Thermoelectric Measurements Research Articles

Enhancing the thermoelectric properties for hot-isostatic-pressed Bi2Te3 nano-powder using graphite nanoparticles

Bismuth telluride (Bi2Te3) is a promising thermoelectric material produced commercially. However, its poor electrical conductivity and low figure of merit, caused by grain boundaries and high thermal conductivity, limit its effectiveness in powder metallurgy production. Herein, effects of adding Graphite nanoparticles (GTNPs) to Bi2Te3 on thermoelectric properties were studied. Three ratios of GTNPs (0.2, 0.35, 0.5 wt%) were added to ball-milled Bi2Te3 nano-powder. The hot isostatic pressing (HIP) sintering technique was employed to prepare the pristine Bi2Te3 and the BT-xGTNPs samples for testing. The crystallographic measurements showed a reduction in the crystallinity of the BT-xGTNPs samples compared to the pure Bi2Te3, whereas the electron microscopy measurements showed smaller grain sizes. This was also confirmed with an increase in the samples’ relative density implying the formation of nano-sized grains. Full electrical, thermal, and thermoelectric measurements were performed and comprehensively discussed in this report for all samples in the temperature range from room temperature (RT) to 570 K. The measurements demonstrated an enhancement for x = 0.35 wt% GTNPs at 540 K up to 43% in the power factor and 51% in the ZT compared to pristine Bi2Te3, which was attributed to the optimum grain size, the lower grain boundaries, and better electrical and thermal conductivity aroused from the precise addition of GTNPs. The best electrical conductivity of ~ 8.2 × 104 S/m and lowest thermal conductivity of ~ 1 W/m·K for the Bi2Te3-containing 0.35 wt% GTNPs at RT even though the sample with 0.5 wt% attained the highest Seebeck coefficient of 154 µV/T at 540 K.

Study on preparation and properties of silver alloy for Mongolian medicine acupuncture

The Mongolian medical silver needles often encounter issues of bending, fracturing, and blunting in clinical applications. Similarly, Mongolian warm needles can cause burns on patients due to inaccurate temperature control. In this study, we developed an Ag85Cu15 alloy specifically for acupuncture needles based on material preparation. By incorporating appropriate amounts of Mn and Ti elements, we were able to enhance the mechanical properties and biocompatibility of the acupuncture needles. Compared to commercially available silver needles, this alloy exhibited a significant increase in microhardness up to 210.2 Hv0.2 and an improved tensile strength of 880.2 MPa. Furthermore, we designed a thermoelectric effect-based temperature measurement model for precise control of the warm needle's temperature, enhancing the therapeutic effectiveness of the treatment.

Self-contained calibration samples and measurements of the thermoelectric figure of merit: A method to improve accuracy

Despite more than seven decades of active research and development in thermoelectricity, the accurate measurement of the thermoelectric (TE) properties of bulk materials has remained a challenge, mainly because of the strong interrelation between thermal and electrical phenomena. This work highlights practical advancements in methods and instrumentation dedicated to the simultaneous measurements of TE properties such as the Seebeck coefficient (S), the thermal (κ), and electrical (σ) conductivities and the dimensionless TE figure of merit ZT = S2σT/κ. The accuracy of a Harman based approach, as implemented by the ZT-Scanner (TEMTE Inc.), applicable to the simultaneous measurement of the above TE properties, has been made possible by a self-contained calibration procedure, which is based on the availability of two samples of the same homogeneous material having different shape factors. It is of practical importance that this approach provides a simple procedure to obtain the calibration for the figure of merit ZT and the thermal conductivity in the temperature interval from 300 to 720 K. In addition, we show that a simplified Harman setup with no thermocouples attached to the sample can also be used for self-contained calibrated ZT measurements. It is concluded that the implemented steady-state approach decreases the relative error down to 1%–2% for ZT measurements and can be recommended for most applications not involving dynamical behavior. In particular, it is proposed that self-generated calibration samples can critically increase the quality and ease of comparison of TE measurements if they are adopted by the TE community.

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.

Electrical properties of strained off-stoichiometric Cu–Cr–O delafossite thin films

Off-stoichiometric Cu–Cr–O delafossite thin films with different thicknesses were grown by metal organic chemical vapor deposition on substrates with different coefficients of thermal expansion. Seebeck thermoelectric coefficient and resistivity measurements were performed on the range of 300–850 K. A qualitative change in the temperature-dependence of the resistivity is observed at the temperature corresponding to the deposition process, where the transition from tensile to compressive strain takes place. Arrhenius plots reveal different slopes in these two thermal ranges. The fact that the shift is more pronounced for the thinner films might indicate the induced strain plays a role in changing electrical behaviour. Furthermore, changes below 0.1% in electrical mobility were measured when the strain is induced by mechanical bending.

Mechanochemical preparation of nanocrystalline stannite/chatkalite composite: kinetics of synthesis and thermoelectric properties

In this study we demonstrate the use of Cu, Fe, Sn and S elemental precursors to synthesize chatkalite/stannite nanocomposite by high-energy milling in both lab-scale and industrial-scale mills. The products were characterized by XRD, SEM, HRTEM, EDX, Mössbauer spectroscopy and magnetometry. For the determination of optimum milling conditions, the magnetization data of the synthesized samples were used as output values using a Taguchi experimental design. The formation of the product proceeds via a multistep process comprising binary sulphides (SnS and CuS) formation at the beginning and chatkalite Cu6FeSn2S8/stannite Cu2FeSnS4 composite as the end products. The TEM images show tightly packed nanosized crystallites with the sizes in the range of tens of nanometers. Mössbauer study unveiled that iron is present in 3+ state instead of 2+ expected for stoichiometric phases. This discrepancy was explained by the presence of a small number of vacancies on Sn sites. Based on the thermoelectric measurements of the hot-pressed pellets, the calculated figure of merit reached a value of ZT = 0.27 at 600 K. The aim of this study is to prepare a representative of a promising class of environmentally acceptable thermoelectric materials in an environmentally sound solvent-free manner and characterize them while studying the kinetics of the reaction via magnetometry and the possibility to scale-up the solid-state synthesis process.

Instability Mechanism in Thermoelectric Mg2(Si,Sn) and the Role of Mg Diffusion at Room Temperature

Mg2(Si,Sn) shows great promise as thermoelectric material as it is made from non‐toxic, abundant, and cost‐effective elements offering high performance. This has been emphasized by several thermoelectric generator prototypes, demonstrating technological maturity. However, material stability is paramount for large‐scale applications whereas we reveal here that the thermal stability of n‐type Mg2(Si,Sn) may be limited even at room temperature (RT). Integral thermoelectric properties measurements, locally resolved Seebeck coefficient analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and atomic force microscopy are employed to assess changes of n‐type samples stored in ambient atmosphere for years, revealing the evolution of the carrier concentration and transport properties in the material as well as surface degradation. This is caused by the diffusion of loosely bound Mg from the bulk towards the surface and subsequent oxidation, leading to a change of Mg‐based intrinsic defect concentrations, thereby degrading the thermoelectric performance. This microscopic mechanism is backed up by first‐principles calculations, revealing that Mg diffusivity in Mg2(Si,Sn) is high at RT and that diffusion occurs mainly via Mg vacancies. The observed much faster degradation of Sn‐rich Mg2(Si,Sn) can be correlated with the higher density of Mg vacancies in Mg2Sn compared to Mg2Si, as predicted from defect formation energies.

Alloying-Induced Structural Transition in the Promising Thermoelectric Compound CaAgSb.

AMX Zintl compounds, crystallizing in several closely related layered structures, have recently garnered attention due to their exciting thermoelectric properties. In this study, we show that orthorhombic CaAgSb can be alloyed with hexagonal CaAgBi to achieve a solid solution with a structural transformation at x ∼ 0.8. This transition can be seen as a switch from three-dimensional (3D) to two-dimensional (2D) covalent bonding in which the interlayer M-X bond distances expand while the in-plane M-X distances contract. Measurements of the elastic moduli reveal that CaAgSb1-xBix becomes softer with increasing Bi content, with the exception of a steplike 10% stiffening observed at the 3D-to-2D phase transition. Thermoelectric transport measurements reveal promising Hall mobility and a peak zT of 0.47 at 620 K for intrinsic CaAgSb, which is higher than those in previous reports for unmodified CaAgSb. However, alloying with Bi was found to increase the hole concentration beyond the optimal value, effectively lowering the zT. Interestingly, analysis of the thermal conductivity and electrical conductivity suggests that the Bi-rich alloys are low Lorenz-number (L) materials, with estimated values of L well below the nondegenerate limit of L = 1.5 × 10-8 W Ω K-2, in spite of the metallic-like transport properties. A low Lorenz number decouples lattice and electronic thermal conductivities, providing greater flexibility for enhancing thermoelectric properties.

GA-BP Optimization Using Hybrid Machine Learning Algorithm for Thermopile Temperature Compensation

Thermoelectric pile, which uses non-contact infrared temperature measurement principle, is widely used in various precision temperature measuring instruments. This paper analyzes environmental temperature's influence on thermoelectric piles' measurement accuracy and proposes a environment temperature compensation based on GA-BP (Genetic Algorithm-Back Propagation) neural network. The GA algorithm makes up for the slow iterative speed and easy to fall into local optimization of BP algorithm. The experimental simulation results show that environment temperature compensation based on GA-BP can accurately correct the measurement error caused by environmental temperature and other factors.

Exploring the Impact of the HOMO-LUMO Gap on Molecular Thermoelectric Properties: A Comparative Study of Conjugated Aromatic, Quinoidal, and Donor-Acceptor Core Systems.

Thermoelectric materials have garnered significant interest for their potential to efficiently convert waste heat into electrical energy at room temperature without moving parts or harmful emissions. This study investigated the impact of the HOMO-LUMO (H-L) gap on the thermoelectric properties of three distinct classes of organic compounds: conjugated aromatics (isoindigos (IIGs)), quinoidal molecules (benzodipyrrolidones (BDPs)), and donor-acceptor systems (bis(pyrrol-2-yl)squaraines (BPSs)). These compounds were chosen for their structural simplicity and linear π-conjugated conductance paths, which promote high electrical conductance and minimize complications from quantum interference. Single-molecule thermoelectric measurements revealed that despite their low H-L gaps, the Seebeck coefficients of these compounds remain low. The alignment of the frontier orbitals relative to the Fermi energy was found to play a crucial role in determining the Seebeck coefficients, as exemplified by the BDP compounds. Theoretical calculations support these findings and suggest that anchor group selection could further enhance the thermoelectric behavior of these types of molecules.

A Novel and Green Method for Preparing Highly Conductive PEDOT:PSS Films for Thermoelectric Energy Harvesting.

As a π-conjugated conductive polymer, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is recognized as a promising environmentally friendly thermoelectric material. However, its low conductivity has limited applications in the thermoelectric field. Although thermoelectric efficiency can be significantly enhanced through post-treatment doping, these processes often involve environmentally harmful organic solvents or reagents. In this study, a novel and environmentally benign method using purified water (including room temperature water and subsequent warm water) to treat PEDOT:PSS film has been developed, resulting in improved thermoelectric performance. The morphology data, chemical composition, molecular structure, and thermoelectric performance of the films before and after treatment were characterized and analyzed using a scanning electron microscope (SEM), Raman spectrum, XRD pattern, X-ray photoelectron spectroscopy (XPS), and a thin film thermoelectric measurement system. The results demonstrate that the water treatment effectively removes nonconductive PSS from PEDOT:PSS composites, significantly enhancing their conductivity. Treated films exhibit improved thermoelectric properties, particularly those treated only 15 times with room temperature water, achieving a high electrical conductivity of 62.91 S/cm, a Seebeck coefficient of 14.53 μV K-1, and an optimal power factor of 1.3282 µW·m-1·K-2. In addition, the subsequent warm water treatment can further enhance the thermoelectric properties of the film sample. The underlying mechanism of these improvements is also discussed.

On the Ytterbium Valence and the Physical Properties in Selected Intermetallic Phases.

The present review summarizes important aspects of the crystal chemistry of ytterbium-based intermetallic compounds along with a selection of their outstanding physical properties. These originate in many cases from the ytterbium valence. Different valence states are possible here, divalent (4f14), intermediate-valent, or trivalent (4f13) ytterbium, resulting in simple diamagnetic, Pauli or Curie-Weiss paramagnetic, or valence fluctuating behavior. Especially, some of the Yb3+ intermetallics have gained deep interest due to their Kondo or heavy Fermion ground states. We have summarized their property investigations using magnetic and transport measurements, specific heat data, NMR, ESR, and Mössbauer spectroscopy, elastic and inelastic neutron scattering, and XAS data as well as detailed thermoelectric measurements.

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Thermoelectric measurements.

TEM-compatible microdevice for the complete thermoelectric characterization of epitaxially integrated Si-based nanowires.

Nanostructured materials present improved thermoelectric properties due to non-trivial effects at the nanoscale. However, the characterization of individual nanostructures, especially from the thermal point of view, is still an unsolved topic. This work presents the complete structural, morphological, and thermoelectrical evaluation of the selfsame individual bottom-up integrated nanowire employing an innovative micro-machined device compatible with transmission electron microscopy whose fabrication is also discussed. Thanks to a design that arranges the nanostructured samples completely suspended, detailed structural analysis using transmission electron microscopy is enabled. In the same device architecture, electrical collectors and isolated heaters are available at both ends of the trenches for thermoelectrical measurements of the nanowire i.e. thermal and electrical properties simultaneously. This allows the direct measurement of the nanowire power factor. Furthermore, micro-Raman thermometry measurements were performed to evaluate the thermal conductivity of the same suspended silicon nanowire. A thermal profile of the self-heating nanowire could be spatially resolved and used to compute the thermal conductivity. In this work, heavily-doped silicon nanowires were grown on this microdevices yielding a thermal conductivity of 30.8 ± 1.7 W Km-1 and a power factor of 2.8 mW mK-2 at an average nanowire temperature of 400 K. Notably, no thermal contact resistance was observed between the nanowire and the bulk, confirming the epitaxial attachment. The device presented here shows remarkable utility in the challenging thermoelectrical characterization of integrated nanostructures and in the development of multiple devices such as thermoelectric generators.

Surface and Electrical Characterization of Non-Stoichiometric Semiconducting Thin-Film Coatings Based on Ti-Co Mixed Oxides Obtained by Gas Impulse Magnetron Sputtering

This article presents a detailed investigation of non-stoichiometric (Ti,Co)Ox thin films prepared using the Gas Impulse Magnetron Sputtering (GIMS) technique. The films were prepared with various Co contents (3 at.%, 19 at.%, 44 at.%, and 60 at.%) and characterized for their material composition, microstructure, and electrical properties. The films exhibited an ohmic behavior with linear current-voltage (I-V) characteristics, and their resistivity values ranged from approximately 10−3 to 104 Ω·cm. The highest resistivity was observed in the film with 3 at.% Co content. Thermoelectric measurements revealed that all of the prepared films displayed n-type semiconducting properties, with the Seebeck coefficient (S) tending close to zero. The resistivity of the films decreased as the temperature increased, affirming their semiconducting nature. The activation energy (Ea) values, determined using the Arrhenius formula, ranged from 0.0058 eV to 0.267 eV, with the highest Ea observed for films containing 3 at.% Co. Additionally, the films’ surface topography and microstructure were examined through Atomic Force Microscopy (AFM) and optical profiler techniques. The results showed that the films had smooth, crack-free surfaces with remarkable homogeneity. The surface diversification decreased with the increase in cobalt in the (Ti,Co)Ox films.

Nickel Oxide Decorated MWCNTs Wrapped Polypyrrole: One Dimensional Ternary Nanocomposites for Enhanced Thermoelectric Performance

AbstractThis study reports on a customized and revised approach to fabricate “nickel oxide decorated multi‐walled carbon nanotubes (MWCNTs) wrapped polypyrrole (PPy)” nanocomposite with enhanced room‐temperature thermoelectric (TE) properties. The nanocomposite is formed through three steps: MWCNTs functionalization via diazonium salt grafting of 5‐amino‐1,2,3‐benzene tricarboxylic acid; in situ generation on their surfaces of NiO nanoparticles with a homogenous distribution; the chemical polymerization of pyrrole using methyl orange as templating and dopant to wrap the MWCNTs‐(COOH)3‐NiO. Various techniques were used as characterization tools, including XRD, TEM, FTIR, Raman, TGA, XPS, and TE measurements. The PPy‐MWCNTs‐(COOH)3‐NiO nanocomposite exhibits significantly higher Seebeck coefficient, electrical conductivity, and power factor than PPy and PPy‐MWCNTs‐(COOH)3. The achieved enhancement in TE properties (figure of merit, ZTPPy‐MWCNTs‐(COOH)3‐NiO=1.51×10−2) is attributed to the presence of NiO, which acts as a dopant and improves the charge carrier density in the nanocomposite. These results offer the potential for waste heat recovery and large‐scale fabrication of high‐performance composites.

Sustainable geopolymer concrete for thermoelectric energy harvesting

Concrete is a widely used material that presents vast opportunities for energy harvesting applications. Among these, thermoelectric concrete shows promising potential for harvesting waste heat generated in urban and industrial environments. However, the development of thermoelectric concrete poses several challenges that need to be addressed, such as the need to accurately account for the intrinsic voltage. This factor is frequently disregarded, but it has a significant impact on the measurement of thermoelectric properties in improving the intrinsically low electrical conductivity and Seebeck coefficient. In this context, this study evaluates the performance of industrially scalable geopolymer-based concrete that incorporates recycled aggregates as low-cost and environmentally friendly additives for thermoelectric energy harvesting applications. The concrete exhibited an intrinsic voltage of 15 mV, and a new test protocol was proposed to exclude its impact on thermoelectric measurements. The geopolymer concrete demonstrated a significantly high Seebeck coefficient of 570 µV/k, surpassing all previously reported values for geopolymer-based materials. Furthermore, it was discovered that the thermoelectric behavior of geopolymer-based concrete is of ionic origin, indicating that further improvements can be made by adjusting the pore solution chemistry. This finding suggests that there is ample opportunity for innovation and optimization in the development of thermoelectric concrete.

Heterogeneous Oriented Structure model of thermoelectric transport in conducting polymers

Understanding transport phenomena in conducting polymers (CP) is a main issue in order to optimize their performance and despite intense investigations, the influence of their microstructure remains controversial. By analyzing the thermoelectric measurements performed on highly oriented and non-oriented CP films, we show that an Heterogeneous Oriented Structure (HOSt) model considering both ordered and disordered domains is able to account for the thermoelectric transport in CP. This model unveils the key role of the crystallinity, the anisotropy and the alignment degree of these domains. It points out the importance of the thermal conductivity in the interpretation of the thermopower α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha $$\\end{document} and explains the frequently observed electrical conductivity σ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sigma $$\\end{document} cut-off in the α-σ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha -\\sigma $$\\end{document} curves due to the disordered domains. By varying the alignment degree depending on the orientation and the anisotropy according to the face-on or the edge-on polymers conformation, the HOSt model successfully describes the overall measured thermoelectric properties by demonstrating its applicability to a wide variety of both oriented and non-oriented CP.

Deconvolution of heat sources for application in thermoelectric micro four-point probe measurements

Joule heating is a primary phenomenon responsible for increasing temperature in electronic devices, and consequently, decreasing the lifetime and performance of electronic devices. However, this unwanted Joule heating can itself be used as a local source of heat to map the temperature-dependent material properties. Recently, micro four-point probe (M4PP) showed a promising potential for characterizing the temperature coefficient of resistance (TCR) and the Seebeck coefficient using Joule heating resulting from the measurement current. Here, we use M4PP to estimate the micrometer scale, relative temperature profile resulting from a single heat source. We introduce a triplet of four-point voltages measured at the second harmonic frequency, to deconvolute the thermoelectric voltage from the three individual heat sources involved. This paper tests and documents the validity of the proposed scheme in the 1–40 μm range on highly doped single crystal Si at 300 K, supporting predominantly Fourier heat transport at these scales. The method of deconvolution of heat sources reduces the complexity in evaluation of length- and time-dependent measurements, specifically used in the characterization of thermoelectric properties. The proposed method may also facilitate a more profound understanding of heat transport on the mesoscopic scale.

Effects of the substituent position on the structural order, work function change, and thermopower of dichloro-substituted benzenethiolate self-assembled monolayers on Au(1 1 1)

The surface structures, electrochemical behaviors, work function changes, and thermopower of dichloro-substituted benzenethiolate self-assembled monolayers (SAMs) on gold surfaces prepared by vapor deposition were investigated using scanning tunneling microscopy (STM), cyclic voltammetry, Kelvin probe force microscopy, and thermoelectric junction measurements to understand the effects of their substituent positions. STM observations revealed that the adsorption of 2,4-dichlorobenzenethiol (2,4-DCBT) on Au(111) at 363 K for 1 h led to the formation of short-range ordered domains with a (5 × 6√7)R20° structure, while the SAMs formed at 363 K for 4 h consisted of long-range well-ordered domains with a (√3 × 5) structure. 3,4-Dichlorobenzenethiol (3,4-DCBT) SAMs showed coexistence of partial ordered domains and a disordered phase, while 3,4-DCBT SAMs showed fully disordered phases regardless of deposition time. Moreover, the Seebeck coefficient (S) increased in the order of 3,4-DCBT (4.6 ± 0.1 μV/K) < 2,4-DCBT (5.0 ± 0.4 μV/K) < 3,5-DCBT (5.2 ± 0.1 μV/K). Interestingly, the trend of S values was qualitatively consistent with that of the work function change (ΔΦ) of the SAMs. The reductive desorption behavior, work function shifts, and thermopower of aromatic thiolate SAMs were significantly modified by the structural order and direction of molecular dipoles of dichloro-substituted benzenethiols.