KR101810649B1 - Fabrication method of graphene composite powders - Google Patents
Fabrication method of graphene composite powders Download PDFInfo
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- KR101810649B1 KR101810649B1 KR1020160030877A KR20160030877A KR101810649B1 KR 101810649 B1 KR101810649 B1 KR 101810649B1 KR 1020160030877 A KR1020160030877 A KR 1020160030877A KR 20160030877 A KR20160030877 A KR 20160030877A KR 101810649 B1 KR101810649 B1 KR 101810649B1
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- thermoelectric material
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- thermoelectric
- powder
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
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- H01L35/16—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/24—Thermal properties
Abstract
The present invention relates to a method for producing a thermoelectric material, which comprises heating a mixture of a thermoelectric material and a graphene powder by an induction melting method to obtain a mixed melt in which graphene is dispersed in the thermoelectric material melt; And spinning the mixed melt on the outer surface of a cylindrical wheel that rotates a cylindrical longitudinal axis with a rotation axis to rapidly quench and solidify the composite melt.
Description
The present invention relates to a method for producing a composite in which graphene is evenly dispersed; A system for this manufacturing method and a composite thus prepared.
In the production of graphene composites in which graphene is uniformly dispersed in a thermoelectric material, a melting method is used, but in such a melting method, a thermoelectric material having a lower melting point than graphene is melted first and graphene is melted There is a problem that it is difficult to obtain even dispersion of the graphene.
In particular, attempts have been made to improve the performance of a thermoelectric material as a composite material with graphene, but it is difficult to evenly disperse the graphene due to the above problems.
The thermoelectric material is a material that can convert thermoelectric energy. Thermoelectric conversion is collectively referred to as the whitening effect and the Peltier effect. The Seebeck effect is a phenomenon in which a current or voltage is generated when a different temperature is applied to a contact point between conductors in a circuit composed of two different conductors, and the heat flow from a hot place to a cold place generates a current. The Peltier effect also refers to the phenomenon that, when a direct current flows through a circuit composed of different conductors, one of the junctions between the different conductors is heated according to the direction of the current while the other is cooled.
The efficiency of thermoelectric conversion depends on the performance of the thermoelectric material. The performance of the thermoelectric material is represented by ZT, which is a dimensionless thermoelectric figure of merit. Where Z is the value obtained by dividing the square of the electrical conductivity (σ) and the Seebeck coefficient (S) by the thermal conductivity (k) (Z = σS 2 / k) and T is the absolute temperature. Therefore, low thermal conductivity is essential to improve performance of thermoelectric materials.
Therefore, the graphene composite thermoelectric material produced by dispersing graphene in a conventional thermoelectric material can be reduced in thermal conductivity through phonon scattering induced by graphene compared to the thermoelectric material in which graphene is not dispersed, The excellent thermoelectric performance can be realized. The advantage of the graphene composite thermoelectric material over conventional thermoelectric materials is already disclosed in Korean Patent Application No. 10-2015-0057760, but no manufacturing method thereof has been proposed.
When a mixture of graphene powder and a conventional thermoelectric material is melted and solidified to produce a graphene composite thermoelectric material by melting, a conventional thermoelectric material having a melting point lower than that of graphene is melted first and graphene is melted by density difference It is difficult to describe the even dispersion of graphene at the time of slow cooling because it floats on top of the molten general thermoelectric material melt.
In addition, it is possible to produce a graphene composite thermoelectric material by preparing a composite powder of graphene, which is a two-dimensional nanomaterial, and a conventional thermoelectric material, and then sintering it to form a graphene composite thermoelectric material. However, it is difficult to achieve homogeneous mixing. Process, the process of pulverizing the synthesized thermoelectric material, and the process of combining the pulverized thermoelectric material with graphene in a mechanical manner, so that practical application may be restricted. On the other hand, by using a chemical method, the graphene powder is coated on the surface of the thermoelectric material powder, or the thermoelectric material is chemically grown on the surface of the graphene powder, There has been a report on one thermoelectric material. For example, a manufacturing method of coating graphene on a zinc oxide nano powder is disclosed in Korean Patent No. 10-1494612. However, due to the troublesome process involving the step of removing the distillation thermoelectric material powder and the process of compounding the same by the chemical method, the practical use of the powder may be restricted.
The present invention overcomes the above-mentioned problems and provides a method for producing a composite in which graphene is evenly dispersed; A system for this production method and a composite thus prepared.
According to an aspect of the present invention, there is provided a method of manufacturing a thermoelectric material, comprising: heating a mixture of a thermoelectric material and a graphene powder by an induction melting method to obtain a mixed melt in which graphene is dispersed in the thermoelectric material melt; And spinning the mixed melt on the outer surface of a cylindrical wheel that rotates a cylindrical longitudinal axis with a rotation axis to rapidly quench and solidify the composite melt.
Induction heating is a method of heating a thermoelectric material using electromagnetic induction. When current is supplied to the coil, eddy currents are generated in the thermoelectric material to be heated, and the joule heating caused by the resistance of the thermoelectric material increases the temperature. The induction heating structure is composed of a coil wound like a combination of one or two electromagnets, and a high frequency alternating current flows through the coil. Loss of magnetic hysteresis is also one of the causes of increasing the temperature of thermoelectric materials.
In the induction melting method of the present invention, the graphene can be uniformly dispersed in the melt by heating the thermoelectric material and the graphene powder mixture by an eddy current. When the graphene is uniformly dispersed and the melt of the thermoelectric material is radiated to the rapidly rotating wheel, the melt rapidly solidifies and a composite material powder in which graphene is uniformly dispersed can be produced. Such a composite material has a small ribbon shape.
The graphene powder may be characterized in that it comprises a reduced graphene oxide powder.
A method for producing a graphene composite material powder.
The thermoelectric material is preferably an antimonide thermoelectric material including a chalcogenide thermoelectric material, CoSb 3 and an alloy thereof, including Bi 2 Te 3 and an alloy thereof, Cu 12 Sb 4 S 13 A half-Heusler thermoelectric material including a tetrahedrite thermoelectric material including HfNiSn, HfCoSb and an alloy thereof, an IV material including Si, Sn, Ge and an alloy thereof, Thermoelectric power generation based on the Seebeck effect, such as thermoelectric material of the pendulum system, and thermoelectric cooling based on the Peltier effect, may be a material known to be realized without complexing with graphene.
Such a thermoelectric material powder can be sintered by a conventional known method such as electrification pressure sintering or high-temperature pressure sintering, which can reduce the thermal conductivity and can be a high-efficiency thermoelectric material.
The composite material powder produced by this method has a ribbon shape. The molten material discharged from the nozzle on the cold surface of the rapidly rotating cylindrical wheel is quenched and the rapidly solidified material is separated from the surface of the cylindrical wheel because the cylindrical wheel rotates rapidly and has a streamlined ribbon shape so as not to touch the surface of the cylindrical wheel Graphene is evenly distributed on the other side.
The thermoelectric material is Bi 2 Te 3 , the composite material powder is in the form of a ribbon, one surface of the composite material powder contains a resinous phase, and the graphene is distributed on the resinous surface side.
In another aspect, the present invention provides an induction melting furnace comprising: an induction melting chamber having a nozzle at the bottom and containing a thermoelectric material powder and a graphene powder mixture; A coil configured to flow a high-frequency current wound on an outer surface of the induction-melting chamber; And a cylindrical wheel spaced apart from the lower end of the nozzle, the cylindrical wheel comprising a cylindrical wheel configured to rotate about a cylindrical longitudinal axis as an axis of rotation, wherein the induction melting chamber is configured to rotate by an eddy current induced by the coil, Wherein the mixture is heated to form a mixed melt in which graphene powder is dispersed and to radiate the mixed melt to the outer surface of the cylindrical wheel through the nozzle.
The cylindrical wheel may include cooling means configured to cool the outer surface thereof.
1 is a schematic diagram illustrating an apparatus for producing a graphene composite material by melt spinning according to the present invention.
FIGS. 2 and 3 show one embodiment of the present invention, which shows a surface shape of a graphene composite thermoelectric material powder produced by applying the proposed method to a Bi 2 Te 3 thermoelectric material, which is a conventional thermoelectric material, It is on a scanning electron microscope.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term "comprises" or "having ", etc. is intended to specify that there is a feature, step, operation, element, part or combination thereof described in the specification, , &Quot; an ", " an ", " an "
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
1 is a schematic diagram illustrating an apparatus for producing a graphene composite material by melt spinning according to the present invention.
As shown in FIG. 1, the
The mixture in the
According to the system and method for producing a graphene composite material of the present invention, it is possible to mass-produce a graphene composite material in which graphene is uniformly dispersed, in particular, a graphene dispersed thermocompression material powder in a simple process.
As an exemplary embodiment of the present invention, Bi 2 Te 3 , which is a thermoelectric material, is induced and annealed with graphene by using the above method and system, and then spun on a cold surface of a rapidly rotating wheel to rapidly solidify the graphene composite thermoelectric material Powder. As shown in FIG. 4, a ribbon-shaped composite material having a length of 2 mm and having a graphene powder having a diameter of about 5 탆 dispersed therein was produced. In addition, as can be seen in Fig. 2, one surface of Bi 2 Te 3 is evenly covered with graphene. As can be seen in FIG. 3, it can be seen that one side thereof is dendritic.
As another exemplary embodiment of the present invention, Cu 2 Se, which is a thermoelectric material, is induced and melted together with graphene using the above method and system, and is radiated on a cold surface of a rapidly rotating wheel to rapidly solidify the graphene composite thermoelectric To prepare a material powder. As shown in Fig. 5, a ribbon-shaped composite material in which graphene powder was dispersed was produced.
Claims (8)
Forming a graphene / thermoelectric material composite having a streamlined ribbon shape in which graphenes are uniformly distributed on one surface by spinning the mixed molten material on the outer surface of a cylindrical wheel rotating on a rotating shaft in a cylindrical longitudinal axis, Including,
Method of manufacturing graphene / thermoelectric material composite.
Characterized in that the graphene powder comprises a reduced graphene oxide powder.
Method of manufacturing graphene / thermoelectric material composite.
Wherein the thermoelectric material is selected from the group consisting of a chalcogenide thermoelectric material, an antimonide thermoelectric material, a tetrahedrite thermoelectric material, a half-Heusler thermoelectric material, and a group IV material Comprising at least one of the semi-
Method of manufacturing graphene / thermoelectric material composite.
Characterized in that the thermoelectric material is Bi 2 Te 3 .
Method of manufacturing graphene / thermoelectric material composite.
In the graphene / thermoelectric material composite, the one side is dendritic and the graphene is uniformly distributed on the dendritic side.
Method of manufacturing graphene / thermoelectric material composite.
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| CN112899550B (en) * | 2021-01-18 | 2022-07-19 | 四川大学 | Zirconium-nickel-tin-based half-heusler-graphene composite thermoelectric material and preparation method thereof |
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| US20060274049A1 (en) | 2005-06-02 | 2006-12-07 | Eastman Kodak Company | Multi-layer conductor with carbon nanotubes |
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| US20060274049A1 (en) | 2005-06-02 | 2006-12-07 | Eastman Kodak Company | Multi-layer conductor with carbon nanotubes |
Non-Patent Citations (2)
| Title |
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| J. Mater. Sci. 2013, Vol. 48, pp. 2745-2760 (2012.09.22.)* |
| Journal of Nanomaterials. 2013, Vol. 2103, Article No. 210767* |
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