Synergistically Optimized Thermoelectric and Mechanical Properties of Mg3.2Bi1.5Sb0.5-SiC Composites.

Motivated by the surging demand for low-temperature waste heat harvesting, materials with both prominent thermoelectric and good mechanical properties are preferred in practical applications. In this present work, the composite exploration of Te-doped Mg3.2Bi1.5Sb0.5-x vol % nanosized SiC (x = 0, 0.05, 0.1, 0.2, and 0.5) was carried out, where nanosized SiC is physically dispersed in the matrix in the form of a second phase. SiC second phase compositing further optimized the matrix carrier concentration, resulting in a higher power factor in the service temperature range (the highest value from 28.9 to 31.7 µW cm-1 K-2), and the (ZT)ave from 0.91 to 0.96 compared with the matrix sample. In addition, the SiC second phase effectively enhanced the mechanical properties of composite materials, including flexural strength, microhardness, and modulus. Because of the simultaneous optimization of thermoelectric and mechanical properties, the overall performance of Te-doped Mg3.2Bi1.5Sb0.5-0.05 vol % SiC composite is leveraged to meet special requirements of power generation. It is expected that the addition of SiC should be broadly applicable to address the physical performance in other thermoelectric systems.

Mechanism of Thermoelectric Performance Enhancement in CaMg2 Bi2 -Based Materials with Different Cation Site Doping.

Chemical bonds determine electron and phonon transport in solids. Tailoring chemical bonding in thermoelectric materials causes desirable or compromise thermoelectric transport properties. In this work, taking an example of CaMg2 Bi2 with covalent and ionic bonds, density functional theory calculations uncover that element Zn, respectively, replacing Ca and Mg sites cause the weakness of ionic and covalent bonding. Electrically, Zn doping at both Ca and Mg sites increases carrier concentration, while the former leads to higher carrier concentration than that of the latter because of its lower vacancy formation energy. Both doping types increase density-of-state effective mass but their mechanisms are different. The Zn doping Ca site induces resonance level in valence band and Zn doping Mg site promotes orbital alignment. Thermally, point defect and the change of phonon dispersion introduced by doping result in pronounced reduction of lattice thermal conductivity. Finally, combining with the further increase of carrier concentration caused by Na doping and the modulation of band structure and the decrease of lattice thermal conductivity caused by Ba doping, a high figure-of-merit ZT of 1.1 at 823 K in Zn doping Ca sample is realized, which is competitive in 1-2-2 Zintl phase thermoelectric systems.

Performance boost for bismuth telluride thermoelectric generator via barrier layer based on low Young's modulus and particle sliding.

The lack of desirable diffusion barrier layers currently prohibits the long-term stable service of bismuth telluride thermoelectric devices in low-grade waste heat recovery. Here we propose a new design principle of barrier layers beyond the thermal expansion matching criterion. A titanium barrier layer with loose structure is optimized, in which the low Young's modulus and particle sliding synergistically alleviates interfacial stress, while the TiTe2 reactant enables metallurgical bonding and ohmic contact between the barrier layer and the thermoelectric material, leading to a desirable interface characterized by high-thermostability, high-strength, and low-resistivity. Highly competitive conversion efficiency of 6.2% and power density of 0.51 W cm-2 are achieved for a module with leg length of 2 mm at the hot-side temperature of 523 K, and no degradation is observed following operation for 360 h, a record for stable service at this temperature, paving the way for its application in low-grade waste heat recovery.

Screening strategy for developing thermoelectric interface materials.

Thermoelectric interface materials (TEiMs) are essential to the development of thermoelectric generators. Common TEiMs use pure metals or binary alloys but have performance stability issues. Conventional selection of TEiMs generally relies on trial-and-error experimentation. We developed a TEiM screening strategy that is based on phase diagram predictions by density functional theory calculations. By combining the phase diagram with electrical resistivity and melting points of potential reaction products, we discovered that the semimetal MgCuSb is a reliable TEiM for high-performance MgAgSb. The MgCuSb/MgAgSb junction exhibits low interfacial contact resistivity (ρc <1 microhm square centimeter) even after annealing at 553 kelvin for 16 days. The fabricated two-pair MgAgSb/Mg3.2Bi1.5Sb0.5 module demonstrated a high conversion efficiency of 9.25% under a 300 kelvin temperature gradient. We performed an international round-robin testing of module performance to confirm the measurement reliability. The strategy can be applied to other thermoelectric materials, filling a vital gap in the development of thermoelectric modules.

Revealing the Chemical Instability of Mg3Sb2-xBix-Based Thermoelectric Materials.

n-Type Mg3Sb2-xBix alloys have been regarded as promising thermoelectric materials due to their excellent performance and low cost. For practical applications, the thermoelectric performance is not the only factor that should be taken into consideration. In addition, the chemical and thermal stabilities of the thermoelectric material are of equal importance for the module design. Previous studies reported that the Mg3Sb2-xBix alloys were unstable in an ambient environment. In this work, we found that Mg3Sb2-xBix alloys reacted with H2O and O2 at room temperature and formed amorphous Mg(OH)2/MgO and crystalline Bi/Sb. The substantial loss of Mg resulted in a significant deterioration in thermoelectric properties, accompanied by the transition from n-type to p-type. With the increase in Bi content, the chemical stability decreased due to the higher formation energy of Mg3Bi2. A chemically stable Mg3Bi2 sample was achieved by coating it with polydimethylsiloxane to isolate H2O and O2 in the air.

Characterizing the thermoelectric cooling performance across a broad temperature range.

Thermoelectric cooling plays an essential role in precisely controlling the temperature of electronics. Characterizing the performance of thermoelectric coolers (TECs) is of great significance for the development of advanced solid-state cooling devices. However, the existing setup for characterizing the cooling performance of TECs has mainly been limited to the near room temperature range. Herein, we report the development of a new setup that is capable of characterizing thermoelectric cooling performance across a broad temperature range (80-350 K). With precise and steady control of the hot-side temperature, measurements of the coefficient of performance and maximum temperature difference at room temperature have been conducted on commercial devices. By comparing the results with the commercial datasheet, it shows that our setup can accurately evaluate the cooling performance of thermoelectric devices. In addition, we further extend the characterization to different hot-side temperatures, e.g., 173, 325, and 350 K, thus demonstrating the capability of our setup for evaluating the thermoelectric performance across a broad temperature range.

Breaking the Minimum Limit of Thermal Conductivity of Mg3 Sb2 Thermoelectric Mediated by Chemical Alloying Induced Lattice Instability.

Thermal properties strongly affect the applications of functional materials, such as thermal management, thermal barrier coatings, and thermoelectrics. Thermoelectric (TE) materials must have a low lattice thermal conductivity to maintain a temperature gradient to generate the voltage. Traditional strategies for minimizing the lattice thermal conductivity mainly rely on introduced multiscale defects to suppress the propagation of phonons. Here, the origin of the anomalously low lattice thermal conductivity is uncovered in Cd-alloyed Mg3 Sb2 Zintl compounds through complementary bonding analysis. First, the weakened chemical bonds and the lattice instability induced by the antibonding states of 5p-4d levels between Sb and Cd triggered giant anharmonicity and consequently increased the phonon scattering. Moreover, the bond heterogeneity also augmented Umklapp phonon scatterings. Second, the weakened bonds and heavy element alloying softened the phonon mode and significantly decreased the group velocity. Thus, an ultralow lattice thermal conductivity of ≈0.33 W m-1 K-1 at 773 K is obtained, which is even lower than the predicated minimum value. Eventually, Na0.01 Mg1.7 Cd1.25 Sb2 displays a high ZT of ≈0.76 at 773 K, competitive with most of the reported values. Based on the complementary bonding analysis, the work provides new means to control thermal transport properties through balancing the lattice stability and instability.

Design of N-Type Textured Bi2 Te3 with Robust Mechanical Properties for Thermoelectric Micro-Refrigeration Application.

Thermoelectric refrigeration is one of the mature techniques used for cooling applications, with the great advantage of miniaturization over traditional compression refrigeration. Due to the anisotropic thermoelectric properties of n-type bismuth telluride (Bi2 Te3 ) alloys, these two common methods, including the liquid phase hot deformation (LPHD) and traditional hot forging (HF) methods, are of considerable importance for texture engineering to enhance performance. However, their effects on thermoelectric and mechanical properties are still controversial and not clear yet. Moreover, there has been little documentation of mechanical properties related to micro-refrigeration applications. In this work, the above-mentioned methods are separately employed to control the macroscopic grain orientation for bulk n-type Bi2 Te3 samples. The HF method enabled the stabilization of both composition and carrier concentration, therefore yielding a higher quality factor to compare with that of LPHD samples, supported by DFT calculations. In addition to superior thermoelectric performance, the HF sample also exhibited robust mechanical properties due to the presence of nano-scale distortion and dense dislocation, which is the prerequisite for realizing ultra-precision machining. This work helps to pave the way for the utilization of n-type Bi2 Te3 for commercial micro-refrigeration applications.

Enhanced Thermoelectric Performance of Yb-Filled Skutterudite with Bottom-Up Formed CoSi2 Nanoparticles.

It is known that Yb-filled skutterudite with excellent thermoelectric performance is promising for a power generation device in the intermediate temperature region. Here we created a new approach to obtain nanostructured materials by adding Si to Co-overstoichiometric Yb-filled skutterudite through high-energy ball milling, which embedded bottom-up formed CoSi2 nanoparticles into grain-refining Yb0.25Co4Sb12, synergistically resulting in the enhanced thermoelectric properties and room-temperature hardness. On one hand, the abundant grain boundaries and phase interfaces effectively blocked the propagation of medium-low frequency phonons, resulting in a lower lattice thermal conductivity. On the other hand, phase interfaces barrier nicely screened a portion of low-energy electrons, leading to an improved power factor. As a result, an enhanced peak ZT value of ∼1.43 at 823 K and a promising average ZT of ∼1.00 between 300 and 823 K were achieved in the Yb0.25Co4Sb12/0.05CoSi2 sample. Meanwhile, such nanostructures also enhanced the hardness through the collective contributions of second phase and fine grain strengthening, which made skutterudite more competitive in practical application.

Insertion of carbon skeleton in Ni/MoO2 heterojunction with porous hollow sphere for efficient alkaline electrochemical hydrogen production.

The catalyst morphology has a strong impact on the activity of electrocatalytic hydrogen production. Considering the effect, we design and fabricate hollow spherical Ni/MoO2 heterojunction. In addition, an amorphous carbon skeleton is inserted into the hollow sphere, which makes the structure more stable and porous. Compared with other morphological Ni/MoO2, the porous hollow spherical Ni/MoO2 (H-Ni/MoO2) with an internal carbon skeleton shows better hydrogen evolution reaction (HER) activity with a small overpotential of 58 mV to reach 10 mA cm-2 and a tafel value of 44.8 mV dec-1 in alkaline media. The developed HER performance of H-Ni/MoO2 can be attributed to the larger active surface area of porous hollow spherical structure and the faster electron transfer and better stability of carbon skeleton. Undoubtedly, the urea plays a crucial role to construct the hollow spherical morphology and being decomposed to form holes and amorphous carbon in the synthesized steps. The soft-template strategy using urea as the addition for forming the porous hollow structure with carbon skeleton can be extended to explore superior non-noble metal for hydrogen production.

Efficient Si Doping Promoting Thermoelectric Performance of Yb-Filled CoSb3-Based Skutterudites.

Nanocomposites have become a widely popular way to assist in the enhancement of thermoelectric performance for filled skutterudites. Herein, we unveil the distinctive effect of Si doping on the classic Yb0.3Co4Sb12. On the one hand, the reduced Yb filling fraction is accompanied by the in-situ precipitated CoSi nanoparticles, which not only enhances the power factor in the intermediate-low temperature range but also reduces electronic thermal conductivity for decreasing the carrier concentration. On the other hand, CoSi nanoparticles intensively disrupt the phonon transport, hiding the increased lattice thermal conductivity due to reduced Yb filling fraction. Although the residual YbSb2 second phases have an adverse effect on the thermoelectric properties, the integration effects achieve a peak ZT value of 1.37 at 823 K and increase ZTave by 21% for the Yb0.3Co4Sb12/0.1Si sample.

Electronic Orbital Alignment and Hierarchical Phonon Scattering Enabling High Thermoelectric Performance p-Type Mg3Sb2 Zintl Compounds.

Environmentally friendly Mg3Sb2-based materials have drawn intensive attention owing to their promising thermoelectric performance. In this work, the electrical properties of p-type Mg3Sb2 are dramatically optimized by the regulation of Mg deficiency. Then, we, for the first time, found that Zn substitution at the Mg2 site leads to the alignment of p x,y and p z orbital, resulting in a high band degeneracy and the dramatically enhanced Seebeck coefficient, demonstrated by the DFT calculations and electronic properties measurement. Moreover, Zn alloying decreases Mg1 (Zn) vacancies formation energy and in turn increases Mg (Zn) vacancies and optimizes the carrier concentration. Simultaneously, the Mg/Zn substitutions, Mg vacancies, and porosity structure suppress the phonon transport in a broader frequency range, leading to a low lattice thermal conductivity of ~0.47 W m-1 K-1 at 773 K. Finally, a high ZT of ~0.87 at 773 K was obtained for Mg1.95Na0.01Zn1Sb2, exceeding most of the previously reported p-type Mg3Sb2 compounds. Our results further demonstrate the promising prospects of p-type Mg3Sb2-based material in the field of mid-temperature heat recovery.

Mediating Point Defects Endows n-Type Bi2 Te3 with High Thermoelectric Performance and Superior Mechanical Robustness for Power Generation Application.

Bi2 Te3 -related alloys dominate the commercial thermoelectric market, but the layered crystal structure leads to the dissociation and intrinsic brittle fracture, especially for single crystals that may worsen the practical efficiency. In this work, point defect configuration by S/Te/I defects engineering is engaged to boost thermoelectric and mechanical properties of n-type Bi2 Te3 alloy, which, coupled with p-type BiSbTe, shows a competitive conversion efficiency for the fabricated module. First, as S alloying suppresses the intrinsic B i T e , antisite defects and forms a donor-like effect, electronic transport properties are optimized, associated with the decreased thermal conductivity due to the point defect scattering. The periodide compound TeI4 is afterward adopted to further tune carrier concentration for the realization of an optimal ZT. Finally, an advanced average ZT of 1.05 with ultra-high compressive strength of 230 MPa is achieved for Bi2 Te2.9 S0.1 (TeI4 )0.0012 . Based on this optimum composition, a fabricated 17-pair module demonstrates a maximum conversion efficiency of 5.37% under the temperature difference of 250 K, rivaling the current state-of-the-art Bi2 Te3 modules. This work reveals the novel mechanism of point defect reconfiguration in synergistic enhancement of thermoelectric and mechanical properties for durably commercial application, which may be applicable to other thermoelectric systems.

Nanotwins Strengthening High Thermoelectric Performance Bismuth Antimony Telluride Alloys.

Bi2 Te3 based thermoelectric alloys have been commercialized in solid-state refrigeration, but the poor mechanical properties restrict their further application. Nanotwins have been theoretically proven to effectively strengthen these alloys and could be sometimes constructed by strong deformation during synthesis. However, the obscure underlying formation mechanism restricts the feasibility of twin boundary engineering on Bi2 Te3 based materials. Herein, thorough microstructure characterizations are employed on a series of Bi0.4 Sb1.6 Te3+ δ alloys to systematically investigate the twins' formation mechanism. The results show that the twins belong to the annealing type formed in the sintering process, which is sensitive to Te deficiency, rather than the deformation one. The Te deficiency combined with mechanical deformation is prerequisite for constructing dense nanotwins. By reducing the δ below -0.01 and undergoing strong deformation, samples with a high density of nanotwins are obtained and exhibit an ultrahigh compressive strength over 250 MPa, nearly twice as strong as the previous record reported in hierarchical nanostructured (Bi, Sb)2 Te3 alloy. Moreover, benefitting from the suppressed intrinsic excitation, the average zT value of this robust material could reach near 1.1 within 30-250 °C. This work opens a new pathway to design high-performance and mechanically stable Bi2 Te3 based alloys for miniature device development.

Electronic Topological Transition as a Route to Improve Thermoelectric Performance in Bi0.5 Sb1.5 Te3.

The electronic structure near the Fermi surface determines the electrical properties of the materials, which can be effectively tuned by external pressure. Bi0.5 Sb1.5 Te3 is a p-type thermoelectric material which holds the record high figure of merit at room temperature. Here it is examined whether the figure of merit of this model system can be further enhanced through some external parameter. With the application of pressure, it is surprisingly found that the power factor of this material exhibits λ behavior with a high value of 4.8 mW m-1 K-2 at pressure of 1.8 GPa. Such an enhancement is found to be driven by pressure-induced electronic topological transition, which is revealed by multiple techniques. Together with a low thermal conductivity of about 0.89 W m-1 K-1 at the same pressure, a figure of merit of 1.6 is achieved at room temperature. The results and findings highlight the electronic topological transition as a new route for improving the thermoelectric properties.

Passive Radiative Cooling Enables Improved Performance in Wearable Thermoelectric Generators.

Wearable thermoelectric generators have great potential to be utilized as the power supply for wearable electronics. However, the limited temperature difference across the thermoelectric generators significantly degrades the output performance, which is anticipated to be improved by enhancing the thermal radiation at the cold side without extra energy consumption. In this paper, the impact of thermal radiation on the performance of thermoelectric generators in different environments is simulated and the enhanced performance in a wearable thermoelectric generator combined with a radiative cooling coating is experimentally verified. Compared with the pristine device, the wearable thermoelectric generator with radiative cooling coating can not only achieve an ≈128% improvement of output power in exposed environments, but also exhibit an ≈96% improvement of output power in non-exposed environments. The indoor output performance of the wearable thermoelectric generator with a radiative cooling coating due to its stable voltage output is extensively investigated, which shows an output power density of ≈5.5 µW cm-2 at the indoor temperature of 295 K, doubled that without a radiative cooling coating. This work paves a new way for further enhancing the performance of thermoelectric generators via passive radiative cooling.

Tuning the Carrier Scattering Mechanism by Rare-Earth Element Doping for High Average zT in Mg3Sb2-Based Compounds.

Mg3Sb2-based compounds are promising thermoelectric materials because of their excellent thermoelectric performance, low cost, and good mechanical properties. In this work, Er, Dy, Gd, and Nd are all confirmed to be effective n-type dopants for optimizing the carrier concentration, increasing the density of states effective mass, and suppressing the ionized impurity scattering of Mg3Sb2-based compounds. By increasing the sintering temperature, a larger grain size can be achieved and can effectively improve the carrier mobility in the whole measured temperature range. As a result, maximum zT values above ∼1.6 at 673 K and average zTs above ∼1.0 between 300 and 673 K were achieved for Mg3.07Er0.03Bi0.5Sb1.5, Mg3.07Dy0.03Bi0.5Sb1.5, and Mg3.07Nd0.03Bi0.5Sb1.5. In addition, a high compressive strength of ∼180 MPa was obtained in Mg3.07Dy0.03Bi0.5Sb1.5. Therefore, rare-earth element-doped Mg3Sb2-based compounds are promising for thermoelectric applications.

Stabilizing the Optimal Carrier Concentration in Al/Sb-Codoped GeTe for High Thermoelectric Performance.

GeTe is a promising thermoelectric material and has attracted growing research interest recently. In this study, the effect of Al doping and Al&Sb codoping on the thermoelectric properties of GeTe was investigated. Due to the presence of a high concentration of intrinsic Ge vacancies, pristine GeTe exhibited a very high hole concentration and unpromising thermoelectric performance. By Sb doping in GeTe, the hole concentration can be effectively reduced, thus improving the thermoelectric performance. Aluminum, as a p-type dopant in GeTe, will increase the hole concentration and lattice thermal conductivity; thus, it has long been considered as an unfavorable dopant for the optimization of GeTe-based materials. However, when Al and Sb were codoped into GeTe, the hole concentration was effectively suppressed, and the lattice thermal conductivity can be reduced. Eventually, a maximum zT of ∼2.0 at 773 K was achieved in Al&Sb-codoped Al0.01Sb0.1Ge0.89Te.

Enhancing Thermoelectric Performance of Yb0.3Co4Sb12 by Synergistically Optimized Carrier Concentration and Ionized Impurity Scattering.

Previous results indicated that acceptor doping was considered an effective clue to substantially suppress electronic thermal conductivity and in the meanwhile hold a rather low lattice thermal conductivity in high Yb-filled skutterudites. However, the strength of ionized impurity scattering needs to be regulated elaborately to balance the enhanced Seebeck coefficient and the deteriorated carrier mobility. In this work, Ge doping not only synergistically modulates the Fermi energy level and strength of ionized impurity scattering to an optimal range and attains a benign power factor but also offers a valuable opportunity to further suppress κe and κ in the classic Yb0.3Co4Sb12 alloy. Since the Yb0.3Co4Sb11.75Ge0.25 sample is endowed with the most highlighted ZT value in the device application temperature range, a promising average ZT value of 1.00 across the 300-823 K is achieved, reaching up to the level of a typical triple-filled skutterudite, which is highly desirable for achieving a satisfactory theoretical conversion efficiency of ∼14.5%. Our work corroborates that the ionized impurity strength is an extremely critical benchmark to obtain desirable thermoelectric performance in the high Yb-filled skutterudites.

Towards tellurium-free thermoelectric modules for power generation from low-grade heat.

Thermoelectric technology converts heat into electricity directly and is a promising source of clean electricity. Commercial thermoelectric modules have relied on Bi2Te3-based compounds because of their unparalleled thermoelectric properties at temperatures associated with low-grade heat (<550 K). However, the scarcity of elemental Te greatly limits the applicability of such modules. Here we report the performance of thermoelectric modules assembled from Bi2Te3-substitute compounds, including p-type MgAgSb and n-type Mg3(Sb,Bi)2, by using a simple, versatile, and thus scalable processing routine. For a temperature difference of ~250 K, whereas a single-stage module displayed a conversion efficiency of ~6.5%, a module using segmented n-type legs displayed a record efficiency of ~7.0% that is comparable to the state-of-the-art Bi2Te3-based thermoelectric modules. Our work demonstrates the feasibility and scalability of high-performance thermoelectric modules based on sustainable elements for recovering low-grade heat.