Efficient Thermoelectric Materials Research Articles

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.

Thermoelectric Properties of Spray Coated n-Type PEDOT:PSS Film

Inorganic thermoelectric (TE) materials have gained significant attention because of their salient properties. However, they possess some significant drawbacks, including high production costs, high heat loss, and fragility. Recently, Organic conducting polymers presented a promising platform as an alternative TE material because of their great mechanical flexibility, high stretchability, and environmental friendliness. In this work, we report for the first time on the TE properties of n-PEDOT:PSS film prepared using spray coating technique. The structural, optical and TE properties of the obtained n-PEDOT:PSS thin film was investigated using X-ray diffraction spectroscopy, UV-vis spectroscopy and Seebeck coefficient measurement systems, respectively. The n-PEDOT:PSS layer showed excellent optical properties with a band gap ranges from 3.91 to 3.78. In addition, the Seebeck coefficient and power factor (PF) were obtained to be 1096.77 µVK-1 and 298.59 µWm-1K-2 respectively, making n-PEDOT:P PSS to be regarded as efficient TE material.

Constructing Coated Grain Nanocomposites and Intracrystalline Precipitates to Simultaneously Improve the Thermoelectric and Mechanical Properties of SnTe by MgB2 and Sb Co‐Doping

AbstractThermoelectric materials should be highly efficient and mechanically robust to satisfy the requirements of engineering applications. Herein, an integrated optimization strategy to improve both the thermoelectric performance and mechanical strength of SnTe is proposed. First, grain boundary engineering is applied to SnTe via MgB2 doping. The decomposition of MgB2 results in the Mg‐substituted SnTe solid solution and a special “core–shell” structure of Mg‐B compounds coated SnTe grain remarkably reducing the lattice thermal conductivity. Subsequently, trivalent Sb atoms are introduced to tune the carrier concentration and optimize the electrical performance of the MgB2‐doped sample. Sb‐rich Sn‐Te precipitates inside the grains further diminish the lattice's thermal conductivity. Consequently, a prominent improvement in average ZT of ≈117% is achieved for Sn0.78Sb0.16Te(MgB2)0.09 compared to pristine Sn1.03Te. Moreover, the compressive yield strength and Vickers hardness of Sn0.78Sb0.16Te(MgB2)0.09 are significantly increased by ≈168% and 176% relative to pristine Sn1.03Te, respectively. The quantitative strengthening models including grain boundary, dislocation, solid solution, intergranular, and precipitation strengthening in MgB2‐ and MgB2‐Sb‐doped Sn1.03Te samples are proposed, showing that the dominant strengthening mechanism is precipitation strengthening. This work provides an avenue for designing efficient and robust thermoelectric materials toward commercial application.

Argon Plasma Bombardment Induces Surface‐Rich Sn Vacancy Defects to Enhance the Thermoelectric Performance of Polycrystalline SnSe

AbstractNanoscale defects can induce the effective modulation of carrier concentration, mobility, and phonon scattering to secure high thermoelectric performance in semiconductors. However, it is still limited to effectively controlling nanoscale defects in thermoelectric materials. Here, argon plasma bombardment is employed to introduce a large number of point defects and dislocations in microcrystalline SnSe powders, synthesized by a solvothermal method. After sintering these powders into polycrystalline bulk materials, bulk SnSe shows the ZT increasing by up to 66.7% (from 0.36 to 0.6 at 773 K). Through detailed micro/nanostructure characterizations and first‐principles calculations, the underlying mechanism is elucidated for the evaluation of thermoelectric performance. This work provides a deep understanding of the mechanism of nanoscale defects in modulating thermoelectric performance and presents experimental evidence and experience for the design and synthesis of efficient thermoelectric materials, making significant contributions to future green energy technologies.

A study of the effect of cerium ion doping concentration on the structural, electrical, and thermoelectric properties of CaMnO3 nanoparticles

Abstract Universally, energy loss in the form of heat is predominant and this heat is irrecoverable waste heat that leads to global warming. Clean, green, eco-friendly, cost-effective, and renewable energy sources are the possible solutions for this energy crisis and global warming issues. Thermoelectric power generation is a promising technology by converting this irrecoverable waste heat directly into electricity without any greenhouse gas emission. Nanostructured CaMnO3 at various cerium concentrations have been successfully prepared by sol–gel hydrothermal method followed by annealing and sintering. Pure and doped samples were systematically characterized by DSC, powder XRD, RAMAN, SEM with EDAX and FTIR spectroscopy. Electrical and thermoelectrical measurements were carried out on the sintered pellets. The XRD analyses confirmed the formation of orthorhombic perovskite structure for all the samples and the average particle size lies in the range of 50–60 nm. FTIR analysis shows the presence of CaMnO3 nanoparticles without any impurities. The temperature dependence of physical properties was performed and analyzed between room temperature and 600 °C. Electrical resistivity strongly depends on the nature of substituent ions and negative values indicate that the electrons are major charge carriers. Large Seebeck coefficient value and high-power factor make Ca1−x Ce x MnO3 an efficient thermoelectric material for energy storage applications.

Highly-efficient sustainable ionic thermoelectric materials using lignin-derived hydrogels

The efficient and economical conversion of low-grade waste heat into electricity has promising potential to combat the greenhouse effect and expedite the shift towards sustainable development. This study presents an innovative and appealing approach through the utilization of lignin, an abundant waste product derived from the paper and pulp industry, to develop hydrogels as compelling and sustainable materials for application in ionic thermoelectricity. Various compositions were evaluated to examine the impacts of varying lignin concentrations, types of electrolytes, concentrations of crosslinkers, and electrolyte concentrations on the ionic thermoelectric performance of the hydrogels. The optimized lignin-derived hydrogel, infiltrated with a 6 M KOH electrolyte, demonstrates high ionic conductivity (226.5 mS/cm) and a superior Seebeck coefficient of 13 mV/K. This results in a remarkable power factor (3831 µW/m·K2) that leads to an impressive Figure of merit (ZTi) (3.75), surpassing most of the existing state-of-the-art materials and making it the most efficient sustainable ionic thermoelectric material reported until now. These findings underscore the exceptional performance of lignin-based hydrogels in the realm of low-grade waste energy harvesting applications. The present study contributes to address the challenges posed by waste heat through effectively harnessing low-grade waste heat through the utilization of sustainable lignin-based hydrogels while reducing the reliance on fossil fuels and minimizing greenhouse gas emissions.Graphical

Direct Imaging of Atomic Rattling Motion in a Clathrate Compound

Controlling nanoscale heat generation, dissipation, and transport is crucial for miniaturizing electronic devices and for designing highly efficient thermoelectric materials. However, it has been challenging to directly measure thermal properties at individual atom level. Herein, direct atomic‐resolution column‐by‐column imaging of the rattling motion of Ba atoms in a clathrate compound Ba8Ga16Ge30 using atomic‐resolution scanning transmission electron microscopy with a segmented detector is shown. The directional anisotropy of the rattling motion is clearly visualized in real space and its amplitude and anisotropy are quantitatively evaluated by Bayesian analysis of the thermal diffuse scattering distribution. These results open a new possibility for directly characterizing nanoscale thermal properties in materials and devices, even those containing heavy elements such as thermoelectric materials.

Seebeck Effect in Molecular Wires Facilitating Long-Range Transport.

The study of molecular wires facilitating long-range charge transport is of fundamental interest for the development of various technologies in (bio)organic and molecular electronics. Defining the nature of long-range charge transport is challenging as electrical characterization does not offer the ability to distinguish a tunneling mechanism from the other. Here, we show that investigation of the Seebeck effect provides the ability. We examine the length dependence of the Seebeck coefficient in electrografted bis-terpyridine Ru(II) complex films. The Seebeck coefficient ranges from 307 to 1027 μV/K, with an increasing rate of 95.7 μV/(K nm) as the film thickness increases to 10 nm. Quantum-chemical calculations unveil that the nearly overlapped molecular-orbital energy level of the Ru complex with the Fermi level accounts for the giant thermopower. Landauer-Büttiker probe simulations indicate that the significant length dependence evinces the Seebeck effect dominated by coherent near-resonant tunneling rather than thermal hopping. This study enhances our comprehension of long-range charge transport, paving the way for efficient electronic and thermoelectric materials.

Origin of brittle behavior of doped PbTe-based thermoelectric materials

Finding new efficient thermoelectric materials is a significant challenge for materials science. It is crucial to have a comprehensive understanding of material-property relationships to develop new materials successfully, given that minor structural or compositional changes can result in significant property changes. This paper extensively utilizes advanced theoretical approaches and investigates the impact of n- and p-type impurities on the mechanical characteristics of PbTe thermoelectric materials. n- and p-type doping of PbTe were studied using various techniques, including elastic tensor calculations, crystal orbital Hamilton population method, and local vibrational theory. Our findings reveal the specific ways in which doping type affects the material's mechanical properties. This information can aid researchers in optimizing PbTe doping strategies.

A Novel Optimization Method for TEG System Performance Based on Temperature and Heat Flux

The thermoelectric generator (TEG) can convert heat to electricity and is widely used. To overcome the limitation for low efficiency of thermoelectric materials, optimizing the performance of TEG in given system is necessary. This study proposes a method to match individual TEG components to the system environment based on two boundary conditions—temperature and heat flux. With this method, TEG geometrical parameters can be determined to optimize the system performance by varying temperature as an independent variable. Using this method, the TEG in an undersea Radioisotope thermoelectric generator (u‐RTG) is optimized. The TEG system exhibits an output power of 14.10 W when powered by a 200 W heat source. The simulate result in the comprehensive system model of u‐RTG is 14.04 W, which has 0.45% deviation from the TEG optimization result. It is proved that the TEG optimized by this method matches the system, the optimization results are accurate.

Thermoelectric Sensor with CuI Supported on Rough Glass.

Thermoelectric generators convert heat into a potential difference with arrays of p- and n-type materials, a process that allows thermal energy harvesting and temperature detection. Thermoelectric sensors have attracted interest in relation to the creation of temperature and combustible gas sensors due to their simple operation principle and self-powering ability. CuI is an efficient p-type thermoelectric material that can be readily produced from a Cu layer by an iodination method. However, the vapor iodination of Cu has the disadvantage of weak adhesion on a bare glass substrate due to stress caused by crystal growth, limiting microfabrication applications of this process. This work presents a rough soda-lime glass substrate with nanoscale cavities to support the growth of a CuI layer, showing good adhesion and enhanced thermoelectric sensitivity. A rough glass sample with nanocavities is developed by reactive ion etching of a photoresist-coated glass sample in which aggregates of carbon residuals and the accumulation of NaF catalyze variable etching rates to produce local isotropic etching and roughening. A thermoelectric sensor consists of 41 CuI/In-CoSb3 thermoelectric leg pairs with gold electrodes for electrical interconnection. A thermoelectric leg has a width of 25 μm, a length of 3 mm, and a thickness of 1 μm. The thermoelectric response results in an open-circuit voltage of 13.7 mV/K on rough glass and 0.9 mV/K on bare glass under ambient conditions. Rough glass provides good mechanical interlocking and introduces important variations of the crystallinity and composition in the supported thermoelectric layers, leading to enhanced thermopower.

Effects of isotropic strain on the structure and transport properties of half-Heusler alloy BiBaK: a first-principles investigation.

In this study, using density functional and Boltzmann transport theories, we systematically investigated the effects of tensile and compressive strains on the elastic properties, phonon dispersion relation, electronic structure, and transport properties of the half-Heusler compound BiBaK. We calculated the elastic constants and phonon dispersion curves for BiBaK, which demonstrated its mechanical and thermodynamic stability, respectively, under different isotropic strains. Further, calculations showed that the electronic structure and energy bandgap of BiBaK changed with the application of isotropic strain. A high power factor and low thermal conductivity are key to improving the performance of thermoelectric materials. The figure of merit of BiBaK is 0.6 when it is unstrained and reaches a maximum value of 0.93 at -9% compressive strain and a temperature of 1200 K, indicating that under isotropic compressive strain, BiBaK compounds are efficient thermoelectric materials for high-temperature applications.

Thermoelectric nanowires for dense 3D printed architectures.

The large-scale employment of 3D printed inorganic thermoelectrics is primarily constrained because of their lower efficiencies as compared to those fabricated from conventional methods such as spark plasma sintering and hot-pressing. This originates from the significant challenge in the densification of printed parts, particularly through the direct-ink-writing fabrication process, which demands a high binder content for printability. To achieve high-density printed thermoelectrics, the ink formulation process often involves the addition of substantial filler content and sintering aids, coupled with prolonged sintering periods. Here, we propose a strategy to resolve the low densification issue of 3D printed thermoelectrics through a binder-less and sintering aid-free thermoelectric nanowire ink system that can achieve dense thermoelectric structures (up to 82.5% theoretical density). The increase in density and corresponding enhancement of thermoelectric material efficiency are attained in a more tunable and controlled manner without compromising the material composition. A high filler-derived density index (FDI) of 2.51 is also achieved, implying the potential to obtain high-density parts with minimal filler content, thus unlocking a cascade of profound impacts. Crucially, this advancement enables the possibilities of anisotropic engineering in thermoelectric materials, thereby shattering the limitations that have hindered the widespread adoption of 3D printed inorganic thermoelectrics.

Thermoelectric performance of chalcogenide-free CaAl-layered double hydroxide–antimony trioxide nanowire composites with low thermal conductivity

Thermoelectric (TE) materials have attracted considerable interest for their potential and the figure of merit ZT serves as a crucial metric for evaluating TE performance. Chalcogenide materials, such as tellurium (Te) and selenium (Se), have been favored for high-performance TE applications. However, their toxic nature raises concerns, demanding exploration of non-toxic alternatives suitable for human-contacting devices.This study focused on antimony trioxide (Sb2O3) due to its high Seebeck coefficient and explored the potential of layered double hydroxide (LDH) materials as a non-toxic alternative for efficient TE materials. Composites of Sb2O3 nanowires integrated with 2D CaAl-LDH were synthesized to reduce thermal conductivity and improve TE performance. The composites displayed enhanced electrical conductivity, resulting in a significantly improved power factor. The introduction of CaAl-LDH facilitated the charge carrier transport paths, leading to better electrical performance. Furthermore, the composites exhibited reduced thermal conductivity due to phonon scattering at the heterointerfaces between Sb2O3 and CaAl-LDH. As a result, the Sb2O3/CaAl-LDH_70 composite achieved a maximal ZT value of 0.0485 at 473 K, demonstrating promising potential for LDH-based composites as environmentally friendly TE materials. These findings contribute to sustainable energy conversion technologies, ensuring progress towards more efficient and biocompatible TE materials.

Ultra-low thermal conductivity and improved thermoelectric performance in La2O3-dispersed Bi2Sr2Co2Oy ceramics

Thermoelectric materials are functional materials that directly convert heat energy and electric energy into each other. Nano-second-phase dispersion is an effective strategy to improve the energy conversion efficiency of thermoelectric materials through the energy filtering effect and the phonon scattering effect. In this study, the solid-state reaction method was used to prepare Bi2Sr2Co2Oy + l wt% La2O3 (l = 0.0, 0.1, 0.25, 0.5, 1.75) thermoelectric composites. An ultra-low thermal conductivity of 0.58 W/Km at 923 K was obtained by dispersing a small quantity of La2O3 as the nano-second-phase additive in the Bi2Sr2Co2Oy matrix. This was attributed to the increased hetero-interfaces and improved phonon scattering through the grain refinement effect. The dimensionless thermoelectric figure of merit (ZT) values of Bi2Sr2Co2Oy + 0.25 wt% La2O3 reached 0.28 at 923 K when their power factors were combined with littlechange, which was 21 % higher than that of the un-optimised pristine Bi2Sr2Co2Oy.

Tweaking the interplay of the layers by substitution in Ca3Co4O9+δ for high efficiency thermoelectric materials

Ca3Co4O9 is a well-known high temperature thermoelectric material owing to its sandwich type layered structure consisting of both conducting and insulating slabs. In the present study we attempt to enhance the electrical conductivity without affecting the thermal conductivity by suitable doping in these layers. Compositions with a general formula Ca3−xSrxCo4−xMgx/2Tix/2O9+δ (0 ≤ x ≤ 0.15) were prepared by conventional solid state method and subjected to routine characterization techniques like XRD, SEM and XPS. Sr substitution in the insulating layer and Mg, Ti substitution in the conductive layer led to a decrease in the electrical resistivity from 17.86 mΩ cm to 9.74 mΩ cm, which resulted in an increase in the power factors. The dimensionless thermoelectric figure of merit ZT is found to be 0.13 at 873 K for x = 0.15, which is ̴2.1 times higher than the parent compound attributed to the excess oxygen in the doped composition.

Molecular Engineering for Enhanced Thermoelectric Performance of Single-Walled Carbon Nanotubes/π-Conjugated Organic Small Molecule Hybrids.

Hybridizing single-walled carbon nanotubes (SWCNTs) with π-conjugated organic small molecules (π-OSMs) offers a promising approach for producing high-performance thermoelectric (TE) materials through the facile optimization of the molecular geometry and energy levels of π-OSMs. Designing a twisted molecular structure for the π-OSM with the highest occupied molecular orbital energy level comparable to the valence band of SWCNTs enables effective energy filtering between the two materials. The SWCNTs/twisted π-OSM hybrid exhibits a high Seebeck coefficient of 110.4 ± 2.6 µV K-1 , leading to a significantly improved power factor of 2,136 µW m-1 K-2 , which is 2.6 times higher than that of SWCNTs. Moreover, a maximum figure of merit over 0.13 at room temperature is achieved via the efficient TE transport of the SWCNTs/twisted π-OSM hybrid. The study highlights the promising potential of optimizing molecular engineering of π-OSMs for hybridization with SWCNTs to create next-generation, efficient TE materials.

Influence of the Mn5Ge3/Ge ohmic-contact interface on the Seebeck coefficient of the Mn5Ge3/Ge bilayer

Thermoelectricity is a well-known effect that can be used to convert heat energy into electrical energy. However, the yield of this conversion is still low compared to current photovoltaic technology. It is limited by the intrinsic properties of materials, leading to intensive materials science investigations for the design of efficient thermoelectric (TE) materials. Interface engineering was shown to be a valuable solution for improving materials’ TE properties, supporting the development of multiphase TE materials. In particular, interfaces have been suggested to promote the increase of the Seebeck coefficient of materials without significantly impacting their electrical conductivity through the so-called energy filtering effect. This work aims at determining experimentally the effect of a metal/semiconductor interface exhibiting an ohmic character on the effective Seebeck coefficient of multiphase materials, focusing on the n-type Mn5Ge3/p-type Ge interface. This interface is shown not to contribute to carrier transport, but to contribute to carrier concentration filtering due to carrier injection or recombination. The Seebeck coefficient of the bi-phase material is shown to be dependent on the direction carriers are crossing the interface. The interface effect mainly results from a modification of charge carrier concentrations in the semiconductor.

Progress and perspectives in thermoelectric generators for waste-heat recovery and space applications

The direct conversion of thermal energy into electrical current via thermoelectric (TE) effects relies on the successful integration of efficient TE materials into thermoelectric generators (TEGs) with optimized characteristics to ensure either optimum output power density or conversion efficiency. Successfully employed for powering deep-space probes and extraterrestrial rovers since the 1960s, the development of this technology for waste-heat-harvesting applications faces several key issues related to the high temperatures and oxidizing conditions these devices are subjected to. This Perspective provides a brief overview of some prospective thermoelectric materials/technologies for use in radioisotope thermoelectric generators utilized in space missions and highlights the progress made in the field over the last years in the fabrication of TEGs. In particular, we emphasize recent developments that enable to achieve increased power densities, thereby opening up novel research directions for mid-range-temperature applications. In addition to showing how using lower quantities of TE materials may be achieved without sacrificing device performance, we provide an outlook of the challenges and open questions that remain to be addressed to make this technology economically and technologically viable in everyday-life environments.

Heat Transport in Clathrate Hydrates Controlled by Guest Frequency and Host-Guest Interaction.

The underlying mechanism of common limited lattice thermal conductivity (κ) in energy-related host-guest crystalline compounds has been an ongoing topic in recent decades. Here, the guest-triggered intrinsic ultralow κ of the representative xenon clathrate hydrate was investigated using the time domain thermoreflectance technique and theoretical calculations. The localized guest modes were observed to hybridize with acoustic branches and severely limit the acoustic κ contribution. Besides, the strong mode coupling enables the reshaping of the overall lattice dynamics, especially for optical branches. More importantly, we identified that guest fillers prompt great phonon scattering in wide frequencies, which originates from both the guest-frequency-controlled enhancement of phase space and the host-guest-interaction-governed lattice anharmonicity. The extremely low guest frequency and strong host-guest interaction and coupling were thereby underlined to play vital but distinct roles in κ minimization. Our results unveil the dominant factors of guest reduction effects and facilitate the design of efficient thermoelectric or other thermal-related materials.