Showing papers on "Thermoelectric effect published in 2018"

Plasmon induced thermoelectric effect in graphene

Abstract: Graphene has emerged as a promising material for optoelectronics due to its potential for ultrafast and broad-band photodetection. The photoresponse of graphene junctions is characterized by two competing photocurrent generation mechanisms: a conventional photovoltaic effect and a more dominant hot-carrier-assisted photothermoelectric (PTE) effect. The PTE effect is understood to rely on variations in the Seebeck coefficient through the graphene doping profile. A second PTE effect can occur across a homogeneous graphene channel in the presence of an electronic temperature gradient. Here, we study the latter effect facilitated by strongly localised plasmonic heating of graphene carriers in the presence of nanostructured electrical contacts resulting in electronic temperatures of the order of 2000 K. At certain conditions, the plasmon-induced PTE photocurrent contribution can be isolated. In this regime, the device effectively operates as a sensitive electronic thermometer and as such represents an enabling technology for development of hot carrier based plasmonic devices.

Carbon-Nanotube-Based Thermoelectric Materials and Devices.

Abstract: Conversion of waste heat to voltage has the potential to significantly reduce the carbon footprint of a number of critical energy sectors, such as the transportation and electricity-generation sectors, and manufacturing processes. Thermal energy is also an abundant low-flux source that can be harnessed to power portable/wearable electronic devices and critical components in remote off-grid locations. As such, a number of different inorganic and organic materials are being explored for their potential in thermoelectric-energy-harvesting devices. Carbon-based thermoelectric materials are particularly attractive due to their use of nontoxic, abundant source-materials, their amenability to high-throughput solution-phase fabrication routes, and the high specific energy (i.e., W g-1 ) enabled by their low mass. Single-walled carbon nanotubes (SWCNTs) represent a unique 1D carbon allotrope with structural, electrical, and thermal properties that enable efficient thermoelectric-energy conversion. Here, the progress made toward understanding the fundamental thermoelectric properties of SWCNTs, nanotube-based composites, and thermoelectric devices prepared from these materials is reviewed in detail. This progress illuminates the tremendous potential that carbon-nanotube-based materials and composites have for producing high-performance next-generation devices for thermoelectric-energy harvesting.

Advances in thermoelectrics

Abstract: Thermoelectric generators, capable of directly converting heat into electricity, hold great promise for tackling the ever-increasing energy sustainability issue. The thermoelectric energy conversio...

Giant anomalous Nernst effect and quantum-critical scaling in a ferromagnetic semimetal

Abstract: In conducting ferromagnets, an anomalous Nernst effect—the generation of an electric voltage perpendicular to both the magnetization and an applied temperature gradient—can be driven by the nontrivial geometric structure, or Berry curvature, of the wavefunction of the electrons1,2 Here, we report the observation of a giant anomalous Nernst effect at room temperature in the full-Heusler ferromagnet Co2MnGa, an order of magnitude larger than the previous maximum value reported for a magnetic conductor3,4 Our numerical and analytical calculations indicate that the proximity to a quantum Lifshitz transition between type-I and type-II magnetic Weyl fermions5–7 is responsible for the observed –Tlog(T) behaviour, with T denoting the temperature, and the enhanced value of the transverse thermoelectric conductivity The temperature dependence of the thermoelectric response in experiments and numerical calculations can be understood in terms of a quantum critical-scaling function predicted by the low-energy effective theory over more than a decade of temperatures Moreover, the observation of an unsaturated positive longitudinal magnetoconductance, or chiral anomaly8–10, also provides evidence for the existence of Weyl fermions11,12 in Co2MnGa A magnetic field and temperature gradient produce a large electric potential in a ferromagnet, indicating the possible presence of Weyl points The specific structure of Weyl points gives the electrons quantum-critical properties

Realizing zT of 2.3 in Ge1-x-y Sbx Iny Te via Reducing the Phase-Transition Temperature and Introducing Resonant Energy Doping.

Abstract: GeTe with rhombohedral-to-cubic phase transition is a promising lead-free thermoelectric candidate. Herein, theoretical studies reveal that cubic GeTe has superior thermoelectric behavior, which is linked to (1) the two valence bands to enhance the electronic transport coefficients and (2) stronger enharmonic phonon-phonon interactions to ensure a lower intrinsic thermal conductivity. Experimentally, based on Ge1-x Sbx Te with optimized carrier concentration, a record-high figure-of-merit of 2.3 is achieved via further doping with In, which induces the distortion of the density of states near the Fermi level. Moreover, Sb and In codoping reduces the phase-transition temperature to extend the better thermoelectric behavior of cubic GeTe to low temperature. Additionally, electronic microscopy characterization demonstrates grain boundaries, a high-density of stacking faults, and nanoscale precipitates, which together with the inevitable point defects result in a dramatically decreased thermal conductivity. The fundamental investigation and experimental demonstration provide an important direction for the development of high-performance Pb-free thermoelectric materials.

Rhombohedral to Cubic Conversion of GeTe via MnTe Alloying Leads to Ultralow Thermal Conductivity, Electronic Band Convergence, and High Thermoelectric Performance

Abstract: In this study, a series of Ge1–xMnxTe (x = 0–0.21) compounds were prepared by a melting–quenching–annealing process combined with spark plasma sintering (SPS). The effect of alloying MnTe into GeTe on the structure and thermoelectric properties of Ge1–xMnxTe is profound. With increasing content of MnTe, the structure of the Ge1–xMnxTe compounds gradually changes from rhombohedral to cubic, and the known R3m to Fm-3m phase transition temperature of GeTe moves from 700 K closer to room temperature. First-principles density functional theory calculations show that alloying MnTe into GeTe decreases the energy difference between the light and heavy valence bands in both the R3m and Fm-3m structures, enhancing a multiband character of the valence band edge that increases the hole carrier effective mass. The effect of this band convergence is a significant enhancement in the carrier effective mass from 1.44 m0 (GeTe) to 6.15 m0 (Ge0.85Mn0.15Te). In addition, alloying with MnTe decreases the phonon relaxation tim...

Discovery of ZrCoBi based half Heuslers with high thermoelectric conversion efficiency.

Abstract: Thermoelectric materials are capable of converting waste heat into electricity. The dimensionless figure-of-merit (ZT), as the critical measure for the material’s thermoelectric performance, plays a decisive role in the energy conversion efficiency. Half-Heusler materials, as one of the most promising candidates for thermoelectric power generation, have relatively low ZTs compared to other material systems. Here we report the discovery of p-type ZrCoBi-based half-Heuslers with a record-high ZT of ∼1.42 at 973 K and a high thermoelectric conversion efficiency of ∼9% at the temperature difference of ∼500 K. Such an outstanding thermoelectric performance originates from its unique band structure offering a high band degeneracy (Nv) of 10 in conjunction with a low thermal conductivity benefiting from the low mean sound velocity (vm ∼2800 m s−1). Our work demonstrates that ZrCoBi-based half-Heuslers are promising candidates for high-temperature thermoelectric power generation. Identifying new compounds with intrinsically high conversion efficiency is the key to demonstrating next-generation thermoelectric modules. Here, Zhu et al. report the discovery of p-type ZrCoBi-based half Heuslers with thermoelectric conversion efficiency of 9% and large high-temperature stability.

Grain boundary dominated charge transport in Mg3Sb2-based compounds

Abstract: Thermally activated mobility near room temperature is a signature of detrimental scattering that limits the efficiency and figure-of-merit zT in thermoelectric semiconductors. This effect has been observed dramatically in Mg3Sb2-based compounds, but also to a lesser extent in other thermoelectric compounds. Processing samples differently or adding impurities such that this effect is less noticeable produces materials with a higher zT. Experiments suggest that the behavior is related to grain boundaries, but impurity scattering has also been proposed. However, conventional models using Matthissen's rule are not able to explain the dramatic change in the temperature dependency of conductivity or drift mobility which is observed in Mg3Sb2-based compounds. We find that it is essential to consider the grain boundary region as an effectively separate phase rather than a scattering center, taking into account the weaker screening in semiconductors compared with classical metals. By modeling a grain boundary phase with a band offset, we successfully reproduce the experimentally observed conductivity versus temperature and thermopower versus conductivity relations, which indicate an improved description of transport. The model shows good agreement with measured grain size dependencies of conductivity, opening up avenues for quantitatively engineering materials with similar behavior. Model estimates predict room for >60% improvement in the room temperature zT of Mg3.2Sb1.5Bi0.49Te0.01 if the grain boundary resistance could be eliminated.

Aqueous thermogalvanic cells with a high Seebeck coefficient for low-grade heat harvest.

Abstract: Thermogalvanic cells offer a cheap, flexible and scalable route for directly converting heat into electricity. However, achieving a high output voltage and power performance simultaneously from low-grade thermal energy remains challenging. Here, we introduce strong chaotropic cations (guanidinium) and highly soluble amide derivatives (urea) into aqueous ferri/ferrocyanide ([Fe(CN)6]4−/[Fe(CN)6]3−) electrolytes to significantly boost their thermopowers. The corresponding Seebeck coefficient and temperature-insensitive power density simultaneously increase from 1.4 to 4.2 mV K−1 and from 0.4 to 1.1 mW K−2 m−2, respectively. The results reveal that guanidinium and urea synergistically enlarge the entropy difference of the redox couple and significantly increase the Seebeck effect. As a demonstration, we design a prototype module that generates a high open-circuit voltage of 3.4 V at a small temperature difference of 18 K. This thermogalvanic cell system, which features high Seebeck coefficient and low cost, holds promise for the efficient harvest of low-grade thermal energy. Achieving high thermopower in liquid-state thermogalvanic cells is vital to realize a low-cost technology solution for thermal-to-electrical energy conversion. Here, the authors present aqueous thermogalvanic cells based on modified electrolyte with enhanced Seebeck coefficient and thermopower.

3D printing of shape-conformable thermoelectric materials using all-inorganic Bi2Te3-based inks

Abstract: Thermoelectric energy conversion offers a unique solution for generating electricity from waste heat. However, despite recent improvements in the efficiency of thermoelectric materials, the widespread application of thermoelectric generators has been hampered by challenges in fabricating thermoelectric materials with appropriate dimensions to perfectly fit heat sources. Herein, we report an extrusion-based three-dimensional printing method to produce thermoelectric materials with geometries suitable for heat sources. All-inorganic viscoelastic inks were synthesized using Sb2Te3 chalcogenidometallate ions as inorganic binders for Bi2Te3-based particles. Three-dimensional printed materials with various geometries showed homogenous thermoelectric properties, and their dimensionless figure-of-merit values of 0.9 (p-type) and 0.6 (n-type) were comparable to the bulk values. Conformal cylindrical thermoelectric generators made of 3D-printed half rings mounted on an alumina pipe were studied both experimentally and computationally. Simulations show that the power output of the conformal, shape-optimized generator is higher than that of conventional planar generators. Three-dimensional printing is changing the way we manufacture objects. Here, Kim et al. develop inks of inorganic thermoelectric materials to 3D print the legs of conformable thermoelectric generators, allowing waste heat recovery from hot water pipes.

Recent Development of Thermoelectric Polymers and Composites.

Abstract: Thermoelectric materials can be used as the active materials in thermoelectric generators and as Peltier coolers for direct energy conversion between heat and electricity. Apart from inorganic thermoelectric materials, thermoelectric polymers have been receiving great attention due to their unique advantages including low cost, high mechanical flexibility, light weight, low or no toxicity, and intrinsically low thermal conductivity. The power factor of thermoelectric polymers has been continuously rising, and the highest ZT value is more than 0.25 at room temperature. The power factor can be further improved by forming composites with nanomaterials. This article provides a review of recent developments on thermoelectric polymers and polymer composites. It focuses on the relationship between thermoelectric properties and the materials structure, including chemical structure, microstructure, dopants, and doping levels. Their thermoelectric properties can be further improved to be comparable to inorganic counterparts in the near future.

High thermoelectric performance in Bi0.46Sb1.54Te3 nanostructured with ZnTe

Abstract: Defect engineering and nano-structuring are the core stratagems for improving thermoelectric properties. In bismuth telluride alloys nanosizing individual crystallites has been extensively studied in efforts to reduce the thermal conductivity, but nanostructuring with second phases has been more challenging. In this study, we demonstrate a thermoelectric figure of merit ZT of 1.4 at 400 K, realized in Zn-containing BiSbTe alloys (specifically Bi0.46Sb1.54Te3) by integrating defect complexity with nanostructuring. We have succeeded in creating nanostructured BiSbTe alloys containing ZnTe nanoprecipitates. We present a melt-spinning-based synthesis that forms in situ ZnTe nanoprecipitates to produce an extremely low lattice thermal conductivity of ∼0.35 W m−1 K−1 at 400 K, approaching the amorphous limit in the Bi2−xSbxTe3 system, while preserving the high power factor of Bi0.46Sb1.54Te3. These samples show excellent repeatability and thermal stability at temperatures up to 523 K. DFT calculations and experimental results show that Zn is inclined to form dual site defects, including two substitutional defects ZnBi/Sb′ and a Te vacancy, to achieve full charge compensation, which was further explicitly corroborated by Positron annihilation measurement. The strong enhancement of thermoelectric properties was validated in a thermoelectric module fabricated with the melt-spun p-legs (ZnTe-nanostructured BiSbTe) and zone-melt n-legs (conventional BiTeSe) which achieved a thermoelectric conversion efficiency of 5.0% when subjected to a temperature gradient of 250 K, representing about 40% improvement compared with a commercial zone-melt-based module. The results presented here represent a significant step forward for applications in thermoelectric power generation.

A review on bismuth telluride (Bi 2 Te 3 ) nanostructure for thermoelectric applications

Abstract: Bismuth Telluride (Bi2Te3) is basically known as an efficient thermoelectric material. Nowadays, it has been attracted a great deal of interest in energy harvesting, chip cooling, chip sensing and other field of material science because of its potential applications. In order to produce Bi2Te3 nanostructure, a number of methods such as solvo and hydro thermal, refluxing, straight forward arc–melting and polyol methods have been employed. Among of them, the solvothermal method has been one of the most common methods to fabricate Bi2Te3 nanostructure in thermoelectric applications. But the development of device–quality material has been a challenging task for the researchers, yet. For this reason, this paper provides a review of current research activities on Bi2Te3 nanostructure growth by several methods and its characterization through theoretical and analytical aspects. Moreover, the paper handles a systematic and intensive research work to develop and understand the materials in nanostructure forms.

Charge and phonon transport in PbTe-based thermoelectric materials

Abstract: PbTe is a typical intermediate-temperature thermoelectric material, which has undergone extensive developments and achieved excellent high thermoelectric performance. In this perspective we summarized several strategies that were successfully applied in PbTe-based thermoelectric materials through manipulating charge and phonon transports, such as optimizing carrier density to tune Fermi level, tailoring band structure to enhance effective mass, and designing all-scale hierarchical architectures to suppress phonon propagation. Meanwhile, due to the different features of conduction and valence bands, we separately introduced the approaches to enhance performance of p-type and n-type PbTe. In p-type PbTe, the strategies of band convergence, band alignment and density of state (DOS) distortion are more effective to achieve high electrical transport properties. By contrast, flattening conduction bands and introducing deep impurity level are more suitable for n-type PbTe. Lastly, several potential strategies were proposed to further improve the thermoelectric performance of PbTe-based materials, which might be extended to other thermoelectric systems.

Compliant and stretchable thermoelectric coils for energy harvesting in miniature flexible devices

Abstract: With accelerating trends in miniaturization of semiconductor devices, techniques for energy harvesting become increasingly important, especially in wearable technologies and sensors for the internet of things. Although thermoelectric systems have many attractive attributes in this context, maintaining large temperature differences across the device terminals and achieving low–thermal impedance interfaces to the surrounding environment become increasingly difficult to achieve as the characteristic dimensions decrease. Here, we propose and demonstrate an architectural solution to this problem, where thin-film active materials integrate into compliant, open three-dimensional (3D) forms. This approach not only enables efficient thermal impedance matching but also multiplies the heat flow through the harvester, thereby increasing the efficiencies for power conversion. Interconnected arrays of 3D thermoelectric coils built using microscale ribbons of monocrystalline silicon as the active material demonstrate these concepts. Quantitative measurements and simulations establish the basic operating principles and the key design features. The results suggest a scalable strategy for deploying hard thermoelectric thin-film materials in harvesters that can integrate effectively with soft materials systems, including those of the human body.

Pyroelectric energy conversion with large energy and power density in relaxor ferroelectric thin films.

Abstract: The need for efficient energy utilization is driving research into ways to harvest ubiquitous waste heat. Here, we explore pyroelectric energy conversion from low-grade thermal sources that exploits strong field- and temperature-induced polarization susceptibilities in the relaxor ferroelectric 0.68Pb(Mg1/3Nb2/3)O3–0.32PbTiO3. Electric-field-driven enhancement of the pyroelectric response (as large as −550 μC m−2 K−1) and suppression of the dielectric response (by 72%) yield substantial figures of merit for pyroelectric energy conversion. Field- and temperature-dependent pyroelectric measurements highlight the role of polarization rotation and field-induced polarization in mediating these effects. Solid-state, thin-film devices that convert low-grade heat into electrical energy are demonstrated using pyroelectric Ericsson cycles, and optimized to yield maximum energy density, power density and efficiency of 1.06 J cm−3, 526 W cm−3 and 19% of Carnot, respectively; the highest values reported to date and equivalent to the performance of a thermoelectric with an effective ZT ≈ 1.16 for a temperature change of 10 K. Our findings suggest that pyroelectric devices may be competitive with thermoelectric devices for low-grade thermal harvesting. Pyroelectric energy conversion in a thin-film relaxor ferroelectric is studied under an electric field, resulting in high energy and power densities. Performance is equivalent to a ZT = 1.16 thermoelectric, competitive for low-grade thermal harvesting.

Data-Driven Design of Ecofriendly Thermoelectric High-Entropy Sulfides.

Abstract: High-entropy compounds with compositional complexity can be designed as new thermoelectric materials. Here a data-driven model was developed, which chose suitable elements to reduce the enthalpy of formation and hence to increase the chance of single phase formation. Using this model, two high-entropy sulfides were designed, metallic Cu5SnMgGeZnS9 and semiconducting Cu3SnMgInZnS7. They were then successfully fabricated as single-phase dense ceramics with homogeneously distributed cations, and their phase stability and atomic local structures were investigated using density functional theory calculations. Finally, a zT value of 0.58 at 773 K was obtained for Cu5Sn1.2MgGeZnS9, where additional Sn was used to tune the carrier concentration. This work provides a simple approach to find new high-entropy functional materials in the largely unexplored multielement chemical space.

Thermoelectric Properties of Poly(3-hexylthiophene) (P3HT) Doped with 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) by Vapor-Phase Infiltration

Abstract: Doping of thin films of semiconducting polymers provides control of their electrical conductivity and thermopower. The electrical conductivity of semiconducting polymers rises nonlinearly with the carrier concentration, and there is a lack of understanding of the detailed factors that lead to this behavior. We report a study of the morphological effects of doping on the electrical conductivity of poly(3-hexylthiophene) (P3HT) thin films doped with small molecule 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). Resonant soft X-ray scattering shows that the morphology of films of P3HT is not strongly changed by infiltration of F4TCNQ from the vapor phase. We show that the local ordering of P3HT, the texture and form factor of crystallites, and the long-range connectivity of crystalline domains contribute to the electrical conductivity in thin films. The thermopower of films of P3HT doped with F4TCNQ from the vapor phase is not strongly enhanced relative to films doped from solution, but the el...

Realizing high performance n-type PbTe by synergistically optimizing effective mass and carrier mobility and suppressing bipolar thermal conductivity

Abstract: Thermoelectric materials enable direct inter-conversion between electrical energy and thermal energy. The conversion efficiency is limited by their complex interdependent thermoelectric parameters. Here, we report that the electrical and thermal transport properties of n-type PbTe can be simultaneously improved by introducing just one component, MnTe. We obtained a maximum ZT of ∼1.6 at 773 K and an average ZTave of >1.0 at 300–873 K in n-type MnTe alloyed PbTe. This remarkably enhanced performance arises from the triple functions of MnTe alloying: (1) making the conduction band flatter to increase the effective mass from 0.31 me to 0.45 me; (2) enlarging the band gap of PbTe to suppress the bipolar thermal conductivity; and (3) introducing point defects instead of nanoprecipitates to reduce the lattice thermal conductivity while maintaining a relatively high carrier mobility. Our results indicate that high performance can be achieved in n-type PbTe by integrating different but synergistic concepts.

Vacancy Manipulation for Thermoelectric Enhancements in GeTe Alloys

Abstract: Optimization of carrier concentration plays an important role on maximizing thermoelectric performance. Existing efforts mainly focus on aliovalent doping, while intrinsic defects (e.g., vacancies) provide extra possibilities. Thermoelectric GeTe intrinsically forms in off-stoichiometric with Ge-vacancies and Ge-precipitates, leading to a hole concentration significantly higher than required. In this work, Sb2Te3 having a smaller cation-to-anion ratio, is used as a solvend to form solid solutions with GeTe for manipulating the vacancies. This is enabled by the fact that each substitution of 3 Ge2+ by only 2 Sb3+ creates 1 Ge vacancy, because of the overall 1:1 cation-to-anion ratio of crystallographic sites in the structure and by the charge neutrality. The increase in the overall Ge-vacancy concentration facilitates Ge-precipitates to be dissolved into the matrix for reducing the hole concentration. In a combination with known reduction in hole concentration by Pb/Ge-substitution, a full optimization on ...

Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping

Abstract: Germanium telluride (GeTe)-based materials, which display intriguing functionalities, have been intensively studied from both fundamental and technological perspectives. As a thermoelectric material, though, the phase transition in GeTe from a rhombohedral structure to a cubic structure at ∼700 K is a major obstacle impeding applications for energy harvesting. In this work, we discovered that the phase-transition temperature can be suppressed to below 300 K by a simple Bi and Mn codoping, resulting in the high performance of cubic GeTe from 300 to 773 K. Bi doping on the Ge site was found to reduce the hole concentration and thus to enhance the thermoelectric properties. Mn alloying on the Ge site simultaneously increased the hole effective mass and the Seebeck coefficient through modification of the valence bands. With the Bi and Mn codoping, the lattice thermal conductivity was also largely reduced due to the strong point-defect scattering for phonons, resulting in a peak thermoelectric figure of merit (ZT) of ∼1.5 at 773 K and an average ZT of ∼1.1 from 300 to 773 K in cubic Ge0.81Mn0.15Bi0.04Te. Our results open the door for further studies of this exciting material for thermoelectric and other applications.