High Thermoelectric Efficiency Research Articles

Resonant phonon modes in fullerene functionalized graphene lead to large tunability of thermal conductivity without impacting the mechanical properties

We investigate the effects of fullerene functionalization on the thermal transport properties of graphene monolayers via atomistic simulations. Our systematic molecular dynamics simulations reveal that the thermal conductivity of pristine graphene can be lowered by more than an order of magnitude at room temperature (and as much as by ∼93% as compared to the thermal conductivity of pristine graphene) via the introduction of covalently bonded fullerenes on the surface of the graphene sheets. We demonstrate large tunability in the thermal conductivity by the inclusion of covalently bonded fullerene molecules at different periodic inclusions, and we attribute the large reduction in thermal conductivities to a combination of resonant phonon localization effects, leading to band anticrossings and vibrational scattering at the sp3 bonded carbon atoms. The torsional force exerted by the fullerene molecules on the graphene sheets and the number of covalent bonds formed between the two carbon allotropes is shown to significantly affect the heat flow across the hybrid structures, while the size of the fullerene molecules is shown to have a negligible effect on their thermal properties. Moreover, we show that even for a large surface coverage, the mechanical properties of these novel materials are uncompromised. Taken together, our work reveals a unique way to manipulate vibrational thermal transport without the introduction of lattice defects, which could potentially lead to high thermoelectric efficiencies in these materials.

Anisotropic thermal expansion and thermodynamic properties of monolayer β -Te

Recently, $\beta$-Te (atomically 2D tellurium) with rectangular crystal structure has been synthesized successfully on highly oriented pyrolytic graphite substrates by using molecular beam epitaxy. It has been found possessing remarkable properties such as ultralow lattice thermal conductivity and high thermoelectric efficiency. Based on the first-principles calculations, we study the thermal expansion and thermomechanic properties of the experimental phase monolayer $\beta$-Te, using quasiharmonic approach. It is found $\beta$-Te shows large positive thermal expansion at elevated temperature, while the linear thermal expansion coefficient is negative along a direction at very low temperature. The linear thermal expansion coefficient along b direction is 4.9*10$^{-5}$ K$^{-1}$ at 500 K, which is considerably large in 2D materials. $\beta$-Te exhibits strong in-plane anisotropy, including thermal expansion, 2D elastic moduli and Poisson's ratios. However, the elastic moduli, Poisson's ratios and the in-plane anisotropy are weakened with increasing temperature, and the variations are dominated by the generalized mode Gr\"{u}neisen parameters.

Thermoelectric efficiency optimization of nanoantennas for solar energy harvesting

We compared 9 × 9 arrays of bimetallic Ni(Nickel)-Pt(Platinum) nanoantennas for a classic and evolutive dipole configuration. We fabricated the nanoantennas by e-beam lithography and characterized them with a solar simulator to analyze the I − V curves. From these curves, a thermoelectric voltage dependence associated by classic and evolutive dipole configuration was observed. We show that the evolutive dipole nanoantennas (EDN) generate up to three times more voltage in contrast with the classic dipole nanoantenna (CDN). Indeed, the evolutive configuration is 1.3 times more efficient than its classical counterpart. The results are corroborated by absorbance of these nanoantennas in the 20 to 36 THz range, where EDN is 40% more efficient than CDN and 30% in the range of 36.1 to 90 THz. Moreover, the experimental results match the thermoelectric behavior obtained using numerical simulations. The EDN can be used in applications ranging from aerospace technology to energy harvesting, photodetector, and sensors, where high thermoelectric efficiency is needed.

Lanthanum based quaternary Heusler alloys LaCoCrX (X = Al, Ga): Hunt for half-metallicity and high thermoelectric efficiency

Abstract Ab-initio framework investigation of physical, structural stability, electro-magnetic, thermodynamic and transport behavior of quaternary La-based Heusler alloys carried out using spin-polarized calculations. The structural characterization in nonmagnetic, ferromagnetic and anti-ferromagnetic states reveal the ordered ferromagnetic LiMgPdSn-type structure as stable phase. The band structure profile show perfect half-metallic character with integral 3.00 µB magnetic moment according to the Slater-Pauling rule. From the temperature variation of Seebeck coefficients, LaCoCrAl (LaCoCrGa) show a descent value of −44 (−38) µV K−1 at 300 K, respectively, conveying the electrons favor the heat carrier mechanism with overall n-type behavior. Insight into variation of lattice thermal conductivity show an exponential decreasing trend for both the compounds intriguing their experimental exploration. The high-pressure study of the variation of specific heat follow the Dulong-Petit law, with low ranges of anharmonicity presence in both the compounds.

Development of integrated two-stage thermoelectric generators for large temperature difference

Multi-stage thermoelectric (TE) modules can withstand a large temperature difference and can be used to obtain a high conversion efficiency. In this study, two-stage PbTe/Bi2Te3 TE modules were developed with an enhanced efficiency through a comprehensive study of device structure design, module fabrication, and performance evaluation. PbTe-based AgPbmSbTem+2 (abbreviated as LAST) is a typically high ZT material, while the corresponding TE module was rarely reported so far. How to utilize LAST to fabricate high efficiency TE modules therefore remains a central problem. Finite element simulation indicates that the temperature stability of the two-stage module for LAST is better than that of two-segmented module. Compared to Cu, Ni, and Ni-Fe alloys, Co-Fe alloy is an effective metallization layer for PbTe due to its low contact resistance and thin diffusion layer. By sintering a slice of Cu on TE legs, pure tinfoil can be used as a common welding method for mid-temperature TE modules. A maximum efficiency (ηmax) of 9.5% was achieved in the range of 303 to 923 K in an optimized PbTe/Bi2Te3 based two-stage module, which was almost twice that of a commercial TE module.

Cu-incorporation by melt-spinning in n-type Bi2Te2.7Se0.3 alloys for low-temperature power generation

Herein, we report the enhanced thermoelectric performance of Cu incorporated Bi2Te2.7Se0.3 prepared by melt spinning. The electronic transport properties were significantly improved by Cu incorporation due to the synergetic effect of carrier tuning, band modification, and electron-phonon transport control. The steady dimensionless thermoelectric figure of merit higher than 0.90 was achieved in the wide range of temperature range of 350–450 K for Cu0.008Bi2Te2.7Se0.3, which is ~30% enhancement in comparison with pristine Bi2Te2.7Se0.3. This result can lead to high thermoelectric power generation efficiency 4.2% at ΔT = 180 K.

Lattice Softening Significantly Reduces Thermal Conductivity and Leads to High Thermoelectric Efficiency.

The influence of micro/nanostructure on thermal conductivity is a topic of great scientific interest, particularly to thermoelectrics. The current understanding is that structural defects decrease thermal conductivity through phonon scattering where the phonon dispersion and speed of sound are assumed to remain constant. Experimental work on a PbTe model system is presented, which shows that the speed of sound linearly decreases with increased internal strain. This softening of the materials lattice completely accounts for the reduction in lattice thermal conductivity, without the introduction of additional phonon scattering mechanisms. Additionally, it is shown that a major contribution to the improvement in the thermoelectric figure of merit (zT > 2) of high-efficiency Na-doped PbTe can be attributed to lattice softening. While inhomogeneous internal strain fields are known to introduce phonon scattering centers, this study demonstrates that internal strain can modify phonon propagation speed as well. This presents new avenues to control lattice thermal conductivity, beyond phonon scattering. In practice, many engineering materials will exhibit both softening and scattering effects, as is shown in silicon. This work shines new light on studies of thermal conductivity in fields of energy materials, microelectronics, and nanoscale heat transfer.

High Thermoelectric Performance in Mg2(Si0.3Sn0.7) by Enhanced Phonon Scattering

Owing to the high thermoelectric (TE) conversion efficiency, low cost, and environmental friendliness Mg2Si0.3Sn0.7 solid solution has emerged as the material of choice for the n-leg of a TE generator for mid-temperature (room temperature to 800 K) applications. Dimensionless TE figure-of-merit (ZT) values of 1.3 (at 700 K) have been reported in this compound when optimally doped. High ZT values in this compound are due to a combination of improved electrical properties (band convergence effect) and reduced lattice thermal conductivity (alloy scattering of phonons). Here we demonstrate that the TE performance in this solid solution can be improved further (ZTmax = 1.7 at T = 673 K, which is a record in silicide-based TE materials) by enhancing phonon scattering with embedded nanoprecipitates. The high ZT values are obtained when Mg2Si0.3Sn0.7 is codoped with Bi and Cr. While Bi helps in optimizing the electrical transport properties, Cr results in formation of nanoprecipitates. Transmission electron micro...

High thermoelectric figure of merit and thermopower in layered perovskite oxides

We predict high thermoelectric efficiency in the layered perovskite La$_2$Ti$_2$O$_7$, based on calculations (mostly ab-initio) of the electronic structure, transport coefficients, and thermal conductivity in a wide temperature range. The figure of merit $ZT$ computed with a temperature-dependent relaxation time increases monotonically from just above 1 at room temperature to over 2.5 at 1200 K, at an optimal carrier density of around 10$^{20}$ cm$^{-3}$. The Seebeck thermopower coefficient is between 200 and 300 $\mu$V/K at optimal doping, but can reach nearly 1 mV/K at low doping. Much of the potential of this material is due to its lattice thermal conductivity of order 1 W/(K m); using a model based on ab initio anharmonic calculations, we interpret this low value as due to effective phonon confinement within the layered-structure blocks.

Composition change-driven texturing and doping in solution-processed SnSe thermoelectric thin films

The discovery of SnSe single crystals with record high thermoelectric efficiency along the b-axis has led to the search for ways to synthesize polycrystalline SnSe with similar efficiencies. However, due to weak texturing and difficulties in doping, such high thermoelectric efficiencies have not been realized in polycrystals or thin films. Here, we show that highly textured and hole doped SnSe thin films with thermoelectric power factors at the single crystal level can be prepared by solution process. Purification step in the synthetic process produced a SnSe-based chalcogenidometallate precursor, which decomposes to form the SnSe2 phase. We show that the strong textures of the thin films in the b–c plane originate from the transition of two dimensional SnSe2 to SnSe. This composition change-driven transition offers wide control over composition and doping of the thin films. Our optimum SnSe thin films exhibit a thermoelectric power factor of 4.27 μW cm−1 K−2.

High thermoelectric efficiency in monolayer PbI2 from 300 K to 900 K

By using a first-principles approach, monolayer PbI2 is found to have great potential in thermoelectric applications.

Thermoelectric properties of heavy fermion CeRhIn5 using density functional theory combined with semiclassical Boltzmann theory.

Experimental evidences show that Ce-based compounds can be good candidates for thermoelectric applications due to their high thermoelectric efficiencies at low temperatures. However, thermoelectric properties have been studied less than the other properties for CeRhIn5, a technologically and fundamentally important compound. Thus, we comprehensively investigate the thermoelectric properties, including the Seebeck coefficient, electrical conductivity, electronic part of thermal conductivity, power factor and electronic figure of merit, by a combination of quantum mechanical density functional and semiclassical Boltzmann theories, including relativistic spin–orbit interactions using different exchange–correlation functionals at temperatures T ≤ 300 K for CeRhIn5 along its a and c crystalline axes. The temperature dependences of the thermoelectric quantities are investigated. Our results reveal a better Seebeck coefficient, electrical conductivity, power factor and thermoelectric efficiency at T ≪ 300, in agreement with various other Ce-based compounds, when a high degree of localization is considered for the 4f-Ce electrons. The Seebeck coefficient, power factor and thermoelectric efficiency are made more efficient near room temperature by decreasing the degree of localization for 4f-Ce electrons. Our results also show that the thermoelectric efficiency along the a crystalline axis is slightly better than that of the c axis. We also investigate the effects of hydrostatic pressure on the thermoelectric properties of the compound at low and high temperatures. The results show that the effects of imposing pressure strongly depend on the degree of localization considered for 4f-Ce electrons.

Synergy between defects, charge neutrality and energy filtering in hyper-doped nanocrystalline materials for high thermoelectric efficiency.

Breaking the conventional decrease of the Seebeck coefficient with increasing conductivity would be a significant advancement towards large thermoelectric power factor enhancement and high thermoelectric efficiency. We report on a mechanism identified in hyper-doped nanocrystalline Si films that can lead to this task: a transition from dominant ionized impurity scattering to dominant phonon scattering upon thermal annealing at a high annealing temperature Ta that takes place to fulfill charge neutrality. We show that the synergy between charge neutrality and energy filtering activated by thermal annealing of the originally defective nanocrystalline sample leads to high mobility, simultaneous increase of the conductivity and the Seebeck coefficient and large enhancement of the thermoelectric power factor. This is demonstrated by means of advanced theoretical modeling and excellent quantitative agreement with the experiment. Our work provides interpretation of so far not understood observations in nanocrystalline Si and indicates a new route for engineering Si as well as other nanostructured materials for high thermoelectric efficiency.

Study of the Plastic Formation in the Production of Thermoelectric Material Based on Bismuth Telluride

We carry out an experimental-theoretical study of the process of the equal-channel angular pressing (ECAP) to obtain a bismuth-telluride-based thermoelectric (TE) material. A brief review of the mathematical modeling of the ECAP process is given, and the effect of the design features and temperature of ECAP regimes on the formation of plastic is studied. The results of calculations of the thermally stressed state of the samples at different stages of the ECAP process are presented. The calculations for the ECAP process are carried out using the Lagrange finite element mesh. During the calculation, the mesh is adjusted to the geometry of the die, becoming rarer or finer depending on the magnitude of the plastic deformation to satisfy the specified calculation accuracy and the convergence of the iterative process. We discuss the results of an experimental study of the structure and properties of the samples obtained with the help of ECAP using various methods (X-ray diffractometry and scanning electron microscopy). The TE characteristics of the obtained materials are measured by the Harman method. Comparative methodological calculations of the ECAP process for a bismuth-telluride-based TE material with a change in the parameters determining the formation of grains are performed (the critical plastic deformation as a function of temperature and the power-law dependence of the rate of this deformation). This allowed us to adjust the design model of the ECAP process using the grain size measurements in the TE material. The results of the calculation of the process of grain formation at different temperatures of plastic molding are presented and compared with the experimental data. The practical result of this research is the improved geometry of the die punch and the validated technological regimes of plastic deformation, which allowed obtaining samples with high TE efficiency values.

Thermoelectric properties of monolayer Sb2Te3

The successful demonstration of monolayer films as promising thermoelectric materials highlights alternative strategies to nanostructuring for achieving high thermoelectric efficiency. Due to this reason, the electronic structure and thermoelectric properties of the monolayer Sb2Te3 are studied by using the density functional theory and the semiclassical Boltzmann transport equation. The dynamical stability of the monolayer Sb2Te3 can be guaranteed by the absence of imaginary frequencies in the phonon band structure. The monolayer Sb2Te3 can reduce the lattice thermal conductivity. The Seebeck coefficient S of the p-type monolayer Sb2Te3 is almost three times as high as those of the n-type monolayer Sb2Te3. The power factor for p-type doping is significantly larger than that for the n-type doping. Our calculated ZT values for the monolayer Sb2Te3 are far higher than those of nanomaterials Sb2Te3, bulk Sb2Te3, and the eutectic PbTe-Sb2Te3 composites, indicating that the thermoelectric performance of low-dimensional structure is indeed superior.

High thermoelectric performance in Cu-doped Bi2Te3 with carrier-type transition

For decades, the Bismuth-telluride (Bi2Te3) has been intensively studied as the thermoelectric (TE) cooler. Still, new ideas and emerging results are put forward for raising the conversion efficiency. Herein, we re-visit the Cu-doped Bi2Te3, and report the high zT values nearing the room temperature, for both the p-type (Cu2Te)0.01(Bi2Te3)0.99/Cu0.01Bi1.99Te3 (zT∼1.2 at 300 K) as well as the n-type (Cu2Te)0.09(Bi2Te3)0.91 (zT∼1.09 at 363 K), respectively. Given that the phase boundary mapping is essential for the optimization of high-efficiency TE materials, the isothermal section of ternary Bi-Cu-Te at 523 K is constructed, by collecting the phase equilibria information of various thermally-equilibrated alloys; it further guides the alloying directions for (Cu2Te)x (Bi2Te3)1-x and CuyBi2-yTe3, respectively. Small modulation in the stoichiometry leads to the carrier type transition. As a consequence, the lamellae composed of Bi2Te3 and Cu7Te5 precipitate along the grain boundary of the n-type (Cu2Te)0.09(Bi2Te3)0.91, resulting in the reduced κ, due to the stronger interfacial phonon scattering, and the higher PF, owing to the higher amounts of Te vacancy (VTe). On the contrary, the promising p-type (Cu2Te)0.01(Bi2Te3)0.99/Cu0.01Bi1.99Te3 features the single-phase Bi2Te3, whereas the soluble Cu introduces extra holes and might therefore promote the p-type conduction.

Importance of grain size for nanostructured poly-Si thermoelectric material

Silicon thermoelectric device is one of the promising energy harvesters due to its compatibility with current semiconductor technology and environment, and various types of nanostructured silicon are studied to improve thermoelectric efficiency. In this work, we investigate thermoelectric performance of poly-Si membranes with PnC nanopatterning. The results show that PnC patterning reduces the thermal conductivity of membranes by 60 %, and grain size control enables more efficient reduction. These effects of nanostructure and grain can be combined, and important for high thermoelectric material efficiency.

Discovery of ZrCoBi based half Heuslers with high thermoelectric conversion efficiency

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

Development of a compact thermoelectric generator consisting of printed circuit heat exchangers

Printed circuit heat exchangers (PCHEs) are employed to improve the compactness of a thermoelectric generator (TEG). PCHEs allows miniaturization of the heat exchanger without excessive additional cost, and permit high temperature and pressure (up to 1100 K and 600 bar) of working fluid, which enable high thermoelectric conversion efficiency. To investigate the pressure loss and thermal resistance of a PCHE in detail, three-dimensional computational fluid dynamic (CFD) analysis is conducted. Experimental results of the proposed TEG with PCHEs are newly presented. The TEG provides power density of 233.1 kW/m3 at inlet temperatures of 448.15 K (hot side) and 293.15 K (cold side), which is the highest value in literature for a low-temperature TEG (<505.15 K hot side). Based on the models of friction and heat transfer in a PCHE validated by the experiment, it is noted that the flow rate required for the heat exchangers in a TEG producing a given amount of electrical power can be reduced by adaption of PCHEs. Such novel results on the TEG with PCHEs might be helpful for more compact design and expands the applicability of TEGs for waste heat recovery.

Pressure-induced enhancement of thermoelectric performance in palladium sulfide

Thermoelectric (TE) materials, which can directly convert waste heat into electric power, have attracted considerable interest because of their reliability and great potential for practical applications, especially in the current time faced with energy shortage. Recent advances in developing TE materials for power generation always optimize at high temperatures with the figure of merit (zT) above 1. However for the cooling or wearable devices, the high-efficiency TE materials with optimized temperature range near room temperature are strongly in demand. If the optimized TE performance can be tuned from high temperature to around room temperature, the extensive commercial application for microdevices could be expected. Here, we choose polycrystalline palladium sulfide as an example to show that pressure can significantly enhance the TE performance. With the measurements of the resistivity, Seebeck coefficient, and thermal conductivity under pressure up to 10 GPa, a times enhancement of the zT value has been obtained around room temperature. The largest value of zT at high pressures near 10 GPa is comparable to the value at ambient pressure near 800 K. The results indicate that pressure as an irreplaceable thermodynamic variable has positively regulated the TE performance around room temperature.