MAX and MXene using vanadium carbide, and their manufacturing methods.

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] This invention relates to MAX and MXene, which use inexpensive vanadium carbides without using expensive vanadium metal, and to a method for producing them. [Background technology]

[0002] Typically, vanadium-based MAX powder is produced by reacting vanadium metal with aluminum and carbon. However, because vanadium metal is expensive, the production of vanadium-based MAX powder is costly, making it difficult to apply to industry.

[0003] Furthermore, vanadium metal readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic components such as carbon, nitrogen, or oxygen.

[0004] Therefore, through long-term efforts and various studies, the applicant has completed the present invention by obtaining MAX and MXene, and their manufacturing methods, using inexpensive vanadium carbides without using expensive vanadium metal. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Korean Published Patent No. 10-2017-0036507 (Published April 3, 2017) [Overview of the Initiative] [Problems that the invention aims to solve]

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

[0007] Furthermore, an object of the present invention is to provide MXene that uses inexpensive vanadium carbide without using expensive vanadium metal.

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

[0009] Furthermore, an 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 addressed by the present invention are not limited to those mentioned above, and any other problems not mentioned can be clearly understood by those skilled in the art from the following description. [Means for solving the problem]

[0011] In order to solve the aforementioned problems, according to one aspect of the present invention, Vanadium carbide consists 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 chemical formulas 1 to 3 is selected. V2AlC ------ (Chem.1) V4AlC3------ (chemical 2) V 12 Al3C8------ (chemical 3) We offer MAX using vanadium carbide.

[0012] According to one embodiment of the present invention, MAX using the vanadium carbide is 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 under vacuum and 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 MAX using the vanadium carbide can eliminate the use of vanadium metal.

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

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

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

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

[0020] V2C ------ (Chemical Formula 4) V4C3------ (Chemical Formula 5) V3C2------ (Chemical Formula 6)

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

[0022] Furthermore, according to another aspect of the present invention, (a-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling device, and then vacuum heat treatment is performed to carry out a carbonization reduction reaction to produce vanadium carbide, (a-2) A method for producing MAX using vanadium carbide is provided, which includes the step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas.

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

[0024] According to one embodiment of the present invention, the high-energy milling is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. In an atmosphere of air, vacuum, nitrogen, or argon, the carbon reduction reaction proceeds. By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the reaction rate of carbon reduction.

[0025] Furthermore, according to another aspect of the present invention, (b-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling apparatus, and then vacuum heat treatment is performed to carry out a carbonization reduction reaction to produce vanadium carbide, (b-2) A step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX using the vanadium carbide, (b-3) A method for producing MXene using vanadium carbide can be provided, which includes the step of aluminum etching and delamination of MAX using vanadium carbide.

[0026] According to one embodiment of the present invention, in the step of producing vanadium carbide by mixing (b-1) vanadium oxide and a carbon compound to form a mixed powder, then refining the particle size using a high-energy milling apparatus and performing vacuum heat treatment to carry out a carbonization reduction 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 one embodiment of the present invention, in the step of producing vanadium carbide by mixing (b-1) vanadium oxide and a carbon compound to form a mixed powder, then refining the particle size using a high-energy milling apparatus and performing vacuum heat treatment to carry out a carbonization reduction reaction, The steel balls in the high-energy milling apparatus may be at least one selected from ceramic balls, metal balls, and cemented carbide balls.

[0028] According to one embodiment of the present invention, in the step of producing vanadium carbide by mixing (b-1) vanadium oxide and a carbon compound to form a mixed powder, then refining the particle size using a high-energy milling apparatus and performing vacuum heat treatment to carry out a carbonization reduction reaction, The vacuum heat treatment The heat treatment temperature may be between 1200°C and 1600°C. The heat treatment time may be between 1 and 5 hours.

[0029] According to one embodiment of the present invention, in the step of producing vanadium carbide by mixing (b-1) vanadium oxide and a carbon compound to form a mixed powder, then refining the particle size using a high-energy milling apparatus and performing vacuum heat treatment to carry out a carbonization reduction reaction, The rotating shaft of the high-energy milling apparatus is rotated at 150 to 250 rpm, and the rotating vessel is rotated at 300 to 500 rpm in the opposite direction to the rotation of the rotating shaft, allowing for high-energy milling for 1 to 20 hours.

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

[0031] According to one embodiment of the present invention, the high-energy mill apparatus is It may also be a planetary ball mill, spex mill, or attritor.

[0032] According to one embodiment of the present invention, in the step of producing MXene using vanadium carbide by aluminum etching and delamination of MAX using vanadium carbide (b-3), The aforementioned aluminum etching can be carried out using hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF2), or a combination thereof, or one or more of these selected from a combination of hydrochloric acid, sulfuric acid, and nitrous acid. [Effects of the Invention]

[0033] According to the present invention, in order to provide MAX using inexpensive vanadium carbide without using expensive vanadium metal, MAX using vanadium carbide has a low oxygen content, small particle size, and 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] Furthermore, because the present invention provides MXene using inexpensive vanadium carbide without using expensive vanadium metal, MXene, being a two-dimensional nanomaterial, has excellent physical properties and can be used in a variety of applications such as semiconductor materials, electronic materials, or catalysts.

[0035] Furthermore, since the present invention provides a method for producing MAX using inexpensive vanadium carbide without using expensive vanadium metal, it offers excellent process stability, enables mass production, and is economical.

[0036] Furthermore, since the present invention provides a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal, it offers excellent process stability, enables mass production, and is economical.

[0037] The effects of the present invention are not limited to those described above, but should be understood to include any effects that can be inferred from the detailed description of the present invention or the structure of the invention as described in the claims. [Brief explanation of the drawing]

[0038] [Figure 1] This is a schematic diagram of the MAX and MXene processes using vanadium carbide according to one embodiment of the present invention. [Figure 2] This is a flowchart illustrating a process for manufacturing MAX using vanadium carbide according to one embodiment of the present invention. [Figure 3] This is a schematic diagram of (a) a high-energy mill apparatus, (b) a rotating plate of the high-energy mill apparatus, (c) a vanadium carbide synthesis apparatus, and (d) a carbon reduction reaction according to one embodiment of the present invention. [Figure 4] This is a flowchart illustrating a process for producing MXene using vanadium carbide according to one embodiment of the present invention. [Figure 5] This is a graph showing the amount of carbon in vanadium carbide according to one embodiment of the present invention, based on the amount of carbon added and the heat treatment temperature. [Figure 6] This is a graph showing the amount of oxygen in vanadium carbide according to one embodiment of the present invention, based on the amount of carbon added and the heat treatment temperature. [Figure 7] These are the XRD patterns of (a)V2AlCMAX and (b)V12Al3C8MAX, which are vanadium-based MAX powders according to one embodiment of the present invention. [Modes for carrying out the invention]

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

[0040] The advantages and features of the present invention, and the methods for achieving them, will become clear when you refer to the embodiments described in detail below, along with the accompanying drawings.

[0041] However, the present invention is not limited to the embodiments disclosed below, but can be embodied in a variety of different forms. These embodiments are provided to complete the disclosure of the present invention and to fully inform those who are ordinary skill in the art to which the invention pertains, and the present invention is defined only by the scope of the claims.

[0042] Furthermore, in explaining the present invention, if it is determined that related known technologies or other elements would obscure the gist of the invention, a detailed explanation thereof will be omitted.

[0043] The present invention will be described in detail below.

[0044] MAX using vanadium carbide This invention provides MAX using inexpensive vanadium carbide without using expensive vanadium metal.

[0045] MAX using the vanadium carbide of the present invention Vanadium carbide consists 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 chemical formulas 1 to 3 can be selected.

[0046] V2AlC ------ (Chem.1) V4AlC3------ (chemical 2) V 12 Al3C8------ (chemical 3)

[0047] This invention provides MAX using inexpensive vanadium carbide without using expensive vanadium metal. As a result, MAX using vanadium carbide has a low oxygen content, small particle size, and excellent physical properties, and can be used in a variety of applications such as MAX precursors, raw materials for cemented carbide materials, catalysts, or semiconductor materials.

[0048] Generally, the manufacturing process for vanadium-based MAX powder involves reacting vanadium metal with aluminum and carbon. However, because vanadium metal is expensive, the production of vanadium-based MAX powder is costly, making it difficult to apply to industry.

[0049] Furthermore, vanadium metal readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic components such as carbon, nitrogen, or oxygen.

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

[0051] Herein, the present invention may also be a MAX that uses an inexpensive vanadium carbide instead of an expensive vanadium metal.

[0052] In this context, vanadium metal is a substance that readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic 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, then refining the particle size using a high-energy milling apparatus, followed by vacuum heat treatment and a carbonization reduction reaction.

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

[0055] In this case, the vanadium carbide may be formed by heat-treating a mixture of vanadium oxide and carbon compound, which has been finely ground, under vacuum and atmospheric pressure.

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

[0057] Here, if the molar ratio of vanadium to carbon is as described above, the vanadium carbide may have excellent physical properties, and the manufactured MAX may also have excellent physical properties.

[0058] In particular, since the oxygen content of MAX is low, MAX may have excellent semiconducting properties.

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

[0060] Here, if the oxygen content is within the above range, V(C) has a high oxygen content. x O 1-x )-type oxidized carbides may not be easily formed.

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

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

[0063] In this case, if 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 a MAX with a high oxygen content.

[0064] At this time, the carbon content of 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 may 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 MAX using the vanadium carbide may be V2AlC, V 12 Al3C8 or V4AlC3.

[0069] Here, the V2AlC can be shown by the following reaction formula 1.

[0070] 2VC 0.5 +Al → V2AlC ------ (Reaction formula 1)

[0071] Also, the V 12 Al3C8 can be shown by the following reaction formula 2.

[0072] 12VC 0.67 +3Al → V 12 Al3C8 ------ (Reaction formula 2)

[0073] And the V4AlC3 can be shown by the following reaction formula 3.

[0074] 4VC 0.75+Al → V4AlC3------ (Reaction Equation 3)

[0075] In this case, the MAX using the vanadium carbide eliminates the need for the use of vanadium metal.

[0076] For example, by using vanadium carbides with vanadium-to-carbon molar ratios of 2:1, 3:2, and 4:3 as raw materials, it is possible to eliminate vanadium metal during the manufacturing process of vanadium-based MAX powder.

[0077] Furthermore, the vanadium oxide may be at least one selected from vanadium pentoxide (V2O5), sodium metavanadate (NaVO3), vanadium trioxide (V2VO3), vanadium oxychloride (VOCl3), and ammonium metavanadate (H4NVO3).

[0078] And the carbon compound is It may be at least 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 include biomass, which is at least one selected from coffee grounds, fallen leaves, and waste wood.

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

[0081] And the high-energy milling described above is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. High-energy milling can be performed in 1 to 20 hours by applying a high energy of 0.6 to 2.4 J / g·s in an atmosphere of air, vacuum, nitrogen, or argon, rotating the rotating shaft at 150 to 250 rpm, and rotating the rotating vessel at 300 to 500 rpm in the opposite direction to the rotation of the rotating shaft.

[0082] Furthermore, the high-energy milling apparatus may be a planetary ball mill, a speck mill, or an attritor.

[0083] In this planetary ball mill, steel balls are loaded into a container along with the raw materials, and the container rotates and revolves at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0084] Furthermore, in the specks mill, steel balls are loaded into the container along with the raw materials, and the container vibrates up and down and left and right at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0085] Furthermore, the attritor is configured such that when steel balls are loaded into the container along with the raw materials, energy is transmitted by the rotational force of the rotor, and the particle size of the mixed powder of vanadium oxide and carbon compound can be reduced to the above range.

[0086] Furthermore, the high-energy milling apparatus can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to the above range by rotating the rotating container containing the mixed powder of vanadium oxide and carbon compound on the rotating plate in opposite directions to the rotation direction of the rotation axis of the rotating plate.

[0087] And the vacuum heat treatment The heat treatment temperature may be between 1200°C and 1600°C. The heat treatment time may be between 1 and 5 hours.

[0088] Here, if the heat treatment temperature of the vacuum heat treatment is within the above range, the low-oxygen vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0089] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus can be subjected to vacuum heat treatment at the heat treatment temperature of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0090] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0091] Furthermore, if the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0092] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus is subjected to vacuum heat treatment during the heat treatment time of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

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

[0094] Furthermore, the carbonization reduction reaction is By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the reaction rate of carbon reduction.

[0095] Figure 1 is a schematic diagram of the MAX and MXene processes using vanadium carbide according to one embodiment of the present invention.

[0096] Referring to Figure 1, in one example, vanadium oxide (V2O5) is mixed with graphite, and the vanadium oxide / graphite mixture (V2O5-C) milled in a high-energy mill is subjected to vacuum heat treatment to produce vanadium carbide (VC x ) is manufactured as a powder.

[0097] Subsequently, the vanadium carbide (VC x ) powder is mixed with aluminum to make vanadium carbide-aluminum (VC x -Al) mixture is manufactured.

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

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

[0100] MAX manufacturing method using vanadium carbide This invention provides a method for producing MAX using inexpensive vanadium carbide, without using expensive vanadium metal.

[0101] The present invention provides a method for producing MAX using vanadium carbide, (a-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling device, and then vacuum heat treatment is performed to carry out a carbonization reduction reaction to produce vanadium carbide, (a-2) The step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX using the vanadium carbide.

[0102] This invention provides a method for producing MAX using inexpensive vanadium carbide without using expensive vanadium metal, resulting in excellent process stability, enabling mass production, and being economical.

[0103] Furthermore, in the step of producing vanadium carbide by mixing the vanadium oxide and carbon compound (a-1) to form a mixed powder, then refining the particle size using a high-energy milling apparatus, vacuum heat treatment, and carbonization reduction reaction, The mixing ratio of the vanadium oxide and the carbon compound may be 1:0.3 to 1:0.5 by weight.

[0104] Here, if the mixing ratio of the vanadium oxide and the carbon compound is within the above range by weight, then V(C) has a high oxygen content. x O 1-x )-type oxidized carbides may not be easily formed.

[0105] In this case, the mixing ratio of the vanadium oxide and the carbon compound may preferably be 1:0.35 to 1:0.45 by weight, and more preferably 1:0.35 to 1:0.4 by weight.

[0106] Here, the high-energy milling is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. In an atmosphere of air, vacuum, nitrogen, or argon, the carbon reduction reaction proceeds. By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the reaction rate of carbon reduction.

[0107] Then, in the step of mixing the vanadium oxide and carbon compound (a-1) to form a mixed powder, and then using a high-energy milling apparatus to refine the particle size with high-energy milling and vacuum heat treatment to carry out a carbonization reduction reaction to produce vanadium carbide, The steel balls in the high-energy milling apparatus may be at least one selected from ceramic balls, metal balls, and cemented carbide balls.

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

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

[0110] Furthermore, in the step of producing vanadium carbide by mixing the vanadium oxide and carbon compound (a-1) to form a mixed powder, then refining the particle size using a high-energy milling apparatus, vacuum heat treatment, and carbonization reduction reaction, The rotating shaft of the high-energy milling apparatus is rotated at 150 to 250 rpm, and the rotating vessel is rotated at 300 to 500 rpm in the opposite direction to the rotation of the rotating shaft, allowing for high-energy milling for 1 to 20 hours.

[0111] Here, the high-energy milling may be a process in which the rotation direction of the rotating shaft and the rotating container are reversed, and the steel balls placed in the rotating container and the mixed powder of vanadium oxide and the carbon compound are milled by friction between them, thereby pulverizing the particles of the mixed powder of 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 vanadium oxide or the carbon compound may be 2 nm to 50 μm.

[0113] Furthermore, the high-energy milling apparatus may be a planetary ball mill, a speck mill, or an attritor.

[0114] In this planetary ball mill, steel balls are loaded into a container along with the raw materials, and the container rotates and revolves at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0115] Furthermore, in the specks mill, steel balls are loaded into the container along with the raw materials, and the container vibrates up and down and left and right at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0116] Furthermore, the attritor can be used to reduce the particle size of the mixed powder of vanadium oxide and carbon compound to the above range by loading steel balls into a container together with the raw materials and transferring energy through the rotational force of the rotor.

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

[0118] Then, in the step of mixing the vanadium oxide and carbon compound (a-1) to form a mixed powder, and then using a high-energy milling apparatus to refine the particle size with high-energy milling and vacuum heat treatment to carry out a carbonization reduction reaction to produce vanadium carbide, The vacuum heat treatment The heat treatment temperature may be between 1200°C and 1600°C. The heat treatment time may be between 1 and 5 hours.

[0119] Here, if the heat treatment temperature of the vacuum heat treatment is within the above range, the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0120] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus can be subjected to vacuum heat treatment at the heat treatment temperature of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0121] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0122] Furthermore, if the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0123] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus is subjected to vacuum heat treatment during the heat treatment time of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

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

[0125] Furthermore, the carbonization reduction reaction is By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the reaction rate of carbon reduction.

[0126] Then, in the step of mixing aluminum with the vanadium carbide (a-2) and heat-treating it under an inert gas to produce MAX using the vanadium carbide, the inert gas may be argon, nitrogen, or hydrogen.

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

[0128] Here, if the heat treatment temperature is within the above range, the MAX using the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0129] In other words, the mixed powder of vanadium carbide and aluminum can be heat-treated at the heat treatment temperature to produce MAX using vanadium carbide that has excellent low-oxygen properties and manufacturing efficiency.

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

[0131] Furthermore, if the heat treatment time falls within the above range, the MAX using the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0132] In other words, the mixed powder of vanadium carbide and aluminum can be heat-treated for the aforementioned heat treatment time to produce MAX using vanadium carbide that has excellent low-oxygen properties and manufacturing efficiency.

[0133] In this case, the heat treatment time for the heat treatment may preferably be 2 to 4 hours, and more preferably 2 to 3 hours.

[0134] Figure 2 is a flowchart of the process for manufacturing MAX using vanadium carbide according to one embodiment of the present invention.

[0135] Referring to Figure 2, first, vanadium oxide and a carbon compound are mixed to form a mixed powder, and then the particle size is refined using a high-energy milling apparatus, followed by vacuum heat treatment to carry out a carbonization reduction reaction and produce vanadium carbide (S110).

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

[0137] Figure 3 shows a schematic diagram of (a) a high-energy mill apparatus, (b) a rotating plate of the high-energy mill apparatus, (c) a vanadium carbide synthesis apparatus, and (d) a carbon reduction reaction according to one embodiment of the present invention.

[0138] Figure 3a is a photograph of a high-energy milling apparatus used for grinding 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 apparatus and the rotation direction of the rotating container containing the mixed powder of vanadium oxide and carbon compound are in opposite directions. These opposing rotational forces can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to 2 nm to 50 μm.

[0140] Referring to Figure 3c, this is a photograph of the apparatus used to synthesize vanadium carbide.

[0141] Figure 3d is a schematic diagram of the carbon-reduction reaction, and the reaction equation for the vanadium carbide produced by the carbon-reduction reaction of vanadium oxide and carbon compounds is shown in reaction equation 4 below.

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

[0143] For example, when vanadium oxide (V2O5) is used as a raw material for the synthesis of low-oxygen vanadium carbide, the vanadium carbide is formed by the reaction of vanadium oxide with carbon, i.e., by carbonization reduction, as shown in reaction equation 5 below.

[0144] V2O5+(5+2x)C→2VC x +5CO ------ (Reaction Equation 5)

[0145] MXene using vanadium carbide This invention provides MXene, which uses inexpensive vanadium carbide without using expensive vanadium metal.

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

[0147] This invention provides MXene, which uses inexpensive vanadium carbide without using expensive vanadium metal. As a two-dimensional nanomaterial, MXene exhibits excellent physical properties and can be used in a variety of 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 delamination of MAX using the vanadium carbide.

[0149] Furthermore, the MXene using the vanadium carbide may be an MXene using a low-cost vanadium carbide without using expensive vanadium metal.

[0150] In this context, vanadium metal is a substance that readily forms carbides, nitrides, or oxides due to its high affinity for nonmetallic components such as carbon, nitrogen, or oxygen.

[0151] The MXene using the vanadium carbide of the present invention can be selected from at least one of the compounds represented by the following chemical formulas 4 to 6.

[0152] V2C ------ (C4) V4C3------ (C5) V3C2------ (C6)

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

[0154] In this case, if 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 MXene with a high oxygen content.

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

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

[0157] Here, if the oxygen content is within the above range, V(C) has a high oxygen content. x O 1-x )-type oxidized carbides may not be easily formed.

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

[0159] Furthermore, the vanadium carbide can be formed by mixing vanadium oxide and a carbon compound, then refining the particle size using a high-energy milling device, followed by vacuum heat treatment and a carbonization reduction reaction.

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

[0161] Referring further to Figure 1, in one example, vanadium oxide (V2O5) is mixed with graphite, and the vanadium oxide / graphite mixture (V2O5-C), which is milled in a high-energy mill, is subjected to vacuum heat treatment to produce vanadium carbide (VCx) powder.

[0162] Subsequently, the vanadium carbide (VC x) powder is mixed with aluminum to make vanadium carbide-aluminum (VC x -Al) mixture is manufactured.

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

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

[0165] Method for producing MXene using vanadium carbide This invention provides a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal.

[0166] The present invention provides a method for producing MXene using vanadium carbide, (b-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling apparatus, and then vacuum heat treatment is performed to carry out a carbonization reduction reaction to produce vanadium carbide, (b-2) A step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX using the vanadium carbide, (b-3) The step of producing MXene using vanadium carbide by aluminum etching and delamination of MAX using vanadium carbide.

[0167] This invention provides a method for producing MXene using inexpensive vanadium carbide without using expensive vanadium metal, resulting in excellent process stability, enabling mass production, and being economical.

[0168] Furthermore, in the step of mixing the vanadium oxide and carbon compound (b-1) to form a mixed powder, then using a high-energy milling apparatus to refine the particle size with high-energy milling, followed by vacuum heat treatment and a carbonization reduction reaction to produce vanadium carbide, The mixing ratio of the vanadium oxide and the carbon compound may be 1:0.3 to 1:0.5 by weight.

[0169] Here, if the mixing ratio of the vanadium oxide and the carbon compound is within the above range by weight, then V(C) has a high oxygen content. x O 1-x )-type oxidized carbides may not be easily formed.

[0170] In this case, the mixing ratio of the vanadium oxide and the carbon compound may preferably be 1:0.35 to 1:0.45 by weight, and more preferably 1:0.35 to 1:0.4 by weight.

[0171] Then, in the step of mixing the (b-1) vanadium oxide and carbon compound to form a mixed powder, and then using a high-energy milling apparatus to refine the particle size with the high-energy milling and vacuum heat treatment to carry out a carbonization reduction reaction to produce vanadium carbide,

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

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

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

[0175] Furthermore, in the step of mixing the vanadium oxide and carbon compound (b-1) to form a mixed powder, then using a high-energy milling apparatus to refine the particle size with high-energy milling, followed by vacuum heat treatment and a carbonization reduction reaction to produce vanadium carbide, The rotating shaft of the high-energy milling apparatus is rotated at 150 to 250 rpm, and the rotating vessel is rotated at 300 to 500 rpm in the opposite direction to the rotation of the rotating shaft, allowing for high-energy milling for 1 to 20 hours.

[0176] Here, the high-energy milling may be a process in which the rotation direction of the rotating shaft and the rotating container are reversed, and the steel balls placed in the rotating container and the mixed powder of vanadium oxide and the carbon compound are milled by friction between them, thereby pulverizing the particles of the mixed powder of vanadium oxide and the carbon compound and reducing the average particle size of the mixed powder to 2 nm to 50 μm.

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

[0178] Furthermore, the high-energy milling apparatus may be a planetary ball mill, a speck mill, or an attritor.

[0179] In this planetary ball mill, steel balls are loaded into a container along with the raw materials, and the container rotates and revolves at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0180] Furthermore, in the specks mill, steel balls are loaded into the container along with the raw materials, and the container vibrates up and down and left and right at high speed, thereby reducing the particle size of the mixed powder of vanadium oxide and carbon compound to the above range.

[0181] Furthermore, the attritor is configured such that when steel balls are loaded into the container along with the raw materials, energy is transmitted by the rotational force of the rotor, and the particle size of the mixed powder of vanadium oxide and carbon compound can be reduced to the above range.

[0182] Furthermore, the high-energy milling apparatus can reduce the particle size of the mixed powder of vanadium oxide and carbon compound to the above range by rotating the rotating container containing the mixed powder of vanadium oxide and carbon compound on the rotating plate in opposite directions to the rotation direction of the rotation axis of the rotating plate.

[0183] Then, in the step of mixing the (b-1) vanadium oxide and carbon compound to form a mixed powder, and then using a high-energy milling apparatus to refine the particle size with the high-energy milling and vacuum heat treatment to carry out a carbonization reduction reaction to produce vanadium carbide, The vacuum heat treatment The heat treatment temperature may be between 1200°C and 1600°C. The heat treatment time may be between 1 and 5 hours.

[0184] Here, if the heat treatment temperature of the vacuum heat treatment is within the above range, the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0185] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus can be subjected to vacuum heat treatment at the heat treatment temperature of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

[0186] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0187] Furthermore, if the heat treatment time of the vacuum heat treatment is within the above range, the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0188] In other words, the mixed powder of vanadium oxide and carbon compound produced by the high-energy milling apparatus is subjected to vacuum heat treatment during the heat treatment time of the vacuum heat treatment to produce vanadium carbide with excellent low-oxygen properties and manufacturing efficiency.

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

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

[0191] Here, if the heat treatment temperature is within the above range, the MAX using the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0192] In other words, the mixed powder of vanadium carbide and aluminum can be heat-treated at the heat treatment temperature to produce MAX using vanadium carbide that has excellent low-oxygen properties and manufacturing efficiency.

[0193] In this case, the heat treatment temperature for the vacuum heat treatment may preferably be 1300°C to 1550°C, and more preferably 1400°C to 1500°C.

[0194] Furthermore, if the heat treatment time falls within the above range, the MAX using the vanadium carbide may exhibit excellent low-oxygen properties and manufacturing efficiency.

[0195] In other words, the mixed powder of vanadium carbide and aluminum is heat-treated during the heat treatment time to produce MAX using vanadium carbide that has excellent low-oxygen properties and manufacturing efficiency.

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

[0197] Furthermore, the carbonization reduction reaction is By using the high-energy milling method to refine the vanadium oxide and carbon compound, the contact area can be increased, thereby increasing the reaction rate of carbon reduction.

[0198] Furthermore, in the step of producing MXene using vanadium carbide by aluminum etching and delamination of MAX using vanadium carbide as described in (b-3), The aforementioned aluminum etching can be carried out using hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF2), or a combination thereof, or one or more of these selected from a combination of hydrochloric acid, sulfuric acid, and nitrous acid.

[0199] Furthermore, 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 flowchart of the process for producing MXene using vanadium carbide according to one embodiment of the present invention.

[0201] Referring to Figure 4, first, vanadium oxide and a carbon compound are mixed to form a mixed powder, and then the particle size is refined using a high-energy milling apparatus, followed by vacuum heat treatment to carry out a carbonization reduction reaction to produce vanadium carbide (S210).

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

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

[0204] The present invention will be described in more detail below with reference to examples. However, the following examples are provided to illustrate the present invention more concretely, and the scope of the present invention is not limited by these examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

[0205] <Examples> <Examples 1-7> Production of Vanadium Carbide A mixed powder of vanadium oxide and carbon compounds was prepared using the components and content shown in Table 1 below.

[0206] Subsequently, the mixed powder was placed together with steel balls into a rotating container in the high-energy mill apparatus shown in Table 1 below.

[0207] Subsequently, when grinding the particles using the high-energy milling apparatus shown in Table 1 below, high energy as shown in Table 1 below was applied under gaseous conditions such as air, vacuum, nitrogen, or argon, and the rotating shaft and rotating container were rotated in opposite directions to produce fine powder through high-energy milling.

[0208] Subsequently, the fine powder was subjected to vacuum heat treatment under the conditions shown in Table 1 below to induce a carbonization reduction reaction and produce vanadium carbide.

[0209] <Comparative Example 1> Production of Vanadium Carbide The comparative example vanadium carbide was produced in the same manner as in Example 1, except that the high-energy mill apparatus used in Example 1 was employed.

[0210] [Table 1]

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

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

[0213] Referring to Table 1 and Figure 6 above, the vanadium carbides of Examples 1 to 7 had oxygen content ranging from 1440 ppm to 3870 ppm, which was significantly lower than the 12,000 ppm oxygen content of the vanadium carbide of Comparative Example 1.

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

[0215] Furthermore, the average particle size of the vanadium carbides in Examples 1 to 7 is 20 nm, which is significantly smaller than the average particle size of the vanadium carbide in Comparative Example 1, which is 10 μm.

[0216] <Example 8> Production of MAX using vanadium carbide A mixed powder was produced by mixing aluminum with the vanadium carbide produced in Examples 1 and 3 described above.

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

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

[0219] <Experimental Example> Analysis of MAX XRD patterns using vanadium carbide Figure 7 shows the crystal structure (XRD) graphs of the vanadium carbides produced in Examples 1 and 3 described above.

[0220] Figure 7 shows the vanadium-based MAX powders produced in Examples 1 and 3 above: (a) V2AlCMAX (b) V 12 This is the XRD pattern of Al3C8MAX.

[0221] Referring to Figure 7a, the XRD pattern of V2AlCMAX in Example 1 above does not show a vanadium metal pattern.

[0222] Referring to Figure 7b, V in the above embodiment 3 12 The XRD pattern of Al3C8MAX does not show a vanadium metal pattern.

[0223] Therefore, the vanadium-based MAX powders of Examples 1 and 3 are (a)V2AlCMAX(b)V 12 Al3C8MAX successfully demonstrated the production of vanadium-based MAX powder using vanadium carbide with controlled carbon content as a raw material, without the use of vanadium metal.

[0224] Up to this point, specific examples of MAX and MXene using the vanadium carbide according to the present invention, and the manufacturing method thereof, have been described. However, it is obvious that various modifications are possible within the limits that do not deviate from the scope of the present invention.

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

[0226] In other words, the embodiments described above should be understood to be illustrative in all respects and not limiting, and the scope of the present invention is indicated by the claims described below rather than by the detailed description, and the meaning and scope of those claims, as well as any modified or altered forms conceived from their equivalent concepts, should all be interpreted as being included within the scope of the present invention.

Claims

1. As MAX containing vanadium carbide, Vanadium carbide consists of vanadium, carbon, and aluminum. It is a raw material for MXene, 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 1) V ４ AlC ３ ------ (Chemistry 2) V １２ Al ３ C ８ ------ (Formula 3) The carbon content of MAX containing the aforementioned vanadium carbide is 8-14 wt%, The oxygen content of MAX containing the aforementioned vanadium carbide is characterized by being 1,000 to 5,000 ppm. MAX contains vanadium carbide.

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

3. MAX containing the vanadium carbide described in claim 1.

3. The MAX containing the aforementioned vanadium carbide is characterized by eliminating the use of vanadium metal. MAX containing the vanadium carbide described in claim 1.

4. A MAX two-dimensional nanomaterial containing the vanadium carbide described in claim 1, MXene contains vanadium carbide.

5. The MXene containing the vanadium carbide is characterized in that at least one of the compounds represented by the following chemical formulas 4 to 6 is selected. MXene containing the vanadium carbide described in claim 4. V ２ C ------ (Chemistry 4) V ４ C ３ ------ (Chemistry 5) V ３ C ２ ------ (Chemistry 6)

6. The carbon content of the MXene containing the aforementioned vanadium carbide is characterized by being 10.5 to 15 wt%. MXene containing the vanadium carbide described in claim 4.

7. (a-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling device, and then vacuum heat treatment is performed to carry out a carbonization reduction reaction to produce vanadium carbide, (a-2) A step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX containing vanadium carbide, including, The manufacturing method for MAX.

8. The particle size of the mixed powder of the vanadium oxide or the carbon compound is characterized by being 2 nm to 50 μm. A method for manufacturing MAX according to claim 7.

9. The aforementioned high-energy milling is After mixing the vanadium oxide and carbon compound, the mixed powder is placed together with steel balls into a rotating container in a high-energy milling apparatus. In an atmosphere of air, vacuum, nitrogen, or argon, the carbon reduction reaction proceeds. The vanadium oxide and carbon compound are refined by high-energy milling to increase the contact area and thereby increase the reaction rate of carbon reduction. A method for manufacturing MAX according to claim 7.

10. (b-1) A step in which vanadium oxide and a carbon compound are mixed to form a mixed powder, the particle size is refined by high-energy milling using a high-energy milling device, and then vacuum heat treatment is carried out to produce vanadium carbide through a carbonization reduction reaction, (b-2) A step of mixing aluminum with the vanadium carbide and heat-treating it under an inert gas to produce MAX containing vanadium carbide, (b-3) The step of producing MXene containing vanadium carbide by aluminum etching and delamination of MAX containing vanadium carbide, including, A method for manufacturing MXene.

11. In the step of producing MXene containing vanadium carbide by aluminum etching and delamination of MAX containing vanadium carbide, The aforementioned aluminum etching process involves hydrofluoric acid (HF), lithium fluoride (LiF), sodium fluoride (NaF), and magnesium fluoride (MgF). ２ The method is characterized by using one or more selected from the following: ), or a combination thereof, or a combination of these with one or more of hydrochloric acid and sulfuric acid. A method for manufacturing MXene according to claim 10.

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