RESUMEN
GeTe-based materials exhibit superior thermoelectric performance, while the development of power generation devices has mainly been limited by the challenge of designing the interface due to the phase transition in GeTe. In this work, via utilizing the low-temperature nano-Ag sintering technique and screening suitable Ti-Al alloys, a reliable interface with excellent connection performance has been realized. The Ti-Al intermetallic compounds effectively inhibit the diffusion process at Ti-34Al/Ge0.9Sb0.1Te interface. Thus, the thickness of the interfacial reaction layer only increases by ≈2.08 µm, and the interfacial electrical contact resistivity remains as low as ≈15.2 µΩ cm2 even after 30 days of isothermal aging at 773 K. A high conversion efficiency of ≈11.3% has been achieved in the GeTe/PbTe module at a hot-side temperature of 773 K and a cold-side temperature of 300 K. More importantly, the module's performance and the reliability of the interface remain consistently stable throughout 50 thermal cycles and long-term aging. This work promotes the application of high-performance GeTe materials for thermoelectric power generation.
RESUMEN
SnSe based compounds have attracted much attention due to the ultra-low lattice thermal conductivity and excellent thermoelectric properties. The origin of the low thermal conductivity has been ascribed to the strong phonon anharmonicity. Generally, the microstructures are also effective in scattering the phonons and further reducing the lattice thermal conductivity. In this work, the microstructures of undoped SnSe and Bi-doped Sn0.97SeBi0.03have been investigated by transmission electron microscopy. A characteristic microstructure of lath-like grains has been observed in SnSe based compounds from perpendicular to the pressure direction. In addition, there exist a large quantity of low-angle grain boundaries and a high concentration of edge dislocations and stacking faults in the grains. All these microstructures result in lattice mismatch and distortion and can act as the phonon scattering centers, which broaden the understanding of the low thermal conductivity of SnSe based compounds.
RESUMEN
The thermoelectric parameters are essentially governed by electron and phonon transport. Since the carrier scattering mechanism plays a decisive role in electron transport, it is of great significance for the electrical properties of thermoelectric materials. As a typical example, the defect-dominated carrier scattering mechanism can significantly impact the room-temperature electron mobility of n-type Mg3Sb2-based materials. However, the origin of such a defect scattering mechanism is still controversial. Herein, the existence of the Mg vacancies and Mg interstitials has been identified by synchrotron powder X-ray diffraction. The relationship among the point defects, chemical compositions, and synthesis conditions in Mg3Sb2-based materials has been revealed. By further introducing the point defects without affecting the grain size via neutron irradiation, the thermally activated electrical conductivity can be reproduced. Our results demonstrate that the point defects scattering of electrons is important in the n-type Mg3Sb2-based materials.
RESUMEN
In thermoelectrics, entropy engineering as an emerging paradigm-shifting strategy can simultaneously enhance the crystal symmetry, increase the solubility limit of specific elements, and reduce the lattice thermal conductivity. However, the severe lattice distortion in high-entropy materials blocks the carrier transport and hence results in an extremely low carrier mobility. Herein, the design principle for selecting alloying species is introduced as an effective strategy to compensate for the deterioration of carrier mobility in GeTe-based alloys. It demonstrates that high configurational entropy via progressive MnZnCdTe3 and Sb co-alloying can promote the rhombohedral-cubic phase transition temperature toward room temperature, which thus contributes to the enhanced density-of-states effective mass. Combined with the reduced carrier concentration via the suppressed Ge vacancies by high-entropy effect and Sb donor doping, a large Seebeck coefficient is attained. Meanwhile, the severe lattice distortions and micron-sized Zn0.6Cd0.4Te precipitations restrain the lattice thermal conductivity approaching to the theoretical minimum value. Finally, the maximum zT of Ge0.82Sb0.08Te0.90(MnZnCdTe3)0.10 reaches 1.24 at 723 K via the trade-off between the degraded carrier mobility and the improved Seebeck coefficient, as well as the depressed lattice thermal conductivity. These results provide a reference for the implementation of entropy engineering in GeTe and other thermoelectric materials.
RESUMEN
In thermoelectrics, the material's performance stems from a delicate tradeoff between atomic order and disorder. Generally, dopants and thus atomic disorder are indispensable for optimizing the carrier concentration and scatter short-wavelength heat-carrying phonons. However, the strong disorder has been perceived as detrimental to the semiconductor's electrical conductivity owing to the deteriorated carrier mobility. Here, we report the sustainable role of strong atomic disorder in suppressing the detrimental phase transition and enhancing the thermoelectric performance in GeTe. We found that AgSnSe2 and Sb co-alloying eliminates the unfavorable phase transition due to the high configurational entropy and achieve the cubic Ge1-x-ySbyTe1-x(AgSnSe2)x solid solutions with cationic and anionic site disorder. Though AgSnSe2 substitution drives the carrier mean free path toward the Ioffe-Regel limit and minimizes the carrier mobility, the increased carrier concentration could render a decent electrical conductivity, affording enough phase room for further performance optimization. Given the lowermost carrier mean free path, further Sb alloying on Ge sites was implemented to progressively optimize the carrier concentration and enhance the density-of-state effective mass, thereby substantially enhancing the Seebeck coefficient. In addition, the high density of nanoscale strain clusters induced by strong atomic disorders significantly restrains the lattice thermal conductivity. As a result, a state-of-the-art zT ≈ 1.54 at 773 K was attained in cubic Ge0.58Sb0.22Te0.8(AgSnSe2)0.2. These results demonstrate that the strong atomic disorder at the high entropy scale is a previously underheeded but promising approach in thermoelectric material research, especially for the numerous low carrier mobility materials.
RESUMEN
The configurational entropy is an emerging descriptor in the functional materials genome. In thermoelectric materials, the configurational entropy helps tune the delicate trade-off between carrier mobility and lattice thermal conductivity, as well as the structural phase transition, if any. Taking GeTe as an example, low-entropy GeTe generally have high carrier mobility and distinguished zT > 2, but the rhombohedral-cubic phase transition restricts the applications. In contrast, despite cubic structure and ultralow lattice thermal conductivity, the degraded carrier mobility leads to a low zT in high-entropy GeTe. Herein, medium-entropy alloying is implemented to suppress the phase transition and achieve the cubic GeTe with ultralow lattice thermal conductivity yet decent carrier mobility. In addition, co-alloying of (Mn, Pb, Sb, Cd) facilitates multivalence bands convergence and band flattening, thereby yielding good Seebeck coefficients and compensating for decreased carrier mobility. For the first time, a state-of-the-art zT of 2.1 at 873 K and average zT ave of 1.3 between 300 and 873 K are attained in cubic phased Ge0.63Mn0.15Pb0.1Sb0.06Cd0.06Te. Moreover, a record-high Vickers hardness of 270 is attained. These results not only promote GeTe materials for practical applications, but also present a breakthrough in the burgeoning field of entropy engineering.
