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1.
Nanotechnology ; 35(31)2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38684153

RESUMO

In materials science, the impact of density on a material's capabilities is profound. Conventional sintering requires high temperatures and is energy-demanding, propelling the pursuit of less intensive, low-temperature densification methods. Electric field-assisted sintering has recently gained attention for its simplicity and effectiveness, offering a new frontier in low-temperature densification. In this study, dense bulk materials were produced by subjecting monophasic Ag2Se powders to electric field-assisted sintering, where a direct current with an average value of 4 A was applied, achieving a peak temperature of 344 K. The novel low-temperature densification mechanism unfolds thus: nanoscale silver protrusions, stimulated by electrical current, engage in a dissociative adsorption reaction with the ambient saturated selenium vapor. This process swiftly engenders the formation of fresh silver selenide (Ag2Se) compounds, initiating nucleation and subsequent growth. Consecutively, these compounds seamlessly occupy and expand, perpetually bridging the interstices amidst the powders. In a scant 8 s, the density swiftly surpassed 99%, yielding a bulk material that exhibited aZTvalue of 1.07 at 390 K. This investigation not only attains an unparalleled density at low temperatures but also charts a pioneering course for material densification in such conditions.

2.
Inorg Chem ; 60(12): 8890-8897, 2021 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-34110152

RESUMO

ZrTe5 has unique features of a temperature-dependent topological electronic structure and anisotropic crystal structure and has obtained intensive attention from the thermoelectric community. This work revealed that the sintered polycrystalline bulk ZrTe5 possesses both (020) and (041) preferred orientations. The transport properties of polycrystalline bulk p-type ZrTe5 exhibits an obvious anisotropic characteristic, that is, the room-temperature resistivity and thermal conductivity, possessing anisotropy ratios of 0.71 and 1.49 perpendicular and parallel to the pressing direction, respectively. The polycrystalline ZrTe5 obtained higher ZT values in the direction perpendicular to the pressing direction, as compared to that in the other direction. The highest ZT value of 0.11 is achieved at 350 K. Depending on the temperature-dependent topological electronic structure, the electronic transport of p-type ZrTe5 is dominated by high-mobility electrons from linear bands and low-mobility holes from the valence band, which, however, are merely influenced by valence band holes at around room temperature. Furthermore, external magnetic fields are detrimental to thermoelectric properties of our ZrTe5, mainly arising from the more prominent negative effects of electrons under fields. This research is instructive to understand the transport features of ZrTe5 and paves the way for further optimizing their ZTs.

3.
J Am Chem Soc ; 141(47): 18900-18909, 2019 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-31680516

RESUMO

Doping in a lattice refers to the introduction of very small quantities of foreign atoms and has a generally small effect on decreasing the lattice thermal conductivity, unlike alloying which involves large fractions of other elements and strongly enhances point defect phonon scattering. Here, we report that, by alloying only 3% of In on the Cu sites of the diamond-like lattice of CuFeS2 chalcopyrite compound (Cu1-xInxFeS2, x = 0.03) has a disproportionally large effect in reducing the lattice thermal conductivity of the compound from 2.32 to 1.36 Wm-1K-1 at 630 K. We find that In is not fully ionized to +3 when on the Cu sublattice and exists mainly in the +1 oxidation state. The 5s2 lone pair of electrons of In+ makes this atom incompatible (referred to as discordant) with the tetrahedral geometry of the crystallographic site. This causes strong local bond distortions thereby softening the In-S and Cu-S chemical bonds and introducing localized low frequency vibrations. The latter couple with the base phonon frequencies of the CuFeS2 matrix enhancing the anharmonicity and decreasing the phonon velocity, and consequently the lattice thermal conductivity. The control material in which the In doping is on the Fe3+ site of the structure at the same doping level (and found in the site-compatible In3+ state), has a far smaller effect on the phonon scattering.

4.
J Am Chem Soc ; 140(7): 2673-2686, 2018 02 21.
Artigo em Inglês | MEDLINE | ID: mdl-29350916

RESUMO

In this study, a series of Ge1-xMnxTe (x = 0-0.21) compounds were prepared by a melting-quenching-annealing process combined with spark plasma sintering (SPS). The effect of alloying MnTe into GeTe on the structure and thermoelectric properties of Ge1-xMnxTe is profound. With increasing content of MnTe, the structure of the Ge1-xMnxTe compounds gradually changes from rhombohedral to cubic, and the known R3m to Fm-3m phase transition temperature of GeTe moves from 700 K closer to room temperature. First-principles density functional theory calculations show that alloying MnTe into GeTe decreases the energy difference between the light and heavy valence bands in both the R3m and Fm-3m structures, enhancing a multiband character of the valence band edge that increases the hole carrier effective mass. The effect of this band convergence is a significant enhancement in the carrier effective mass from 1.44 m0 (GeTe) to 6.15 m0 (Ge0.85Mn0.15Te). In addition, alloying with MnTe decreases the phonon relaxation time by enhancing alloy scattering, reduces the phonon velocity, and increases Ge vacancies all of which result in an ultralow lattice thermal conductivity of 0.13 W m-1 K-1 at 823 K. Subsequent doping of the Ge0.9Mn0.1Te compositions with Sb lowers the typical very high hole carrier concentration and brings it closer to its optimal value enhancing the power factor, which combined with the ultralow thermal conductivity yields a maximum ZT value of 1.61 at 823 K (for Ge0.86Mn0.10Sb0.04Te). The average ZT value of the compound over the temperature range 400-800 K is 1.09, making it the best GeTe-based thermoelectric material.

5.
Inorg Chem ; 57(19): 12125-12131, 2018 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-30212191

RESUMO

This work shows that the thermoelectric properties of Cr2Se3 material are improved by doping with Ag. The influence of doping with Ag on the phase composition, microstructure, and thermoelectric properties of Ag2 xCr2-2 xSe3 ( x = 0-0.02) compounds was thoroughly investigated. Ag atoms prefer to occupy the 6c Wyckoff position of the space group, accompanied expansion of the lattice and distortion of the octahedral structure units. The electrical conductivity increases at elevated temperature, while the lattice thermal conductivity decreases significantly through Ag doping, which is primarily attributed to the distorted structure and enhanced alloy scattering. Therefore, it produces a peak ZT value of 0.27 at 673 K for Ag0.04Cr1.96Se3, which shows an increase of 23% compared with that of the undoped Cr2Se3 compound.

6.
Small ; 10(1): 66-72, 2014 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-23894065

RESUMO

Resistivity and resistance measurements have been carried out for thin films of cryptomelane-type manganese oxide (OMS-2) grown onto (001), (110), and (111)STO single crystals substrates via pulsed laser deposition. While the symmetries of the (001) and (111)STO substrate surfaces give deposits consisting of multiple nanofiber arrays with isotropic in-plane resistivities, only a single nanofiber array is formed on (110)STO giving highly anisotropic electrical properties with very low resistivity values measured parallel to the fibers and similar to the lowest value ever reported.

7.
Phys Chem Chem Phys ; 16(43): 23576-83, 2014 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-25178356

RESUMO

Mg2Si1-xSnx solid solutions are promising thermoelectric materials for power generation applications in the 500-800 K range. Outstanding n-type forms of these solid solutions have been developed in the past few years with the thermoelectric figure of merit ZT as high as 1.4. Unfortunately, no comparable performance has been achieved so far with p-type forms of the structure. In this work, we use Li doping on Mg sites in an attempt to enhance and control the concentration of hole carriers. We show that Li as well as Ga is a far more effective p-type dopant in comparison to Na or K. With the increasing content of Li, the electrical conductivity rises rapidly on account of a significantly enhanced density of holes. While the Seebeck coefficient decreases concomitantly, the power factor retains robust values supported by a rather high mobility of holes. Theoretical calculations indicate that Mg2Si0.3Sn0.7 intrinsically possesses the almost convergent double valence band structure (the light and heavy band), and Li doping retains a low density of states (DOS) on the top of the valence band, contrary to the Ga doping at the sites of Si/Sn. Low temperature specific heat capacity studies attest to a low DOS effective mass in Li-doped samples and consequently their larger hole mobility. The overall effect is a large power factor of Li-doped solid solutions. Although the thermal conductivity increases as more Li is incorporated in the structure, the enhanced carrier density effectively shifts the onset of intrinsic excitations (bipolar effect) to higher temperatures, and the beneficial role of phonon Umklapp processes as the primary limiting factor to the lattice thermal conductivity is thus extended. The final outcome is the figure of merit ZT ∼ 0.5 at 750 K for x = 0.07. This represents a 30% improvement in the figure of merit of p-type Mg2Si1-xSnx solid solutions over the literature values. Hence, designing low DOS near Fermi level EF for given carrier pockets can serve as an effective approach to optimize the PF and thus ZT value.

8.
ACS Appl Mater Interfaces ; 16(17): 22189-22196, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38651521

RESUMO

Understanding mass transfer mechanisms is vital for developing new material synthesis and densification technologies. Ion transport, serving both mass and charge transfer, is essential for the rapid preparation of high-performance fast ionic conductor thermoelectric materials like Zn4Sb3 and Cu2Q (Q = S, Se). In the case of dual-cation fast ion conductor materials like CuAgSe, exploring the relationship between cation transport becomes pertinent. In this study, copper (Cu) and selenium (Se) undergo a reaction in the presence of an electric field (∼15 A), resulting in the formation of the CuSe compound. Subsequent to this initial reaction, a subsequent thermal environment facilitates the interaction among Cu, CuSe, and Ag2Se, culminating in the rapid formation and densification of CuAgSe (with a relative density exceeding 99%) in just 30 s. Evidently, the diffusion of copper ions substantiates a pivotal role in facilitating mass transfer. As a result, CuAg1+xSe samples with different silver contents (x = 0.01, 0.02, 0.03, 0.04 and 0.05) can effectively inhibit cation vacancy, and introduce highly ordered Ag nanotwins to enhance the electrical transport performance. For CuAg1.04Se, a peak ZT value of 1.0 can be achieved at 673 K, which is comparable to the literatures. This work will guide the future electric field-assisted rapid mass transfer of materials.

9.
ACS Appl Mater Interfaces ; 16(13): 16505-16514, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38527233

RESUMO

The micro thermoelectric device (m-TED) boasts features such as adjustable volume, straightforward structure, and precise, rapid temperature control, positioning it as the only current solution for managing the temperature of microelectronic systems. It is extensively utilized in 5G optical modules, laser lidars, and infrared detection. Nevertheless, as the size of the m-TED diminishes, the growing proportion of interface damages the device's operational reliability, constraining the advancement of the m-TED. In this study, we used commercially available bismuth telluride materials to construct the m-TED. The device's reliability was tested under various temperatures: -40, 85, 125, and 150 °C. By deconstructing and analyzing the devices that failed during the tests, we discovered that the primary cause of device failure was the degradation of the solder layer. Moreover, we demonstrated that encapsulating the device with polydimethylsiloxane (PDMS) could effectively delay the deterioration of its performance. This study sparks new insights into the service reliability of m-TEDs and paves the way for further optimizing device interface design and enhancing the device manufacturing process.

10.
Heliyon ; 8(8): e10025, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36033285

RESUMO

The thermoelements of the traditional thin-film thermoelectric cooler (TEC) are connected electrically in series, thus the performance of traditional thin-film TEC reduces sharply when there is something wrong with any thermoelement. On account of this deficiency, we proposed a novel thin-film TEC with a couple of thermoelements electrically connected in parallel and then electrically connected in series to the next couple of thermoelements. The performance and reliability of the novel thin-film TEC is compared with the traditional thin-film TEC. The maximum cooling capacity, the maximum cooling temperature, and the coefficient of performance of the novel and the traditional thin-film TEC are systematically studied and compared when 0, 2, and 4 thermoelements are disabled, respectively. The results show that the performance and reliability of the novel thin-film TEC are superior to that of the traditional thin-film TEC, while the optimal electric current of the novel thin-film TEC current is 2.14 times of that for the traditional thin-film TEC. This work is of great significance to improving the performance and reliability of thin-film thermoelectric devices consisting of dozens of small thermoelements.

11.
Rev Sci Instrum ; 93(4): 045105, 2022 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-35489943

RESUMO

Wearable thermoelectric generators can harvest heat from the human body to power an intelligent electronic device, which plays an important role in wearable electronics. However, due to the complexity of human skin, there is still no unified standard for performance testing of wearable thermoelectric generators under wearable conditions. Herein, a test platform suitable for a wearable thermoelectric generator was designed and built by simulating the structure of the arm. Based on the biological body temperature regulation function, water flow and water temperature substitute blood flow and blood temperature, the silicone gel with some thickness simulates the skin layer of the human arm, thus achieving the goal of adjusting the thermal resistance of human skin. Meanwhile, the weight is used as the contact pressure to further ensure the reliability and accuracy of the test data. In addition, the environment regulatory system is set up to simulate the outdoor day. Actually, the maximum deviation of the performance of the thermoelectric generator worn on the test platform and human arm is ∼5.2%, indicating the accuracy of objective evaluation.


Assuntos
Temperatura Alta , Dispositivos Eletrônicos Vestíveis , Humanos , Reprodutibilidade dos Testes , Temperatura , Água
12.
ACS Appl Mater Interfaces ; 13(38): 45736-45743, 2021 Sep 29.
Artigo em Inglês | MEDLINE | ID: mdl-34519489

RESUMO

The Cu2Se compound possesses extraordinary thermoelectric performance at high temperatures and shows great potential for the application of waste heat recycling. However, a thermoelectric device usually undergoes mechanical vibration, mechanical and/or thermal cycling, and thermal shock in service. Therefore, mechanical properties are of equal importance as thermoelectric performance. However, the mechanical performance and stability of the Cu2Se compound during long-term service at high temperatures have rarely been reported. In this study, we systematically investigated the mechanical properties of Cu2Se compounds synthesized by three varied methods (melting (M), self-propagating high-temperature synthesis (SHS), and a combination of SHS and ultrasonic treatment (UT)) and investigated the thermal stability of the SHS-UT compound under different annealing temperatures. The SHS-UT process effectively refines the grain size from 19 µm for the melting sample to 5 µm for the SHS-UT sample. The high density of grain boundaries in the SHS-UT sample effectively dissipates the energy of crack propagation; thus, the mechanical properties are greatly improved. The compressive strength, bending strength, and Vickers hardness of the SHS-UT sample are 147 MPa, 52.6 MPa, and 0.46 GPa, respectively, which are 21.5, 16.6, and 35.3% higher than those of the melting sample, respectively. Moreover, excellent thermal stability is achieved in the compound prepared by SHS and ultrasonication at a temperature below 873 K. After annealing at temperatures up to 873 K for 7 days, the excellent thermoelectric performance of the Cu2Se compound is well maintained with a ZT value exceeding 1.80 at 873 K. However, with further increasing the annealing temperature to 973 K, the volatilization of Se and the precipitation of Cu result in the instability and significantly deteriorated thermoelectric performance of the material. This work provides an avenue for boosting the mechanical properties and commercial application of Cu2Se.

13.
ACS Appl Mater Interfaces ; 13(49): 58974-58981, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34854669

RESUMO

Bi2Te3-based materials are dominating thermoelectrics for almost all of the room-temperature applications. To meet the future demands, both their thermoelectric (TE) and mechanical properties need to be further improved, which are the requisite for efficient TE modules applied in areas such as reliable micro-cooling. The conventional zone melting (ZM) and powder metallurgy (PM) methods fall short in preparing Bi2Te3-based alloys, which have both a highly textured structure for high TE properties and a fine-grained microstructure for high mechanical properties. Herein, a mechanical exfoliation combined with spark plasma sintering (ME-SPS) method is developed to prepare Bi0.5Sb1.5Te3 with highly improved mechanical properties (correlated mainly to the dislocation networks), as well as significantly improved thermoelectric properties (correlated mainly to the texture structure). In the method, both the dislocation density and the orientation factor (F) can be tuned by the sintering pressure. At a sintering pressure of 20 MPa, an exceptional F of up to 0.8 is retained, leading to an excellent power factor of 4.8 mW m-1 K-2 that is much higher than that of the PM polycrystalline. Meanwhile, the method can readily induce high-density dislocations (up to ∼1010 cm-2), improving the mechanical properties and reducing the lattice thermal conductivity as compared to the ZM ingot. In the exfoliated and then sintered (20 MPa) sample, the figure-of-merit ZT = 1.2 (at 350 K), which has increased by about ∼20%, and the compressive strength has also increased by ∼20%, compared to those of the ZM ingot, respectively. These results demonstrate that the ME-SPS method is highly effective in preparing high-performance Bi2Te3-based alloys, which are critical for TE modules in commercial applications at near-room temperature.

14.
ACS Appl Mater Interfaces ; 13(10): 11977-11984, 2021 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-33685121

RESUMO

Exploring the origin of intrinsic low thermal conductivity in BiCuSeO is of great significance for searching new oxide thermoelectric (TE) materials. In addition, from the perspective of material preparation, it is of great value to further develop the TE performance optimization strategy of BiCuSeO-based materials. In this work, the low-temperature TE transport properties of Pb-doped BiCuSeO-based materials are investigated. It is found that Pb doping can greatly optimize the carrier concentration, soften the lattice, and reduce the lattice thermal conductivity. The addition of Cu2Se significantly enhanced the grain texture and then increased the interface concentration parallel to the pressure direction in the sintering process, which further reduced the lattice thermal conductivity of the material. Finally, the ZT value of Bi0.96Pb0.04CuSeO-6 mol % Cu2Se bulk material is as high as 0.85 at 840 K. This provides important guidance to improve the properties of TE materials via interface engineering.

15.
Nat Commun ; 12(1): 6077, 2021 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-34667162

RESUMO

Mobile ion-enabled phenomena make ß-Zn4Sb3 a promising material in terms of the re-entry phase instability behavior, mixed electronic ionic conduction, and thermoelectric performance. Here, we utilize the fast Zn2+ migration under a sawtooth waveform electric field and a dynamical growth of 3-dimensional ionic conduction network to achieve ultra-fast synthesis of ß-Zn4Sb3. Moreover, the interplay between the mobile ions, electric field, and temperature field gives rise to exquisite core-shell crystalline-amorphous microstructures that self-adaptively stabilize ß-Zn4Sb3. Doping Cd or Ge on the Zn site as steric hindrance further stabilizes ß-Zn4Sb3 by restricting long-range Zn2+ migration and extends the operation temperature range of high thermoelectric performance. These results provide insight into the development of mixed-conduction thermoelectric materials, batteries, and other functional materials.

16.
ACS Appl Mater Interfaces ; 13(47): 56446-56455, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34787999

RESUMO

P-type SnTe-based compounds have attracted extensive attention because of their high thermoelectric performance. Previous studies have made tremendous efforts to investigate native atomic defects in SnTe-based compounds, but there has been no direct experimental evidence so far. On the basis of MBE, STM, ARPES, DFT calculations, and transport measurements, this work directly visualizes the dominant native atomic defects and clarifies an alternative optimization mechanism of electronic transport properties via defect engineering in epitaxially grown SnTe (111) films. Our findings prove that positively charged Sn vacancies (VSn) and negatively charged Sn interstitials (Sni) are the leading native atomic defects that dominate electronic transport in SnTe, in contrast to previous studies that only considered VSn. Increasing the substrate temperature (Tsub) and decreasing the Te/Sn flux ratio during film growth reduces the density of VSn while increasing the density of Sni. A high Tsub results in a low hole density and high carrier mobility in SnTe films. The SnTe film grown at Tsub = 593 K and Te/Sn = 2/1 achieves its highest power factor of 1.73 mW m-1 K-2 at 673 K, which is attributed to the optimized hole density of 2.27 × 1020 cm-3 and the increased carrier mobility of 85.6 cm2 V-1 s-1. Our experimental studies on the manipulation of native atomic defects can contribute to an increased understanding of the electronic transport properties of SnTe-based compounds.

17.
ACS Appl Mater Interfaces ; 12(35): 39425-39433, 2020 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-32805902

RESUMO

To recover the low-grade waste heat (300-500 K), it is of urgent importance to develop and improve the thermoelectric performance at a low-temperature region. Herein, we have realized a record high ZT value of 1.4 at 410 K and a record high average ZT value of 0.6 in the temperature interval from 300 to 400 K for Sb-doped Ag2SbxTe1-x (x = 0-0.03) compounds, which show an improvement of 180 and 120% compared to pristine Ag2Te, respectively. Sb doping increases the carrier concentration and electrical conductivity, leading to a remarkable improvement of electrical transport properties. The Ag2Sb0.015Te0.985 sample obtains the maximal power factor of 1.07 × 10-3 W m-1 K-2 at 410 K, which is increased by 80% in comparison to that of pristine Ag2Te. Moreover, as a result of the intensified alloying phonon scattering by Sb doping, Ag2Sb0.01Te0.99 possesses the minimum lattice thermal conductivity of 0.35 W m-1 K-1 at 300 K, which demonstrates a decline of 57% compared to that of pristine Ag2Te. All of these produce a great enhancement on the thermoelectric performance of Ag2Te materials, which shows great potential in the application of recycling the low-grade waste heat at a low-temperature region.

18.
ACS Appl Mater Interfaces ; 12(23): 26330-26341, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32401006

RESUMO

Cd-containing polycrystalline Bi0.46Sb1.54Te3 samples with precisely controlled phase composition were synthesized by conventional melting-quenching-annealing technique and a melt-spinning method. The pseudo ternary phase diagram for Cd-Bi/Sb-Te in the region near Bi0.46Sb1.54Te3 was systematically studied. Cd serves as an acceptor dopant contributing holes, whereas for samples doped with CdTe, the combined effects of the substitution of Sb/Bi with Cd and the formation of Sb/BiTe antisite defects leads to the increase in hole concentration. Moreover, upon doping with Cd, the lattice thermal conductivity decreases significantly owing to the intensified point defect phonon scattering. The sample with Cd content of 0.01 attains the maximum ZT of 1.15 at 425 K. The utilization of melt-spinning method brings about the in situ nanostructured CdTe and grain size refinement, which further reduce the lattice thermal conductivity while preserving excellent electrical performance. As a result, a higher ZT of 1.30 at 425 K is realized with CdTe content x = 0.005.

19.
Adv Mater ; 32(40): e2003730, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-32875625

RESUMO

The applications of mixed ionic-electronic conductors are limited due to phase instability under a high direct current and large temperature difference. Here, it is shown that Cu2 Se is stabilized through regulating the behaviors of Cu+ ions and electrons in a Schottky heterojunction between the Cu2 Se host matrix and in-situ-formed BiCuSeO nanoparticles. The accumulation of Cu+ ions via an ionic capacitive effect at the Schottky junction under the direct current modifies the space-charge distribution in the electric double layer, which blocks the long-range migration of Cu+ and produces a drastic reduction of Cu+ ion migration by nearly two orders of magnitude. Moreover, this heterojunction impedes electrons transferring from BiCuSeO to Cu2 Se, obstructing the reduction reaction of Cu+ into Cu metal at the interface and hence stabilizes the ß-Cu2 Se phase. Furthermore, incorporation of BiCuSeO in Cu2 Se optimizes the carrier concentration and intensifies phonon scattering, contributing to the peak figure of merit ZT value of ≈2.7 at 973 K and high average ZT value of ≈1.5 between 400 and 973 K for the Cu2 Se/BiCuSeO composites. This discovery provides a new avenue for stabilizing mixed ionic-electronic conduction thermoelectrics, and gives fresh insights into controlling ion migration in these ionic-transport-dominated materials.

20.
ACS Appl Mater Interfaces ; 12(17): 19664-19673, 2020 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-32255612

RESUMO

Defect engineering is the core strategy for improving thermoelectric properties. Herein, cation doping along with modulation of cation vacancy has been developed in GeTe-based materials as an effective method to induce vacancy-based defects to boost their thermoelectric performance. A series of ternary compounds of Ge9Sb2Te12-x (x = 0, 0.03, 0.06, 0.09, 0.12, 0.15) was prepared by vacuum-melting and annealing combined with the spark plasma sintering (SPS) process. The role of Sb doping and cation vacancy on thermoelectric properties was systematically investigated. It is found that alloying Sb2Te3 into GeTe increases the concentration of cation vacancies, which is corroborated by both positron annihilation measurements and theoretical calculations. The vacancies, stacking faults, and planar defect interactions determine the thermoelectric transport properties. Adjusting the deficiency of Te effectively tunes the concentration of cation vacancies and dopant defects in the structure. In turn, this tunes the carrier concentration close to its optimum. A high power factor of 32.6 µW cm-1 K-2 is realized for Ge9Sb2Te11.91 at 725 K. Moreover, large strains induced by the defect structures, including Sb dopant, vacancy, staking faults, as well as planar defects intensify phonon scattering, leading to a significant decrease in the thermal conductivity from 7.6 W m-1 K-1 for pristine GeTe to 1.18 W m-1 K-1 for Ge9Sb2Te11.85 at room temperature. All of the above contribute to a high ZT value of 2.1 achieved for the Ge9Sb2Te11.91 sample at 775 K.

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