High Thermoelectric Performance in PbSe–NaSbSe2 Alloys from Valence Band Convergence and Low Thermal Conductivity

PbSe is an attractive thermoelectric material due to its favorable electronic structure, high melting point, and lower cost compared to PbTe. Herein, the hitherto unexplored alloys of PbSe with NaSbSe₂ (NaPb_mSbSe_m+2) are described and the most promising p‐type PbSe‐based thermoelectrics are found among them. Surprisingly, it is observed that below 500 K, NaPb_mSbSe_m+2 exhibits unorthodox semiconducting‐like electrical conductivity, despite possessing degenerate carrier densities of ≈10²⁰ cm^?3. It is shown that the peculiar behavior derives from carrier scattering by the grain boundaries. It is further demonstrated that the high solubility of NaSbSe₂ in PbSe augments both the thermoelectric properties while maintaining a rock salt structure. Namely, density functional theory calculations and photoemission spectroscopy demonstrate that introduction of NaSbSe₂ lowers the energy separation between the L‐ and Σ‐valence bands and enhances the power factors under 700 K. The crystallographic disorder of Na⁺, Pb²⁺, and Sb³⁺ moreover provides exceptionally strong point defect phonon scattering yielding low lattice thermal conductivities of 1–0.55 W m^‐1 K^‐1 between 400 and 873 K without nanostructures. As a consequence, NaPb₁₀SbSe₁₂ achieves maximum ZT ≈1.4 near 900 K when optimally doped. More importantly, NaPb₁₀SbSe₁₂ maintains high ZT across a broad temperature range, giving an estimated record ZT_avg of ≈0.64 between 400 and 873 K, a significant improvement over existing p‐type PbSe thermoelectrics.     

n‐Type SnSe2 Oriented‐Nanoplate‐Based Pellets for High Thermoelectric Performance

It is reported that electron doped n‐type SnSe₂ nanoplates show promising thermoelectric performance at medium temperatures. After simultaneous introduction of Se deficiency and Cl doping, the Fermi level of SnSe₂ shifts toward the conduction band, resulting in two orders of magnitude increase in carrier concentration and a transition to degenerate transport behavior. In addition, all‐scale hierarchical phonon scattering centers, such as point defects, nanograin boundaries, stacking faults, and the layered nanostructures, cooperate to produce very low lattice thermal conductivity. As a result, an enhanced in‐plane thermoelectric figure of merit ZT_max of 0.63 is achieved for a 1.5 at% Cl doped SnSe_1.95 pellet at 673 K, which is much higher than the corresponding in‐plane ZT of pure SnSe₂ (0.08).     

Skutterudite Unicouple Characterization for Energy Harvesting Applications

Skutterudites are promising thermoelectric materials because of their high figure of merit, ZT, and good thermomechanical properties. This work reports the effective figure of merit, ZT_eff, and the efficiency of skutterudite legs and a unicouple working under a large temperature difference. The p‐ and n‐type legs are fabricated with electrodes sintered directly to the skutterudite during a hot pressing process. CoSi₂ is used as the electrode for the n‐type skutterudite (Yb_0.35Co₄Sb₁₂) and Co₂Si for the p‐type skutterudite (NdFe_3.5Co_0.5Sb₁₂). A technique is developed to measure the ZT_eff of individual legs and the efficiency of a unicouple. An ZT_eff of 0.74 is determined for the n‐type legs operating between 52 and 595 °C, and an ZT_eff of 0.51 for the p‐type legs operating between 77 and 600 °C. The efficiency of the p–n unicouple is determined to be 9.1% operating between ～70 and 550 °C.     

The Role of Zn in Chalcopyrite CuFeS2: Enhanced Thermoelectric Properties of Cu1–xZnxFeS2 with In Situ Nanoprecipitates

Chalcopyrite (CuFeS₂) is a widespread natural mineral, composed of earth‐abundant and nontoxic elements. It has been considered a promising n‐type material for thermoelectric applications. In this work, a series of Zn‐doped Cu_1–xZn_xFeS₂ (x = 0–0.1) compounds are synthesized by vacuum melting combined with the plasma activated sintering process. The role of Zn in the chalcopyrite and its different effects on thermoelectric properties, depending on its concentration and location in the crystal lattice, are discussed. It is found that Zn is an effective donor which increases the carrier concentration and improves the thermoelectric properties of CuFeS₂. When the content of Zn exceeds the solubility limit, Zn partially enters the Cu sites and forms in situ ZnS nanophase. This, in turn, shifts the balance between the anion and cation species which is re‐established by the formation of antisite Fe/Cu defects. Beyond maintaining charge neutrality of the structure, such antisite defects relieve the lattice strain in the matrix and increase the solubility of Zn further. The highest ZT value of 0.26 is achieved at 630 K for Cu_0.92Zn_0.08FeS₂, which represents an enhancement of about 80% over that of the pristine CuFeS₂ sample.     

Crystal Structure Induced Ultralow Lattice Thermal Conductivity in Thermoelectric Ag9AlSe6

Recent discoveries of novel thermoelectric materials largely rely on an intrinsic low lattice thermal conductivity. This results from various mechanisms including low sound velocity, complex crystal structure, liquid‐like ions, and lattice anharmonicity. Here semiconducting Ag₉AlSe₆ with many weakly bonded and highly disordered cations is shown to be a promising novel thermoelectric material, due to its ultralow lattice thermal conductivity (κ_L) of ≈0.3 W m^?1 K^?1 in the entire temperature range. Such a low κ_L is believed to be a result of its (1) complex crystal structure for a small population of acoustic phonons, (2) soft bonding for an overall low sound velocity (1300 m s^?1), and (3) massive disordering of Ag ions. Its electronic transport properties can be well understood by a single parabolic band model with acoustic scattering. The achieved thermoelectric figure of merit (zT) can be as high as unity, which is unlike conventional thermoelectric materials, which rely heavily on a high power factor. This work not only demonstrates Ag₉AlSe₆ as a promising thermoelectric material, but also paves the way for the exploration of novel thermoelectrics with a complex crystal structure with weakly bonded and highly disordered constituent elements in the structure.     

Toward High‐Thermoelectric‐Performance Large‐Size Nanostructured BiSbTe Alloys via Optimization of Sintering‐Temperature Distribution

High thermoelectric performance of mechanically robust p‐type Bi₂Te₃‐based materials prepared by melt spinning (MS) combined with plasma‐activated sintering (PAS) method can be obtained with small, laboratory grown samples. However, large‐size samples are required for commercial applications. Here, large‐size p‐type Bi₂Te₃‐based ingots with 30, 40, and 60 mm in diameter are produced by MS‐PAS, and the influence of temperature distribution during the sintering process on the composition and thermoelectric properties is systematically studied for the first time. Room‐temperature scanning Seebeck Microprobe results show that the large‐size ingot is inhomogeneous, induced by ellipsoidal‐shape‐distributed temperature field during the sintering process, which is verified by finite‐element analysis. Although some temperature differences are unavoidable in the sintering process, homogeneity and mechanical properties of ingots can be improved by appropriately extending the sintering time and design of graphite die. Samples cut from ingots attain the peak ZT value of 1.15 at 373 K, about 17% enhancement over commercial zone‐melted samples. Moreover, the compressive and bending strengths are improved by several times as well. It is important to ascertain that large‐size p‐type Bi₂Te₃‐based thermoelectric materials with high thermoelectric performance can be fabricated by MS‐PAS.     

Improving Thermoelectric Performance of α‐MgAgSb by Theoretical Band Engineering Design

α‐MgAgSb is recently discovered to be a new class of thermoelectric material near room temperature. A competitive ZT of 1.4 at 525 K is achieved in Ni‐doped α‐MgAgSb, and the measured efficiency of energy conversion reaches a record value of 8.5%, which is even higher than that of the commercially applied material bismuth telluride. On the other hand, the band structure of α‐MgAgSb is believed to be unprofitable to the power factor, owing to the less degenerate valence valleys. Here, this paper reports a systematic theoretical study on the thermoelectric properties by using the electron/phonon structure and transport calculations. Based on the careful analysis of Fermi surface, a principled scheme is presented to design band engineering in α‐MgAgSb. Following the given rules, several effective dopants are predicted. As two examples, Zn‐ and Pd‐doped α‐MgAgSb are numerically confirmed to exhibit an extraordinary ZT value of 2.0 at 575 K and a high conversion efficiency of 12.6%, owing to the effects of band convergence. This work develops an applicable scheme for the purposive design of band engineering, and the idea can be simply applied to more thermoelectric materials.     

Controlling Metallurgical Phase Separation Reactions of the Ge0.87Pb0.13Te Alloy for High Thermoelectric Performance

We demonstrate the potential of metallurgical controlling of the phase separation reaction, by means of spark plasma sintering consolidation and subsequently controlled heat treatments sequence, for enhancement the thermoelectric properties of the p‐type Ge_0.87Pb_0.13Te composition. Very high ZTs of up to ～2, attributed to the nucleation of sub‐micron phase separation domains and to comparable sized twinning and dislocation networks features, were observed. Based on the experimentally measured transport properties, combined with the previously reported phase separated n‐type (Pb_0.95Sn_0.05Te)_0.92(PbS)_0.08 composition, a maximal efficiency value of ～11.5% was theoretically calculated. These ZT and efficiency values are among the highest reported for single composition non‐segmented bulk material legs.     

Enhanced Thermoelectric and Mechanical Properties in Yb0.3Co4Sb12 with In Situ Formed CoSi Nanoprecipitates

Filled Skutterudites are one group of the most promising thermoelectric materials in real power generation applications. Herein, homogeneously dispersed multiscale CoSi nanostructures are successfully embedded into grains of the classic skutterudite system, Yb_0.3Co₄Sb₁₂, by the in situ precipitation method. Such nanoprecipitates contribute much to the synergistic enhancement of thermoelectric and mechanical properties. On one hand, by the fine deployment of multiscale CoSi nanoparticles, the lattice thermal conductivity is significantly depressed almost to the theoretical limit because of the disrupted propagation of the heat‐carrying phonons at phase boundaries. On the other hand, low‐energy electrons are effectively screened due to the energy filtering effect by the interfacial potential barrier between the CoSi nanoprecipitate and the matrix, resulting in an enhanced power factor. Taken together, an enhanced peak ZT value of ≈1.5 at 873 K for the Yb_0.3Co₄Sb₁₂/0.05CoSi composite is obtained with a high average ZT ≈0.95 between 300 and 873 K through decoupling the electrical and thermal transport parameters. Moreover, such a microstructure with multiscale CoSi nanoparticles shows significantly improved mechanical properties owing to particle hardening, making it more competitive for practical applications.     

Weak Electron Phonon Coupling and Deep Level Impurity for High Thermoelectric Performance Pb1−xGaxTe

High ZT of 1.34 at 766 K and a record high average ZT above 1 in the temperature range of 300‐864 K are attained in n‐type PbTe by engineering the temperature‐dependent carrier concentration and weakening electron–phonon coupling upon Ga doping. The experimental studies and first principles band structure calculations show that doping with Ga introduces a shallow level impurity contributing extrinsic carriers and imparts a deeper impurity level that ionizes at higher temperatures. This adjusts the carrier concentration closer to the temperature‐dependent optimum and thus maximizes the power factor in a wide temperature range. The maximum power factor of 35 µW cm⁻¹ K⁻² is achieved for the Pb_0.98Ga_0.02Te compound, and is maintained over 20 µWcm⁻¹ K⁻² from 300 to 767 K. Band structure calculations and X‐ray photoelectron spectroscopy corroborate the amphoteric role of Ga in PbTe as the origin of shallow and deep levels. Additionally, Ga doping weakens the electron–phonon coupling, leading to high carrier mobilities in excess of 1200 cm² V⁻¹ s⁻¹. Enhanced point defect phonon scattering yields a reduced lattice thermal conductivity. This work provides a new avenue, beyond the conventional shallow level doping, for further improving the average ZT in thermoelectric materials.     

Thermoelectric Nanostructures: From Physical Model Systems towards Nanograined Composites

Thermoelectric materials could play an increasing role for the efficient use of energy resources and waste heat recovery in the future. The thermoelectric efficiency of materials is described by the figure of merit ZT = (S²σT)/κ (S Seebeck coefficient, σ electrical conductivity, κ thermal conductivity, and T absolute temperature). In recent years, several groups worldwide have been able to experimentally prove the enhancement of the thermoelectric efficiency by reduction of the thermal conductivity due to phonon blocking at nanostructured interfaces. This review addresses recent developments from thermoelectric model systems, e.g. nanowires, nanoscale meshes, and thermionic superlattices, up to nanograined bulk‐materials. In particular, the progress of nanostructured silicon and related alloys as an emerging material in thermoelectrics is emphasized. Scalable synthesis approaches of high‐performance thermoelectrics for high‐temperature applications is discussed at the end.     

Three‐Stage Inter‐Orthorhombic Evolution and High Thermoelectric Performance in Ag‐Doped Nanolaminar SnSe Polycrystals

The ultrahigh thermoelectric performance of SnSe‐based single crystals has attracted considerable interest in their polycrystalline counterparts. However, the temperature‐dependent structural transition in SnSe‐based thermoelectric materials and its relationship with their thermoelectric performance are not fully investigated and understood. In this work, nanolaminar SnSe polycrystals are prepared and characterized in situ using neutron and synchrotron powder diffraction measurements at various temperatures. Rietveld refinement results indicate that there is a complete inter‐orthorhombic evolution from Pnma to Cmcm by a series of layer slips and stretches along the a‐ and b‐axes over a 200 K temperature range. This phase transition leads to drastic enhancement of the carrier concentration and phonon scattering above 600 K. Moreover, the unique nanolaminar structure effectively enhances the carrier mobility of SnSe. Their grain and layer boundaries further improve the phonon scattering. These favorable factors result in a high ZT of 1.0 at 773 K for pristine SnSe polycrystals. The thermoelectric performances of polycrystalline SnSe are further improved by p‐type and n‐type dopants (i.e., doped with Ag and SnCl₂, respectively), and new records of ZT are achieved in Ag_0.015Sn_0.985Se (ZT of 1.3 at 773 K) and SnSe_0.985Cl_0.015 (ZT of 1.1 at 773 K) polycrystals.     

High‐Performance GeTe‐Based Thermoelectrics: from Materials to Devices

High‐performance GeTe‐based thermoelectrics have been recently attracting growing research interest. Here, an overview is presented of the structural and electronic band characteristics of GeTe. Intrinsically, compared to low‐temperature rhombohedral GeTe, the high‐symmetry and high‐temperature cubic GeTe has a low energy offset between L and Σ points of the valence band, the reduced direct bandgap and phonon group velocity, and as a result, high thermoelectric performance. Moreover, their thermoelectric performance can be effectively enhanced through either carrier concentration optimization, band structure engineering (bandgap reduction, band degeneracy, and resonant state engineering), or restrained lattice thermal conductivity (phonon velocity reduction or phonon scattering). Consequently, the dimensionless figure of merit, ZT values, of GeTe‐based thermoelectric materials can be higher than 2. The mechanical and thermal stabilities of GeTe‐based thermoelectrics are highlighted, and it is found that they are suitable for practical thermoelectric applications except for their high cost. Finally, it is recognized that the performance of GeTe‐based materials can be further enhanced through synergistic effects. Additionally, proper material selection and module design can further boost the energy conversion efficiency of GeTe‐based thermoelectrics.     

Studies on Thermoelectric Properties of n‐type Polycrystalline SnSe1‐xSx by Iodine Doping

Iodine‐doped n‐type SnSe polycrystalline by melting and hot pressing is prepared. The prepared material is anisotropic with a peak ZT of ≈0.8 at about 773 K measured along the hot pressing direction. This is the first report on thermoelectric properties of n‐type Sn chalcogenide alloys. With increasing content of iodine, the carrier concentration changed from 2.3 × 10¹⁷ cm^?3 (p‐type) to 5.0 × 10¹⁵ cm^?3 (n‐type) then to 2.0 × 10¹⁷ cm^?3 (n‐type). The decent ZT is mainly attributed to the intrinsically low thermal conductivity due to the high anharmonicity of the chemical bonds like those in p‐type SnSe. By alloying with 10 at% SnS, even lower thermal conductivity and an enhanced Seebeck coefficient were achieved, leading to an increased ZT of ≈1.0 at about 773 K measured also along the hot pressing direction.     

Mechanically Robust BiSbTe Alloys with Superior Thermoelectric Performance: A Case Study of Stable Hierarchical Nanostructured Thermoelectric Materials

Bismuth telluride based thermoelectric materials have been commercialized for a wide range of applications in power generation and refrigeration. However, the poor machinability and susceptibility to brittle fracturing of commercial ingots often impose significant limitations on the manufacturing process and durability of thermoelectric devices. In this study, melt spinning combined with a plasma‐activated sintering (MS‐PAS) method is employed for commercial p‐type zone‐melted (ZM) ingots of Bi_0.5Sb_1.5Te₃. This fast synthesis approach achieves hierarchical structures and in‐situ nanoscale precipitates, resulting in the simultaneous improvement of the thermoelectric performance and the mechanical properties. Benefitting from a strong suppression of the lattice thermal conductivity, a peak ZT of 1.22 is achieved at 340 K in MS‐PAS synthesized structures, representing about a 40% enhancement over that of ZM ingots. Moreover, MS‐PAS specimens with hierarchical structures exhibit superior machinability and mechanical properties with an almost 30% enhancement in their fracture toughness, combined with an eightfold and a factor of six increase in the compressive and flexural strength, respectively. Accompanied by an excellent thermal stability up to 200 °C for the MS‐PAS synthesized samples, the MS‐PAS technique demonstrates great potential for mass production and large‐scale applications of Bi₂Te₃ related thermoelectrics.     

Optimum Carrier Concentration in n‐Type PbTe Thermoelectrics

Taking La‐ and I‐doped PbTe as an example, the current work shows the effects of optimizing the thermoelectric figure of merit, zT, by controlling the doping level. The high doping effectiveness allows the carrier concentration to be precisely designed and prepared to control the Fermi level. In addition to the Fermi energy tuning, La‐doping modifies the conduction band, leading to an increase in the density of states effective mass that is confirmed by transport, infrared reflectance and hard X‐ray photoelectron spectroscopy measurements. Taking such a band structure modification effect into account, the electrical transport properties can then be well‐described by a self‐consistent single non‐parabolic Kane band model that yields an approximate (m*T)^1.5 dependence of the optimal carrier concentration for a peak power factor in both doping cases. Such a simple temperature dependence also provides an effective approximation of carrier concentration for a peak zT and helps to explain, the effects of other strategies such as lowering the lattice thermal conductivity by nanostructuring or alloying in n‐PbTe, which demonstrates a practical guide for fully optimizing thermoelectric materials in the entire temperature range. The principles used here should be equally applicable to other thermoelectric materials.     

Thermoelectric Property Study of Nanostructured p‐Type Half‐Heuslers (Hf,Zr, Ti)CoSb0.8Sn0.2

Based on the best peak theromoelectric figure‐of‐merit value (ZT) of ca. 0.8 in Hf_0.5Zr_0.5CoSb_0.8Sn_0.2 and ca. 1 in Hf_0.8Ti_0.2CoSb_0.8Sn_0.2, the effect of Ti on thermoelectric properties is studied in (Hf, Zr, Ti)CoSb_0.8Sn_0.2, with the aim of further improving the ZT and reducing the usage of Hf. By either partial replacement of Hf and Zr with Ti in Hf_0.5Zr_0.5CoSb_0.8Sn_0.2 or partial replacement of Hf and Ti with Zr in Hf_0.8Ti_0.2CoSb_0.8Sn_0.2, a peak ZT of ≥1 is achieved at 800°C in Hf_0.44Zr_0.44Ti_0.12CoSb_0.8Sn_0.2. This composition has two advantages over the previous two best compositions: higher ZT than Hf_0.5Zr_0.5CoSb_0.8Sn_0.2 and less Hf than in Hf_0.8Ti_0.2CoSb_0.8Sn_0.2. A higher ZT with less Hf is very much desired since Hf is much more expensive than other constituent elements. The ZT improvement is the result of thermal conductivity reduction due to phonon scattering by both alloy and the nanostructure effect.     

An Integrated Approach to Thermoelectrics: Combining Phonon Dynamics,Nanoengineering, Novel Materials Development,Module Fabrication,and Metrology

This review discusses the longstanding efforts to develop advanced thermoelectrics through a multidisciplinary approach by combining condensed matter physics, nanotechnology, solid‐state chemistry, electrical engineering, mechanical engineering, and metrology. The phonon dynamics of skutterudites, clathrates, tetrahedrites, and layered LaOBiSSe are investigated through inelastic neutron scattering, allowing insights into their low lattice thermal conductivity due to rattling in a cage as well as under planar coordination. The electrical resistivity, Seebeck coefficient, and Hall coefficient of Bi‐nanowires are successfully measured with a home‐made system, demonstrating a size effect in thermoelectric and galvanomagnetic phenomena. For PbTe‐based bulk thermoelectrics, an exceptionally high figure of merit ZT (≈1.8 at 800 K) is achieved through nanostructuring. Moreover, correspondingly high conversion efficiency (≈11% for a temperature difference of 590 K) is demonstrated in nanostructured PbTe‐based modules. Sulfides (tetrahedrite, colusite, and CdI₂‐type layered systems) and arsenides (LnFeAsO and BaZn₂As₂) are developed as environmentally friendly and emerging thermoelectric materials, respectively. The output power and efficiency of modules with novel materials, including nanostructured PbTe, Zn₄Sb₃, and clathrates, are measured with the highly accurate self‐made system. Future opportunities and challenges for the widespread use of thermoelectric waste heat recovery and energy harvesting are also discussed.     

High‐Efficiency Thermoelectric Power Generation Enabled by Homogeneous Incorporation of MXene in (Bi,Sb)2Te3 Matrix

The (Bi,Sb)₂Te₃ (BST) compounds have long been considered as the benchmark of thermoelectric (TE) materials near room temperature especially for refrigeration. However, their unsatisfactory TE performances in wide‐temperature range severely restrict the large‐scale applications for power generation. Here, using a self‐assembly protocol to deliver a homogeneous dispersion of 2D inclusion in matrix, the first evidence is shown that incorporation of MXene (Ti₃C₂T_x) into BST can simultaneously achieve the improved power factor and greatly reduced thermal conductivity. The oxygen‐terminated Ti₃C₂T_x with proper work function leads to highly increased electrical conductivity via hole injection and retained Seebeck coefficient due to the energy barrier scattering. Meanwhile, the alignment of Ti₃C₂T_x with the layered structure significantly suppresses the phonon transport, resulting in higher interfacial thermal resistance. Accordingly, a peak ZT of up to 1.3 and an average ZT value of 1.23 from 300 to 475 K are realized for the 1 vol% Ti₃C₂T_x/BST composite. Combined with the high‐performance composite and rational device design, a record‐high thermoelectric conversion efficiency of up to 7.8% is obtained under a temperature gradient of 237 K. These findings provide a robust and scalable protocol to incorporate MXene as a versatile 2D inclusion for improving the overall performance of TE materials toward high energy‐conversion efficiency.     

Lithium Doping to Enhance Thermoelectric Performance of MgAgSb with Weak Electron–Phonon Coupling

Despite the unfavorable band structure with twofold degeneracy at the valence band maximum, MgAgSb is still an excellent p‐type thermoelectric material for applications near room temperature. The intrinsically weak electron–phonon coupling, reflected by the low deformation potential E_def ≈ 6.3 eV, plays a crucial role in the relatively high power factor of MgAgSb. More importantly, Li is successfully doped into Mg site to tune the carrier concentration, leading to the resistivity reduction by a factor of 3 and a consequent increase in power factor by ≈30% at 300 K. Low lattice thermal conductivity can be simultaneously achieved by all‐scale hierarchical phonon scattering architecture including high density of dislocations and nanoscale stacking faults, nanoinclusions, and multiscale grain boundaries. Collectively, much higher average power factor ≈25 μW cm^?1 K^?2 with a high average ZT ≈ 1.1 from 300 to 548 K is achieved for 0.01 Li doping, which would result in a high output power density ≈1.56 W cm^?2 and leg efficiency ≈9.2% by calculations assuming cold‐side temperature T_c = 323 K, hot‐side temperature T_h = 548 K, and leg length = 2 mm.