0000000000048548
AUTHOR
G. Jeffrey Snyder
Engineering half-Heusler thermoelectric materials using Zintl chemistry
In this Review, the structure, bonding and defects of half-Heusler compounds are explained in terms of the framework of Zintl (or valence-precise) chemistry. This deeper understanding of the structure and electronic properties of half-Heusler compounds should aid the design of improved thermoelectric materials.
Effect of Isovalent Substitution on the Thermoelectric Properties of the Cu2ZnGeSe4–xSx Series of Solid Solutions
Knowledge of structure–property relationships is a key feature of materials design. The control of thermal transport has proven to be crucial for the optimization of thermoelectric materials. We report the synthesis, chemical characterization, thermoelectric transport properties, and thermal transport calculations of the complete solid solution series Cu_2ZnGeSe_(4–x)S_x (x = 0–4). Throughout the substitution series a continuous Vegard-like behavior of the lattice parameters, bond distances, optical band gap energies, and sound velocities are found, which enables the tuning of these properties adjusting the initial composition. Refinements of the special chalcogen positions revealed a chang…
Phonon Scattering through a Local Anisotropic Structural Disorder in the Thermoelectric Solid Solution Cu_2Zn_(1−x)Fe_xGeSe_4
Inspired by the promising thermoelectric properties of chalcopyrite-like quaternary chalcogenides, here we describe the synthesis and characterization of the solid solution Cu(2)Zn(1-x)Fe(x)GeSe(4). Upon substitution of Zn with the isoelectronic Fe, no charge carriers are introduced in these intrinsic semiconductors. However, a change in lattice parameters, expressed in an elongation of the c/a lattice parameter ratio with minimal change in unit cell volume, reveals the existence of a three-stage cation restructuring process of Cu, Zn, and Fe. The resulting local anisotropic structural disorder leads to phonon scattering not normally observed, resulting in an effective approach to reduce th…
Effect of anion substitution on the structural and transport properties of argyrodites Cu7PSe6−xSx
Inspired by the good performance of argyrodites as ion conducting thermoelectrics and as solid electrolytes we investigated the effect of isovalent S2- substitution for Se2- in Cu7PSe6. At room temperature Cu7PSe6 crystallizes in the primitive cubic β-polymorph of the argyrodite structure and transforms to the face-centered high-temperature (HT) γ-modification above 320 K. The transition for the homologous Cu7PS6 occurs at 510 K. Promising thermoelectric and ion conducting properties are observed only in the HT modification, where the cations are mobile. Using Rietveld refinements against X-ray diffraction data the effect of isovalent S2- substitution for Se2- on the structural and transpor…
Segmented Thermoelectric Oxide-Based Module for High-Temperature Waste Heat Harvesting
We report a high-performance thermoelectric (TE) oxide-based module using the segmentation of half-Heusler Ti_(0.3)Zr_(0.35)Hf_(0.35)CoSb_(0.8)Sn_(0.2) and misfit-layered cobaltite Ca_3Co_4O_(9+δ) as the p-leg and 2 % Al-doped ZnO as the n-leg. The maximum output power of a 4-couple segmented module at ΔT=700 K attains a value of approximately 6.5 kW m^(−2), which is three times higher than that of the best reported non-segmented oxide module. The TE properties of individual legs, as well as the interfacial contact resistances, were characterized as a function of temperature. Numerical modeling was used to predict the efficiency and to evaluate the influence of the electrical and thermal lo…
Thermoelectric properties of Zn-doped Ca_(3)AlSb_(3)
Polycrystalline samples of Ca_(3)Al_(1)−_(x)Zn_(x)Sb_(3), with x = 0.00, 0.01, 0.02, and 0.05 were synthesized via a combined ball milling and hot pressing technique and the influence of zinc as a dopant on the thermoelectric properties was studied and compared to the previously reported transport properties of sodium-doped Ca_(3)AlSb_(3). Consistent with the transport in the sodium-doped material, substitution of aluminum with zinc leads to p-type carrier conduction that can be sufficiently explained with a single parabolic band model. It is found that, while exhibiting higher carrier mobilities, the doping effectiveness of zinc is lower than that of sodium and the optimum carrier concentr…
Optimization of the carrier concentration in phase-separated half-Heusler compounds
Inspired by the promising thermoelectric properties of phase-separated half-Heusler materials, we investigated the influence of electron doping in the n-type Ti_(0.3−x)Zr_(0.35)Hf_(0.35)NiSn compound. The addition of Nb to this compound led to a significant increase in its electrical conductivity, and shifted the maximum Seebeck coefficient to higher temperatures owing to the suppression of intrinsic carriers. This resulted in an enhancement of both the power factor α^2σ and figure of merit, zT. The applicability of an average effective mass model revealed the optimized electron properties for samples containing Nb. There is evidence in the literature that the average effective mass model i…
Influence of a nano phase segregation on the thermoelectric properties of the p-type doped stannite compound Cu(2+x)Zn(1-x)GeSe4.
Engineering nanostructure in bulk thermoelectric materials has recently been established as an effective approach to scatter phonons, reducing the phonon mean free path, without simultaneously decreasing the electron mean free path for an improvement of the performance of thermoelectric materials. Herein the synthesis, phase stability, and thermoelectric properties of the solid solutions Cu_(2+x)Zn_(1–x)GeSe_4 (x = 0–0.1) are reported. The substitution of Zn^(2+) with Cu^+ introduces holes as charge carriers in the system and results in an enhancement of the thermoelectric efficiency. Nano-sized impurities formed via phase segregation at higher dopant contents have been identified and are l…
Rapid Microwave Preparation of Thermoelectric TiNiSn and TiCoSb Half-Heusler Compounds
The 18-electron ternary intermetallic systems TiNiSn and TiCoSb are promising for applications as high-temperature thermoelectrics and comprise earth-abundant, and relatively nontoxic elements. Heusler and half-Heusler compounds are usually prepared by conventional solid state methods involving arc-melting and annealing at high temperatures for an extended period of time. Here, we report an energy-saving preparation route using a domestic microwave oven, reducing the reaction time significantly from more than a week to one minute. A microwave susceptor material rapidly heats the elemental starting materials inside an evacuated quartz tube resulting in near single phase compounds. The initia…
Band convergence in the non-cubic chalcopyrite compounds Cu_2MGeSe_4
Inspired by recent theoretical predictions on band convergence in the tetragonal chalcopyrite compounds, we have explored the influence of the crystal structure on the transport and bandstructure of different quaternary chalcopyrites. In theory, a changing lattice parameter ratio of c/2a towards unity should lead to band convergence due to a more cubic and higher symmetry structure. In accordance with this prediction, the different solid solutions explored in this manuscript show a significant impact on the electronic transport depending on the ratio of the lattice parameters. An increasing lattice parameter ratio results in an increase of the carrier effective masses which can be explained…
INFLUENCE OF THE CHEMICAL POTENTIAL ON THE CARRIER EFFECTIVE MASS IN THE THERMOELECTRIC SOLID SOLUTION Cu2Zn1-xFexGeSe4
In this paper, we describe the synthesis and characterization of the solid solution Cu 2 Zn 1-x Fe x GeSe 4. Electronic transport data have been analyzed using a single parabolic band model and have been compared to Cu 2+x Zn 1-x GeSe 4. The effective mass of these undoped, intrinsically hole conducting materials increases linearly with increasing carrier concentration, showing a non-parabolic transport behavior within the valence band.
Thermoelectric Transport in Cu7PSe6 with High Copper Ionic Mobility
Building on the good thermoelectric performances of binary superionic compounds like Cu2Se, Ag2Se and Cu2S, a better and more detailed understanding of phonon-liquid electron-crystal (PLEC) thermoelectric materials is desirable. In this work we present the thermoelectric transport properties of the compound Cu7PSe6 as the first representative of the class of argyrodite-type ion conducting thermoelectrics. With a huge variety of possible compositions and high ionic conductivity even at room temperature, the argyrodites represent a very good model system to study structure-property relationships for PLEC thermoelectric materials. We particularly highlight the extraordinary low thermal conduct…
ChemInform Abstract: Thermoelectric Transport in Cu7PSe6with High Copper Ionic Mobility.
The copper ion conducting argyorite-type title compound is synthesized from the elements (evacuated quartz ampule, 1323 K, 3 h, and 773 K, 72 h) and its thermoelectric transport properties are studied.
High Electron Mobility and Disorder Induced by Silver Ion Migration Lead to Good Thermoelectric Performance in the Argyrodite Ag8SiSe6
Superionic chalcopyrites have recently attracted interest in their use as potential thermoelectric materials because of extraordinary low thermal conductivities. To overcome long-term stability issues in thermoelectric generators using superionic materials at evaluated temperatures, materials need to be found that show good thermoelectric performance at moderate temperatures. Here, we present the structural and thermoelectric properties of the argyrodite Ag8SiSe6, which exhibits promising thermoelectric performance close to room temperature.
High performance p-type segmented leg of misfit-layered cobaltite and half-Heusler alloy
In this study, a segmented p-type leg of doped misfit-layered cobaltite Ca_(2.8)Lu_(0.15)Ag_(0.05)Co_4O_(9+δ) and half-Heusler Ti_(0.3)Zr_(0.35)Hf_(0.35)CoSb_(0.8)Sn_(0.2) alloy was fabricated and characterized. The thermoelectric properties of single components, segmented leg, and the electrical contact resistance of the joint part were measured as a function of temperature. The output power generation characteristics of segmented legs were characterized in air under various temperature gradients, ΔT, with the hot side temperature up to 1153 K. At ΔT ≈ 756 K, the maximum conversion efficiency reached a value of ∼5%, which is about 65% of that expected from the materials without parasitic l…
Influence of Compensating Defect Formation on the Doping Efficiency and Thermoelectric Properties of Cu2-ySe1–xBrx
The superionic conductor Cu_(2−δ)Se has been shown to be a promising thermoelectric at higher temperatures because of very low lattice thermal conductivities, attributed to the liquid-like mobility of copper ions in the superionic phase. In this work, we present the potential of copper selenide to achieve a high figure of merit at room temperature, if the intrinsically high hole carrier concentration can be reduced. Using bromine as a dopant, we show that reducing the charge carrier concentration in Cu_(2−δ)Se is in fact possible. Furthermore, we provide profound insight into the complex defect chemistry of bromine doped Cu_(2−δ)Se via various analytical methods and investigate the conseque…
Optimum Carrier Concentration in n-Type PbTe Thermoelectrics
Taking La- and I-doped PbTe as an example, the current work shows the effects of optimizing the thermoelectric figure of merit, zT, by controlling the doping level. The high doping effectiveness allows the carrier concentration to be precisely designed and prepared to control the Fermi level. In addition to the Fermi energy tuning, La-doping modifies the conduction band, leading to an increase in the density of states effective mass that is confirmed by transport, infrared reflectance and hard X-ray photoelectron spectroscopy measurements. Taking such a band structure modification effect into account, the electrical transport properties can then be well-described by a self-consistent single…
Bond strength dependent superionic phase transformation in the solid solution series Cu2ZnGeSe4−xSx
Recently, copper selenides have shown to be promising thermoelectric materials due to their possible superionic character resulting from mobile copper cations. Inspired by this recent development in the class of quaternary copper selenides we have focused on the structure-to-property relationships in the solid solution series Cu2ZnGeSe4−xSx. The material exhibits an insulator-to-metal transition at higher temperatures, with a transition temperature dependent on the sulfur content. However, the lattice parameters show linear thermal expansion at elevated temperatures only and therefore no indication of a structural phase transformation. 63Cu nuclear magnetic resonance shows clear indications…
Thermoelectric properties of Sr_3GaSb_3 – a chain-forming Zintl compound
Inspired by the promising thermoelectric properties in the Zintl compounds Ca_3AlSb_3 and Ca_5Al_2Sb_6, we investigate here the closely related compound Sr_3GaSb_3. Although the crystal structure of Sr_3GaSb_3 contains infinite chains of corner-linked tetrahedra, in common with Ca_3AlSb_3 and Ca_5Al_2Sb_6, it has twice as many atoms per unit cell (N = 56). This contributes to the exceptionally low lattice thermal conductivity (κ_L = 0.45 W m^(−1) K^(−1) at 1000 K) observed in Sr_3GaSb_3 samples synthesized for this study by ball milling followed by hot pressing. High temperature transport measurements reveal that Sr_3GaSb_3 is a nondegenerate semiconductor (consistent with Zintl charge-coun…
Resolving the true band gap of ZrNiSn half-Heusler thermoelectric materials
N-type XNiSn (X = Ti, Zr, Hf) half-Heusler (HH) compounds possess excellent thermoelectric properties, which are believed to be attributed to their relatively high mobility. However, p-type XNiSn HH compounds have poor figures of merit, zT, compared to XCoSb compounds. This can be traced to the suppression of the magnitude of the thermopower at high temperatures. E_g = 2eS_(max)T_(max) relates the band gap to the thermopower peak. However, from this formula, one would conclude that the band gap of p-type XNiSn solid solutions is only one-third that of n-type XNiSn, which effectively prevents p-type XNiSn HHs from being useful thermoelectric materials. The study of p-type HH Zr_(1−x)Sc_xNiSn…