Highly stabilized and efficient thermoelectric copper selenide.

The liquid-like feature of thermoelectric superionic conductors is a double-edged sword: the long-range migration of ions hinders the phonon transport, but their directional segregation greatly impairs the service stability. We report the synergetic enhancement in figure of merit (ZT) and stability in Cu1.99Se-based superionic conductors enabled by ion confinement effects. Guided by density functional theory and nudged elastic band simulations, we elevated the activation energy to restrict ion migrations through a cation-anion co-doping strategy. We reduced the carrier concentration without sacrificing the low thermal conductivity, obtaining a ZT of ∼3.0 at 1,050 K. Notably, the fabricated device module maintained a high conversion efficiency of up to ∼13.4% for a temperature difference of 518 K without obvious degradation after 120 cycles. Our work could be generalized to develop electrically and thermally robust functional materials with ionic migration characteristics.

Wide-temperature-range thermoelectric n-type Mg3(Sb,Bi)2 with high average and peak zT values.

Mg3(Sb,Bi)2 is a promising thermoelectric material suited for electronic cooling, but there is still room to optimize its low-temperature performance. This work realizes >200% enhancement in room-temperature zT by incorporating metallic inclusions (Nb or Ta) into the Mg3(Sb,Bi)2-based matrix. The electrical conductivity is boosted in the range of 300-450 K, whereas the corresponding Seebeck coefficients remain unchanged, leading to an exceptionally high room-temperature power factor >30 µW cm-1 K-2; such an unusual effect originates mainly from the modified interfacial barriers. The reduced interfacial barriers are conducive to carrier transport at low and high temperatures. Furthermore, benefiting from the reduced lattice thermal conductivity, a record-high average zT > 1.5 and a maximum zT of 2.04 at 798 K are achieved, resulting in a high thermoelectric conversion efficiency of 15%. This work demonstrates an efficient nanocomposite strategy to enhance the wide-temperature-range thermoelectric performance of n-type Mg3(Sb,Bi)2, broadening their potential for practical applications.

Bi-Deficiency Leading to High-Performance in Mg3 (Sb,Bi)2 -Based Thermoelectric Materials.

Mg3 (Sb,Bi)2 is a potential nearly-room temperature thermoelectric compound composed of earth-abundant elements. However, complex defect tuning and exceptional microstructural control are required. Prior studies have confirmed the detrimental effect of Mg vacancies (VMg ) in Mg3 (Sb,Bi)2 . This study proposes an approach to mitigating the negative scattering effect of VMg by Bi deficiency, synergistically modulating the electrical and thermal transport properties to enhance the thermoelectric performance. Positron annihilation spectrometry and Cs -corrected scanning transmission electron microscopy analyses indicated that the VMg tends to coalesce due to the introduced Bi vacancies (VBi ). The defects created by Bi deficiency effectively weaken the scattering of electrons from the intrinsic VMg and enhance phonon scattering. A peak zT of 1.82 at 773 K and high conversion efficiency of 11.3% at ∆T = 473 K are achieved in the optimized composition of Mg3 (Sb,Bi)2 by tuning the defect combination. This work demonstrates a feasible and effective approach to improving the performance of Mg3 (Sb,Bi)2 as an emerging thermoelectric material.

Evolution of defect structures leading to high ZT in GeTe-based thermoelectric materials.

GeTe is a promising mid-temperature thermoelectric compound but inevitably contains excessive Ge vacancies hindering its performance maximization. This work reveals that significant enhancement in the dimensionless figure of merit (ZT) could be realized by defect structure engineering from point defects to line and plane defects of Ge vacancies. The evolved defects including dislocations and nanodomains enhance phonon scattering to reduce lattice thermal conductivity in GeTe. The accumulation of cationic vacancies toward the formation of dislocations and planar defects weakens the scattering against electronic carriers, securing the carrier mobility and power factor. This synergistic effect on electronic and thermal transport properties remarkably increases the quality factor. As a result, a maximum ZT > 2.3 at 648 K and a record-high average ZT (300-798 K) were obtained for Bi0.07Ge0.90Te in lead-free GeTe-based compounds. This work demonstrates an important strategy for maximizing the thermoelectric performance of GeTe-based materials by engineering the defect structures, which could also be applied to other thermoelectric materials.

Boosting the High Performance of BiFeO3-BaTiO3 Lead-Free Piezoelectric Ceramics: One-Step Preparation and Reaction Mechanisms.

One of the notorious problems in BiFeO3-based piezoelectric ceramics is how to limit the formation of Bi25FeO39 and Bi2Fe4O9 impurities to achieve excellent piezoelectric performance. In this study, a one-step preparation technology, namely, excluding PVA, calcining, and sintering are completed in one step, instead of three steps in the ordinary sintering method, is developed to prepare BiFeO3-xBaTiO3 (BF-xBT) ceramics. The significance of this one-step method is that the thermodynamically unstable region of BiFeO3 is successfully avoided based on the Gibbs free energy of BiFeO3, Bi25FeO39, and Bi2Fe4O9. Benefiting from preventing the formation of Bi25FeO39 and Bi2Fe4O9 impurities, the resultant ceramics show dense structures, macroscopic stripe domains, and a small number of island domains and display saturated P-E curves, sharp I-V characteristics, butterfly-shape S-E loops, and good piezoelectric properties (d33 = 174-199 pC/N; TC = 494-513 °C). By analyzing X-ray diffraction patterns of BF-xBT (0 ≤ x ≤ 1) powders at different calcination temperatures (Tcal), the different reaction mechanisms between 750 °C ≤ Tcal ≤ 900 °C and 950 °C ≤ Tcal ≤ 1000 °C are revealed. When 750 °C ≤ Tcal ≤ 900 °C, Bi3+ diffuses into Fe2O3 particles to form BiFeO3 and Bi25FeO39 and then reacts with BaTiO3; in this temperature range, the formed Bi25FeO39 is hard to eliminate. At 950 °C ≤ Tcal ≤ 1000 °C, Bi3+ and Fe ions simultaneously diffuse into BaTiO3 to form BF-xBT, which is beneficial to preventing the formation of Bi25FeO39 and the improvement of performance.

Reducing Lattice Thermal Conductivity of MnTe by Se Alloying toward High Thermoelectric Performance.

Lead-free manganese telluride has been considered to be a promising candidate for mid-temperature thermoelectric materials. In this work, we report point defect scattering-induced reduction of thermal conductivity in MnTe with Se alloying, fabricated by a facile method combining mechanical alloying and spark plasma sintering. A low lattice thermal conductivity of 0.56 W/mK was obtained for MnTe0.92Se0.08, which is quite close to the amorphous limits. A detailed Debye model analysis reveals the underlying mechanism of phonon scattering and well predicts the thermal conductivity with different contents of Se. Meanwhile, a slight increase of carrier concentration was also observed after Se alloying, accompanied by a variation of energy gap that may be associated with the competition among anions in trapping charges. Further Na doping leads to enhanced electrical transport properties, achieving a maximum ZT value of 1.03 at 873 K. An average ZT of 0.52 and a calculated efficiency of more than 9% also suggest the promising application of MnTe at medium temperatures.

A novel fabrication method of copper-reduced graphene oxide composites with highly aligned reduced graphene oxide and highly anisotropic thermal conductivity.

Recently, metals with graphene and graphene oxide have been extensively used to enhance the mechanical and anisotropic thermal properties of composites. A novel facile fabrication approach of layer by layer self-assembly followed by hot press sintering was adopted to make copper-reduced graphene oxide composites. The microstructure and heat dissipation properties of pure copper and copper-reduced graphene oxide composites were analyzed with the help of SEM and continuous laser machine analysis. Thermal diffusivity of pure copper and copper-reduced graphene oxide composites was examined in different directions to measure the anisotropic thermal properties by using different volumetric percentages of reduced graphene oxide in the composites. Extraordinarily high anisotropic thermal conductivity of the copper-reduced graphene oxide composites was obtained at a very low concentration of 0.8 vol% reduced graphene oxide, with the difference between the thermal conductivity in-plane and through-plane being a factor of 8.82. Laser test results confirmed the highly anisotropic behavior of our copper-reduced graphene oxide composite with the remarkable property of heat dissipation. The three point bending test was also performed to check the flexural strength of the composites. At 0.6 vol% rGO, the flexural strength was noted (∼127 MPa), and it is 22% higher than that of pure sintered Cu. The high value of anisotropic thermal conductivity and higher flexural strength exhibited by the copper-reduced graphene oxide composite produced using a simple two-step fabrication method give us new hope to use these materials as heat sinks in thermal packaging systems.