Thermoelectricity at a gallium-mercury liquid metal interface.

We present experimental evidence of a thermoelectric effect at the interface between two liquid metals. Using superimposed layers of mercury and gallium in a cylindrical vessel operating at room temperature, we provide a direct measurement of the electric current generated by the presence of a thermal gradient along a liquid-liquid interface. At the interface between two liquids, temperature gradients induced by thermal convection lead to a complex geometry of electric currents, ultimately generating current densities near boundaries that are significantly higher than those observed in conventional solid-state thermoelectricity. When a magnetic field is applied to the experiment, an azimuthal shear flow, exhibiting opposite circulation in each layer, is generated. Depending on the value of the magnetic field, two different flow regimes are identified, in good agreement with a model based on the spatial distribution of thermoelectric currents, which has no equivalent in solid systems. Finally, we discuss various applications of this effect, such as the efficiency of liquid metal batteries.

A unified understanding of minimum lattice thermal conductivity.

We propose a first-principles model of minimum lattice thermal conductivity ([Formula: see text]) based on a unified theoretical treatment of thermal transport in crystals and glasses. We apply this model to thousands of inorganic compounds and find a universal behavior of [Formula: see text] in crystals in the high-temperature limit: The isotropically averaged [Formula: see text] is independent of structural complexity and bounded within a range from ∼0.1 to ∼2.6 W/(m K), in striking contrast to the conventional phonon gas model which predicts no lower bound. We unveil the underlying physics by showing that for a given parent compound, [Formula: see text] is bounded from below by a value that is approximately insensitive to disorder, but the relative importance of different heat transport channels (phonon gas versus diffuson) depends strongly on the degree of disorder. Moreover, we propose that the diffuson-dominated [Formula: see text] in complex and disordered compounds might be effectively approximated by the phonon gas model for an ordered compound by averaging out disorder and applying phonon unfolding. With these insights, we further bridge the knowledge gap between our model and the well-known Cahill-Watson-Pohl (CWP) model, rationalizing the successes and limitations of the CWP model in the absence of heat transfer mediated by diffusons. Finally, we construct graph network and random forest machine learning models to extend our predictions to all compounds within the Inorganic Crystal Structure Database (ICSD), which were validated against thermoelectric materials possessing experimentally measured ultralow κL. Our work offers a unified understanding of [Formula: see text], which can guide the rational engineering of materials to achieve [Formula: see text].

Direct visualization of polaron formation in the thermoelectric SnSe.

SnSe is a layered material that currently holds the record for bulk thermoelectric efficiency. The primary determinant of this high efficiency is thought to be the anomalously low thermal conductivity resulting from strong anharmonic coupling within the phonon system. Here we show that the nature of the carrier system in SnSe is also determined by strong coupling to phonons by directly visualizing polaron formation in the material. We employ ultrafast electron diffraction and diffuse scattering to track the response of phonons in both momentum and time to the photodoping of free carriers across the bandgap, observing the bimodal and anisotropic lattice distortions that drive carrier localization. Relatively large (18.7 Å), quasi-one-dimensional (1D) polarons are formed on the 300-fs timescale with smaller (4.2 Å) 3D polarons taking an order of magnitude longer (4 ps) to form. This difference appears to be a consequence of the profoundly anisotropic electron-phonon coupling in SnSe, with strong Fröhlich coupling only to zone-center polar optical phonons. These results demonstrate a high density of polarons in SnSe at optimal doping levels. Strong electron-phonon coupling is critical to the thermoelectric performance of this benchmark material and, potentially, high performance thermoelectrics more generally.

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.

Nanoconfinement Effect in Water Processable Discrete Molecular Complex-Based Hybrid Piezo- and Thermo-Electric Nanogenerator.

Water-processable hybrid piezo- and thermo-electric materials have an increasing range of applications. We use the nanoconfinement effect of ferroelectric discrete molecular complex [Cu(l-phe)(bpy)(H2O)]PF6·H2O (1) in a nonpolar polymer 1D-nanofiber to envision the high-performance flexible hybrid piezo- and thermo-electric nanogenerator (TEG). The 1D-nanoconfined crystallization of 1 enhances piezoelectric throughput with a high degree of mechano-sensitivity, i.e., 710 mV/N up to 3 N of applied force with 10,000 cycles of unaffected mechanical endurance. Thermoelectric properties analysis shows a noticeable improvement in Seebeck coefficient (∼4 fold) and power factor (∼6 fold) as compared to its film counterpart, which is attributed to the enhanced density of states near the Fermi edges as evidenced by ultraviolet photoelectric spectroscopy and density functional based theoretical calculations. We report an aqueous processable hybrid TEG that provides an impressive magnitude of Seebeck coefficient (∼793 µV/K) and power factor (∼35 mWm-1K-2) in comparison to a similar class of materials.

Bismuth Telluride Supported Sub-1 nm Polyoxometalate Cluster for High-Efficiency Thermoelectric Energy Conversion.

Size plays a crucial role in chemistry and material science. Subnanometer polyoxometalate (POM) clusters have gained attention in various fields, but their use in thermoelectrics is still limited. To address this issue, we propose the POM clusters as an effective second phase to enhance the thermoelectric properties of Bi0.4Sb1.6Te3. Thanks to their subnanometer size, POM clusters improve electrical transport behavior through the superposition of atomic orbitals and the interfacial scattering effect. Furthermore, their ultrasmall size strongly reduces thermal conductivity. Consequently, the introduction of a mere 0.1 mol % of POM into the Bi0.4Sb1.6Te3 matrix realizes a state-of-the-art zT value of 1.46 at 348 K, a 45% enhancement over Bi0.4Sb1.6Te3 (1.01), along with a maximum thermoelectric-conversion efficiency of the integrated module of 6.0%. The enhancement of carrier mobility and the suppression of thermal conduction achieved by introducing the subnanometer clusters hold promise for various applications, such as electronic devices and thermal management.

Plasmonic Nanoparticles Boost Solar-to-Electricity Generation at Ambient Conditions.

Sunlight-to-electricity conversion using solar thermoelectric generators (STEGs) is a proven technology to meet our ever-growing energy demand. However, STEGs are often operated under a vacuum with customized thermoelectric materials to achieve high performance. In this work, the incorporation of plasmonic gold nanoparticle (AuNP) based solar absorbers enabled the efficient operation of STEGs under ambient conditions with commercially available thermoelectric devices. AuNPs enhanced the performance of STEG by ∼9 times, yielding an overall solar-to-electricity conversion efficiency of ∼9.6% under 7.5 W cm-2 solar irradiance at ambient conditions. Plasmonic heat dissipated by AuNPs upon solar irradiation was used as the thermal energy source for STEGs. High light absorptivity, photothermal conversion efficiency (∼95%), and thermal conductivity of AuNPs enabled the efficient generation and transfer of heat to STEGs, with minimal radiative and convective heat losses. The power generated from plasmon-powered STEGs is used to run electrical devices as well as produce green hydrogen via the electrolysis of water.

Thickness-Dependent Magnetic Breakdown in ZrSiSe Nanoplates.

We report a study of thickness-dependent interband and intraband magnetic breakdown by thermoelectric quantum oscillations in ZrSiSe nanoplates. Under high magnetic fields of up to 30 T, quantum oscillations arising from degenerated hole pockets were observed in thick ZrSiSe nanoplates. However, when decreasing the thickness, plentiful multifrequency quantum oscillations originating from hole and electron pockets are captured. These multiple frequencies can be explained by the emergent interband magnetic breakdown enclosing individual hole and electron pockets and intraband magnetic breakdown within spin-orbit coupling (SOC) induced saddle-shaped electron pockets, resulting in the enhanced contribution to thermal transport in thin ZrSiSe nanoplates. These experimental frequencies agree well with theoretical calculations of the intriguing tunneling processes. Our results introduce a new member of magnetic breakdown to the field and open up a dimension for modulating magnetic breakdown, which holds fundamental significance for both low-dimensional topological materials and the physics of magnetic breakdown.

Enhanced Selective Ion Transport in Highly Charged Bacterial Cellulose/Boron Nitride Composite Membranes for Thermo-Osmotic Energy Harvesting.

Significant untapped energy exists within low-grade heat sources and salinity gradients. Traditional nanofluidic membranes exhibit inherent limitations, including low ion selectivity, high internal resistance, reliance on nonrenewable resources, and instability in aqueous solutions, invariably constraining their practical application. Here, an innovative composite membrane-based nanofluidic system is reported, involving the strategy of integrating tailor-modified bacterial nanofibers with boron nitride nanosheets, enabling high surface charge densities while maintaining a delicate balance between ion selectivity and permeability, ultimately facilitating effective thermo-osmotic energy harvesting. The device exhibits an impressive output power density of 10 W m-2 with artificial seawater and river water at a 50 K temperature gradient. Furthermore, it demonstrates robust power density stability under prolonged exposure to salinity gradients or even at elevated temperatures. This work opens new avenues for the development of nanofluidic systems utilizing composite materials and presents promising solutions for low-grade heat recovery and osmotic energy harvesting.

Theoretical Perspective of Enhancing Order in n-Doped Thermoelectric Polymers through Side Chain Engineering: The Interplay of Counterion-Backbone Interaction and Side Chain Steric Hindrance.

Donor-acceptor (D-A) copolymers doped with n-type dopants are widely sought after for their potential in organic thermoelectric devices. However, the existing structural disorder significantly hampers their charge transport and thermoelectric performance. In this Letter, we propose a mechanism to mitigate this disorder through side chain engineering. Utilizing molecular dynamics simulations, we demonstrate that strong Coulomb interactions between counterions and charged polymer backbones induce a transition in the stacking arrangement of the polymer backbones from a slipped to a vertical configuration. However, the presence of side chain steric hindrance impedes the formation of closely packed and ordered vertical stacking arrangements, resulting in greater distances between adjacent backbones and a higher level of structural disorder in the doped films. Therefore, we propose minimizing side chain steric hindrance to enhance the structural order in doped films. Our findings provide essential insights for advancing high-performance thermoelectric polymers.

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.

Micromechanism for Copper-Deficiency Enhanced Stability: A Quasi In Situ TEM Study of Electric-Induced Structural Evolution in Cu2-x(S, Se) Liquid-Like Thermoelectric Materials.

Cu-based liquid-like thermoelectric materials have garnered tremendous attention due to their inherent ultralow lattice thermal conductivity. However, their practical application is hampered by stability issues under a large current or temperature gradient. It has been reported that introduction of copper vacancies can enhance the chemical stability, whereas the micromechanism behind this macroscopic improvement still remains unknown. Here, we have established a quasi in situ TEM method to examine and compare the structural evolution of Cu2-xS0.2Se0.8 (x = 0, 0.05) under external electric fields. It is then found that the preset Cu vacancies could favor the electric-induced formation of a more stable intermediate phase, i.e., the hexagonal CuSe-type structure in the form of either lamellar defects (majorly) or long-range order (minorly), in which ordering of S and Se also occurred. Thereby, copper and chalcogen atoms could largely be solidified into the matrix, and the elemental deposition and evaporation process is mitigated under an electric field.

Opto-electronic and thermophysical characteristics of A2TlAgF6 (A = Rb, Cs) for green technology applications.

Lead-free double perovskites are unique materials for transport and optoelectronic applications that use clean resources to generate energy. Using first-principle computations, this study thoroughly investigates the structural, thermoelectric, and optical attributes of A2TlAgF6 (A = Rb, Cs). Tolerance factor and formation energy estimates are used to verify that these materials exist in the cubic phase. Elastic constants with high melting temperature values are ductile when evaluated for mechanical stability using the Born stability criterion. The optical absorption band is adjusted from 2 to 4 eV via band gaps of 1.88 and 1.99 eV, as indicated by band structures. Analysis of optical properties reveals perfect absorption in the visible spectrum, whole polarization, and low optical loss. Furthermore, thermoelectric properties are assessed at 300, 500, and 700 K in the range of -0.5 to 3 eV for chemical potential (µ). The materials exhibit significant improvements in the Figure of Merit scale due to their elevated electrical conductivity, Seebeck coefficient, and extremely low thermal conductivity values.

Enhanced Thermoelectric Performance of Nanostructured 2D Tin Telluride.

A lot of experimental studies are conducted on theoretically predicted thermoelectric 2D materials. Such materials can pave the way for charging ultra-thin electronic devices, self-charging wearable devices, and medical implants. This study systematically explores the thermoelectric attributes of bulk and 2D nanostructured Tin Telluride (SnTe), employing experimental investigations and theoretical analyses based on semiclassical Boltzmann transport theory. The bulk SnTe is synthesized through flame melting, while the 2D SnTe is produced via liquid phase exfoliation. The comprehensive assessment of thermoelectric properties integrated experimental measurements utilizing a Physical Property Measurement System and theoretical calculations from the BoltzTraP code. Experimental thermoelectric studies show a high ZT of 0.17 for 2D SnTe when compared to bulk (0.005) at room temperature. This rise in ZT is due to the high Seebeck coefficient and low thermal conductivity of nanostructured 2D SnTe. Density functional theory (DFT) studies reveal the contribution of the density of states (DOS) and energy bandgap in enhancing the Seebeck coefficient and lowering thermal conductivity by interface scattering.

All-Scale Hierarchical Structuring, Optimized Carrier Concentration, and Band Manipulation Lead to Ultra-High Thermoelectric Performance in Eco-Friendly MnTe.

MnTe emerges as an enormous potential for medium-temperature thermoelectric applications due to its lead-free nature, high content of Mn in the earth's crust, and superior mechanical properties. Here, it is demonstrate that multiple valence band convergence can be realized through Pb and Ag incorporations, producing large Seebeck coefficient. Furthermore, the carrier concentration can be obviously enhance by Pb and Ag codoping, contributing to significant enhancement of power factor. Moreover, microstructural characterizations reveal that PbTe nanorods can be introduced into MnTe matrix by alloying Pb. This can modify the microstructure into all-scale hierarchical architectures (including PbTe nanorods, enhances point-defect scattering, dense dislocations and stacking faults), strongly lowering lattice thermal conductivity to a record low value of 0.376 W m-1 K-1 in MnTe system. As a result, an ultra-high ZT of 1.5 can be achieved in MnTe thermoelectric through all-scale hierarchical structuring, optimized carrier concentration, and valence band convergence, outperforming most of MnTe-based thermoelectric materials.

Synergistic Interactions in Sequential Process Doping of Polymer/Single-Walled Carbon Nanotube Nanocomposites for Enhanced n-Type Thermoelectric Performance.

This study focuses on the fabrication of nanocomposite thermoelectric devices by blending either a naphthalene-diimide (NDI)-based conjugated polymer (NDI-T1 or NDI-T2), or an isoindigo (IID)-based conjugated polymer (IID-T2), with single-walled carbon nanotubes (SWCNTs). This is followed by sequential process doping method with the small molecule 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI) to provide the nanocomposite with n-type thermoelectric properties. Experiments in which the concentrations of the N-DMBI dopant are varied demonstrate the successful conversion of all three polymer/SWCNT nanocomposites from p-type to n-type behavior. Comprehensive spectroscopic, microstructural, and morphological analyses of the pristine polymers and the various N-DMBI-doped polymer/SWCNT nanocomposites are performed in order to gain insights into the effects of various interactions between the polymers and SWCNTs on the doping outcomes. Among the obtained nanocomposites, the NDI-T1/SWCNT exhibits the highest n-type Seebeck coefficient and power factor of -57.7 µV K-1 and 240.6 µW m-1 K-2 , respectively. However, because the undoped NDI-T2/SWCNT exhibits a slightly higher p-type performance, an integral p-n thermoelectric generator is fabricated using the doped and undoped NDI-T2/SWCNT nanocomposite. This device is shown to provide an output power of 27.2 nW at a temperature difference of 20 K.

Realizing High Thermoelectric Properties in Bi2S3 Bulk via Band Engineering and Nanorods Compositing.

Bismuth sulfide is a promising thermoelectric material because of its low cost and toxicity; however, its low electrical conductivity limits its thermoelectric properties. In this study, Bi2S3+x wt% HfCl4 (x = 0, 0.25, 0.5, 0.75, and 1.0) bulk samples are fabricated using a combination of melting and spark plasma sintering. The microstructures, electronic structures, and thermoelectric properties of the composites are characterized. The results of electronic structure calculations show that doping with HfCl4 produces an impurity energy level that narrows the bandgap and allows the Fermi energy level to enter the conduction band, leading to a favorable increase in carrier concentration. By regulating the HfCl4 doping concentration, the electrical conductivity of the 0.75 wt% doped sample reaches 253 Scm-1 at 423 K and its maximum ZT value is 0.47 at 673 K. Moreover, the sample is compounded with Bi2S3 nanorods prepared by the hydrothermal method, reducing thermal conductivity by 30% due to the introduction of additional interfaces and pores. This resulted in a final ZT value of 0.61 at 673 K, which is approximately eight times higher than that of pure Bi2S3. This step-by-step optimization approach provides a valuable methodology for enhancing the performance of other thermoelectric material systems.

Optimization of Mechanical and Thermoelectric Properties of SnTe-Based Semiconductors by Mn Alloying Modulated Precipitation Evolution.

Multiscale defects engineering offers a promising strategy for synergistically enhancing the thermoelectric and mechanical properties of thermoelectric semiconductors. However, the specific impact of individual defects, in particular precipitation, on mechanical properties remains ambiguous. In this work, the mechanical and thermoelectric properties of Sn1.03- xMnxTe (x = 0-0.30) semiconductors are systematically studied. Mn-alloying induces dense dislocations and Mn nano-precipitates, resulting in an enhanced compressive strength with x increased to 0.15. Quantitative calculations are performed to assess the strengthening contributions including grain boundary, solid solution, dislocation, and precipitation strengthening. Due to the dominant contribution of precipitation strengthening, the yield strength of the x = 0.10 sample is improved by ≈74.5% in comparison to the Mn-free Sn1.03Te. For x ≥ 0.15, numerous MnTe precipitates lead to a synergistic enhancement of strength-ductility. In addition, multiscale defects induced by Mn alloying can scatter phonons over a wide frequency spectrum. The peak figure of merit ZT of ≈1.3 and an ultralow lattice thermal conductivity of ≈0.35 Wm-1 K-1 are obtained at 873 K for x = 0.10 and x = 0.30 samples respectively. This work reveals tha precipitation evolution optimizes the mechanical and thermoelectric properties of Sn1.03- xMnxTe semiconductors, which may hold potential implications for other thermoelectric systems.

CdSe Quantum Dots Enable High Thermoelectric Performance in Solution-Processed Polycrystalline SnSe.

Here, a high peak ZT of ≈2.0 is reported in solution-processed polycrystalline Ge and Cd codoped SnSe. Microstructural characterization reveals that CdSe quantum dots are successfully introduced by solution process method. Ultraviolet photoelectron spectroscopy evinces that CdSe quantum dots enhance the density of states in the electronic structure of SnSe, which leads to a large Seebeck coefficient. It is found that Ge and Cd codoping simultaneously optimizes carrier concentration and improves electrical conductivity. The enhanced Seebeck coefficient and optimization of carrier concentration lead to marked increase in power factor. CdSe quantum dots combined with strong lattice strain give rise to strong phonon scattering, leading to an ultralow lattice thermal conductivity. Consequently, high thermoelectric performance is realized in solution-processed polycrystalline SnSe by designing quantum dot structures and introducing lattice strain. This work provides a new route for designing prospective thermoelectric materials by microstructural manipulation in solution chemistry.

A Current Development of Energy Harvesting Systems for Energy-Independent Bioimplantable Biosensors.

Biosensors have emerged as vital tools for the detection and monitoring of essential biological information. However, their efficiency is often constrained by limitations in the power supply. To address this challenge, energy harvesting systems have gained prominence. These off-grid, independent systems harness energy from the surrounding environment, providing a sustainable solution for powering biosensors autonomously. This continuous power source overcomes critical constraints, ensuring uninterrupted operation and seamless data collection. In this article, a comprehensive review of recent literature on energy harvesting-based biosensors is presented. Various techniques and technologies are critically examined, including optical, mechanical, thermal, and wireless power transfer, focusing on their applications and optimization. Furthermore, the immense potential of these energy harvesting-driven biosensors is highlighted across diverse fields, such as medicine, environmental surveillance, and biosignal analysis. By exploring the integration of energy harvesting systems, this review underscores their pivotal role in advancing biosensor technology. These innovations promise improved efficiency, reduced environmental impact, and broader applicability, marking significant progress in the field of biosensors.