Potential Thermoelectric Material Research Articles

Tuning conduction properties and clarifying thermoelectric performance of P-type half-Heusler alloys TiNi1−xCoxSn (0 ≤ x ≤ 0.15)

TiNiSn is an N-type thermoelectric material with a high-power factor composed of low toxicity and abundant elements. TiNiSn also shows P-type electrical conduction by hole doping. In this study, we tune the conduction properties of TiNi1−xCoxSn (0 ≤ x ≤ 0.15) with Co substitution at the Ni site. The samples were prepared by the arc melting method, and thermoelectric properties were investigated up to 800 K. The results of the Hall effect and the Seebeck coefficient measurements indicate that the majority of charge carriers changes from electrons to holes at x ≥ 0.03, suggesting that Co acts as an acceptor. We report for the first time that Ti0.994Ni1.00Co0.051Sn1.01 exhibits ZT = 0.12 at 675 K. This work reveals that Ti0.994Ni1.00Co0.051Sn1.01 could be a potential P-type thermoelectric material operating at high temperatures.

Boosting the thermoelectric performance of Bi2S3 by CeCl3 addition and hydrothermal synthesis

Bi2S3 is a potential thermoelectric material due to its high Seebeck coefficient (S), low thermal conductivity (κ) and environmentally friendly elemental composition. However, pristine Bi2S3 suffers from a low thermoelectric performance primarily owing to the intrinsic low electrical conductivity (σ). In this work, we employ CeCl3 doping to promote the σ of Bi2S3 by a hydrothermal method. Doping 1.0 % mol CeCl3 provides more electrons to increase the carrier concentration to 2.73 × 1019 cm−3 of Bi2S3 at room temperature, which leads to significant high σ and power factor of 242 μW m−1 K−2 at 573 K. In addition, the formation of micro–nano pores in the doped Bi2S3 bulk samples contribute to the phonon scattering as well as the reduction of lattice thermal conductivity. A peak ZT of ∼0.31 at 623 K is obtained in the Bi2S3 bulk sample doped with 1.0 % mol CeCl3, which is almost twice as high as the pristine Bi2S3. Simultaneously, the Vickers hardness of 1.0 % mol CeCl3 doped Bi2S3 samples achieves to approximately 1.28 GPa, which is enhanced by nearly 40 % compared to pristine Bi2S3. This study has provided a facile method for realizing high thermoelectric performance and high mechanical property of Bi2S3 materials.

Enhancement in power factor through rare-earth samarium doping in Cu2SnSe3 system

Cu2SnSe3 has drawn enough attention as a potential thermoelectric material due to its unique electronic and thermal properties. We present the impact of Sm doping on the Cu2SnSe3 system’s Sn site. The polycrystalline samples of Cu2Sn1-x Sm x Se3 (0 ≤ x ≤ 0.08) were prepared using the solid-state reaction technique followed by conventional sintering. The crystal structure was characterized using XRD and the results reveal that the samples have a diamond cubic structure with a space group of F4̄3m. Scanning Electron Microscopy (SEM) analysis indicates a uniform surface homogeneity within the sample. Furthermore, the introduction of Sm causes a reduction in porosity. The electrical transport characteristics were studied in the mid temperature range of 300–650 K. The Seebeck coefficient of all the samples were found to be positive within the temperature range under study, suggesting that holes constitute the majority charge carriers. This is also confirmed by the Hall measurements as the carrier concentration was positive for all the samples. The inclusion of Sm has led to a reduction of electrical resistivity and Seebeck coefficient and hence power factor of ~539 μW mK−2 for x = 0.08 at 630 K which is ten times greater as compared to x = 0 whose power factor is ~56 μW mK−2 at 630 K is achieved which makes it suitable for thermoelectric applications.

Electrical and thermal transport properties of Cr2Se3-Cr2Te3 solid-solution alloy system and estimation of optimal thermoelectric properties

Cr2Se3 is a layered narrow-bandgap semiconductor with a low lattice thermal conductivity of ∼1 W/mK, which can be considered as a potential thermoelectric material. A solid-solution alloy system with Cr2Te3 can be designed to manipulate the electrical and thermal transport properties. In this study, a series of Cr2Se3-Cr2Te3 solid-solution alloys (Cr2(Se1-xTex)3, x = 0, 0.33, 0.5, 0.67, 0.83, and 1) were synthesized, and their electrical and thermal transport properties were investigated. Regarding the electrical transport properties, the power factor (∼0.35 mW/mK2) of Cr2Se3 gradually and significantly decreased as the Te content (x) increased owing to the significant decrease in the Seebeck coefficient that resulted from the large increase in the carrier concentration. Regarding the thermal transport properties, the total thermal conductivity increased with x as a result of the large increase in the electrical conductivity, despite the continuous decrease in the lattice thermal conductivity. Consequently, the thermoelectric figure of merit (zT ∼ 0.20) of Cr2Se3 gradually and significantly decreased to 0.009 for Cr2Te3 at 700 K; thus, no enhancement of zT was observed from the experimental results of simple solid-solution alloying. On the other hand, the thermoelectric quality factors of the solid-solution compositions for x = 0.33–0.83 were found to be enhanced compared to that of the Cr2Se3 sample, implying that zT could be further enhanced by optimizing the carrier concentration. Indeed, enhanced zT values were estimated based on a single parabolic band model for the solid-solution compositions with x = 0.33–0.83 if the carrier concentration was optimized to ∼1019 cm−3, which was found to be owing to the increased nondegenerate and weighted mobility (inferring weaker carrier–phonon interaction). Therefore, it is suggested that the solid-solution alloying approach could provide a feasible strategy to enhance the thermoelectric performance by reducing carrier-phonon interaction when further combined with carrier concentration optimization.

Excellent thermoelectric performance of Fe2NbAl alloy induced by strong crystal anharmonicity and high band degeneracy

Full-Heusler alloys with earth-abundant elements exhibit high mechanical strength and favorable electrical transport behavior, but their high intrinsic lattice thermal conductivity limits potential thermoelectric application. Here, the thermoelectric transport properties of Fe-based Full-Heusler Fe2MAl (M = V, Nb, Ta) alloys are comprehensively investigated utilizing density functional theory. The results suggest that Fe2NbAl exhibits exceptionally low lattice thermal conductivity due to low phonon velocities and weakly bound Nb atoms. In Fe2NbAl, the underbonding of the Nb atoms leads large Grüneisen parameters and high anharmonic scattering rates of low-frequency acoustic phonon. Meanwhile, the high band degeneracy and large electrical conductivity lead to a maximum p-type power factor of 255.6 μW·K−2·cm−1 at 900 K. The combination of low lattice thermal conductivity and favorable electrical transport properties leads a maximum p-type dimensionless figure of merit of 1.7. Our work indicates Fe2NbAl, as a low-cost, environmentally friendly, is a potential high-performance p-type thermoelectric material.

Enhanced thermoelectric properties of n-type sulfide compound Bi2SeS2 by Cl doping

Sulfides composed of an eco-friendly and low-cost composition have received widespread attention as a substitute for traditional thermoelectric materials. However, n-type sulfides with high performance are rare compared with p-type ones. This work revealed that Bi2SeS2 with n-type conductivity characteristics is a potential thermoelectric material, whose ZT value reaches ∼ 0.70 at 773 K for the Cl doped sample Bi2Se0.98S2Cl0.02. Cl serving as a carrier donor can increase the electrical conductivity by optimizing the carrier concentration. Coupled with a moderate Seebeck coefficient in the range of 100–200 μV/K, a high power factor of ∼6.46 μWcm−1K−2 at 773 K was achieved. In addition, the lattice thermal conductivity reduces because of the formation of precipitates, as well as the induced mass and stress fluctuations due to the doping of heterogeneous Cl element, which effectively suppress the increase in total thermal conductivity. The combination of optimized power factor and low thermal conductivity leads to a final high ZT value, which is relatively higher than or comparable to most other reported n-type sulfide thermoelectric material.

Theoretical investigation into potential thermoelectric material Monolayer InI with direct bandgap and ultralow lattice thermal conductivity

Monolayer metal iodides are garnering widespread attention due to their ultralow lattice thermal conductivity and their potential applications in the field of thermoelectrics. Here, we utilized first-principles calculations and Boltzmann transport theory to thoroughly investigate the thermoelectric behavior of monolayer InI. Results indicate that this material functions as a direct bandgap semiconductor and features an exceptionally low lattice thermal conductivity of 0.27 W m−1K−1 at 300 K, a result of its low group velocities and short phonon lifetimes. Furthermore, transport coefficients were calculated with enhanced precision through the Wannier interpolation method, incorporating the HSE06 hybrid functional and spin-orbit coupling (SOC) effects. Remarkably, the maximum thermoelectric figure of merit (ZT) values for monolayer InI demonstrate substantial growth with increased temperatures, surging from 0.31 at 300 K to 1.20 at 450 K for p-type, and escalating from 0.26 at 300 K to 0.72 at 450 K for n-type. These promising low-temperature thermoelectric properties exhibited by monolayer InI suggest its suitability for integration into the production of thermoelectric devices.

Principles and Methods for Improving the Thermoelectric Performance of SiC: A Potential High-Temperature Thermoelectric Material.

Thermoelectric materials that can convert thermal energy to electrical energy are stable and long-lasting and do not emit greenhouse gases; these properties render them useful in novel power generation devices that can conserve and utilize lost heat. SiC exhibits good mechanical properties, excellent corrosion resistance, high-temperature stability, non-toxicity, and environmental friendliness. It can withstand elevated temperatures and thermal shock and is well suited for thermoelectric conversions in high-temperature and harsh environments, such as supersonic vehicles and rockets. This paper reviews the potential of SiC as a high-temperature thermoelectric and third-generation wide-bandgap semiconductor material. Recent research on SiC thermoelectric materials is reviewed, and the principles and methods for optimizing the thermoelectric properties of SiC are discussed. Thus, this paper may contribute to increasing the application potential of SiC for thermoelectric energy conversion at high temperatures.

Investigation on the electrical and thermal properties of Cr-doped FeSe2 alloys

FeSe2 is a p-type semiconductor with a narrow band gap, which can be considered a potential thermoelectric material. Herin, the electrical and thermal properties of Cr-doped FeSe2, Fe1-xCrxSe2 (x = 0, 0.03, 0.06, and 0.09), polycrystalline alloys are investigated. All compositions show single-phase marcasite structures of FeSe2 with gradual decreases in lattice parameters with Cr doping x. With increasing x, the electrical conductivity gradually increases from 13 (x = 0) to 46 S/cm (x = 0.09), owing to a large increase in carrier concentration originated from the substitution of Cr2+ and Cr3+ at the Fe site. However, the magnitude of Seebeck coefficient decreases considerably at 300 K, resulting in decrease in power factor. In addition, the density-of-state effective mass decreases significantly from 6.0 m0–1.04 m0. At 700 K, the decrease in Seebeck coefficient is less severe. Although the total and lattice thermal conductivity decrease at all temperatures owing to additional phonon scattering of the extrinsic Cr ions, a thermoelectric figure of merit, zT, generally decreases compared to that of the pristine sample due to power factor decrease at 300 K. Meanwhile, a slight increase of zT to 0.11 is observed for x = 0.06 at 700 K.

Vacancy Suppression and Resonant Level Rendering Extraordinary Power Factor in Sn0.99In0.01Te/Tourmaline Composite.

SnTe, as a potential medium-temperature thermoelectric material, reaches a maximum power factor (PF)usually above 750K, which is not conducive to continuous high-power output in practical applications. In this study, PF is maintained at high values between 18.5 and 25µWcm-1K-2 for Sn0.99In0.01Te-xwt% tourmaline samples within the temperature range of 323 to 873K, driving the highest PFeng of 1.2Wm-1K-1 and PFave of 22.5µWcm-1K-2, over 2.5 times that of pristine SnTe. Such an extraordinary PF is attributed to the synergy of resonant levels and Sn vacancy suppression. Specifically, the Seebeck coefficient increases dramatically, reaching 88µVK-1 at room temperature. Meanwhile, by Sn vacancy suppression, carrier concentration, and mobility are optimized to ≈1019cm-3 and 740cm2V-1s-1, respectively. With the tourmaline compositing, Sn vacancies are further suppressed and the thermal conductivity simultaneously decreases, with the minimum lattice thermal conductivity of 0.9W m-1 K-1. Finally, the zT value ≈0.8 is obtained in the Sn0.99In0.01Te sample. The peak of the power output density reaches 0.89W cm-2 at a temperature difference of 600K. Such SnTe alloys with high and "temperature-independent" PF will offer an option for realizing high output power in thermoelectric devices.

Origin of low lattice thermal conductivity in promising ternary PbmBi2S3+m (m = 1–10) thermoelectric materials

Ternary Pb-Bi-S compounds emerge as potential thermoelectric materials owing to low thermal conductivity, but the origin of their intrinsic low lattice thermal conductivities lacks further investigation. Herein, a series of ternary PbmBi2S3+m (m = 1–10) compounds are synthesized and their crystal structure evolutions with increasing m values are clearly unclosed. The room-temperature lattice thermal conductivities in PbBi2S4, Pb3Bi2S6 and Pb6Bi2S9 can reach at 0.57, 0.56 and 0.80 W m−1 K−1, respectively, outperforming other ternary sulfur-based compounds. Theoretical calculations show that the low lattice thermal conductivities in PbmBi2S3+m (m = 1–10) mainly originate from soft phonon dispersion caused by strong lattice anharmonicity, and both asymmetric chemical bond and lone pair electrons (Pb 6s2 and Bi 6s2) can favorably block phonon propagation. Furthermore, the elastic measurements also confirm relatively low sound velocities and shear modulus, and the Grüneisen parameter (γ) calculated by sound velocities can reach at 1.67, 1.85 and 1.94 in PbBi2S4, Pb3Bi2S6 and Pb6Bi2S9, respectively. Finally, the intrinsic low lattice thermal conductivities in PbmBi2S3+m (m = 1–10) contribute to promising thermoelectric performance, and the maximum ZT values of 0.47, 0.38 and 0.45 can be achieved in undoped PbBi2S4, Pb3Bi2S6 and Pb6Bi2S9, respectively.

Boosting Thermoelectric Performance of PbBi2Te4 via Reduced Carrier Scattering and Intensified Phonon Scattering.

Materials with low intrinsic lattice thermal conductivity are crucial in the pursuit of high-performance thermoelectric (TE) materials. Here, the TE properties of PbBi2Te4-xSex (0 ≤ x ≤ 0.6) samples are systematically investigated for the first time. Doping with Se in PbBi2Te4 can simultaneously reduce carrier concentration and increase carrier mobility. The Seebeck coefficient is significantly increased by doping with Se, based on the density functional theory calculation, it is shown to be due to the increased bandgap and electronic density of states. In addition, the lattice strain is enhanced due to the difference in the size of Se and Te atoms, and the multidimensional defects formed by Se doping, such as vacancies, dislocations, and grain boundaries, enhance the phonon scattering and reduce the lattice thermal conductivity by about 37%. Finally, by using Se doping to reduce carrier concentration and thermal conductivity, a large ZTmax = 0.56 (at 574K) is achieved for PbBi2Te3.5Se0.5, which is around 64% larger than those of the PbBi2Te4 pristine sample. This work not only demonstrates that PbBi2Te4 is a potential medium temperature thermoelectric material, but also provides a reference for enhancing thermoelectric properties through defect and energy band engineering.

High-Throughput Strategies in the Discovery of Thermoelectric Materials.

Searching for new high-performance thermoelectric (TE) materials that are economical and environmentally friendly is an urgent task for TE society, but the advancements are greatly limited by the time-consuming and high cost of the traditional trial-and-error method. The significant progress achieved in the computing hardware, efficient computing methods, advance artificial intelligence algorithms, and rapidly growing material data have brought a paradigm shift in the investigation of TE materials. Many electrical and thermal performance descriptors are proposed and efficient high-throughput (HTP) calculation methods are developed with the purpose to quickly screen new potential TE materials from the material databases. Some HTP experiment methods are also developed which can increase the density of information obtained in a single experiment with less time and lower cost. In addition, machine learning (ML) methods are also introduced in thermoelectrics. In this review, the HTP strategies in the discovery of TE materials are systematically summarized. The applications of performance descriptor, HTP calculation, HTP experiment, and ML in the discovery of new TE materials are reviewed. In addition, the challenges and possible directions in future research are also discussed.

Facile synthesize and enhanced thermoelectric performance of PbS with Cl doping and PbSe alloying

Besides inferior conversion efficiency, the widespread application of thermoelectric materials currently faces the challenges of the rare and high cost of constituent elements, complex and time-consuming synthesis. Therefore, it is urgent to develop facile synthesized methods and high-performance thermoelectric materials consisting of elements with earth-abundance and low cost. Meeting above partial requirement, lead sulfide (PbS) recently was identified as a potential thermoelectric material to substitute current commercial PbTe. In this paper, a one-step high-pressure method was employed to facile and fast synthesis of PbS. Trace Cl doping tunes the carrier concentration of PbS effectively, which optimizes the electrical transport properties. Further PbSe alloying sharply reduces the thermal conductivity of PbS. Therefore, an enhanced zT∼1.0 @ 700 K was obtained for PbS doped with 0.3 at% Cl and alloyed with 25 at% PbSe, which is comparable to the commercially applied PbTe. These results indicate that high-pressure combing with Cl-doping and PbSe-alloying provide a facile method and strategy to fabricate high-performance PbS-based thermoelectric materials.

Augmented near-room-temperature power factor of homogenously grown thermoelectric ZnO films

Future applications in power generation for wearable and portable electronics or active cooling for chips will benefit from near-room-temperature thermoelectric performance enhancement. Ga-doped ZnO (GZO) thin films are potential thermoelectric materials as they have the advantages of high cost-effectiveness, low toxicity, excellent stability, and high optical transparency. Inserting a ZnO buffer layer between the sapphire substrate and GZO thin films could contribute to optimizing carrier mobility and further improving electrical transport properties. However, thermoelectric performance at near-room-temperature ranges still needs to be promoted for practical applications. In this present study, ZnO single-crystal slices were directly selected as substrates for homogenously growing GZO thin films to further modify the substrate–film interface. The high Hall mobility of 47 cm2 V−1 s−1 and weighted mobility of 75 cm2 V−1 s−1 could be realized, resulting in better electrical transport performance. Consequently, the homogenously grown GZO thin films possessed competitively prominent power factor values of 333 μW m−1 K−2 at 300 K and 391 μW m−1 K−2 at 373 K. This work offers an effective avenue for optimizing the thermoelectric properties of oxide-based thin films via homogenous growth.

Two-dimensional Be2P4 as a promising thermoelectric material and anode for Na/K-ion batteries.

Incredibly effective and flexible energy conversion and storage systems hold great promise for portable self-powered electronic devices. Owing to their large surface area, exceptional atomic structures, superior electrical conductivity and good mechanical flexibility, two-dimensional (2D) materials are recognized as an attractive option for energy conversion and storage application. In this work, we examined the stability, electronic, thermoelectric and electrochemical aspects of a novel 2D Be2P4 monolayer by adopting density functional theory (DFT). The Be2P4 monolayer exhibits a direct semiconductor gap of 0.9 eV (HSE06), large Young's modulus (∼198 GPa), high carrier mobility (∼104 cm2 V-1 s-1) and a low excitonic binding energy of 0.11 eV. Our calculated findings suggest that Be2P4 shows a lattice thermal conductivity of 1.02 W m K-1 at 700 K, resulting in moderate thermoelectric performance (ZT ∼ 0.7), encouraging its use in thermoelectric materials. In addition, a higher adsorption energy of -2.28 eV (-2.52 eV) and less diffusion barrier of 0.22 eV (0.17 eV) for Na(K)-ion batteries promote fast ion transport in the Be2P4 monolayer. This material also shows a high specific capacity and superior energy density of 8460 W h kg-1 (8883 W h kg-1) for Na(K)-ion batteries. Thus, our results offer insightful information for investigating potential thermoelectric and flexible anode materials based on the Be2P4 monolayer.

Decomposed defect formation energy for analysis of doping process: The case of n-type and p-type doping of β-FeSi2

Defect formation energy governs the thermodynamics of a specific dopant within the host material. Here, we introduce an approach to decomposing the defect formation energy into intuitive components, each representing a distinct physical step in the process of defect formation. Through this approach, we illustrate that adhering solely to conventional criteria, such as ionic radius, may overlook potential dopants. Taking β-FeSi2, a promising high-temperature thermoelectric material, as an example, we demonstrate that non-intuitive chemical interactions can play a more significant role in lowering the defect formation energy. As a result, Ir on Fe site is found to exhibit unexpected low defect formation energy among the 26 candidate dopants and has been employed in experiment to enhance the thermoelectric figure of merit of n-type β-FeSi2. The understanding gained from this work could be of general interest for addressing the doping limit issue for other potential thermoelectric materials.

Exploring properties of organometallic double perovskite (CH3NH3)2AgInCl6: A novel material for energy conversion devices

Distinct types of materials are being explored for usage in thermoelectric (TE) and photovoltaic (PV) systems in order to alleviate the energy problem. In order to create nontoxic, more stable, and best-performance energy convergence devices, the state-of-the-art hybrid halide double perovskites (HHDPs) compound has been identified as a potential TE material and potential replacement for hazardous lead. We have proposed a new HHDP material (CH3NH[Formula: see text]AgInCl6 and performed its theoretical investigation via the full potential linear augmented plane wave (FP-LAPW) method. The computational results show that the studied compound exhibits a direct bandgap of 3.708[Formula: see text]eV and has exceptional PV characteristics in the ultraviolet (UV) region. The obtained thermodynamic (TD) characteristics confirm that the titled compound is thermally stable at various temperatures and pressures. At 300 K, the examined HHDP material has the highest ZT (=2.23) in the p-region. Materials with higher ZTe values are substantially more important for generating electrical energy through waste heat. The ZTe result validates the use of these materials in TE devices at ambient temperature. The parameters of this compound have been computed for the first time. This study identifies (CH3NH[Formula: see text]AgInCl6 as a novel HHDP compound. Through an in-depth exploration of its properties, this study offers valuable insight for further research with potential applications in clean energy systems.

Enhancement of the thermoelectric performance of half-metallic full-Heusler Mn2VAl alloys via antisite defect engineering and Si partial substitution

A half-metallic full-Heusler Mn2VAl alloy is a potential p-type thermoelectric material that can directly generate electricity from waste heat via the Seebeck effect. For practical use, the Seebeck coefficient S of Mn2VAl should be increased while maintaining a high electrical conductivity σ from its half-metallic character. Herein, we achieved this objective through antisite defect engineering. Theoretically, it was predicted that the S was maximized by regulating partial density of states of majority-spin sp-electrons through the control of the fraction of antisite defect, fAD, between V and Al atoms in Mn2VAl. Experimentally, a significant increase in S and a slight decrease in σ were observed for an Mn2VAl sample with an optimal fAD = 33%, enhancing the thermoelectric power factor PF by 2.7 times from an Mn2VAl sample with fAD = 14%. Furthermore, we combined the antisite defect engineering with a partial substitution method. An Mn2V(Al0.96Si0.04) sample with fAD = 33% exhibited the highest PF = 4.5 × 10−4 W·m−1·K−2 at 767 K among the samples. The maximum dimensionless figure-of-merit zT of the Mn2V(Al0.96Si0.04) sample with fAD = 33% was measured to be 3.4 × 10−2 at 767 K, which is the highest among the p-type half-metallic full-Heusler alloys.

Enhancing Thermoelectric Performance in P-Type Sb2Te3-Based Compounds Through Nb─Ag Co-Doping with Donor-Like Effect.

P-type Sb2Te3 has been recognized as a potential thermoelectric material for applications in low-medium temperature ranges. However, its inherent high carrier concentration and lattice thermal conductivity led to a relatively low ZT value, particularly around room temperature. This study addresses these limitations by leveraging high-energy ball milling and rapid hot-pressing techniques to substantially enhance the Seebeck coefficient and power factor of Sb2Te3, yielding a remarkable ZT value of 0.55 at 323K due to the donor-like effect. Furthermore, the incorporation of Nb─Ag co-doping increases hole concentration, effectively suppressing intrinsic excitations ≈548K while maintaining the favorable power factor. Simultaneously, the lattice thermal conductivity can be significantly reduced upon doping. As a result, the ZT values of Sb2Te3-based materials attain an impressive range of 0.5-0.6 at 323K, representing an almost 100% improvement compared to previous research endeavors. Finally, the ZT value of Sb1.97Nb0.03Ag0.005Te3 escalates to 0.92 at 548K with a record average ZT value (ZTavg) of 0.75 within the temperature range of 323-573K. These achievements hold promising implications for advancing the viability of V-VI commercialized materials for low-medium temperature application.