Patent Application
20240082910
This application claims the benefit of Korean Patent Application No. 10-2022-0113864, filed on Sep. 8, 2022, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
The present disclosure relates to thermoelectric composite with high-entropy alloy dispersed and method for preparing the same.
This research was supported by the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-2022M3C1A3091988).
Embodiments of the inventive concept described herein relate to a thermoelectric composite with high-entropy alloy (HEA) dispersed and a method for preparing the same.
A thermoelectric material is a material that may be applied to active cooling, cogeneration, and the like using the Peltier effect and the Seebeck effect. The Peltier effect is a phenomenon in which heat release and heat absorption respectively occur at both ends because of movement of holes of a p-type material and electrons of an n-type material when a DC voltage is applied. In addition, the Seebeck effect refers to a phenomenon in which a flow of electric current occurs in a material because of movement of electrons and holes when heat is supplied from an external heat source, causing power generation.
In past 50 years, a material with a higher performance has not been found, so that a (Bi,Sb)2(Te,Se)3 based compound is used as the thermoelectric material. A Seebeck coefficient is proportional to a gradient of an electron state density near a Fermi plane, so that the electron must have a high superposition of energy and a relatively great effective mass. On the other hand, the effective mass must be small to maintain high electrical conductivity.
However, in most materials, the electrical conductivity and the Seebeck coefficient exhibit a trade-off relationship rather than an independent relationship. This is because it is difficult to simultaneously adjust the Seebeck coefficient and the electrical conductivity in a bulk sample. Accordingly, when exhibiting a high electrical conductivity, the thermoelectric material has a low Seebeck coefficient value, and when exhibiting a low electrical conductivity, the thermoelectric material has a high Seebeck coefficient value. Various methods have been proposed to solve such difficulties caused by the trade-off relationship, but an experimental proof is insufficient.
Embodiments of the inventive concept provide a thermoelectric composite with high-entropy alloy particles dispersed at an interface of a thermoelectric material and a method for preparing the same.
According to an exemplary embodiment, a thermoelectric composite with high-entropy alloy dispersed includes a thermoelectric material TE having a composition in Formula 1 below, and high-entropy alloy particles M having a composition in the Formula 1 below and dispersed in the thermoelectric material.
TE(x %)+M(y %) [Formula 1]
In the Formula 1, a volume ratio or a molar ratio x of the thermoelectric material to the thermoelectric composite is smaller than 100, and a volume ratio or a molar ratio y of the high-entropy alloy particles to the thermoelectric composite is greater than 0 and smaller than 20.
In one implementation, the thermoelectric material may include at least one of a (Bi,Sb)2(Te,Se)3-based compound, a Sb2Te3-based compound, a CoSb3-based compound, a PbTe-based compound, a GeTe-based compound, or a SiGe-based compound.
In one implementation, the high-entropy alloy particles may have a composition in Chemical Formula 1 below.
(M1)x1(M2)x2(M3)x3 . . . (Mn)xn [Chemical Formula 1]
In the Chemical Formula 1, M1 to Mn are transition metals including at least one of Nb, Ta, Ti, Hf, Zr, W, Mo, Cr, V or Re, respectively, n is the number of metal elements contained in the high-entropy alloy particles, and x1 to xn represent molar ratios of M1 to Mn, respectively.
In the Chemical Formula 1, n has a range of 4≤n≤10, and xn has a range of 5≤xn≤50.
In one implementation, the thermoelectric material may be sintered by at least one method of hot-press, hot-deformation, or hot-extrusion.
In one implementation, the thermoelectric material may contain a doped dopant.
In one implementation, a thermal conductivity at a room temperature may be equal to or smaller than 2 W/mK based on x and y in the Formula 1.
In one implementation, an electrical conductivity at a room temperature may be equal to or greater than 100 S/cm based on x and y in the Formula 1.
In one implementation, a thermoelectric figure of merit (ZT) may be equal to or greater than 1.0 based on x and y in the Formula 1.
In one implementation, the high-entropy alloy particles may be synthesized using a ball-milling method.
According to another exemplary embodiment, a method for preparing a thermoelectric composite with high-entropy alloy dispersed includes preparing a thermoelectric material TE having a composition in Formula 1 below, and dispersing high-entropy alloy particles M having a composition in the Formula 1 below in the thermoelectric material.
TE(x %)+M(y %) [Formula 1]
In the Formula 1, a volume ratio or a molar ratio x of the thermoelectric material to the thermoelectric composite is smaller than 100, and a volume ratio or a molar ratio y of the high-entropy alloy particles to the thermoelectric composite is greater than 0 and smaller than 20.
The above and other objects and features will become apparent from the following description with reference to the following figures, wherein like reference numerals refer to like parts throughout the various figures unless otherwise specified, and wherein:
Hereinafter, specific details for implementation of the inventive concept will be described in detail with reference to the accompanying drawings. However, in the following description, when there is a risk of unnecessarily obscuring the gist of the inventive concept, detailed descriptions of well-known functions or components will be omitted.
In the accompanying drawings, the same reference numerals are given to the same or corresponding components. In addition, in the following description of the embodiments, duplicated descriptions of the same or corresponding components may be omitted. However, omission of description of a component does not imply that such component is not included in an embodiment.
Advantages and characteristics of the disclosed embodiments, and methods of achieving them will become clear with reference to the embodiments to be described later in conjunction with the accompanying drawings. However, the inventive concept is not limited to the embodiments disclosed below and is able to be embodied in various different forms, and the present embodiments are merely provided to make the inventive concept complete and to fully inform the person skilled in the art of the scope of the invention.
The terms used in the present document will be briefly described, and the disclosed embodiments will be described in detail. The terms used in the present document have been selected from general terms that are currently widely used as much as possible while considering functions in the inventive concept, but these may change depending on the intention of engineers working in the related field, precedents, or the emergence of new technologies. In addition, in a specific case, there is also a term arbitrarily selected by the applicant, and in this case, the meaning thereof will be described in detail in the description. Therefore, the term used in the inventive concept should be defined based on the meaning of the term and the overall contents of the inventive concept, not just the name thereof.
The singular expression herein includes the plural expression unless the context clearly dictates otherwise. In addition, the plural expression includes the singular expression unless the context clearly dictates otherwise. When it is said that a certain part ‘includes’ a certain component throughout the present document, it means that other components may be further included without excluding other components unless otherwise stated.
A high-entropy alloy (HEA) refers to a single solid solution in which five or more major elements having similar atomic radii have a composition close to equiatomic. The high-entropy alloy has a severely distorted lattice structure and thus has characteristics such as higher specific strength, wear resistance, and deformation resistance at a high temperature compared to a conventional metal material. Based on the excellent characteristics as described above, the high-entropy alloy may be utilized in related industries such as energy/automotive/electronics.
A thermoelectric figure of merit (ZT), which is a dimensionless figure of merit, is used as an index for determining a performance of a thermoelectric material. The thermoelectric figure of merit may be defined by Mathematical Equation 1. Thermoelectric figure of merit means an energy conversion efficiency, and it is required to increase an electrical conductivity and a Seebeck coefficient and decrease a thermal conductivity for increasing the thermoelectric figure of merit. In this regard, based on the fact that the electrical conductivity and the Seebeck coefficient depend on charge scattering and the thermal conductivity depends on lattice scattering, it is possible to finely control the thermoelectric figure of merit of the thermoelectric composite.
ZT=(S{circumflex over ( )}2σ)/κT [Mathematical Equation 1]
(S: Seebeck coefficient, σ: electrical conductivity, κ: thermal conductivity, T: absolute temperature, S{circumflex over ( )}2 σ: PF (Power Factor))
Hereinafter, an experimental example for preparing a thermoelectric composite with the high-entropy alloy dispersed will be described.
Step 1: A BiTe-based thermoelectric material compound, which is a base material, is synthesized by melting in a quartz vacuum tube. In this regard, Bi, Sb, and Te are quantified in a calculated molar ratio in a glove bag to prevent oxidation and then put into a quartz tube and vacuum-sealed.
Step 2: Polycrystal synthesis is performed by melting the sealed quartz tube by maintaining the same at a temperature of about 700 to 900° C. The synthesized Bi0.4Sb1.6Te3.01 compound is pulverized using a ball mill or a hand grinding scheme.
Step 3: High-entropy alloy element powders such as Nb, Ta, Hf, Zr, and Ti are mixed with each other in a ratio of 2/6:1/6:1/6:1/6:1/6, and then ball milled at a room temperature at 400 RPM for 12 hours using a planetary ball mill to prepare high-entropy alloy powder Ta1/6Nb2/6Hf1/6Zr1/6Ti1/6. In addition, because the high-entropy alloy powder is prepared by high energy generated from friction resulted from the great number of ball milling, the ball milling is performed under an argon gas atmosphere to prevent metals from being oxidized during the ball milling. In this regard, a range of an amount of powder to be pulverized may be about 100 g when using laboratory equipment, and up to several kilograms when using ball milling equipment for mass production.
Step 4: 0.0, 0.05, and 0.1 vol % of the high-entropy alloy powder Ta1/6Nb2/6Hf1/6Zr1/6Ti1/6 are weighted to BiTe-based thermoelectric material (BST) powder Bi0.4Sb1.6Te3.01 to form mixtures, and each mixture is put into a sample vial and rotated for 24 hours using a roller to be mixed evenly with each other. Accordingly, the thermoelectric material contains the high-entropy alloy powder Ta1/6Nb2/6Hf1/6Zr1/6Ti1/6 as a dopant.
Step 5: The mixed powder is put into a carbon mold and sintered at 520° C. for 1 hour at a high temperature and a high pressure. In this regard, as the sintering process, a hot-press process, a hot-deformation process, or a hot-extrusion process may be used.
In the above experimental example, Bi0.4Sb1.6Te3.01 was used as the thermoelectric material, but the inventive concept is not limited thereto. For example, the thermoelectric material may include at least one of a (Bi,Sb)2(Te,Se)3-based compound, a Sb2Te3-based compound, a CoSb3-based compound, a PbTe-based compound, a GeTe-based compound, or a SiGe-based compound. In addition, the Ta1/6Nb2/6Hf1/6Zr1/6Ti1/6 was used as the high-entropy alloy, but the high-entropy alloy may be replaced with a material having a composition of Chemical Formula 1.
(M1)x1(M2)x2(M3)x3 . . . (Mn)xn [Chemical Formula 1]
In Chemical Formula 1, M1 to Mn are transition metals including at least one of Nb, Ta, Ti, Hf, Zr, W, Mo, Cr, V, or Re, respectively, and n is the number of metal elements contained in high-entropy alloy particles, and each of x1 to xn represents a molar ratio of each of M1 to Mn. In Chemical Formula 1, n has a range of 4≤n≤10, and xn has a range of 5≤xn≤50.
Referring to
Referring to
Referring to
Referring to
Referring to
Table 1 shows a value of VH (Vickers Hardness) based on a dispersion volume ratio of the high-entropy alloy particles of the thermoelectric composite according to one embodiment of the inventive concept.
That is, referring to
TE(x %)+M(y %) [Formula 1]
In Formula 1, a volume ratio or a molar ratio x of the thermoelectric material is smaller than 100, and a volume ratio or a molar ratio y of the high-entropy alloy particles is greater than 0 and smaller than 20.
The above description of the inventive concept is provided to enable those skilled in the art to make or use the inventive concept. Various modifications of the inventive concept will be readily apparent to those skilled in the art, and the general principles defined herein may be applied in various modifications without departing from the spirit or scope of the inventive concept. Thus, the inventive concept is not intended to be limited to the examples described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Although the inventive concept has been described in relation to some embodiments herein, various modifications and changes may be made without departing from the scope of the inventive concept that may be understood by those skilled in the art. Moreover, it should be understood that such modifications and variations fall within the scope of the claims appended herein.
According to some embodiments of the inventive concept, the thermoelectric composite having the high thermoelectric figure of merit by reducing the thermal conductivity without the significant decrease in the Seebeck coefficient may be provided.
According to some embodiments of the inventive concept, as the thermoelectric composite having high mechanical strength is provided, a thermoelectric device may be stably used even in an environment with high vibration or impact.
According to some embodiments of the inventive concept, as the thermoelectric composite with the high thermoelectric figure of merit is prepared, a performance of a present commercial thermoelectric device may be improved, and the thermoelectric material may be used in fields such as a refrigerator, an air conditioner, and a vehicle air conditioning system, which have been difficult to apply the thermoelectric material because of low energy efficiency.
While the inventive concept has been described with reference to exemplary embodiments, it will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the inventive concept. Therefore, it should be understood that the above embodiments are not limiting, but illustrative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0113864 | Sep 2022 | KR | national |
