nb)‐Stabilized δ‐Bi2O3

Classical electrostriction, describing a second‐order electromechanical response of insulating solids, scales with elastic compliance, S, and inversely with dielectric susceptibility, ε. This behavior, first noted 20 years ago by Robert Newnham, is shown to apply to a wide range of electrostrictors including polymers, glasses, crystalline linear dielectrics, and relaxor ferroelectrics. Electrostriction in fluorite ceramics of (Y, Nb)‐stabilized δ‐Bi₂O₃ is examined with 16%–23% vacant oxygen sites. Given the values of compliance and dielectric susceptibility, the electrostriction coefficients are orders of magnitude larger than those expected from Newnham's scaling law. In ambient temperature nanoindentation measurements, (Y, Nb)‐stabilized δ‐Bi₂O₃ displays primary creep. These findings, which are strikingly similar to those reported for Gd‐doped ceria, support the suggestion that ion conducting ceramics with the fluorite structure, a large concentration of anion vacancies and anelastic behavior, may constitute a previously unknown class of electrostrictors.     

On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr‐Doped CeyCo4Sb12

The beneficial effect of impurity scattering on thermoelectric properties has long been disregarded even though possible improvements in power factor have been suggested by Ioffe more than a half century ago. Here it is theoretically and experimentally demonstrated that proper intensification of ionized impurity scattering to charge carriers can benefit the thermoelectric figure of merit (ZT) by increasing the Seebeck coefficient and decreasing the electronic thermal conductivity. The optimal strength of ionized impurity scattering for maximum ZT depends on the Fermi level and the density of states effective mass. Cr‐doping in Ce_yCo₄Sb₁₂ progressively increases the strength of ionized impurity scattering, and significantly improves the Seebeck coefficient, resulting in high power factors of 45 μW cm^?1 K^?2 with relatively low electrical conductivity. This effect, combined with the increased Ce‐filling fraction and thus decreased lattice thermal conductivity by charge compensation of Cr‐dopant, gives rise to a maximum ZT of 1.3 at 800 K and a large average ZT of 1.1 between 500 and 850 K, ≈30% and ≈20% enhancements as compared with those of Cr‐free sample, respectively. Furthermore, this study also reveals that carrier scattering parameter can be another fundamental degree of freedom to optimize electrical properties and improve thermal‐to‐electricity conversion efficiencies of thermoelectric materials.     

Mg3+δSbxBi2−x Family: A Promising Substitute for the State‐of‐the‐Art n‐Type Thermoelectric Materials near Room Temperature

The Bi₂Te_3?xSe_x family has constituted n‐type state‐of‐the‐art thermoelectric materials near room temperature (RT) for more than half a century, which dominates the active cooling and novel heat harvesting application near RT. However, the drawbacks of a brittle nature and Te‐content restricts the possibility for exploring potential applications. Here, it is shown that the Mg_3+δSb_xBi_2?x family ((ZT)_avg = 1.05) could be a promising substitute for the Bi₂Te_3?xSe_x family ((ZT)_avg = 0.9–1.0) in the temperature range of 50–250 °C based on the comparable thermoelectric performance through a synergistic effect from the tunable bandgap using the alloy effect and the suppressible Mg‐vacancy formation using an interstitial Mn dopant. The former is to shift the optimal thermoelectric performance to near RT, and the latter is helpful to partially decouple the electrical transport and thermal transport in order to get an optimal RT power factor. The positive temperature dependence of the bandgap suggests this family is also a superior medium‐temperature thermoelectric material for the significantly suppressed bipolar effect. Furthermore, a two times higher mechanical toughness, compared with the Bi₂Te_3?xSe_x family, allows for a promising substitute for state‐of‐the‐art n‐type thermoelectric materials near RT.     

Interfacial Reaction Between Nb Foil and n-Type PbTe Thermoelectric Materials During Thermoelectric Contact Fabrication

PbTe is a high-conversion-efficiency thermoelectric (TE) material that is commonly used in space exploration applications. Integration of PbTe in TE devices has a significant impact on the conversion efficiency and reliability of TE devices. Hence, our effort focuses on developing novel approaches for bonding metallic contacts to PbTe to improve device performance and reliability. In this study, pure Nb foil was directly bonded to PbTe-based TE materials to fabricate the hot-side contacts of TE elements using a rapid hot-press. The materials were sintered at 700°C under pressure of 40 MPa for various holding times. We found that a reaction layer of needle-like Nb₃Te₄ mixed with Pb forms at the interface of the Nb/PbTe joints and that Pb is distributed in the gaps of the Nb₃Te₄ grains. We analyze the resulting microstructure and finally calculate the time exponent of the growth kinetics of the Nb₃Te₄ layer. Fracture surface analysis showed that the Nb/PbTe joint fractures at the interface between Nb and Nb₃Te₄ and within the PbTe matrix, indicating that the bonding between Nb and Nb₃Te₄ is weak.     

Achieving zT > 1 in Inexpensive Zintl Phase Ca9Zn4+xSb9 by Phase Boundary Mapping

Complex multinary compounds (ternary, quaternary, and higher) offer countless opportunities for discovering new semiconductors for applications such as photovoltaics and thermoelectrics. However, controlling doping has been a major challenge in complex semiconductors as there are many possibilities for charged intrinsic defects (e.g., vacancies, interstitials, antisite defects) whose energy depends on competing impurity phases. Even in compounds with no apparent deviation from a stoichiometric nominal composition, such defects commonly lead to free carrier concentrations in excess of 10²⁰ cm^?3. Nevertheless, by slightly altering the nominal composition, these defect concentrations can be tuned with small variation of the chemical potentials (composition) of each element. While the variation of chemical composition is undetectable, it is shown that the changes can be inferred by mapping (in nominal composition space) the boundaries where different competing impurity phases form. In the inexpensive Zintl compound Ca₉Zn_4+x Sb₉, the carrier concentrations can be finely tuned within three different three‐phase regions by altering the nominal composition (x = 0.2–0.8), enabling the doubling of thermoelectric performance (zT). Because of the low thermal conductivity, the zT can reach as high as 1.1 at 875 K, which is one of the highest among the earth abundant p‐type thermoelectrics with no ion conducting.     

Efficient Field Emission from Vertically Aligned Cu2O1‐δ(111) Nanostructure Influenced by Oxygen Vacancy

In the architecture described, cuprous oxide (Cu₂O) is tamed to be highly (111) plane oriented nanostructure through adjusting the deposition postulate by glancing angle deposition technique. In the controlled atmosphere oxygen vacancy is introduced into the Cu₂O crystal subsequently fostering an impurity energy state (E_im) close to the conduction band. Our model of Cu₂O electronic structure using density functional theory suggests that oxygen vacancies enhance the electron donating ability because of unshared d‐electrons of Cu atoms (nearest to the vacancy site), allowing to pin the work function energy level around 0.28 eV compared to the bulk. This result is also complemented by Kelvin probe force microscopy analysis and X‐ray photoelectron spectroscopy method. Oxygen vacancy in Cu₂O (Cu₂O_1‐δ) exhibits promising field emission properties with interesting field electron tunneling behavior at different applied fields. The films show very low turn‐on and threshold voltages of value 0.8 and 2.4 V μm^?1 respectively which is influenced by the oxygen vacancy. Here, a correlation between the work function modulation due to the oxygen vacancy and enhancement of field emission of Cu₂O_1–δ nanostructure is demonstrated. This work reveals a promising new vision for Cu₂O as a low power field emitter device.     

Charge‐Compensated Compound Defects in Ga‐containing Thermoelectric Skutterudites

Heavy doping changes an intrinsic semiconductor into a metallic conductor by the introduction of impurity states. However, Ga impurities in thermoelectric skutterudite CoSb₃ with lattice voids provides an example to the contrary. Because of dual‐site occupancy of the single Ga impurity charge‐compensated compound defects are formed. By combining first‐principle calculations and experiments, we show that Ga atoms occupy both the void and Sb sites in CoSb₃ and couple with each other. The donated electrons from the void‐filling Ga (Ga_VF) saturate the dangling bonds from the Sb‐substitutional Ga (Ga_Sb). The stabilization of Ga impurity as a compound defect extends the region of skutterudite phase stability toward Ga_0.15Co₄Sb_11.95 whereas the solid–solution region in other directions of the ternary phase diagram is much smaller. A proposed ternary phase diagram for Ga‐Co‐Sb is given. This compensated defect complex leads to a nearly intrinsic semiconductor with heavy Ga doping in CoSb₃ and a much reduced lattice thermal conductivity (κ_L) which can also be attributed to the effective scattering of both the low‐ and high‐frequency lattice phonons by the dual‐site occupant Ga impurities. Such a system maintains a low carrier concentration and therefore high thermopower, and the thermoelectric figure of merit quickly increases to 0.7 at a Ga doping content as low as 0.1 per Co₄Sb₁₂ and low carrier concentrations on the order of 10¹⁹ cm^?3.     

Fe-based semiconducting Heusler alloys

A brief overview of the current state of research on Fe-based semiconducting Heusler alloys is given. The most significant achievement in this area is the increase of thermoelectric figure of merit to ZT > 1 in the p-type Fe(V,Nb)Sb-based compounds. Besides these compounds, growing attention has been paid in recent years to the study of promising thermoelectric materials based on Fe₂TiZ (Z = Al, Si, Sn) Heusler alloys and the investigation of multifunctional Fe₂MnZ (Z = Al, Si) compounds, which may be of interest as thermoelectric materials as well as magnetic semiconductors with a high Curie temperature.     

Polaron Transport and Thermoelectric Behavior in La‐Doped SrTiO3 Thin Films with Elemental Vacancies

The electrodynamic properties of La‐doped SrTiO₃ thin films with controlled elemental vacancies are investigated using optical spectroscopy and thermopower measurement. In particular, a correlation between the polaron formation and thermoelectric properties of the transition metal oxide (TMO) thin films is observed. With decreasing oxygen partial pressure during the film growth (P(O₂)), a systematic lattice expansion is observed along with the increased elemental vacancy and carrier density, experimentally determined using optical spectroscopy. Moreover, an absorption in the mid‐infrared photon energy range is found, which is attributed to the polaron formation in the doped SrTiO₃ system. Thermopower of the La‐doped SrTiO₃ thin films can be largely modulated from –120 to –260 μV K^?1, reflecting an enhanced polaronic mass of ≈3 < m _polron/m < ≈4. The elemental vacancies generated in the TMO films grown at various P(O₂) influences the global polaronic transport, which governs the charge transport behavior, including the thermoelectric properties.     

Point Defect Engineering of High‐Performance Bismuth‐Telluride‐Based Thermoelectric Materials

Developing high‐performance thermoelectric materials is one of the crucial aspects for direct thermal‐to‐electric energy conversion. Herein, atomic scale point defect engineering is introduced as a new strategy to simultaneously optimize the electrical properties and lattice thermal conductivity of thermoelectric materials, and (Bi,Sb)₂(Te,Se)₃ thermoelectric solid solutions are selected as a paradigm to demonstrate the applicability of this new approach. Intrinsic point defects play an important role in enhancing the thermoelectric properties. Antisite defects and donor‐like effects are engineered in this system by tuning the formation energy of point defects and hot deformation. As a result, a record value of the figure of merit ZT of ≈1.2 at 445 K is obtained for n‐type polycrystalline Bi₂Te_2.3Se_0.7 alloys, and a high ZT value of ≈1.3 at 380 K is achieved for p‐type polycrystalline Bi_0.3Sb_1.7Te₃ alloys, both values being higher than those of commercial zone‐melted ingots. These results demonstrate the promise of point defect engineering as a new strategy to optimize thermoelectric properties.     

High‐Performance Sodium‐Ion Hybrid Supercapacitor Based on Nb2O5@Carbon Core–Shell Nanoparticles and Reduced Graphene Oxide Nanocomposites

Sodium‐ion hybrid supercapacitors (Na‐HSCs) have potential for mid‐ to large‐scale energy storage applications because of their high energy/power densities, long cycle life, and the low cost of sodium. However, one of the obstacles to developing Na‐HSCs is the imbalance of kinetics from different charge storage mechanisms between the sluggish faradaic anode and the rapid non‐faradaic capacitive cathode. Thus, to develop high‐power Na‐HSC anode materials, this paper presents the facile synthesis of nanocomposites comprising Nb₂O₅@Carbon core–shell nanoparticles (Nb₂O₅@C NPs) and reduced graphene oxide (rGO), and an analysis of their electrochemical performance with respect to various weight ratios of Nb₂O₅@C NPs to rGO (e.g., Nb₂O₅@C, Nb₂O₅@C/rGO‐70, ‐50, and ‐30). In a Na half‐cell configuration, the Nb₂O₅@C/rGO‐50 shows highly reversible capacity of ≈285 mA h g^?1 at 0.025 A g^?1 in the potential range of 0.01–3.0 V (vs Na/Na⁺). In addition, the Na‐HSC using the Nb₂O₅@C/rGO‐50 anode and activated carbon (MSP‐20) cathode delivers high energy/power densities (≈76 W h kg^?1 and ≈20 800 W kg^?1) with a stable cycle life in the potential range of 1.0–4.3 V. The energy and power densities of the Na‐HSC developed in this study are higher than those of similar Li‐ and Na‐HSCs previously reported.     

Improved‐Performance Dye‐Sensitized Solar Cells Using Nb‐Doped TiO2 Electrodes: Efficient Electron Injection and Transfer

Well‐crystallized Nb‐doped anatase TiO₂ nanoparticles are prepared by a novel synthetic route and successfully used as the photoanode of dye‐sensitized solar cells (DSSCs). The homogenous distribution of Nb in the TiO₂ lattice is confirmed by scanning transmission electron microscopy (STEM) elemental mapping and line‐scanning analyses. After Nb doping, the conductivity of the TiO₂ powder increases, and its flat‐band potential (V_fb) has a positive shift. The energy‐conversion efficiency of a cell based on 5.0 mol% Nb‐doped TiO₂ is significantly better, by about 18.2%, compared to that of a cell based on undoped TiO₂. The as‐prepared Nb‐doped TiO₂ material is proven in detail to be a better photoanode material than pure TiO₂, and this new synthetic approach using a water‐soluble precursor provides a simple and versatile way to prepare excellent photoanode materials.     

Evaluation of Half‐Heusler Compounds as Thermoelectric Materials Based on the Calculated Electrical Transport Properties

A theoretical evaluation of the thermoelectric‐related electrical transport properties of 36 half‐Heusler (HH) compounds, selected from more than 100 HHs, is carried out in this paper. The electronic structures and electrical transport properties are studied using ab initio calculations and the Boltzmann transport equation under the constant relaxation time approximation for charge carriers. The electronic structure results predict the band gaps of these HH compounds, and show that many HHs are narrow‐band‐gap semiconductors and, therefore, are potentially good thermoelectric materials. The dependence of Seebeck coefficient, electrical conductivity, and power factor on the Fermi level is investigated. Maximum power factors and the corresponding optimal p‐ or n‐type doping levels, related to the thermoelectric performance of materials, are calculated for all HH compounds investigated, which certainly provide guidance to experimental work. The estimated optimal doping levels and Seebeck coefficients show reasonable agreement with the measured results for some HH systems. A few HHs are recommended to be potentially good thermoelectric materials based on our calculations.     

Searching General Sufficient‐and‐Necessary Conditions for Ultrafast Hydrogen‐Evolving Electrocatalysis

The development of cost‐effective and high‐performance electrocatalysts for the hydrogen evolution reaction (HER) is one critical step toward successful transition into a sustainable green energy era. Different from previous design strategies based on single parameter, here the necessary and sufficient conditions are proposed to develop bulk non‐noble metal oxides which are generally considered inactive toward HER in alkaline solutions: i) multiple active sites for different reaction intermediates and ii) a short reaction path created by ordered distribution and appropriate numbers of these active sites. Computational studies predict that a synergistic interplay between the ordered oxygen vacancies (at pyramidal high‐spin Co³⁺ sites) and the O 2p ligand holes (OLH; at metallic octahedral intermediate‐spin Co⁴⁺ sites) in RBaCo₂O_5.5+δ (δ = 1/4; R = lanthanides) can produce a near‐ideal HER reaction path to adsorb H₂O and release H₂, respectively. Experimentally, the as‐synthesized (Gd_0.5La_0.5)BaCo₂O_5.75 outperforms the state‐of‐the‐art Pt/C catalyst in many aspects. The proof‐of‐concept results reveal that the simultaneous possession of ordered oxygen vacancies and an appropriate number of OLH can realize a near‐optimal synergistic catalytic effect, which is pivotal for rational design of oxygen‐containing materials.     

Improving Spin‐Transport by Disorder

A new scheme dedicated to improving spin‐transport characteristics by applying random disorder as a constructive agent is reported. The approach paves the way for the construction of novel systems with a surprising combination of properties, which are either extremely rare or even entirely absent within the known classes of ordered materials: half‐metals with no net magnetization and magnetic semiconductors. As a real case example for the applicability of the scheme, it is shown that a series of such materials can be derived from the tetragonal Heusler compound Mn₃Ga by substituting Mn with a 3d‐transition metal.     

Thermomagnetic Properties Improved by Self‐Organized Flower‐Like Phase Separation of Ferromagnetic Co2Dy0.5Mn0.5Sn

A thermodynamically stable phase separation of Co₂Dy_0.5Mn_0.5Sn into the Heusler compound Co₂MnSn and Co₈Dy₃Sn₄ is induced by rapid cooling from the liquid phase. The phase separation forms an ordered flower‐like structure on the microscale. The increased scattering of phonons at the phase boundaries reduces the thermal conductivity and thus improves thermoelectric and spincaloric properties.     

Thermoelectric Properties of Nb-Doped Ordered Mesoporous TiO<Subscript>2</Subscript>

Mesoporous materials have pores with diameters between 2 nm and 50 nm, the presence of which generally decreases the thermal conductivity of the material. By incorporating mesoporous structures into thermoelectric materials, the thermoelectric properties of these materials can be improved. Although TiO₂ is an ordinary insulator, reduced TiO₂ shows better electrical conductivity and is therefore a potential thermoelectric material. Furthermore, the addition of a dopant to TiO₂ can improve its electrical conductivity. We hypothesized that, by doping ordered mesoporous TiO₂ films with niobium, we would be able to minimize the thermal conductivity and maximize the electrical conductivity. To investigate the effects of Nb doping and a mesoporous structure on the thermoelectric characteristics of TiO₂ films, Nb-doped mesoporous films were investigated using x-ray diffraction, ellipsometry, four-point probe measurements, and thermal conductivity analysis. We found that Nb doping of ordered mesoporous TiO₂ films improved their thermoelectric properties.