Thermal Transport Properties Research Articles

Mapping of Long-Wavelength Phonon Contribution in the Thermal Transport of Alloyed Semiconductor Superlattices.

The mapping of long-wavelength phonons is important to understand and manipulate the thermal transport in multilayered structures, but it remains a long-standing challenge due to the collective behaviors of phonons. In this study, an experimental demonstration of mapping the long-wavelength phonons in an alloyed Al0.1Ga0.9As/Al0.9Ga0.1As superlattice system is reported. Multiple strategies to filter out the short- to mid-wavelength phonons are used. The phonon mean-free-path-dependent thermal transport properties directly demonstrate both the suppression effect of the ErAs nanoislands and the contribution of long-wavelength phonons. The contribution from phonons with mean free path longer than 1 μm is clearly demonstrated. A model based on the Boltzmann transport equation is proposed to calculate and describe the thermal transport properties, which depicts a clear physical picture of the transport mechanisms. This method can be extended to map different wavelength phonons and become a universal strategy to explore their thermal transport in various application scenarios.

Simultaneous measurement of thermal conductivity and emissivity of micro/nanomaterials

Although thermal conductivity of micro/nano scale material has been readily measured, the high specific surface area leads to non-negligible radiative heat transfer. Here, a method for simultaneous measurement of intrinsic thermal conductivity and emissivity of micro/nano materials was developed and verified. The physical model of this measurement principle consisted of two parallel platinum wires, which serve as both heaters and heat flux meters. Thermal conductivity and emissivity can be derived by comparing the changes in the average temperature rise of the heater and sensor platinum wires before and after attaching the test sample. The thermal conductivity and emissivity of an individual platinum wire were determined to 71.7 W/(m·K) and 0.14, which are consistent with the reference values. Subsequently, the thermal conductivity and emissivity of the polymer composite fiber were measured to be 1.45 W/(m·K), 0.73 and 1.87 W/(m·K), 0.8 at different composite filler concentrations. In principle, this method is applicable for accurately measuring the thermal transport properties of any micro/nano wires using appropriate sensors.

Numerical investigation of the overall thermal and thermodynamic performance of a high concentration ratio parabolic trough solar collector with a novel modified twisted tape insert using supercritical CO2 as the working fluid

Supercritical CO2 (sCO2) is favoured as the next-generation working fluid for advanced high-temperature and high-concentration ratio parabolic trough solar collectors (PTSC) due to the fluid’s low cost, availability and thermal stability at high temperatures. However, the lower thermal transport properties of sCO2 compared to conventional working fluids necessitate heat transfer enhancement of receivers using sCO2. In this study, a combined and extensively validated approach using Monte-Carlo ray tracing for optical analysis and computational fluid dynamics (CFD) for thermal and thermodynamic analysis were used to investigate the overall thermal and thermodynamic performance of a high concentration ratio sCO2-based PTSC with a modified twisted tape (MTT) inserts in the receiver. MTT inserts with twist ratios in the range of 2.0 to 4.0 and width ratios in the range of 0.75 to 0.95 were investigated. Results show enhancement of the heat transfer performance by up to 73% and thermal efficiency by 6%, and reduction of the receiver heat losses and circumferential temperature gradients when the MTT inserts are used. In addition to presenting results using the first law of thermodynamics, this study also considered the second law of thermodynamics by evaluating the entropy generation rates due to heat transfer and fluid friction irreversibilities. Results showed that the use of MTT inserts caused a reduction in the total entropy generation rates, with the lowest irreversibility occurring at a Reynolds number of 1,650,000 for a twist ratio of 2.0 and width ratio of 0.95.

Unleashing the power of artificial intelligence in phonon thermal transport: Current challenges and prospects

The discovery of advanced thermal materials with exceptional phonon properties drives technological advancements, impacting innovations from electronics to superconductors. Understanding the intricate relationship between composition, structure, and phonon thermal transport properties is crucial for speeding up such discovery. Exploring innovative materials involves navigating vast design spaces and considering chemical and structural factors on multiple scales and modalities. Artificial intelligence (AI) is transforming science and engineering and poised to transform discovery and innovation. This era offers a unique opportunity to establish a new paradigm for the discovery of advanced materials by leveraging databases, simulations, and accumulated knowledge, venturing into experimental frontiers, and incorporating cutting-edge AI technologies. In this perspective, first, the general approach of density functional theory (DFT) coupled with phonon Boltzmann transport equation (BTE) for predicting comprehensive phonon properties will be reviewed. Then, to circumvent the extremely computationally demanding DFT + BTE approach, some early studies and progress of deploying AI/machine learning (ML) models to phonon thermal transport in the context of structure–phonon property relationship prediction will be presented, and their limitations will also be discussed. Finally, a summary of current challenges and an outlook of future trends will be given. Further development of incorporating AI/ML algorithms for phonon thermal transport could range from phonon database construction to universal machine learning potential training, to inverse design of materials with target phonon properties and to extend ML models beyond traditional phonons.

First-principles calculation of P-type Mg3Sb2 thermoelectric performance modification by Ge and Si doping

Mg3Sb2 has been considered a highly promising thermoelectric material for mid-temperature applications. Optimizing the properties of the material is crucial for accelerating its commercial use. In this work, first-principles molecular simulations of P-type Mg3Sb2 doped with the carbon group elements Ge and Si have been carried out. Results indicate that doping with Ge and Si enhances the thermodynamic stability and electrical conductivity of the material. This improvement is achieved by decreasing the bandgap, increasing the local and peak density of states, flattening the band structure, and elevating the relative mass of carriers. Additionally, doping with Ge and Si decreases the phonon velocity and Debye temperature, which weakens the thermal transport properties of the material. These findings suggest that Ge and Si doping is an effective method for improving the thermoelectric properties of the material. At the same doping concentration, the Si single-doped system possesses the smallest bandgap value with the highest peak density of states and forms an indirect bandgap, leading to the best electrical transport properties; the Ge single-doped system has the lowest phonon velocity and Debye temperature, which has the most significant effect in attenuating the thermal transport properties of the material; and the Ge–Si co-doped system has the highest relative mass of carriers, which is conducive to the enhancement of Seebeck coefficient. The results offer theoretical guidance for experimentally analyzing the effects of Ge and Si doping on the thermoelectric properties of Mg3Sb2.

Star poly(ionic liquid)s: Chain architecture‐property relationships

AbstractIn this study, we report the synthesis of 3‐, 4‐, and 6‐arm star poly(ionic liquid)s (PILs) (specifically, star poly(vinylbenzyl methylimidazolium bis(trifluoromethane)sulfonimide) (poly(VBMIm‐TFSI))) via reversible addition‐fragmentation chain transfer (RAFT) polymerization with a core‐first approach, followed by quaternization and anion exchange. The impact of star polymer architecture on properties was explored by measuring the thermal, mechanical, and ion transport properties of each star PIL compared to those of an analogous linear PIL. The star PILs exhibited up to 2‐fold higher ionic conductivity, 150% higher elastic modulus, and 465% higher ultimate tensile strength compared to the analogous linear PIL. The Williams‐Landel‐Ferry (WLF) equation was employed to explore the effect of increased free volume on the improved ion transport properties of the star PILs. These results highlight the impact of star polymer architecture on PILs and star PILs as promising materials for electrochemical energy devices.

Nonlinearity effects on thermal transport properties of a mass-spring chain

Using Green’s function technique, we present a self-consistent formalism to study the phonon transport properties of an extended nonlinear mass-spring chain. We calculate the phonon transmission coefficient, thermal conductivity, and specific heat for some chains with different configurations of masses feeling the nonlinearity potential. The numerical results show that in a critical value of the nonlinearity coefficient, a sharp decrease in thermal conductivity will be observed. The same scenario happens in a critical temperature proportional to the inverse of the nonlinearity coefficient for the specific heat. Indeed, thermal conductor-insulator transition can occur in the system depending on the strength and distribution of nonlinearity. The model can aid our understanding of the effect of lattice nonlinearity on the thermal properties of one-dimensional materials to design the thermal switches.

Integration of layered group IV selenides: From SnSe–SnSe2-xSx core-shell crystals to complex (SnSe–SnSe2-xSx)-GeSe van der waals heterostructures

The layered semiconductor tin selenide (SnSe) has received extensive interest due to its promising thermoelectric and ferroelectric properties. Integrating SnSe with other layered crystals in heterostructures can enable the modification of charge- and thermal transport, electrical polarization, and other properties such as chemical stability, optoelectronics, and photonics. Here, we demonstrate the vapor transport synthesis of single-crystalline SnSe monochalcogenide flakes that are spontaneously encapsulated in a thin layered SnSe2-xSx dichalcogenide shell. In a second growth step, such SnSe–SnSe2-xSx heterostructures are integrated with the monochalcogenide GeSe, which is laterally stitched to the SnSe side facets while preserving the dichalcogenide shell across the basal facets. This architecture is confirmed by optical microscopy, electron microscopy and diffraction, energy dispersive X-ray and Raman spectroscopies, as well as cathodoluminescence spectroscopy. The results extend our capabilities for materials integration by forming complex heterostructures with both vertical van der Waals interfaces and covalent lateral interfaces between layered semiconductors.

Dual-optimization of transport properties enabled by high-pressure treatments for CuInTe2 thermoelectric materials

CuInTe2 is the focus of much research interest in I-III-VI2 diamondoid compounds due to its potentially high thermoelectric performance. However, its unmatched transport behaviors among electrical and thermal properties seriously impede enhanced thermoelectric performance. In this work, we demonstrate that high pressure can dual-optimize the electrical and thermal transport properties, leading to enhanced thermoelectric performance in CuInTe2 with cationic defects. The results indicate that the carrier concentration level is increased while greatly enhancing carrier mobility owing to the influence of high pressure on the band and electronic structures, realizing an excellent power factor of 1406 μWm−1K−2. Furthermore, high-pressure treatments and cationic defects can introduce multiple defect structures with various sizes, strongly scattering full-frequency phonons to reduce lattice thermal conductivity. With these great merits enabled by high pressure, the thermoelectric performance of CuInTe2 with cationic defects is improved and a maximum zT of 1.12 is obtained at 773 K, fully verifying the advantages of high-pressure treatments in terms of improving transport properties.

Multifunctional properties of carbon nanotube yarn/aerogel laminate composites

This work explores the multifunctional performance of scalable carbon nanotube (CNT) yarn laminate composites. Tensile, thermal, electrical, and electromagnetic interference (EMI) shielding properties are compared to state-of-the-art unidirectional IM7/5250-4 carbon fiber composite (CFRP). CNT laminates achieved a specific tensile modulus of 249.7 ± 22.3 GPa/(g/cm3), which is over double the specific modulus of the CFRP, while maintaining a specific tensile strength of 1.88 ± 0.17 GPa/(g/cm3) which is comparable to the CFRP. CNT yarn laminates demonstrated superior thermal transport properties, with in-plane thermal conductivity of 75.78 ± 14.3 W/mK, over 13 times higher than the CFRP. CNT yarn laminates were also superior in electrical conductivity, achieving a longitudinal conductivity of 5359 ± 417 S/cm and transverse conductivity of 36.87 ± 2.55 S/cm. This translated to superior EMI shielding properties, achieving over 100 dB in the X-band, which is nearly double that of the CFRP. Incorporating CNT aerogel interwoven between CNT yarns reduced the large property variance observed in the measurements, demonstrating a multifunctional material with tensile, thermal, electrical, and EMI properties superior to the CFRP, while potentially mitigating the scalability challenges inherent to CNT nanomaterials.

Anomalous thermal transport and high thermoelectric performance of Cu-based vanadate CuVO3

Thermoelectric (TE) conversion technology, capable of transforming heat into electricity, is critical for sustainable energy solutions. Many promising TE materials contain rare or toxic elements, so the development of cost-effective and eco-friendly high-performance TE materials is highly urgent. Herein, we explore the thermal transport and TE properties of transition metal vanadate CuVO3 by using first-principles calculation. On the basis of the unified theory of heat conduction, we uncover the hierarchical thermal transport feature in CuVO3, where wave-like tunneling makes a significant contribution to the lattice thermal conductivity (κl) and results in the anomalously weak temperature dependence of κl. This is primarily attributable to the complex phononic band structure caused by the heterogeneity of Cu–O and V–O bonds. Simultaneously, we report a high power factor of 5.45 mW·K−2·m−1 realized in hole-doped CuVO3, which arises from a high electrical conductivity and a large Seebeck coefficient enabled by the multiple valleys and large electronic density of states near the valence band edge. Impressively, the low κl and the high power factor make p-typed CuVO3 have ZT of up to 1.39, with the excellent average ZT above 1.0 from 300 to 600 K, which is superior to most reported Cu-based TE materials. Our findings suggest that the CuVO3 compound is a promising candidate for energy conversion applications in innovative TE devices.

Tuning Thermal Conductivity of Hybrid Perovskites through Halide Alloying.

Tuning the thermal transport properties of hybrid halide perovskites is critical for their applications in optoelectronics, thermoelectrics, and photovoltaics. Here, an effective strategy is demonstrated to modulate the thermal transport property of hybrid perovskites by halide alloying. A highly tunable thermal conductivity of mixed-halide hybrid perovskites is achieved due to halide-alloying and structural distortion. The experimental measurements show that the room temperature thermal conductivity of MAPb(BrxI1- x)3 (x = 0─1) can be largely modulated from 0.27 ± 0.07W m-1 K-1 (x = 0.5) to 0.47 ± 0.09W m-1 K-1 (x = 1). Molecular dynamics simulations further demonstrate that the thermal conductivity reduction of hybrid halide perovskites results from the suppression of the mean free paths of the low-frequency acoustic and optical phonons. It is found that halide alloying and the induced structural distortion can largely increase the scatterings of optical and acoustic phonons, respectively. The confined diffusion of MA+ cations in the octahedra cage is found to act as an additional thermal transport channel in hybrid perovskites and can contribute around 10-20% of the total thermal conductivity. The findings provide a strategy for tailoring the thermal transport in hybrid halide perovskites, which may largely benefit their related applications.

Sulfonated poly(ether ether ketone)-Protic ionic Liquid-Based anhydrous Proton-Conducting composite polymer electrolyte membranes for High-Temperature fuel cell applications

A high-temperature polymer electrolyte membrane fuel cell (PEMFC) has enormous potential to produce clean energy with minimal environmental pollution along with high energy density and conversion efficiency. In the present work, anhydrous proton-conducting polymer electrolyte membranes for prospective high-temperature fuel cell application were successfully prepared using different protic ionic liquids (PILs) and sulfonated poly(ether ether ketone) (SPEEK). The protic ionic liquids (PILs), 2-hydroxyethylammonium formate, diethylmethyl ammonium triflate, 1-ethylimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl imidazolium bis(trifluoro methylsulfonyl)imide, and diethylmethylammonium methanesulfonate were selected based on their favorable physicochemical properties. The effect of the incorporation of the PIL on the structural, thermal, and electrical transport properties of the composite SPEEK polymer electrolyte membranes was studied. The prepared polymer electrolyte membranes (PEMs) were characterized using Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and electrochemical impedance spectroscopy (EIS) techniques. FTIR results indicated an interaction between the PIL and the SPEEK, which resulted in homogeneous and flexible membranes. The DSC results confirmed good miscibility and elucidated plasticizing effect of the incorporated PIL on the SPEEK polymer matrix. All the PEMs showed good thermal stability and high-temperature anhydrous proton conductivity, achieving best proton conductivity, ≈8 × 10–3 S cm−1 at 120 °C and low activation energy ≈0.26 eV, making it suitable for prospective high-temperature PEMFC applications.

First-principles investigation of elastic anisotropy and thermal transport property of transition metal monosilicides CrSi, TiSi, and ZrSi under pressure

In this paper, the influence of pressure on the elastic anisotropy and thermodynamics of CrSi, TiSi, and ZrSi monosilicides are investigated by the first-principles method. Those three alloys have elastic anisotropy, and the degree of anisotropy meets the relationships TiSi > ZrSi > CrSi. In addition, all the elastic anisotropy is enhanced with the increasing pressures. The melting point and Vicker’s hardness are investigated, and the results show that CrSi, TiSi, and ZrSi alloys may be promising high-temperature and hard materials. Furthermore, the lattice thermal conductivity is calculated by Slack’s equation only using the elastic properties. The pressure-dependent Debye temperature, Grüneisen parameter, and lattice thermal conductivity are systematically analyzed. Debye temperature enhances with increasing pressure while the Grüneisen parameter reduces with pressure. Consequently, the lattice thermal conductivity can be enhanced by the pressure, which benefits heat transportation. The calculation reveals that the pressure can effectively control the elastic anisotropy, Deby temperature, Grüneisen parameter, and the lattice thermal conductivity, which is useful for its practical application in industry.

Strain-tunable elastic, electronic, and thermal transport properties of two-dimensional CaI2 monolayer: A first-principles study

Despite the increasing attention on two-dimensional (2D) metal iodides in recent years for their appropriate bandgaps and exceptional optical properties, there is limited understanding of their intriguing thermal transport properties. Here, the strain-tunable mechanic, electronic, and transport properties of the monolayer CaI2 are calculated in detail by combining first-principles calculations with Boltzmann transport theory. We have checked its thermal, dynamic, and mechanical stability by computing ab-initio molecular dynamics, phonon spectra and elastic constants, respectively. The calculation results from the PBE-GGA and HSE06 methods indicate that the monolayer CaI2 is an indirect semiconductor, with band gaps of 3.92 eV and 5.12 eV, respectively. Additionally, the effective masses and Fermi velocities for both holes and electrons are also obtained, which indicates that the monolayer CaI2 owns the excellent electronic transport property. These mechanical constants and electronic parameters are also highly sensitive to the external strain. The calculated real lattice thermal conductivity of the monolayer CaI2 at 300 K is about 1.01 W/mK, which is rather low among 2D materials, implying its potential application in heat insulation materials or thermal insulation material. With the biaxial tensile strain increasing, its lattice thermal conductivity would further decrease. The difference in lattice thermal conductivities between 0 % and 2 % strain, as well as between 4 % and 6 % strain, is much smaller than that between 2 % and 4 % strains. Subsequently, the group velocities, phonon scattering rates, and cumulative lattice thermal conductivities of the monolayer CaI2 are discussed under the different strains.

Predicting thermal transport properties in phononic crystals via machine learning

Although anisotropic phononic crystals (PnCs) could be utilized to control the phonon dispersions and thermal transports, rapidly discovering their properties presents a significant challenge due to the enormous consumption of traditional computational methods. In this study, we have developed machine learning techniques to forecast the thermal conductance of anisotropic PnCs (GPnC and GPnC/Gmem) based on the elastic constants, taking conventional inorganic and halide perovskites as examples for their thermoelectric applications. Our findings suggest that predicting GPnC/Gmem is more challenging than predicting GPnC attribute to the complex influence factors and spatial distribution patterns of the former. The GPnC and GPnC/Gmem of the weakest thermal anisotropic materials—all hexagonals are invariants in the (0 0 1) plane, because the velocities in this plane are direction-independent. The GPnC and GPnC/Gmem of the strongest thermal anisotropic material FAPbI3 reaches the minimum and maximum values in [1 1 0] and [1 0 0] directions, respectively. Ultimately, our machine learning models can map the hidden complex nonlinear relationships between target thermal properties and mechanical features to provide valuable insight for accurate and efficient prediction and analysis of the thermal behaviors of PnCs at a mesoscopic level under low temperatures.

Synergistic role of Sn-doping on the thermal and electrical properties of sinnerite Cu6As4S9

Sinnerite Cu6As4S9 has been identified as a promising material for optoelectronic applications, with potential for other energy-related applications; however, knowledge of the electrical and thermal properties as well as the mechanisms underlying transport in sinnerite is lacking. We present an investigation of the synthesis, structural, thermal and electrical transport properties of stoichiometric and Sn-doped Cu6As4S9. Sinnerite has a triclinic lattice structure, with highly distorted local atomic coordination environments that, in part, results in its complex structure and bonding. Our results and analyses indicate As 4s2 lone pair-induced distortions and strong lattice anharmonicity that leads to a relatively short phonon mean free path, resulting in intrinsically very low thermal conductivity. The electrical resistivity for both compositions, Cu6As4-xSnxS9 (x = 0, 0.2), are relatively high and varies little with temperature, typical of degenerate semiconductors. An increase in mobility and electrical conductivity was obtained by Sn doping in Cu6As3.8Sn0.2S9. This work demonstrates an effective route to synthesize bulk sinnerite as well as advances the knowledge of the properties of sinnerite, as this and other ternary chalcogenides continue to be of interest for potential technologically significant applications.

Investigating the Thermal Conductance of the Cu/Si Interface Using the Molecular Dynamics Method

Investigating thermal transport at the Cu/Si interface holds significant importance, as understanding interface thermal conductance is crucial for enhancing materials interface thermal management, designing thermal interface materials, and improving the performance of thermoelectric devices. In this study, we conducted molecular dynamics simulations in conjunction with the Green–Kubo relation to calculate the thermal conductance of the Cu/Si interface. We successfully obtained Cu/Si interface potentials using the lattice inversion method. Our findings revealed that the thermal conductance of the Cu/Si interface is notably influenced by the interface structure. Specifically, the thermal conductance of the Cu(001)/Si(001) interface and the Cu(111)/Si(111) interface are similar, and both are higher than that of the Cu(110)/Si(110) interface. Furthermore, through first-principles calculations of the adhesion energy, we discovered that interface binding strength plays a critical role in determining interface thermal transport properties, and the influence of pressure was also discussed. This study contributes not only to the understanding of the thermal transport mechanisms at the Cu/Si interface but also provides important insights for designing novel interface materials.

Pseudo-nanostructure and trapped-hole release induce high thermoelectric performance in PbTe.

Thermoelectric materials can realize direct and mutual conversion between electricity and heat. However, developing a strategy to improve high thermoelectric performance is challenging because of strongly entangled electrical and thermal transport properties. We demonstrate a case in which both pseudo-nanostructures of vacancy clusters and dynamic charge-carrier regulation of trapped-hole release have been achieved in p-type lead telluride-based materials, enabling the simultaneous regulations of phonon and charge carrier transports. We realized a peak zT value up to 2.8 at 850 kelvin and an average zT value of 1.65 at 300 to 850 kelvin. We also achieved an energy conversion efficiency of ~15.5% at a temperature difference of 554 kelvin in a segmented module. Our demonstration shows promise for mid-temperature thermoelectrics across a range of different applications.

Topological Phonons and Thermoelectric Conversion in Crystalline Materials

AbstractTopological phononics, a fascinating frontier in condensed matter physics, holds great promise for advancing energy‐related applications. Topologically nontrivial phonons typically possess gapless edge or surface states. These exotic states of lattice vibrations, characterized by their nontrivial topology, offer unique opportunities for manipulating and harnessing energy transport. The exploration of topological phonons opens new avenues in understanding and controlling thermal transport properties, with potential applications in fields such as thermoelectric materials, phononic devices, and waste heat recovery. Here, an overview of concepts such as Berry curvature and topological invariants, along with the applications of phonon tight‐binding method and nonequilibrium Green's function method in the field of topological phononics is provided. This review encompasses the latest research progress of various topological phonon states within crystalline materials, including topological optical phonons, topological acoustical phonons, and higher‐order topological phonons. Furthermore, the study delves into the prospective applications of topological phonons in the realm of thermoelectric conversion, focusing on aspects like size effects and symmetry engineering.