Thermoelectric Figure Of Merit Research Articles

Enhancing thermoelectric efficiency of benzodithiophene-thienothiophene copolymers through doping-induced charge transfer

Organic thermoelectric materials have been gaining increasing interest due to their capacity to convert waste heat into electricity. This study explores the impact of doping-induced charge transfer states on the thermoelectric properties of benzodithiophene-thieno[3,2-b]thiophene-based polymers (PBDTTT) doped with 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). Detailed structural, optical, and electrical analyses were conducted on two specific polymers, PBDTTT:C (P1) and PBDTTT:EFT (P2). The investigation revealed distinct doping behaviors: P1 formed a partial charge transfer (PCT) complex, whereas P2 predominantly formed an integer charge transfer (ICT) complex. This distinction is attributed to the inherent structural differences and varying aggregation capabilities of the polymers. As a result, P2 exhibited enhanced electrical conductivity and a superior thermoelectric power factor compared to P1. This study emphasizes the critical role of polymer aggregation and charge-transfer mechanisms in optimizing the thermoelectric performance of conjugated polymers. It offers valuable insights for the development of efficient thermoelectric materials and the advancement of energy conversion technologies.

Ultralow thermal conductivity and high thermoelectric performance induced by dimensionality reduction in chain-like compounds X2PtSe2 (X=K, rb)

Balancing low lattice thermal conductivity (κL) with a high power factor is a major challenge in the research of thermoelectric (TE) materials. In this paper, we report on a class of chain-like compounds, X2PtSe2(X = K, Rb), characterized by strong lattice anharmonicity, weak bonds, and low phonon group velocities. Using first-principles calculations in conjunction with self-consistent phonon theory and the Boltzmann transport equation, we systematically investigate the thermal and electrical transport properties of X2PtSe2(X = K, Rb). At room temperature, the κL of K2PtSe2 and Rb2PtSe2 in the direction perpendicular to the Pt–Se chains is only 0.15 and 0.10 Wm−1K−1, respectively. Additionally, due to the low-dimensional nature of the Pt–Se chains, these compounds exhibit a ‘pudding-mold type’ band structure, contributing to a TE power factor. At 300K, under n-type doping, K2PtSe2 and Rb2PtSe2 achieve TE figures of merit (ZT) values of 1.66 and 1.67, respectively, in the direction perpendicular to the Pt–Se chains. At 500K, the ZT value of Rb2PtSe2 approaches 4, far surpassing traditional TE materials. These results indicate that the chain-like compounds X2PtSe2(X = K, Rb) exhibit excellent TE performance, achieving energy conversion efficiencies comparable to commercial transducer devices.

Epitaxial growth of high-quality Mg3Sb2 thin films on annealed c-plane Al2O3 substrates and their thermoelectric properties

High-quality epitaxial Mg3Sb2 thin films are promising thermoelectric materials to enable practical applications of compact and environmentally friendly thermoelectric conversion at RT. In this study, high-quality single-crystal Mg3Sb2 with high c-plane orientation was epitaxially grown directly on annealed c-Al2O3 substrates without passive layers. These thin films exhibited about three times higher thermoelectric power factor than any previously reported values due to high carrier mobility. The ultra-smooth surface of the annealed c-Al2O3 substrate facilitated the formation of high-quality Mg3Sb2 thin films without passive layers or polycrystalline interfaces that could be carrier scatters.

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.

Self-powered PEDOT: PSS/CSWCNT/Mxenes thermoelectric films and wearable electronics devices

In this work, Ti3C2–Cl is introduced into poly(3,4-ethylenedioxythiophene): poly(4-styrenesulfonic acid) / single-walled carbon nanotubes (PEDOT: PSS/SWCNT, noted as PPSC) films to prepare ternary thermoelectric films of PEDOT: PSS/SWCNT/Ti3C2–Cl (PPSCT). The microscopic morphology, structures, and thermoelectric properties of PPSC and PPSCT films show that the introduction of Ti3C2–Cl results in a tendency of decreasing electrical as well as thermal conductivity, and the Seebeck coefficient is increased. When the content of Ti3C2–Cl reaches 8 wt%, the conductivity, Seebeck coefficient, and thermal conductivity of the PPSCT films reach the optimum values of 1683 S/cm, 21.69 μV/K, and 14.97 W/mK, respectively, and the power factor (PF) and thermoelectric figure of merit (ZT) are 79.23 μW/mK2 and 1.58 × 10–3. The UPS and Hall effect results reveal that the improvement of the Seebeck effect of PPSCT mainly results from the ternary interfacial energy barrier as well as the change of carrier concentration. In addition, the wearable electronics devices demonstrate an output voltage of 4.5 mV and an output power of 54.36 nW under a 50 K temperature difference. The device displays a good monitoring sensitivity by reaching an output voltage of 0.6 mV at a 7 K temperature difference between the skin and the environment.

Order-N calculations for thermoelectric power factor based on linear response theory

We present an order-N quantum transport calculation methodology to evaluate thermoelectric transport coefficients, such as electric conductivity and Seebeck coefficient. Different from a conventional method using the electric conductivity spectrum, it obtains the coefficients directly from the correlation function between heat and electric current based on linear response theory. As an example, we apply the methodology to a two-dimensional square-lattice model with static disorder and confirm that the calculated results are consistent with those obtained by the conventional method. The proposed methodology provides an effective approach to evaluate the thermoelectric performance of micron-scale materials based on quantum mechanics from an atomistic viewpoint.

Combination of Counterion Size and Doping Concentration Determines the Electronic and Thermoelectric Properties of Semiconducting Polymers.

In both chemical and electrochemical doping of organic semiconductors (OSCs), a counterion, either from the electrolyte or ionized dopant, balances the charge introduced to the OSC. Despite the large influence of this counterion on OSC optical and electronic response, there remains substantial debate on how a fundamental parameter, ion size, impacts these properties. This work resolves much of this debateby accounting for two doping regimes. In the low-doping regime, the Coulomb binding energies between charge carrierson the OSC and the counterions are significant, and larger counterions lead to decreased Coulomb interactions, more delocalized charge carriers, and higher electrical conductivities. In the high-doping regime, the Coulomb binding energies become negligible due to the increased dielectric constant of the films and a smoothing of the energy landscape; thereby, the electrical conductivities depend primarily on the extent of morphological disorder in the OSC. Moreover, in regioregular poly(3-hexylthiophene), rr-P3HT, smaller counterions lead to greater bipolaron concentrations in the low-doping regime due to the increased Coulomb interactions. Emphasizing the impact of the counterion size, it is shown that larger counterions can lead to increased thermoelectric power factors for rr-P3HT.

Enhanced thermoelectric properties of carbon nanotubes/polyaniline fibers through engineering doping level and orientation

The rapid progress of miniaturized wearable electronics has put forward great requirements for organic fiber-based thermoelectric (TE) generators. Despite polyaniline (PANI) exhibits many outstanding attributes such as facile synthesis and low cost, as well as good environmental and thermal stability, only a few PANI-based fibers were fabricated and their TE efficiency needs to be further improved. In this work, the TE performance of wet-spun carbon nanotubes (CNTs)/PANI fibers was improved by synergistic engineering doping level of PANI and orientation of the fibers. The doping degree was optimized by varying coagulation baths, bath durations, and dopant loadings in the spinning solution, followed by fixing process during air drying to decrease shrinkage and enhance orientation of the fiber. Hexane coagulated CNTs/PANI fibers exhibited a higher doping degree of PANI compared to that of acetone and ethyl acetate, resulting in a maximum TE power factor of 77.4 μW m−1K−2 for 71 wt% CNTs/PANI fibers at PANI/dopant molar ratio of 2:1.25. Further fixing process induced a more oriented structure along the fibers, facilitating carrier transport and contributing to a significantly increased conductivity of 2155 S cm−1. Consequently, the CNTs/PANI fibers reached an optimal power factor of 91.8 μW m−1K−2. With outstanding TE performance and mechanical properties, the resultant fibers were assembled to fabricate a flexible TE generator, which generated a high output power of 2.5 nW with a temperature gradient of 10 K. These results demonstrate the potential of high-performance CNTs/PANI fibers to harvest body heat for the power supply of the wearable electronics.

Achieving thermoelectric properties of ultra-high-performance concrete using carbon nanotubes and fibers

The study investigated the impact of carbon nanotubes (CNTs), carbon fibers (CFs), steel fibers, and varying water-to-binder (W/B) ratios on the thermoelectric and mechanical properties of ultra-high-performance concrete (UHPC). Flowability tests revealed reduced flow with decreased water content and the addition of CNTs or CFs, particularly pronounced at a lower W/B ratio. Thermal gravimetric analysis and Fourier-transform infrared spectroscopy demonstrated differences in peak intensities and shifts in peaks related to the hydration products of the UHPC by the incorporation of the CNTs and CFs. The compressive strength and tensile performance increased with reduced W/B ratios and the inclusion of steel fibers, whereas the CNTs and CFs affected the strength differently based on their dispersion and interaction with other components that influenced porosity. The presence of steel fibers reduces the percolation threshold for CNTs and CFs, indicating a synergistic effect that enhances electron transport connectivity. The thermal conductivity increased with the addition of CNTs, CFs, and steel fibers, enhancing heat transfer within the UHPC. The thermoelectric figure of merit (ZT) values highlighted the combined impact of CNTs, CFs, steel fibers, and W/B ratios on the thermoelectric efficiency of the UHPC, showing significant improvements with the inclusion of steel fibers and the interplay between the CNTs and W/B ratios. Ultimately, upon introducing 1.5 % steel fibers and 0.3 % CNTs, a substantial enhancement in the thermoelectric ZT was observed, surpassing the standard UHPC values by 12 orders of magnitude.

Extraordinary Thermoelectric Properties of Topological Surface States in Quantum-Confined Cd3As2 Thin Films.

Topological insulators and semimetals have been shown to possess intriguing thermoelectric properties promising for energy harvesting and cooling applications. However, thermoelectric transport associated with the Fermi arc topological surface states on topological Dirac semimetals remains less explored. This work systematically examines thermoelectric transport in a series of topological Dirac semimetal Cd3As2 thin films grown by molecular beam epitaxy. Surprisingly, significantly enhanced Seebeck effect and anomalous Nernst effect are found at cryogenic temperatures when the Cd3As2 layer is thin. In particular, a peak Seebeck coefficient of nearly 500µVK-1 and a corresponding thermoelectric power factor over 30mWK-2m-1 are observed at 5K in a 25-nm-thick sample. Combining angle-dependent quantum oscillation analysis, magnetothermoelectric measurement, transport modeling, and first-principles simulation, the contributions from bulk and surface conducting channels are isolated and the unusual thermoelectric properties are attributed to the topological surface states. The analysis showcases the rich thermoelectric transport physics in quantum-confined topological Dirac semimetal thin films and suggests new routes to achieving high thermoelectric performance at cryogenictemperatures.

Wenzhou TE: A First-Principle-Calculated Thermoelectric Materials Database.

Since the implementation of the Materials Genome Project by the Obama administration in the United States, the development of various computational materials' databases has fundamentally expanded the choice of industries such as materials and energy. In the field of thermoelectric materials, the thermoelectric figure of merit (ZT) quantifies the performance of the material. From the viewpoint of calculations for vast materials, the ZT values are not easily obtained due to their computational complexity. Here, we show how to build a database of thermoelectric materials based on first-principle calculations for the electronic and heat transport of materials. Firstly, the initial structures are classified according to the values of bandgap and other basic properties using the clustering algorithm K-means in machine learning, and high-throughput first principle calculations are carried out for narrow-bandgap semiconductors which exhibit a potential thermoelectric application. The present framework of calculations mainly includes a deformation potential module, an electrical transport performance module, a mechanical and a thermodynamic properties module. We have also set up a search webpage for the calculated database of thermoelectric materials, providing search facilities and the ability to view the related physical properties of materials. Our work may inspire the construction of more computational databases of first-principle thermoelectric materials and accelerate research progress in the field of thermoelectrics.

Enhancement of Phase Stability and Thermoelectric Performance of Meta‐Stable AgSbTe2 by Thermal Cycling Process

AbstractThermoelectric materials are crucial components in thermoelectric devices employed for environmentally friendly solid‐state cooling and waste heat recovery, demanding not only high performance but also superior thermal or phase stability. The high‐performance thermoelectric material AgSbTe2 encounters challenges when utilized in thermoelectric modules due to the precipitation of Ag2Te, resulting in both thermally unstable characteristics and diminished performance. In this study, a thermal cycling process is employed to enhance the thermal stability and thermoelectric performance of AgSbTe2. Through thermal cycling, secondary phases of AgSbTe2 are made uniform, and the undesired Ag2Te is substituted with Sb2Te3 using an optimized thermal cycling process. As a result, the thermal stability of AgSbTe2 is enhanced due to its meta‐stable state, with <5% variance in thermoelectric figure of merit (ZT) measurements, and the ZT value is raised from 0.8 to 1.7 at 643 K through the optimized thermal cycling. The findings indicate that thermal cycling is an effective strategy for enhancing the thermal stability and thermoelectric performance of AgSbTe2, presenting a novel approach for achieving uniform secondary phases in materials with phase separation or phase change characteristics.

Optimizing thermoelectric performance of BiSbPbTe thin films through controlled post-annealing: A comprehensive structural and electronic study

This study investigates the structural and electronic properties of BiSbPbTe thin films, focusing on the impact of post-annealing time and temperature. The X-ray diffraction (XRD) analysis reveals a stable rhombohedral phase formation in all samples, with no secondary phases detected within the detection limit. The high crystallinity of the films is confirmed, and post-annealing leads to an increase in peak intensity, indicating enhanced crystalline structure. Surface morphology analysis using scanning electron microscopy (SEM) demonstrates a transition from inhomogeneous features in as-grown films to homogeneous and dense formations in post-annealed films. The grain size increases with post-annealing time, attributed to diffusion, energy minimization, nucleation, growth, and thermal activation processes. The electronic transport properties, including carrier concentration and conductivity, are influenced by post-annealing temperature and duration. A stable carrier concentration is observed for films post-annealed for up to 2 h, while longer durations decrease due to reduced defect vacancies and grain boundaries. The increase in charge carrier mobility, confirmed by SEM results, contributes to enhanced electrical conductivity. The Seebeck coefficient shows an initial enhancement up to 2 h post-annealing, attributed to defect creation and increased grain boundaries. However, further increases in post-annealing duration result in a decrease in the Seebeck coefficient due to enhanced charge carrier mobility and reduced grain boundaries. The thermoelectric power factor (4.4 μW/cm1K2), determined by the square of the Seebeck coefficient and electrical conductivity, reaches its maximum value in the 2-h post-annealed sample, emphasizing the importance of optimizing post-annealing conditions for improved thermoelectric performance.

Nanocrystal-based thermoelectric SnTe-NaSbSe2 alloys with strengthened band convergence and reduced thermal conductivity

Ternary I-V-VI2 colloidal NaSbSe2 nanocrystals are herein used to improve the performance of lead-free SnTe thermoelectric materials. We showcase a versatile bottom-up engineering approach to produce nanocrystal-based SnTe-NaSbSe2 alloys from the rapid hot press of colloidal nanocrystal building blocks. The incorporation of NaSbSe2 nanocrystals significantly enhances the Seebeck coefficient of SnTe. The band convergence and simultaneous increasing band gap of SnTe-NaSbSe2 alloys are certified by the first-principles density functional theory calculations. Besides, defect engineering generated by the incorporation of NaSbSe2 nanocrystals such as Sn vacancies, substitution point defects, dense dislocations, and strains generated by the NaSbSe2 nanoparticles incorporation result in a dramatic reduction of the lattice thermal conductivity below the amorphous limit of pure SnTe, down to 0.38 W m−1 K−1. As a consequence, power factors enhance up to 1.77 mW m−1 K−2, which is ∼193 % higher than that of the pristine SnTe, and thermoelectric figures of merit up to 1.15 at 823 K for (SnTe)0.85(NaSbSe2)0.15 are achieved.

Defect modification in enhancing thermopower factor of ZnO films without doping

This study was focused on unraveling the close dependence of the structural, morphological, and thermoelectric properties of sputtered ZnO films on base pressure. The ZnO film deposited at an optimized base pressure of 5 × 10−6 torr exhibited the highest thermoelectric power factor of 374.6 μW/mK2, corresponding to an electrical conductivity of 265 S/cm and a Seebeck coefficient of −124 μV/K at 583 K. The obtained results revealed that the positive effect of base pressure on enhancing thermoelectric properties of ZnO films is attributed to point-defect modification, including zinc vacancies, singly-, and doubly-charged oxygen vacancies. Based on these results, we propose that defect engineering is a facile and effective approach for improving the thermoelectric behavior of ZnO films, even without doping by controlling the sputtering conditions.

Electron-Phonon Interaction Mediated Gigantic Enhancement of Thermoelectric Power Factor Induced by Topological Phase Transition.

We propose an effective strategy to significantly enhance the thermoelectric power factor (PF) of a series of 2D semimetals and semiconductors by driving them toward a topological phase transition (TPT). Employing first-principles calculations with an explicit consideration of electron-phonon interactions, we analyze the electronic transport properties of germanene across the TPT by applying hydrogenation and biaxial strain. We reveal that the nontrivial semimetal phase, hydrogenated germanene with 8% biaxial strain, achieves a considerable 4-fold PF enhancement, attributed to the highly asymmetric electronic structure and semimetallic nature of the nontrivial phase. We extend the strategy to another two representative 2D materials (stanene and HgSe) and observe a similar trend, with a marked 7-fold and 5-fold increase in PF, respectively. The wide selection of functional groups, universal applicability of biaxial strain, and broad spectrum of 2D semimetals and semiconductors render our approach highly promising for designing novel 2D materials with superior thermoelectric performance.

DFT combined to Boltzmann transport theory for optoelectronic and thermoelectric properties investigations for Se (4 & 8 (at.%)) doped Li2SnS3

Cubic Li2SnS3 emerges as a noteworthy ionic conductor and a viable electrode material for lithium secondary batteries. Its application extends to solar cell technologies, owing to its commendable optoelectronic properties and high-power conversion efficiency. In this study, we present density functional theory (DFT)-based first principles calculations for Li2SnS3-xSex (x = 0, 4, and 8% (atomic percent (at.%)) utilizing the modified Becke Johnson (mBJ) approximations, proposing a compelling alternative. Our investigation reveals significant optical absorption in the ultraviolet region for Li2SnS3-xSex (x = 0, 4, and 8%), accompanied by modest effective mass and indirect band gaps of 2.18 eV for the pristine material. Conversely, doped materials exhibit direct band gaps, with values of 2.113 eV for 4% and 2.026 eV for 8%. Furthermore, the calculated thermoelectric power factor underscores the potential and efficacy of Li2SnS3-xSex in thermoelectric energy devices. The findings not only highlight the material’s promise for solar applications but also underscore its candidacy as a novel solid-state electrolyte for lithium-ion batteries. This stems from its robust thermal stability and notable lithium-ion conductivity, positioning Li2SnS3 as a compelling candidate for advanced energy storage technologies.

Topological Electronic Transition Contributing to Improved Thermoelectric Performance in p-Type Mg3Sb2- xBix Solid Solutions.

Topological electronic transition is the very promising strategy for achieving high band degeneracy (NV) and for optimizing thermoelectric performance. Herein, this work verifies in p-type Mg3Sb2- xBix that topological electronic transition could be the key mechanism responsible for elevating the NV of valence band edge from 1 to 6, leading to much improved thermoelectric performance. Through comprehensive spectroscopy characterizations and theoretical calculations of electronic structures, the topological electronic transition from trivial semiconductor is unambiguously demonstrated to topological semimetal of Mg3Sb2- xBix with increasing the Bi content, due to the strong spin-orbit coupling of Bi and the band inversion. The distinct evolution of Fermi surface configuration and the multivalley valence band edge with NV of 6 are discovered in the Bi-rich compositions, while a peculiar two-step band inversion is revealed for the first time in the end compound Mg3Bi2. As a result, the optimal p-type Mg3Sb0.5Bi1.5 simultaneously obtains a positive bandgap and high NV of 6, and thus acquires the largest thermoelectric power factor of 3.54 and 6.93 µW cm-1 K-2 at 300 and 575 K, respectively, outperforming the values in other compositions. This work provides important guidance on improving thermoelectric performance of p-type Mg3Sb2- xBix utilizing the topological electronic transition.

Impact of Spin-Entropy on the Thermoelectric Properties of a 2D Magnet.

Heat-to-charge conversion efficiency of thermoelectric materials is closely linked to the entropy per charge carrier. Thus, magnetic materials are promising building blocks for highly efficient energy harvesters as their carrier entropy is boosted by a spin degree of freedom. In this work, we investigate how this spin-entropy impacts heat-to-charge conversion in the A-type antiferromagnet CrSBr. We perform simultaneous measurements of electrical conductance and thermocurrent while changing magnetic order using the temperature and magnetic field as tuning parameters. We find a strong enhancement of the thermoelectric power factor at around the Néel temperature. We further reveal that the power factor at low temperatures can be increased by up to 600% upon applying a magnetic field. Our results demonstrate that the thermoelectric properties of 2D magnets can be optimized by exploiting the sizable impact of spin-entropy and confirm thermoelectric measurements as a sensitive tool to investigate subtle magnetic phase transitions in low-dimensional magnets.

Study of mechanical, thermodynamic, thermoelectric, and optical properties of Cs2SbAuX6 (X = Cl, Br, I) for energy harvesting applications

The inorganic double perovskites (DPs) Cs2SbAuX6 (X = Cl, Br, I) are an emerging applicant for solar cells, optoelectronic, and thermoelectrics to acquire clean energy. Therefore, the present research thoroughly addresses the mechanical, thermodynamic, optical, and thermoelectric characteristics by modified Becke and Johnson potential of Trans and Balaha (TB-mBJ) and BoltzTraP code. The structural stability is narrated from the tolerance factor and thermodynamic stability by formation energy. Born criteria assure the mechanical existence of cubic structures. The Cs2SbAu(Cl/Br)6 is ductile, and Cs2SbAuI6 has brittle behavior with a metallic nature. The band structures analysis reports the narrow band gaps for Cl/Br and the zero band gap for I-based DPs. The optical properties are studied by dielectric constants, absorption bands, refractive index, and other dependent optical parameters. Lastly, thermoelectric characteristics regarding Seebeck coefficient, electrical conductivity, power factor, thermal conductivity, and figure of merit in the temperature range 200–600K are analyzed. ZT's significant value at room temperature makes them potential candidates for thermoelectric generators.