MAX AND MXene USING VANADIUM CARBIDE AND METHOD FOR MANUFACTURING SAME

Abstract

To provide MAX and MXene using low-cost vanadium carbide instead of an expensive vanadium metal, and a method for preparing same.SOLUTION: There is provided MAX using low-cost vanadium carbide, wherein the MAX consists of vanadium carbide of vanadium, aluminum, and carbon, and is used as a raw material for MXene, which is a two-dimensional nanomaterial, and is at least one selected from compounds represented V2AlC, V4AlC3, and V12Al3C8.SELECTED DRAWING: Figure 5

Description

Technical Field

[0001] The present invention relates to MAX and MXene using inexpensive vanadium carbide without using expensive vanadium metal, and a method for producing the same.

Background Art

[0002] Generally, in the production process of vanadium-based MAX powder, vanadium metal is reacted with aluminum and carbon to produce vanadium-based MAX powder. However, since vanadium metal is expensive, it is costly to produce vanadium-based MAX powder, and it is difficult to apply it in the industry.

[0003] In addition, vanadium metal is a substance that easily forms carbides, nitrides, or oxides due to its high affinity with non-metallic components such as carbon, nitrogen, or oxygen.

[0004] Therefore, the applicant of the present application has, through long-term and great efforts and various studies, obtained MAX and MXene using inexpensive vanadium carbide without using expensive vanadium metal, and a method for producing the same, and completed the present invention.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, an object of the present invention is to provide MAX using inexpensive vanadium carbide without using expensive vanadium metal.

[0007] Another object of the present invention is to provide MXene using inexpensive vanadium carbide without using expensive vanadium metal.

[0008] Another object of the present invention is to provide a method for producing MAX using inexpensive vanadium carbide without using expensive vanadium metal.

[0009] Another object of the present invention is to provide a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal.

[0010] The problems of the present invention are not limited to the problems mentioned above, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

Means for Solving the Problems

[0011] According to one aspect of the present invention, in order to solve the above problems, The vanadium carbide is composed of vanadium, aluminum and carbon, It is used as a raw material for MXene, which is a two-dimensional nanomaterial, At least one of the compounds represented by the following Chemical Formulas 1 to 3 is selected, V 2 AlC ------ (Chemical Formula 1) V 4 AlC 3 ------ (Chemical Formula 2) V 12 Al 3 C 8 ------ (Chemical Formula 3) Provide MAX using vanadium carbide.

[0012] According to one embodiment of the present invention, the MAX using the vanadium carbide A mixture of vanadium carbide and aluminum may be formed by heat treatment under an inert gas.

[0013] According to an embodiment of the present invention, the vanadium carbide may be formed by heat-treating a mixture of vanadium oxide and carbon compound in a vacuum and at normal pressure after the vanadium oxide and the carbon compound are refined.

[0014] According to an embodiment of the present invention, the vanadium carbide may have a vanadium:carbon molar ratio of vanadium to carbon of 2:1, 3:2 or 4:3.

[0015] According to an embodiment of the present invention, the use of vanadium metal can be eliminated in MAX using the vanadium carbide.

[0016] According to an embodiment of the present invention, the carbon content of MAX using the vanadium carbide may be 8 to 14 wt%.

[0017] According to an embodiment of the present invention, the oxygen content of MAX using the vanadium carbide may be 1,000 to 5,000 ppm.

[0018] Also, according to another aspect of the present invention, There is provided MXene using vanadium carbide, which is a two-dimensional nanomaterial formed by aluminum etching and delamination of MAX using the vanadium carbide.

[0019] According to an embodiment of the present invention, the MXene using the vanadium carbide can select at least any one of the compounds represented by the following Chemical Formulas 4 to 6.

[0020] V 2 C ------ (Chemical Formula 4) V 4 C 3 ------ (Chemical Formula 5) V 3 C 2 ------ (Chemical Formula 6)

[0021] According to one embodiment of the present invention, the carbon content of MXene using the vanadium carbide may be 10.5 to 15 wt%.

[0022] Also, according to another aspect of the present invention, (a-1) After mixing a vanadium oxide and a carbon compound to form a mixed powder, subjecting the particle size to high-energy milling to refine it by the high-energy milling and then performing vacuum heat treatment to cause a carboreduction reaction to produce vanadium carbide; (a-2) mixing aluminum with the vanadium carbide and performing heat treatment under an inert gas to produce MAX using the vanadium carbide, and providing a method for producing MAX including these steps.

[0023] According to one embodiment of the present invention, the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0024] According to one embodiment of the present invention, the high-energy milling After mixing the vanadium oxide and the carbon compound, the mixed powder is put into a rotating container in a high-energy milling device together with steel balls, and then In an atmosphere of air, vacuum, nitrogen or argon, the carboreduction reaction The vanadium oxide and the carbon compound can be refined by the high-energy milling to increase the contact area and increase the reaction rate of carboreduction.

[0025] Also, according to another aspect of the present invention, (b-1) After mixing a vanadium oxide and a carbon compound to form a mixed powder, subjecting the particle size to high-energy milling to refine it by the high-energy milling and then performing vacuum heat treatment to cause a carboreduction reaction to produce vanadium carbide; (b-2) mixing aluminum with the vanadium carbide and performing heat treatment under an inert gas to produce MAX using the vanadium carbide, and (b-3) Manufacturing steps of MXene including using the vanadium carbide MAX for aluminum etching and delamination can be provided.

[0026] According to an embodiment of the present invention, in the step of manufacturing vanadium carbide by mixing the vanadium oxide and the carbon compound in (b-1) to form a mixed powder, and then refining the particle size by high-energy milling with a high-energy mill device, followed by vacuum heat treatment and carboreduction reaction, The mixing ratio of the vanadium oxide and the carbon compound may be 1:0.3 to 1:0.5 by weight.

[0027] According to an embodiment of the present invention, in the step of manufacturing vanadium carbide by mixing the vanadium oxide and the carbon compound in (b-1) to form a mixed powder, and then refining the particle size by high-energy milling with a high-energy mill device, followed by vacuum heat treatment and carboreduction reaction, The steel balls of the high-energy mill device may be at least any one selected from ceramic balls, metal balls, and cemented carbide balls.

[0028] According to an embodiment of the present invention, in the step of manufacturing vanadium carbide by mixing the vanadium oxide and the carbon compound in (b-1) to form a mixed powder, and then refining the particle size by high-energy milling with a high-energy mill device, followed by vacuum heat treatment and carboreduction reaction, The heat treatment temperature of the vacuum heat treatment may be 1200°C to 1600°C, and the heat treatment time may be 1 hour to 5 hours.

[0029] According to an embodiment of the present invention, in the step of manufacturing vanadium carbide by mixing the vanadium oxide and the carbon compound in (b-1) to form a mixed powder, and then refining the particle size by high-energy milling with a high-energy mill device, followed by vacuum heat treatment and carboreduction reaction, The rotating shaft of the high-energy mill device is rotated at 150 to 250 rpm, and the rotating container is rotated in the direction opposite to the rotation direction of the rotating shaft at 300 to 500 rpm, and high-energy milling can be performed for 1 to 20 hours.

[0030] According to an embodiment of the present invention, in the step of manufacturing MAX using vanadium carbide by mixing aluminum with the (b-2) vanadium carbide and performing heat treatment under an inert gas, the heat treatment temperature may be 1200°C to 1600°C, and the heat treatment time may be 1 hour to 5 hours.

[0031] According to an embodiment of the present invention, the high-energy mill device may be a planetary ball mill, a spex mill, or an attritor.

[0032] According to an embodiment of the present invention, in the step of manufacturing MXene using vanadium carbide by subjecting MAX using the (b-3) vanadium carbide to aluminum etching and delamination, the aluminum etching can be performed using one or more selected from hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF 2 ), or a combination thereof, or a combination of these with one or more of hydrochloric acid, sulfuric acid, and nitric acid.

Advantages of the Invention

[0033] According to the present invention, without using expensive vanadium metal, MAX using inexpensive vanadium carbide is provided. Therefore, MAX using vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as MAX precursors, raw materials for cemented carbide materials, catalysts, or semiconductor materials.

[0034] In addition, the present invention provides MXene using inexpensive vanadium carbide without using expensive vanadium metal. MXene, which is a two-dimensional nanomaterial, has excellent physical properties and can be used in various applications such as semiconductor materials, electronic materials, or catalysts.

[0035] In addition, the present invention provides a method for manufacturing MAX using inexpensive vanadium carbide without using expensive vanadium metal. The method is excellent in process stability, enables mass production, and is economical.

[0036] In addition, the present invention provides a method for manufacturing MXene using inexpensive vanadium carbide without using expensive vanadium metal. The method is excellent in process stability, enables mass production, and is economical.

[0037] The effects of the present invention are not limited to the above effects, and it should be understood that the effects include any effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.

Brief Description of the Drawings

[0038]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0039] Hereinafter, preferred embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

[0040] The advantages and features of the present invention, and the method for achieving them, will become clear by referring to the embodiments described in detail later together with the accompanying drawings.

[0041] However, the present invention is not limited to the embodiments disclosed below, but is embodied in various different forms. However, this embodiment is provided to make the disclosure of the present invention complete and to fully inform those with ordinary knowledge in the technical field to which the present invention pertains of the scope of the invention, and the present invention is only defined by the scope of the claims.

[0042] Also, when explaining the present invention, if it is determined that related known technologies or the like obscure the gist of the present invention, detailed description thereof will be omitted.

[0043] Hereinafter, the present invention will be described in detail.

[0044] MAX using vanadium carbide The present invention provides MAX using low-cost vanadium carbide without using expensive vanadium metal.

[0045] The MAX using vanadium carbide of the present invention is composed of vanadium, aluminum, and carbon of vanadium carbide, is used as a raw material for MXene, which is a two-dimensional nanomaterial, At least one of the compounds represented by the following Chemical Formulas 1 to 3 can be selected.

[0046] V 2 AlC ------ (Chemical Formula 1) V 4 AlC 3 ------ (Chemical Formula 2) V 12 Al 3 C 8 ------ (Chemical Formula 3)

[0047] The present invention provides MAX using inexpensive vanadium carbide without using expensive vanadium metal. The MAX using vanadium carbide has a low oxygen content, a small particle size, excellent physical properties, and can be used in various applications such as a MAX precursor, a raw material for a cemented carbide material, a catalyst, or a semiconductor material.

[0048] Generally, in the production process of vanadium-based MAX powder, vanadium metal is reacted with aluminum and carbon to produce vanadium-based MAX powder. However, since vanadium metal is expensive, it is costly to produce vanadium-based MAX powder, and it is difficult to apply it to the industry.

[0049] In addition, vanadium metal is a substance that easily forms carbides, nitrides, or oxides due to its high affinity with non-metallic components such as carbon, nitrogen, or oxygen.

[0050] Therefore, the present applicant has completed the present invention by obtaining MAX and MXene using inexpensive vanadium carbide without using expensive vanadium metal through long-term and extensive efforts and various studies.

[0051] Here, the present invention may be MAX using inexpensive vanadium carbide without using expensive vanadium metal.

[0052] At this time, vanadium metal is a substance that easily forms carbides, nitrides, or oxides due to its high affinity with non-metallic components such as carbon, nitrogen, or oxygen.

[0053] The vanadium carbide of the present invention can be formed by mixing vanadium oxide and a carbon compound, and then subjecting the mixture to high-energy milling to refine the particle size, followed by vacuum heat treatment and carboreduction reaction.

[0054] That is, the MAX using the vanadium carbide may be A mixture of vanadium carbide and aluminum may be formed by heat treatment under an inert gas.

[0055] At this time, the vanadium carbide may be formed by heat treating a mixture of refined vanadium oxide and carbon compound under vacuum and normal pressure.

[0056] Also, the vanadium carbide may have a vanadium:carbon molar ratio of 2:1, 3:2, or 4:3.

[0057] Here, when the vanadium-to-carbon molar ratio is the above ratio, the physical properties of the vanadium carbide may be excellent, and the physical properties of the produced MAX may also be excellent.

[0058] In particular, since the oxygen content of the MAX is low, the MAX may be excellent in semiconductivity.

[0059] At this time, the oxygen content may be 1,000 to 5,000 ppm.

[0060] Here, when the oxygen content is within the above range, V(C x O 1-x ) type oxycarbides with a large amount of oxygen may not be easily formed.

[0061] At this time, the content of the oxygen may preferably be 1,000 to 4,980 ppm, and more preferably 1,000 ppm to 4,950 ppm.

[0062] And the carbon content of the MAX using the vanadium carbide may be 8 to 14 wt%.

[0063] Here, when the carbon content of the MAX using the vanadium carbide is within the above range, the MAX using the vanadium carbide may not easily form MAX with a large amount of oxygen.

[0064] At this time, the carbon content of the MAX using the vanadium carbide may preferably be 8.2 to 13.8 wt%, and more preferably 8.5 to 13.5 wt%.

[0065] And the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0066] Here, when the particle size of the mixed powder of the vanadium oxide or the carbon compound is within the above range, the contact area between the vanadium oxide and the carbon compound increases, and the reaction rate of carbonization reduction can increase.

[0067] At this time, the particle size of the mixed powder of the vanadium oxide or the carbon compound may preferably be 2 nm to 48 μm, and more preferably 2 nm to 45 μm.

[0068] And the MAX using the vanadium carbide is V 2 AlC, V 12 Al 3 C 8 Or V 4 AlC 3 It may be.

[0069] Here, the V 2 AlC can be shown by the following reaction formula 1.

[0070] 2VC 0.5 +Al → V 2 AlC ------ (Reaction formula 1)

[0071] Also, the said V 12 Al 3 C 8 can be shown by the following reaction formula 2.

[0072] 12VC 0.67 +3Al → V 12 Al 3 C 8 ------ (Reaction formula 2)

[0073] And, the said V 4 AlC 3 can be shown by the following reaction formula 3.

[0074] 4VC 0.75 +Al → V 4 AlC 3 ------ (Reaction formula 3)

[0075] Here, the MAX using the said vanadium carbide can exclude the use of vanadium metal.

[0076] In one example, when using vanadium carbides with a vanadium:carbon molar ratio of vanadium to carbon of 2:1, 3:2, or 4:3 as raw materials, vanadium metal can be excluded in the manufacturing process of vanadium-based MAX powder.

[0077] Also, the said vanadium oxide is vanadium pentoxide (V 2 O 5 ), sodium metavanadate (NaVO 3 ), vanadium trioxide (V 2 VO 3 ), vanadium oxychloride (VOCl 3 ), and ammonium metavanadate (H 4 NVO 3It may be at least any one selected from among them.

[0078] And the carbon compound may be at least any one selected from industrial carbon powder, coke, coal, coal tar, activated carbon, graphite, natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, industrial diamond, and carbon fiber.

[0079] Here, the carbon compound may further contain biomass which is at least any one selected from coffee grounds, fallen leaves, and waste wood.

[0080] Also, the carbon compound may further contain a reducing gas containing carbon, which is at least any one selected from carbon monoxide, methane, and hydrocarbon.

[0081] And the high-energy milling After mixing the vanadium oxide and the carbon compound, the mixed powder is put into a rotating container in a high-energy milling device together with steel balls, and then in an atmosphere of air, vacuum, nitrogen or argon, high energy of 0.6 - 2.4 J / g·s is input, the rotating shaft is rotated at 150 - 250 rpm, the rotating container is rotated in the direction opposite to the rotation direction of the rotating shaft at 300 - 500 rpm, and high-energy milling can be carried out for 1 - 20 hours.

[0082] Also, the high-energy milling device may be a planetary ball mill, a Spex mill or an attritor.

[0083] Here, in the planetary ball mill, steel balls are loaded into the container together with the raw materials, the container rotates and revolves at high speed, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0084] In addition, in the spec mill, steel balls are charged into a container together with raw materials, and the container vibrates vertically and horizontally at high speed, so that the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0085] And in the attritor, steel balls are charged into a container together with raw materials, and energy is transmitted by the rotational force of a rotor, so that the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0086] In addition, in the high-energy mill device, the rotation direction of the rotating container containing the mixed powder of the vanadium oxide and the carbon compound on the rotating plate and the rotation direction of the rotation axis of the rotating plate are rotated in opposite directions to each other, so that the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0087] And for the vacuum heat treatment the heat treatment temperature may be 1200°C to 1600°C, and the heat treatment time may be 1 hour to 5 hours.

[0088] Here, when the heat treatment temperature of the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may be excellent in low-oxygen characteristics and production efficiency.

[0089] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy mill device is vacuum heat-treated according to the heat treatment temperature of the vacuum heat treatment, and vanadium carbide excellent in low-oxygen characteristics and production efficiency can be produced.

[0090] At this time, the heat treatment temperature of the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0091] And when the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may be excellent in low-oxygen characteristics and production efficiency.

[0092] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy milling apparatus is vacuum heat-treated during the heat treatment time of the vacuum heat treatment to produce vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0093] At this time, the heat treatment time of the vacuum heat treatment may preferably be 2 hours to 4 hours, and more preferably 2 hours to 3 hours.

[0094] Also, the carbothermal reduction reaction The vanadium oxide and the carbon compound can be refined by the high-energy milling to increase the contact area and increase the reaction rate of the carbothermal reduction.

[0095] FIG. 1 is a process schematic diagram of MAX and MXene using vanadium carbide according to an embodiment of the present invention.

[0096] Referring to FIG. 1, in one example, vanadium oxide of vanadium pentoxide (V 2 O 5 ) is mixed with graphite and milled by a high-energy milling apparatus to obtain a vanadium oxide / graphite mixture (V 2 O 5 -C), which is then vacuum heat-treated to produce a powder of vanadium carbide (VC x ).

[0097] Thereafter, aluminum is mixed with the powder of the vanadium carbide (VC x ) to produce a vanadium carbide-aluminum (VC x -Al) mixture.

[0098] Thereafter, the vanadium carbide-aluminum (VC x -Al) mixture is heat-treated in an argon atmosphere to produce a powder of vanadium-aluminum-carbon-based carbide (V-Al-C).

[0099] Subsequently, the powder of vanadium-aluminum-carbon carbide (V-Al-C) is chemically etched to produce MXene (MXene), and its physical properties are evaluated.

[0100] Manufacturing method of MAX using vanadium carbide The present invention provides a method for producing MAX using inexpensive vanadium carbide without using expensive vanadium metal.

[0101] The method for producing MAX using vanadium carbide of the present invention (a-1) After mixing vanadium oxide and a carbon compound to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling device, followed by vacuum heat treatment to cause a carboreduction reaction to produce vanadium carbide; (a-2) mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX using the vanadium carbide.

[0102] The present invention provides a method for producing MAX using inexpensive vanadium carbide without using expensive vanadium metal, which is excellent in process stability, enables mass production, and is economical.

[0103] Also, in the step of (a-1) mixing vanadium oxide and a carbon compound to form a mixed powder, then refining the particle size by high-energy milling using a high-energy milling device, followed by vacuum heat treatment to cause a carboreduction reaction to produce vanadium carbide, the mixing ratio of the vanadium oxide and the carbon compound may be such that vanadium oxide:carbon compound is 1:0.3 to 1:0.5 by weight.

[0104] Here, when the mixing ratio of the vanadium oxide and the carbon compound is within the above range by weight, V(C x O 1-x )-type oxycarbide with a large amount of oxygen may not be easily formed.

[0105] At this time, the mixing ratio of the vanadium oxide and the carbon compound is preferably such that vanadium oxide:carbon compound may be 1:0.35 to 1:0.45 by weight, and more preferably, vanadium oxide:carbon compound may be 1:0.35 to 1:0.4 by weight.

[0106] Here, the high-energy milling is After mixing the vanadium oxide and the carbon compound, the mixed powder is put into a rotating container in a high-energy milling device together with steel balls, and then In an atmosphere of air, vacuum, nitrogen or argon, the carbothermal reduction reaction is The vanadium oxide and the carbon compound can be refined by the high-energy milling to increase the contact area and increase the reaction rate of the carbothermal reduction.

[0107] And after mixing the (a-1) vanadium oxide and the carbon compound to form a mixed powder, in the step of producing vanadium carbide by refining the particle size by the high-energy milling in a high-energy milling device, followed by vacuum heat treatment and carbothermal reduction reaction, The steel balls of the high-energy milling device may be at least any one selected from ceramic balls, metal balls, and cemented carbide balls.

[0108] Specifically, the material of the steel balls may be steel, tungsten or zirconia.

[0109] Here, the shape of the steel balls may be at least any one selected from spherical, star-shaped, angular, and columnar.

[0110] Also, after mixing the (a-1) vanadium oxide and the carbon compound to form a mixed powder, in the step of producing vanadium carbide by refining the particle size by the high-energy milling in a high-energy milling device, followed by vacuum heat treatment and carbothermal reduction reaction, The rotating shaft of the high-energy mill device is rotated at 150 to 250 rpm, and the rotating container is rotated in the direction opposite to the rotation direction of the rotating shaft at 300 to 500 rpm, and high-energy milling can be performed for 1 to 20 hours.

[0111] Here, the high-energy milling may be a process of milling by rubbing the steel balls charged into the rotating container and the mixed powder of the vanadium oxide and the carbon compound while rotating the rotating shaft and the rotating container in opposite directions to each other, pulverizing the particles of the mixed powder of the vanadium oxide and the carbon compound, and reducing the average particle size of the mixed powder to 2 nm to 50 μm.

[0112] Therefore, the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0113] Also, the high-energy mill device may be a planetary ball mill, a Spex mill, or an attritor.

[0114] Here, in the planetary ball mill, steel balls are charged into a container together with the raw material, the container rotates and revolves at high speed, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0115] Also, in the Spex mill, steel balls are charged into a container together with the raw material, the container vibrates up and down and left and right at high speed, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0116] And in the attritor, steel balls are charged into a container together with the raw material, energy is transmitted by the rotational force of a rotor, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0117] Further, the high-energy mill apparatus can rotate the rotation direction of the rotary container containing the mixed powder of the vanadium oxide and the carbon compound on the rotary plate and the rotation direction of the rotation axis of the rotary plate in opposite directions to reduce the particle size of the mixed powder of the vanadium oxide and the carbon compound to the above range.

[0118] And after mixing the (a-1) vanadium oxide and the carbon compound to form a mixed powder, in the step of producing vanadium carbide by subjecting the particle size to fine pulverization by high-energy milling by a high-energy mill apparatus and then performing vacuum heat treatment to cause a carboreduction reaction, Regarding the vacuum heat treatment the heat treatment temperature may be 1200°C to 1600°C, and the heat treatment time may be 1 hour to 5 hours.

[0119] Here, when the heat treatment temperature of the vacuum heat treatment is within the above range, the vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0120] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy mill apparatus can be vacuum heat-treated according to the heat treatment temperature of the vacuum heat treatment to produce vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0121] At this time, the heat treatment temperature of the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0122] And when the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0123] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy mill apparatus can be vacuum heat-treated during the heat treatment time of the vacuum heat treatment to produce vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0124] At this time, the heat treatment time of the vacuum heat treatment may preferably be 2 to 4 hours, and more preferably 2 to 3 hours.

[0125] Also, the carbothermal reduction reaction The vanadium oxide and the carbon compound can be refined by the high-energy ball milling to increase the contact area and increase the reaction rate of the carbothermal reduction.

[0126] Then, when aluminum is mixed with the (a-2) vanadium carbide and heat-treated under an inert gas to produce MAX using vanadium carbide, the inert gas may be argon, nitrogen, or hydrogen.

[0127] Also, the heat treatment temperature may be 1200°C to 1600°C, and the heat treatment time may be 1 to 5 hours.

[0128] Here, when the heat treatment temperature is within the above range, the MAX using vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0129] That is, the mixed powder of the vanadium carbide and aluminum is heat-treated at the heat treatment temperature to produce MAX using vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0130] At this time, the heat treatment temperature of the heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0131] Then, when the heat treatment time is within the above range, the MAX using vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0132] That is, the mixed powder of the vanadium carbide and aluminum is heat-treated for the heat treatment time to produce MAX using vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0133] At this time, the heat treatment time of the heat treatment is preferably 2 hours to 4 hours, and more preferably 2 hours to 3 hours.

[0134] Figure 2 is a process flow diagram of a method for manufacturing MAX using vanadium carbide according to an embodiment of the present invention.

[0135] Referring to Figure 2, first, a vanadium oxide and a carbon compound are mixed to form a mixed powder, and then the particle size is refined by high-energy milling and vacuum heat-treated by a high-energy mill device to cause a carboreduction reaction to produce vanadium carbide (S110).

[0136] Thereafter, aluminum is mixed with the vanadium carbide and heat-treated under an inert gas to produce MAX using vanadium carbide (S120).

[0137] Figure 3 is a schematic diagram of (a) a high-energy mill device, (b) a rotating plate of the high-energy mill device, (c) a vanadium carbide synthesizing device, and (d) a carboreduction reaction according to an embodiment of the present invention.

[0138] Figure 3a is a photograph of a high-energy mill device for refining and mixing raw materials.

[0139] Referring to Figure 3b, the rotation direction of the main shaft of the rotating plate of the high-energy mill device and the rotation direction of the rotating container containing the mixed powder of the vanadium oxide and the carbon compound are opposite to each other, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to 2 nm to 50 μm by these reverse rotational forces.

[0140] Referring to Figure 3c, it is a photograph of a device for synthesizing vanadium carbide.

[0141] Figure 3d is a schematic diagram of the carbothermal reduction reaction. The reaction formula of vanadium carbide produced by the carbothermal reduction reaction between vanadium oxide and carbon compound is as shown in the following Reaction Formula 4.

[0142] VOa +(x+a)C→VCx +aCO ------ (Reaction Formula 4)

[0143] And, in one example, when vanadium(V) oxide is used as a raw material for the synthesis of low-oxygen vanadium carbide 2 O 5 ), vanadium carbide is formed as shown in the following Reaction Formula 5 by the reaction of carbon with vanadium oxide, that is, by carbothermal reduction.

[0144] V 2 O 5 +(5+2x)C→2VC x +5CO ------ (Reaction Formula 5)

[0145] MXene using vanadium carbide The present invention provides MXene using low-cost vanadium carbide without using expensive vanadium metal.

[0146] The present invention provides MXene using vanadium carbide, which is a two-dimensional nanomaterial formed by aluminum etching and interlayer delamination of MAX using the vanadium carbide.

[0147] The present invention provides MXene using low-cost vanadium carbide without using expensive vanadium metal. Therefore, it has excellent physical properties of MXene, which is a two-dimensional nanomaterial, and can be used in various applications such as semiconductor materials, electronic materials, or catalysts.

[0148] Here, the MXene using the vanadium carbide may be a two-dimensional nanomaterial formed by aluminum etching and interlayer delamination of MAX using the vanadium carbide.

[0149] Also, the MXene using the vanadium carbide may be an MXene using inexpensive vanadium carbide without using expensive vanadium metal.

[0150] At this time, vanadium metal is a substance that easily forms carbides, nitrides, or oxides due to its high affinity with non-metallic components such as carbon, nitrogen, or oxygen.

[0151] The MXene using the vanadium carbide of the present invention can select at least any one of the compounds represented by the following Chemical Formulas 4 to 6.

[0152] V 2 C ------ (Chemical Formula 4) V 4 C 3 ------ (Chemical Formula 5) V 3 C 2 ------ (Chemical Formula 6)

[0153] Also, the carbon content of the MXene using the vanadium carbide may be 10.5 to 15 wt%.

[0154] Here, when the carbon content of the MXene using the vanadium carbide is within the above range, the MAX using the vanadium carbide may not easily form an MXene with a large amount of oxygen.

[0155] At this time, the carbon content of the MXene using the vanadium carbide may preferably be 10.6 to 14.8 wt%, and more preferably 10.7 to 14.5 wt%.

[0156] And, the oxygen content of the MXene using the vanadium carbide may be 1,000 to 5,000 ppm.

[0157] Here, when the oxygen content is within the above range, a large amount of oxygen V(Cx O 1-x ) type carbide may not be easily formed.

[0158] At this time, the content of the oxygen may preferably be 1,000 to 4,980 ppm, and more preferably 1,000 ppm to 4,950 ppm.

[0159] Further, the vanadium carbide can be formed by mixing a vanadium oxide and a carbon compound, then refining the particle size by high-energy milling using a high-energy mill device, subjecting it to vacuum heat treatment, and causing a carboreduction reaction.

[0160] Figure 1 is a process schematic diagram of MAX and MXene using vanadium carbide according to an embodiment of the present invention.

[0161] Referring further to Figure 1, in one example, vanadium oxide of vanadium pentoxide (V 2 O 5 ) is mixed with graphite and milled with a high-energy mill device to obtain a vanadium oxide / graphite mixture (V 2 O 5 -C), which is subjected to vacuum heat treatment to produce vanadium carbide (VCx) powder.

[0162] Thereafter, aluminum is mixed with the vanadium carbide (VC x ) powder to produce a vanadium carbide-aluminum (VC x -Al) mixture.

[0163] Thereafter, the vanadium carbide-aluminum (VC x -Al) mixture is heat-treated in an argon atmosphere to produce vanadium-aluminum-carbon-based carbide (V-Al-C) powder.

[0164] Thereafter, the vanadium-aluminum-carbon-based carbide (V-Al-C) powder is chemically etched to produce MXene (MXene), and its physical properties are evaluated.

[0165] Manufacturing method of MXene using vanadium carbide The present invention provides a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal.

[0166] The method for producing MXene using vanadium carbide of the present invention comprises: (b-1) After mixing vanadium oxide and a carbon compound to form a mixed powder, subjecting the particle size to high-energy milling to make it finer by a high-energy mill device, followed by vacuum heat treatment and a carboreduction reaction to produce vanadium carbide; (b-2) Mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX using vanadium carbide; (b-3) Subjecting the MAX using vanadium carbide to aluminum etching and interlayer delamination to produce MXene using vanadium carbide.

[0167] The present invention provides a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal, which has excellent process stability, enables mass production, and is economical.

[0168] Also, in the step of (b-1) mixing vanadium oxide and a carbon compound to form a mixed powder, subjecting the particle size to high-energy milling to make it finer by a high-energy mill device, followed by vacuum heat treatment and a carboreduction reaction to produce vanadium carbide, the mixing ratio of the vanadium oxide to the carbon compound may be such that the weight ratio of vanadium oxide:carbon compound is 1:0.3 to 1:0.5.

[0169] Here, when the mixing ratio of the vanadium oxide to the carbon compound is within the above range by weight, VO(C x O 1-x ) type oxycarbide may not be easily formed.

[0170] At this time, the mixing ratio of the vanadium oxide and the carbon compound is preferably such that the weight ratio of vanadium oxide:carbon compound may be 1:0.35 to 1:0.45, and more preferably, the weight ratio of vanadium oxide:carbon compound may be 1:0.35 to 1:0.4.

[0171] And after mixing the (b-1) vanadium oxide and the carbon compound to form a mixed powder, in the step of producing vanadium carbide by subjecting the particle size to high-energy milling to make it finer, followed by vacuum heat treatment and carbonization reduction reaction using a high-energy milling device,

[0172] The steel balls of the high-energy milling device may be at least any one selected from ceramic balls, metal balls, and cemented carbide balls.

[0173] Specifically, the material of the steel balls may be steel, tungsten, or zirconia.

[0174] Here, the shape of the steel balls may be at least any one selected from spherical, star-shaped, angular, and columnar shapes.

[0175] Also, after mixing the (b-1) vanadium oxide and the carbon compound to form a mixed powder, in the step of producing vanadium carbide by subjecting the particle size to high-energy milling to make it finer, followed by vacuum heat treatment and carbonization reduction reaction using a high-energy milling device, The rotating shaft of the high-energy milling device is rotated at 150 to 250 rpm, and the rotating container is rotated at 300 to 500 rpm in the direction opposite to the rotation direction of the rotating shaft, and high-energy milling can be performed for 1 to 20 hours.

[0176] Here, in the high-energy milling process, while the rotation directions of the rotating shaft and the rotating container are opposite to each other, the steel balls charged into the rotating container are rubbed against the mixed powder of the vanadium oxide and the carbon compound to mill them, and the particles of the mixed powder of the vanadium oxide and the carbon compound are pulverized to reduce the average particle size of the mixed powder to 2 nm to 50 μm, which may be a process.

[0177] Therefore, the particle size of the mixed powder of the vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0178] Also, the high-energy mill device may be a planetary ball mill, a Spex mill, or an attritor.

[0179] Here, in the planetary ball mill, steel balls are charged into the container together with the raw materials, and the container rotates and revolves at high speed, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0180] Also, in the Spex mill, steel balls are charged into the container together with the raw materials, and the container vibrates up and down and left and right at high speed, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0181] And in the attritor, steel balls are charged into the container together with the raw materials, and energy is transmitted by the rotational force of the rotor, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0182] Also, in the high-energy mill device, the rotation direction of the rotating container containing the mixed powder of the vanadium oxide and the carbon compound on the rotating plate and the rotation direction of the rotating shaft of the rotating plate are rotated in opposite directions to each other, and the particle size of the mixed powder of the vanadium oxide and the carbon compound can be reduced to the above range.

[0183] Then, after mixing the vanadium oxide of (b-1) and a carbon compound to form a mixed powder, the particle size is refined by high-energy milling in a high-energy milling apparatus and vacuum heat-treated to cause a carboreduction reaction to produce vanadium carbide. Of the vacuum heat treatment The heat treatment temperature may be 1200°C to 1600°C. The heat treatment time may be 1 hour to 5 hours.

[0184] Here, when the heat treatment temperature of the vacuum heat treatment is within the above range, the vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0185] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy milling apparatus is vacuum heat-treated according to the heat treatment temperature of the vacuum heat treatment to produce vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0186] At this time, the heat treatment temperature of the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0187] And when the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0188] That is, the mixed powder of the vanadium oxide and the carbon compound generated by the high-energy milling apparatus is vacuum heat-treated during the heat treatment time of the vacuum heat treatment to produce vanadium carbide excellent in low oxygen characteristics and production efficiency.

[0189] At this time, the heat treatment time of the vacuum heat treatment may preferably be 2 hours to 4 hours, and more preferably 2 hours to 3 hours.

[0190] Then, in the step of producing MAX using vanadium carbide by mixing aluminum with the (b-2) vanadium carbide and performing heat treatment under an inert gas, the heat treatment temperature may be 1200°C to 1600°C, and the heat treatment time may be 1 hour to 5 hours.

[0191] Here, when the heat treatment temperature is within the above range, the MAX using vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0192] That is, the mixed powder of the vanadium carbide and aluminum is heat treated at the heat treatment temperature to produce MAX using vanadium carbide that is excellent in low oxygen characteristics and production efficiency.

[0193] At this time, the heat treatment temperature of the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0194] And when the heat treatment time is within the above range, the MAX using vanadium carbide may be excellent in low oxygen characteristics and production efficiency.

[0195] That is, the mixed powder of the vanadium carbide and aluminum is heat treated during the heat treatment time to produce MAX using vanadium carbide that is excellent in low oxygen characteristics and production efficiency.

[0196] At this time, the heat treatment time of the vacuum heat treatment may preferably be 2 hours to 4 hours, and more preferably 2 hours to 3 hours.

[0197] In addition, the carbothermal reduction reaction can refine the vanadium oxide and carbon compound by the high-energy ball milling to increase the contact area and increase the reaction rate of carbothermal reduction.

[0198] Also, in the step of manufacturing MXene using vanadium carbide by performing aluminum etching and delamination on the MAX using the vanadium carbide (b-3), the aluminum etching can be carried out using one or more selected from hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF 2 ), or a combination thereof, or a combination of these with one or more of hydrochloric acid, sulfuric acid, and nitric acid.

[0199] And the delamination can be carried out using tetrabutylammonium hydroxide (TBAOH), tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), or tetramethylammonium hydroxide (TMAOH).

[0200] Figure 4 is a process flow diagram of a method for manufacturing MXene using vanadium carbide according to an embodiment of the present invention.

[0201] Referring to Figure 4, first, a vanadium oxide and a carbon compound are mixed to form a mixed powder, and then the particle size is refined by high-energy milling in a high-energy milling device and vacuum heat-treated to cause a carbothermal reduction reaction to produce vanadium carbide (S210).

[0202] Thereafter, aluminum is mixed with the vanadium carbide and heat-treated under an inert gas to produce MAX using vanadium carbide (S220).

[0203] Thereafter, the MAX using vanadium carbide is subjected to aluminum etching and delamination to produce MXene using vanadium carbide (S230).

[0204] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are for more specifically explaining the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

[0205] <Example> <Examples 1 to 7> Production of vanadium carbide A mixed powder of vanadium oxide and a carbon compound was produced with the components and contents shown in Table 1 below.

[0206] Thereafter, the mixed powder was put into the rotating container in the high-energy mill device shown in Table 1 below together with steel balls.

[0207] Thereafter, when pulverizing the particles with the high-energy mill device shown in Table 1 below, under the gas conditions of an atmosphere of air, vacuum, nitrogen or argon, the high energy shown in Table 1 below was input, and the rotating shaft and the rotating container were rotated in different directions from each other, and high-energy milling was performed to produce a fine powder.

[0208] Thereafter, the fine powder was vacuum heat-treated under the conditions shown in Table 1 below to cause a carboreduction reaction to produce vanadium carbide.

[0209] <Comparative Example 1> Production of vanadium carbide Except for using the high-energy mill device in Example 1 above, vanadium carbide of the comparative example was produced in the same manner as in Example 1.

[0210] [Table 1]

[0211] Figure 5 is a graph of the carbon content in vanadium carbide according to the carbon input amount and heat treatment temperature in Examples 1 to 7 above.

[0212] Figure 6 is a graph of the oxygen content in vanadium carbide according to the carbon input amount and heat treatment temperature in Examples 1 to 7 above.

[0213] Referring to Table 1 and FIG. 6 above, the vanadium carbides of Examples 1 to 7 had an oxygen content of 1440 ppm to 3870 ppm, which was much less than the oxygen content of 12,000 ppm of the vanadium carbide of Comparative Example 1.

[0214] Therefore, the vanadium carbides of Examples 1 to 7 are shown to contain less oxygen.

[0215] Also, the average particle size of the vanadium carbides of Examples 1 to 7 was 20 nm, showing a very small average particle size compared to the average particle size of 10 μm of the vanadium carbide of Comparative Example 1.

[0216] <Example 8> Production of MAX using vanadium carbide Aluminum was mixed with the vanadium carbides produced in Example 1 and Example 3 above to produce a mixed powder.

[0217] Thereafter, the mixed powder was heat-treated at 1500 °C for 3 hours under an argon gas to produce MAX using the vanadium carbide.

[0218] <Comparative Example 2> Production of MAX MAX was produced in the same manner as in Example 8, except that the vanadium carbide of Comparative Example 1 was used.

[0219] <Experimental Example> Analysis of XRD pattern of MAX using vanadium carbide The crystal structure (XRD) graphs of the vanadium carbides produced in Example 1 and Example 3 above are shown in FIG. 7.

[0220] FIG. 7 is the XRD pattern of (a) V 2 AlC MAX (b) V 12 Al 3 C 8 MAX, which are vanadium-based MAX powders according to Example 1 and Example 3.

[0221] Referring to FIG. 7a, for the V in Example 1 above 2 In the XRD pattern of 2 AlCMAX, no vanadium metal pattern is shown.

[0222] Referring to FIG. 7b, for the V in Example 3 above 12 Al 3 C 8 In the XRD pattern of 12 Al 3 C 8 MAX, no vanadium metal pattern is shown.

[0223] Therefore, for the vanadium-based MAX powders of Example 1 and Example 3 above, (a) V 2 AlCMAX and (b) V 12 Al 3 C 8 MAX 2 AlCMAX(b)V 12 Al 3 C 8 MAX, it was confirmed that vanadium-based MAX powders were successfully produced without using vanadium metal, using vanadium carbide with controlled carbon content as a raw material.

[0224] So far, specific examples of MAX and MXene using vanadium carbide according to the present invention and the manufacturing method thereof have been described. However, it is obvious that various implementation variations are possible within the scope not departing from the present invention.

[0225] Therefore, the scope of the present invention should not be defined only by the described embodiments, but should be defined by not only the claims described later but also those equivalent to the claims.

[0226] That is, it should be understood that the foregoing embodiments are illustrative in every respect and not restrictive, and the scope of the present invention is shown by the claims described later rather than the detailed description, and any changes or modifications contemplated from the meaning and scope of the claims and their equivalent concepts are all construed as being included in the scope of the present invention.

Claims

1. Vanadium carbide is made of vanadium, aluminum and carbon, It is used as a raw material for MXene, a two-dimensional nanomaterial. At least one of the compounds represented by the following formulas 1 to 3 is selected, V ２ AlC ------ (Chemistry 1) V ４ AlC ３ ------ (chemical 2) V １２ Al ３ C ８ ------ (Formula 3) MAX uses vanadium carbide.

2. MAX, which uses the vanadium carbide, The mixture of vanadium carbide and aluminum is formed by heat treatment under an inert gas. MAX using the vanadium carbide according to claim 1.

3. The vanadium carbide is formed by finely grinding vanadium oxide and a carbon compound, and then heat-treating the mixture of the vanadium oxide and the carbon compound under vacuum and normal pressure. MAX using the vanadium carbide according to claim 1.

4. The vanadium carbide is characterized in that the molar ratio of vanadium to carbon is 2:1, 3:2 or 4:

3. MAX using the vanadium carbide according to claim 1.

5. The vanadium carbide-based MAX is characterized by excluding the use of vanadium metal. MAX using the vanadium carbide according to claim 1.

6. The carbon content of the vanadium carbide-based MAX is 8 to 14 wt %. MAX using the vanadium carbide according to claim 1.

7. The oxygen content of the vanadium carbide-based MAX is 1,000 to 5,000 ppm. MAX using the vanadium carbide according to claim 1.

8. A two-dimensional nano-material formed by aluminum etching and delamination of the vanadium carbide-based MAX according to claim 1. MXene uses vanadium carbide.

9. The MXene using vanadium carbide is characterized in that at least one of the compounds represented by the following Chemical Formula 4 to Chemical Formula 6 is selected: MXene using the vanadium carbide according to claim 8. V ２ C ------ (Chemistry 4) V ４ C ３ ------ (Chemistry 5) V ３ C ２ ------ (Chemistry 6)

10. The carbon content of the MXene using vanadium carbide is 10.5 to 15 wt %. MXene using the vanadium carbide according to claim 8.

11. (a-1) mixing vanadium oxide and a carbon compound to form a mixed powder, and then reducing the particle size by high-energy milling using a high-energy milling device, and subjecting the resulting mixture to a vacuum heat treatment and a carbonization-reduction reaction to produce vanadium carbide; (a-2) mixing the vanadium carbide with aluminum and heat treating the mixture under an inert gas to prepare MAX using vanadium carbide; Including, How MAX is manufactured.

12. The particle size of the mixed powder of the vanadium oxide or the carbon compound is 2 nm to 50 μm. A method for producing MAX according to claim 11.

13. The high energy milling After mixing the vanadium oxide and the carbon compound, the mixed powder is charged into a rotating container in a high-energy mill together with steel balls, and then The carbonization reduction reaction is carried out in an atmosphere of air, vacuum, nitrogen or argon, The vanadium oxide and the carbon compound are finely milled by the high energy milling to increase the contact area and increase the reaction rate of the carbonization reduction. A method for producing MAX according to claim 11.

14. (b-1) mixing vanadium oxide and a carbon compound to form a mixed powder, and then reducing the particle size by high-energy milling using a high-energy milling device, and subjecting the resulting mixture to a vacuum heat treatment and a carbonization-reduction reaction to produce vanadium carbide; (b-2) mixing the vanadium carbide with aluminum and heat treating the mixture under an inert gas to prepare MAX using vanadium carbide; (b-3) preparing vanadium carbide-based MXene by aluminum etching and delaminating the vanadium carbide-based MAX; Including, Method for producing MXene.

15. In the step (b-3) of preparing vanadium carbide-containing MXene by subjecting vanadium carbide-containing MAX to aluminum etching and delamination, The aluminum etching may be performed using hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF ２ ), or a combination thereof, or a combination thereof with one or more of hydrochloric acid, sulfuric acid, and nitric acid, A method for producing MXene according to claim 14.

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