Two-dimensional mxene surface-modified with organic material, mxene organic ink, method for producing same, and application thereof

Abstract

The present invention relates to two-dimensional MXene surface-modified with an organic material, an MXene organic ink, and a method for producing same, and more specifically, to a two-dimensional MXene surface-modified with an electrophilic organic material bonded to the surface of two-dimensional MXene surface-modified with an organic / inorganic base to have nucleophilic properties by deprotonating the two-dimensional MXene using the organic / inorganic base.

Description

Organic surface-modified two-dimensional MXene, MXene organic ink, manufacturing method thereof, and application thereof

[0001] The present invention relates to a two-dimensional MXene surface-modified with an organic material, an organic MXene ink, a method for producing the same, and applications and uses of a MXene-polymer composite using the same (e.g., an electrically conductive MXene-polymer composite, an electromagnetic shielding MXene-polymer composite, or an electrically conductive film, an electromagnetic shielding MXene-polymer fiber, a bioelectronic material, etc.).

[0002] Conventional metal materials such as copper and silver have high electrical conductivity and have been used in various ways as electrodes and wiring in electronic devices in the semiconductor, display, and information and communication fields. However, their use is limited due to reasons such as relatively high density, high manufacturing cost, difficulty in applying printing process, oxidation and corrosiveness, and insufficient flexibility.

[0003] MXene is a novel nanomaterial with a two-dimensional structure that has high electrical conductivity and excellent solvent dispersibility (mainly in water and hydrophilic solvents). Therefore, research on the development of MXene and MXene / polymer composite materials is very active in the fields of flexible electrodes for printed electronics, thin-film sensors, high-power batteries and supercapacitors, and electromagnetic shielding.

[0004] MXene materials are two-dimensional crystal structure nanomaterials made of transition metal carbide, transition metal nitride, and transition metal carbonitride. They have excellent electrical conductivity, surface property controllability, and solution processability, and their potential applications are being highlighted in a wide variety of fields, including flexible electrodes, conductive adhesives / bonds, electromagnetic shielding, flexible heaters, sensors, energy storage, conversion, and generation electrodes, and light-emitting diode displays.

[0005] MXenes are two-dimensional crystalline transition metal carbides. Twenty different MXene compositions have been synthesized so far, including Ti2C, Ti3C2, Nb2C, V2C, Ta4C3, Mo2TiC2, Mo2Ti2C3, and Cr2TiC2. These MXenes exhibit the best electrical conductivity among the recently developed two-dimensional materials.

[0006] MXene can be synthesized from a ceramic material commonly referred to as MAX. MAX has a layered structure of transition metals [e.g., titanium (Ti), niobium (Nb), vanadium (V), tantalum (Ta), molybdenum (Mo), chromium (Cr)], carbon, and Group 14 elements [e.g., aluminum (Al) or silicon (Si)]. By selectively removing only the Group 14 elements through an etching process, a two-dimensional MXene is obtained.

[0007] In most cases up to now, the etching process has been carried out using a strong acid in an aqueous medium, which causes the surface of MXene to have terminal groups such as -OH, =O, -F, and -Cl, and among these, the -OH functional group in particular gives MXene hydrophilic properties.

[0008] MXenes with high electrical conductivity properties can be synthesized from a ceramic material generally referred to as MAX. Specifically, MAX is a three-component layered structure compound of a transition metal (titanium (Ti), niobium (Nb), vanadium (V), tantalum (Ta), molybdenum (Mo), chromium (Cr)) where M represents a transition metal, a Group 14 element (such as aluminum (Al) or silicon (Si)) where A represents a group 14 element, and carbon or nitrogen where X represents a group 14 element. By selectively removing only the A component, such as aluminum, through an etching process using a strong acid such as hydrofluoric acid (HF), a two-dimensional MXene with only the transition metal and carbon (or nitrogen) remaining is obtained. Due to the synthetic route in acid and aqueous solution, the surface of MXene has terminal functional groups such as -OH, =O, -F, -Cl, etc., and especially, the -OH functional group makes MXene hydrophilic. MXene synthesized in this way has excellent water dispersibility, and such MXene can be applied to flexible electrodes using solution process, conductive adhesive / bonding materials, electromagnetic shielding, flexible heaters, sensors, energy storage, conversion, generation electrodes, light-emitting diode displays, etc., and has an advantage in manufacturing films and coatings with high electrical conductivity.

[0009] In this way, MXene manufactured by a chemical etching process has the advantage of being easy to disperse in water due to the large amount of functional groups such as -OH or =O (hydroxyl or oxide), -F, -Cl, etc. present on the surface. However, MXene dispersed in an aqueous solution is easily oxidized by water molecules themselves and dissolved oxygen dissolved in water, turning into metal oxides and losing electrical conductivity properties, making it vulnerable to oxidation. In addition, MXene, which can only be dispersed in water due to its surface hydrophilicity, has a low binding force with other hydrophobic materials (polymers, organic substances, etc.), making it extremely difficult to form a homogeneous composite material with organic monomers or organic polymers. In addition, for applications such as spray coating, spin coating, slot die coating, roll-to-roll coating, gravure coating, bar coating, and inkjet printing, which are advantageous film and coating solution processes in the electronics industry, there is a need for stably dispersed MXene organic inks in various polar and non-polar organic solvents other than water dispersion, especially in industrial-specific organic solvents.

[0010] That is, due to the hydrophilic nature of the MXene surface, MXene can only be dispersed in water, and thus has low interaction and bonding strength with other hydrophobic organic materials (polymers, organic substances), so it has been used very restrictively in forming a uniform composite material. In addition, because a long drying process is required at high temperatures to remove water with a high boiling point and heat of vaporization after the solution process, its application to liquid printing processes such as spray coating, spin coating, inkjet printing, bar coating, gravure coating, and web coating has also been limited.

[0011] Accordingly, the present invention has been devised to solve the above-described conventional problems, and according to an embodiment of the present invention, the purpose is to provide a two-dimensional MXene surface-modified with an organic material capable of involving a covalent bond-based reaction mechanism.

[0012] According to an embodiment of the present invention, the M-OH moiety of the MXene surface is replaced with M(transition metal)-O using an organic / inorganic base. - The purpose is to provide a manufacturing method capable of chemically modifying a two-dimensional maxine surface with various organic substances having electrophilic properties by converting them into .

[0013] According to an embodiment of the present invention, the purpose is to provide a maxine organic ink having excellent dispersion stability and oxidation stability in various hydrophilic or hydrophobic organic solvents of almost all polarity ranges depending on the type of organic substance introduced.

[0014] And according to an embodiment of the present invention, the purpose is to provide composite applications that can be used in various industries, such as electrically conductive MXene-polymer composites, electromagnetic shielding MXene-polymer composites, or electrically conductive films, electromagnetic shielding MXene-polymer fibers, and bioelectronic materials, using such conductive MXene organic ink.

[0015] According to an embodiment of the present invention, by chemically modifying the surface of a two-dimensional maxene with various organic substances, the object is to have excellent dispersion stability and oxidation stability in almost all ranges of organic solvents (polar and non-polar), while at the same time maintaining the excellent electrical conductivity and electromagnetic shielding properties of the two-dimensional maxene material to the greatest extent possible.

[0016] In addition, according to an embodiment of the present invention, it is an object to provide a maxine organic ink that can be applied to various fields such as electrically conductive fibers, biocompatible polymer composites having electrical conductivity, and electromagnetic shielding materials through complexation with almost any range of hydrophilic or hydrophobic polymers.

[0017] Meanwhile, the technical tasks to be achieved in the present invention are not limited to the technical tasks mentioned above, and other technical tasks not mentioned can be clearly understood by a person having ordinary knowledge in the technical field to which the present invention belongs from the description below.

[0018] The first object of the present invention can be achieved by providing a two-dimensional MXene, which is surface-modified with an organic / inorganic base, by deprotonating the two-dimensional MXene using an organic / inorganic base to have nucleophilic properties.

[0019] And the above organic / inorganic base is MO to M-OH group on the surface of Maxene - It can be characterized as a base that can be changed into .

[0020] In addition, the organic / inorganic base may be characterized by being at least one selected from among Ammonia solution, Triethylamine, Pyridine, LiHMDS, NaHMDS, KHMDS, LiOH, NaOH, KOH, LiOEt, NaOEt, KOEt, or NaH.

[0021] And the above two-dimensional maxine, which is the target of surface modification, is M n+1 X n A two-dimensional array of crystal cells having an empirical formula of at least one layer, wherein each X is positioned within an octahedral array of a plurality of M's, wherein M is at least one metal selected from the group consisting of a Group IIIB metal, a Group IVB metal, a Group VB metal, and a Group VIB metal, and each X is C, N, or a combination thereof, and n is 1, 2, 3, or 4.

[0022] In addition, the above two-dimensional maxine, which is the target of surface modification, is M'2M" n X n+1A crystal cell having an empirical formula of at least one layer comprising a two-dimensional array, wherein each X is located within an octahedral array of a plurality of M' and M", wherein M' and M" are different metals selected from the group consisting of a Group IIIB metal, a Group IVB metal, a Group VB metal, and a Group VIB metal, and each X is C, N, or a combination thereof, and n is 1 or 2.

[0023] The second object of the present invention can be achieved by providing a two-dimensional organic MXene, which is surface-modified with an electrophilic organic substance that binds to the surface of the two-dimensional MXene according to the first object mentioned above.

[0024] And the above electrophilic organic material is MO of the two-dimensional MXene surface - It can be characterized by being covalently bonded with .

[0025] In addition, the organic material may be characterized by including at least one selected from a carbonyl group (-CO), a carboxylic acid group (-CO2H), an aldehyde group (-CHO), an ester group (-COC-), a halogen group (-F, -Cl, -Br, -I), phosphorous acid (-PO3H3), a sulfonyl group (-SO2R, R=alkyl, aryl), a sulfonic acid group (-SO3H), a silyl group (-SiR3, R=alkyl, aryl), and an isocyanate (-NCO) directly or indirectly connected to an aryl group, an alkyl group, or a heterocyclic compound.

[0026] And the above organic surface-modified two-dimensional maxine may be characterized by being expressed by at least one of the following chemical formulas 1 to 10.

[0027] [Chemical Formula 1]

[0028]

[0029] [Chemical Formula 2]

[0030]

[0031]

[0032] [Chemical Formula 3]

[0033]

[0034]

[0035] [Chemical Formula 4]

[0036]

[0037] [Chemical Formula 5]

[0038]

[0039] [Chemical Formula 6]

[0040]

[0041] [Chemical Formula 7]

[0042]

[0043] [Chemical Formula 8]

[0044]

[0045] [Chemical Formula 9]

[0046]

[0047] [Chemical Formula 10]

[0048]

[0049] [Chemical Formula 11]

[0050]

[0051] Here, R1 to R3 are each independently an alkyl group or an allyl group within C1 to C20,

[0052] L serves as a linker to connect oxygen and substituent A, and substituent A is selected from (C6-C30)aryl and (C4-C30)heteroaryl or can be connected to each other to form a ring, and the heteroaryl and heteroarylene include one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P.

[0053] And the organic material may be characterized by being included among compounds represented by at least one of the following structures.

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] The third object of the present invention can be achieved by a MXene organic ink in which a two-dimensional MXene surface-modified with an organic material according to the second object mentioned above is dispersed in an organic solvent.

[0060] The fourth object of the present invention can be achieved by a MXene-polymer composite, which is a composite of the MXene organic ink and a polymer according to the third object mentioned above.

[0061] The fifth object of the present invention is a method for manufacturing a two-dimensional MXene surface-modified with an organic material according to the second object mentioned above, wherein (1) the two-dimensional MXene is dispersed in an aprotic organic solvent with an organic / inorganic base so that the surface is MO - A method for manufacturing an organic surface-modified two-dimensional maxine, comprising: (1) preparing a two-dimensional maxine organic dispersion having a shape; (2) preparing an electrophilic organic substance and dispersing it in an organic solvent to prepare an organic substance dispersion; and (3) mixing and stirring the organic substance dispersion and the two-dimensional maxine organic dispersion to modify the surface of the two-dimensional maxine with the organic substance.

[0062] And the mixture of the organic / inorganic base and the organic material may be characterized in that the organic / inorganic base and the organic material are mixed in a volume ratio of 1:1 to 10.

[0063] The sixth object of the present invention is a method for producing a MXene organic ink, which can be achieved by a method for producing a MXene organic ink, comprising the steps of: producing an organic surface-modified two-dimensional MXene by the method according to the fifth object mentioned above; and dispersing the organic surface-modified two-dimensional MXene in an organic solvent.

[0064] And the above-mentioned solvent may be characterized as being an industrial organic solvent.

[0065] In addition, the industrial organic solvent may be characterized by including at least one selected from 2-methoxy ethanol (2ME), propylene glycol methyl ether (PGME), tetrahydrofuran (THF), dimethylformamide, propyleneglycol monomethyl ether acetate (PGME), chloroform, diethylene glycol monobutyl ether, chlorobenzene, 1,2-dichlorobenzene, 1,2-dichloroethane, toluene, cyclohexanone, and methyl ethyl ketone (MEK).

[0066] And the above-mentioned Maxine organic ink may be characterized in that it is applied to at least one of an electrically conductive film, an electromagnetic shielding film, a Maxine-polymer composite, an electromagnetic shielding Maxine-polymer composite, an electromagnetic shielding Maxine-polymer fiber, and a bioelectronic material.

[0067] According to the two-dimensional MXene surface-modified with an organic material according to an embodiment of the present invention, the existing M-OH moiety of the two-dimensional MXene material is deprotonated using an organic / inorganic base to form MO - (For example, by changing to Ti-O Enolate), the 2D MXene surface can be given a stronger nucleophile property, and thus, various organic substances with electrophile properties can be used for surface modification, and thus, it can be stably dispersed in almost any range of hydrophilic or hydrophobic organic solvents, especially industrial organic solvents, so that it can be applied to more efficient and general-purpose technologies. In addition, it has the effect of greatly improving the long-term stability of the 2D MXene material through surface modification of the 2D MXene material, which is one of the major shortcomings of the existing 2D MXene material, against chemical oxidation.

[0068] According to the organic surface-modified two-dimensional MXene and the MXene organic ink containing the same according to an embodiment of the present invention, it is possible to form a complex with various hydrophobic polymers, and the high-quality MXene-polymer complex ink has the advantage of being applicable to various fields such as conductive films, conductive fibers, and electromagnetic shielding materials due to its excellent electrical conductivity and coatability.

[0069] Meanwhile, the effects that can be obtained from the present invention are not limited to the effects mentioned above, and other effects that are not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

[0070] The following drawings attached to this specification illustrate preferred embodiments of the present invention and, together with the detailed description of the invention, serve to further understand the technical idea of ​​the present invention, and therefore, the present invention should not be interpreted as being limited to matters described in such drawings.

[0071] Figure 1 is a schematic diagram schematically showing a surface-modified two-dimensional maxine structure according to Examples 1 to 3 of the present invention;

[0072] Figure 2 shows the results of confirming the dispersibility of the surface-modified two-dimensional maxine according to Example 1 of the present invention in various industrial organic solvents.

[0073] Figure 3 shows the results of confirming the dispersibility of the surface-modified two-dimensional maxene according to Examples 2 to 3 of the present invention in THF organic solvent.

[0074] Figure 4 is the result of UV-Visible Spectrometry of the surface-modified two-dimensional maxine according to Example 1 of the present invention.

[0075] Figure 5 shows the X-ray diffraction (XRD) results of the surface-modified two-dimensional maxene according to Example 1 of the present invention.

[0076] Figure 6 shows the thermogravimetric analysis (TGA) results of the surface-modified two-dimensional maxine according to Example 1 of the present invention.

[0077] Figure 7 is a result of the electrical conductivity of a two-dimensional maxine film produced by vacuum filtration using a surface-modified two-dimensional maxine organic ink according to Example 1 of the present invention.

[0078] Figure 8 shows the results of a high-quality BA-MXene / PDMS polymer composite ink obtained by complexing a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention with various hydrophobic polymers.

[0079] Figure 9 shows the results of a high-quality, flexible BA-MXene / PDMS composite in the form of a pad made by composite with a PDMS polymer having flexible and biocompatible properties using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention.

[0080] Figure 10 is a scanning electron microscope (SEM) image result of a BA-MXene / PDMS composite made using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention.

[0081] Figure 11 shows the results of electrical conductivity of a BA-MXene / PDMS composite made using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention.

[0082] Figure 12 is an image of a Bu-MXene / Epoxy composite sheet made using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention and a general-purpose epoxy resin.

[0083] FIG. 13 is an image of a BA-MXene / TPU composite sheet made using a surface-modified two-dimensional MXene organic ink and TPU, a high-elastic polymer, according to Example 1 of the present invention.

[0084] The above-described purposes, other purposes, features, and advantages of the present invention will be readily understood through the following preferred embodiments, illustrated in the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments presented herein are provided to ensure that the disclosure is thorough and complete, and to ensure that the spirit of the present invention is fully conveyed to those skilled in the art.

[0085] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. In addition, in the drawings, the thicknesses of the components are exaggerated for the purpose of effectively explaining the technical contents.

[0086] Embodiments described herein will be described with reference to cross-sectional and / or plan views, which are ideal illustrative illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for effective explanation of the technical content. Therefore, the shapes of the illustrative drawings may be modified due to manufacturing techniques and / or tolerances. Therefore, embodiments of the present invention are not limited to the specific shapes illustrated, but also include variations in shapes resulting from the manufacturing process. For example, regions illustrated at right angles may be rounded or have a predetermined curvature. Therefore, the regions illustrated in the drawings have properties, and the shapes of the regions illustrated in the drawings are intended to illustrate specific shapes of regions of the device and are not intended to limit the scope of the invention. Although terms such as "first" and "second" are used to describe various components in various embodiments of the present invention, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments.

[0087] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise. As used herein, the words "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0088] In describing the specific embodiments below, various specific details have been included to further explain the invention and facilitate understanding. However, readers with sufficient knowledge of the field to understand the present invention will recognize that the present invention can be used without these specific details. In some cases, it is noted in advance that commonly known but largely unrelated aspects of the invention have been omitted to avoid unnecessary confusion in the description of the invention.

[0089] Hereinafter, the composition, function, and manufacturing method of the organic surface-modified two-dimensional maxine according to the present invention will be described.

[0090] In one aspect, the present invention may relate to a two-dimensional MXene surface-modified with an organic material capable of involving a covalent bond-based reaction mechanism (including a condensation reaction, a nucleophilic substitution reaction, and a polymerization reaction, etc.).

[0091] In one embodiment, the organic / inorganic base may be at least one selected from Ammonia solution, Triethylamine, Pyridine, LiHMDS, NaHMDS, KHMDS, LiOH, NaOH, KOH, LiOEt, NaOEt, KOEt, or NaH. It is not limited thereto, and as shown in the figure below, the M-OH group on the MXene surface may be MO - Any base that can be changed to is applicable.

[0092]

[0093]

[0094] In one embodiment, the organic / inorganic base is not limited to the examples of the bases presented above, and may include a similar structure, and may be formed by deprotonation of the -OH group on the surface of the MXene, which is the core reaction mechanism of the present invention, to form "MO-" [e.g., "Ti-O- "(Ti-O - It can contain any base that plays a role in forming [Enolate].

[0095]

[0096] In one embodiment, the organic material includes any organic material having electrophilic properties and any organic material capable of inducing covalent bonding between the two-dimensional maxene surface and the organic material.

[0097] Representative examples include carboxyl group (-COOH), aldehyde (-CHO), acyl halide (-COX), and ester (-ROR). ' -), sulfonic acid (-SO3H), sulfonyl halide (-SO2X), phosphoric acid (H3PO4), phosphorous acid (H3PO3R), alkyl (or aryl) halides, silyl groups (-SiR3, R = alkyl, aryl), isocyanates (-NCO), etc. (where R, R' are carbon)

[0098] In one embodiment, the form of the two-dimensional maxine compound surface-treated with the organic material may include any one of the compound structures represented by the following chemical formulas 1 to 10.

[0099] [Chemical Formula 1]

[0100]

[0101] Here, L is a linker that connects oxygen and substituent A. There are various groups expressed in chemical formulas 2 to 10 below, and direct connection is also possible without this. Substituent A is selected from (C6-C30) aryl and (C4-C30) heteroaryl, or can be connected to each other to form a ring;

[0102] The above heteroaryl and heteroarylene contain one or more heteroatoms selected from B, N, O, S, P(=O), Si and P.

[0103] The term “aryl” as used herein refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, including single or fused ring systems, each ring suitably containing 4 to 7, preferably 5 or 6, ring atoms, and even including a form in which multiple aryls are connected by single bonds. Examples include, but are not limited to, phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. At this time, the naphthyl includes 1-naphthyl and 2-naphthyl, the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.

[0104] The term “heteroaryl” as used herein refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, which may be a monocyclic or polycyclic aromatic hydrocarbon radical containing 3 to 8 ring atoms, each ring containing one or more heteroatoms selected from B, N, O, S, P(=O), Si and P, and includes a single or fused ring system, each ring suitably containing 3 to 7, preferably 5 or 6 ring atoms, and includes a form in which multiple heteroaryls are connected by single bonds. Monocyclic heteroaryl, such as furyl, thiophenyl, pyrrolyl, pyranyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.; and polycyclic heteroaryls such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinolizinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc.; and the like.

[0105]

[0106] [Chemical Formula 2]

[0107]

[0108]

[0109] [Chemical Formula 3]

[0110]

[0111]

[0112] [Chemical Formula 4]

[0113]

[0114] [Chemical Formula 5]

[0115]

[0116] Here, R1 to R3 are each independently an alkyl group or an allyl group within C1 to C20.

[0117] [Chemical Formula 6]

[0118]

[0119] [Chemical Formula 7]

[0120]

[0121] [Chemical Formula 8]

[0122]

[0123] [Chemical Formula 9]

[0124]

[0125] [Chemical Formula 10]

[0126]

[0127] [Chemical Formula 11]

[0128]

[0129] When using an organic material having two or more functional groups, a structure can be created in which MAXene and MAXene are connected (for example, using two functional groups) as above.

[0130]

[0131] In one embodiment, the organic material may include, but is not limited to, compounds represented by various structures in the figure below.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137] In this way, the two-dimensional maxine according to one aspect of the present invention is formed by MO of the maxine surface due to an organic / inorganic base. -The two-dimensional MXene surface can be modified with various types of organic compounds by forming covalent bonds with various types of electrophilic organic compounds (including condensation reactions that produce water as a byproduct).

[0138] In one implementation example, the two-dimensional maxine is M n+1 X n The crystal cell having the empirical formula of may include at least one layer forming a two-dimensional array.

[0139] Here, each X is positioned within an octahedral array of a plurality of M's, wherein M is at least one metal selected from the group consisting of a Group IIIB metal, a Group IVB metal, a Group VB metal, and a Group VIB metal, each X is C, N, or a combination thereof, and n can be 1, 2, 3, or 4.

[0140] In one implementation example, M can be, for example, but not limited to, Sc, Y, Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W or a combination thereof, and M n+1 X n The empirical formula may be, but is not limited to, Sc2C, Ti2C, Ti3C2, Nb2C, V2C, Ta4C3, Mo2TiC2, Mo2Ti2C3, Cr2TiC2, Ti2N, Ti3CN, Mo2C, Nb4C3, Zr3C2, Ti4N3, V4C3, Hf3C2, Mo2N, Cr2C, Zr2C, Nb2C, Hf2C, V3C2, Ta3C2, or Ti4C3, for example.

[0141] In another implementation example, the two-dimensional maxine is M'2M" n X n+1 The crystal cell having the empirical formula of may include at least one layer forming a two-dimensional array.

[0142] Here, each X is positioned within an octahedral array composed of a plurality of M' and M", wherein M' and M" are different metals selected from the group consisting of Group IIIB metals, Group IVB metals, Group VB metals and Group VIB metals, each X is C, N or a combination thereof, and n can be 1 or 2.

[0143] In other implementation examples, M can be, for example, but not limited to, Ti, V, Nb, Ta, Cr, Mo or a combination thereof, and M'2M" n X n+1 The empirical formulas are, for example, Mo2VC2, Mo2TaC2, Mo2NbC2, Cr2VC2, Cr2TaC2, Cr2NbC2, Ti2TaC2, Ti2NbC2, V2TaC 2, V2TiC 2, It may be, but is not limited to, Mo2V2C3, Mo2Nb2C3, Mo2Ta2C3, Cr2Ti2C3, Cr2Ta2C3, Cr2V2C3, Cr2Nb2C3, Nb2Ta2C3, Ti2Nb2C3, Ti2Ta2C3, V2Nb2C3, V2Ta2C3 or V2Ti2C3.

[0144] In one embodiment, the two-dimensional MXene to be surface-modified may be a free-standing two-dimensional assembly in which the crystal structures are continuously independent, or a stacked assembly in which the crystal structures are stacked. In the case of a stacked assembly, atoms, ions, or molecules may be intercalated between at least some layers, and the intercalated atoms or ions may be lithium. Accordingly, the surface-modified two-dimensional MXene according to one embodiment of the present invention may also be used in energy storage devices such as batteries and supercapacitors.

[0145] In addition, the surface-modified two-dimensional maxene according to one embodiment of the present invention maintains the crystal structure of the two-dimensional maxene before surface modification as shown in FIG. 1, and thus has excellent electrical conductivity, magnetic loss, and dielectric loss characteristics as its unique properties, and thus can be used as a conductive flexible electrode, heater, or electromagnetic shielding material and electromagnetic absorber.

[0146]

[0147] In another aspect, the present invention may relate to a method for manufacturing a two-dimensional maxine surface-modified with the above-described various organic materials.

[0148] In one embodiment, the method for manufacturing the surface-modified two-dimensional maxine comprises:

[0149] (1) The above organic / inorganic base and the two-dimensional MXene are dispersed in an aprotic organic solvent so that the surface is MO. - A step of preparing a two-dimensional MXene organic dispersion having a form (e.g., Ti-O Enolate);

[0150] (2) a step of preparing an electrophilic organic solution; and

[0151] (3) A method is provided, including a step of mixing and stirring the electrophilic organic solution and the two-dimensional maxine organic dispersion to modify the two-dimensional maxine surface with an organic material.

[0152] As the above metal and organic material are as described above, their description is omitted below.

[0153] In one embodiment, the organic solvent is C1-C 20 It could be cheap alcohol.

[0154] In one embodiment, the organic solvent may be ethanol.

[0155] In one embodiment, the mixture of the organic / inorganic base and the organic material may be a mixture of the organic / inorganic base and the organic material in a volume ratio of 1:1 to 4.

[0156] Specifically, the volume ratio of the organic / inorganic base and the organic material is 1:1 or more, 1:1.1 or more, 1:1.2 or more, 1:1.3 or more, 1:1.4 or more, 1:1.5 or more, 1:1.6 or more, 1:1.7 or more, 1:1.8 or more, 1:1.9 or more, 1:2 or more, 1:2.1 or more, 1:2.2 or more, 1:2.3 or more, 1:2.4 or more, 1:2.5 or more, 1:2.6 or more, 1:2.7 or more, 1:2.8 or more, 1:2.9 or more, 1:3 or more, 1:3.1 or more, 1:3.2 or more, 1:3.3 or more, 1:3.4 or more, 1:3.5 or more, 1:3.6 or more, 1:3.7 or more, 1:3.8 or more, or 1:3.9 or more, and further, the volume ratio of the organic / inorganic base and the organic material may be 1:4 or less, 1:3.9 or less, 1:3.8 or less, 1:3.7 or less, 1:3.6 or less, 1:3.5 or less, 1:3.4 or less, 1:3.3 or less, 1:3.2 or less, 1:3.1 or less, 1:3 or less, 1:2.9 or less, 1:2.8 or less, 1:2.7 or less, 1:2.6 or less, 1:2.5 or less, 1:2.4 or less, 1:2.3 or less, 1:2.2 or less, 1:2.1 or less, 1:2 or less, 1:1.9 or less, It can be 1:1.8 or less, 1:1.7 or less, 1:1.6 or less, 1:1.5 or less, 1:1.4 or less, 1:1.3 or less, 1:1.2 or less, or 1:1.1 or less.

[0157]

[0158] In another aspect, the present invention may relate to a method for producing a MXene organic ink containing a two-dimensional MXene surface-modified with the organic material.

[0159] In one embodiment, the organic solvent may be an alkane, an olefin, an alcohol, an aldehyde, an amine, an ester, an ether, a ketone, an aromatic hydrocarbon, a hydrogenated hydrocarbon, a terpene olefin, a halogenated hydrocarbon, a heterocyclic compound, a nitrogen-containing compound, a sulfur-containing compound, etc., and may be, for example, at least one selected from the group consisting of ethanol, methanol, isopropyl alcohol, n-hexanol, acetone, methyl ethyl ketone, acetonitrile, dimethyl sulfoxide, dimethylformamide, propylene carbonate, N-methyl-2-pyrrolidone, dichloromethane, chloroform, toluene, 1,2-dichlorobenzene, phenol, and tetrahydrofuran, but is not limited thereto, and MO, a surface modification method of a two-dimensional MXene - Any organic solvent that follows the reaction mechanism of forming covalent bonds between organic substances and can be dispersed as a result can be used.

[0160] In one implementation example, the stirring speed in the step (3) can be selected as an appropriate speed by a person skilled in the art according to conditions such as the volume of the solution, the presence or absence of a stirrer and a magnetic bar, and stirring by simply shaking by hand is also possible as long as a reaction in the solution phase can be induced.

[0161] In one embodiment, the stirring in step (3) may be performed at a temperature above the freezing point and below the boiling point of the organic solvent used. Preferably, the stirring in step (3) may be performed at a temperature of -78°C to 40°C. For example, the stirring in the step (3) above may be performed at a temperature of -78°C or higher, 11°C or higher, 12°C or higher, 13°C or higher, 14°C or higher, 15°C or higher, 16°C or higher, 17°C or higher, 18°C ​​or higher, 19°C or higher, 20°C or higher, 21°C or higher, 22°C or higher, 23°C or higher, 24°C or higher, 25°C or higher, 26°C or higher, 27°C or higher, 28°C or higher, 29°C or higher, 30°C or higher, 31°C or higher, 32°C or higher, 33°C or higher, 34°C or higher, 35°C or higher, 36°C or higher, 37°C or higher, 38°C or higher, or 39°C or higher, and further, the stirring in the step (3) above may be performed at a temperature of 40°C or lower, 39°C or lower, 38°C or lower, 37°C or lower, 36°C or lower, 35°C or lower, It can be performed at a temperature of 34℃ or less, 33℃ or less, 32℃ or less, 31℃ or less, 30℃ or less, 29℃ or less, 28℃ or less, 27℃ or less, 26℃ or less, 25℃ or less, 24℃ or less, 23℃ or less, 22℃ or less, 21℃ or less, 20℃ or less, 19℃ or less, 18℃ or less, 17℃ or less, 16℃ or less, 15℃ or less, 14℃ or less, 13℃ or less, 12℃ or less, or 11℃ or less.

[0162] In one implementation example, the stirring in step (3) may be performed for 0.1 to 48 hours. For example, the stirring in the step (3) may be performed for 0.1 hour or more, 0.7 hours or more, 0.9 hours or more, 1 hour or more, 2 hours or more, 4 hours or more, 6 hours or more, 8 hours or more, 10 hours or more, 12 hours or more, 14 hours or more, 16 hours or more, 18 hours or more, 20 hours or more, or 22 hours or more, and further, the stirring in the step (3) may be performed for 48 hours or less, 40 hours or less, 36 hours or less, 30 hours or less, 22 hours or less, 20 hours or less, 18 hours or less, 16 hours or less, 14 hours or less, 12 hours or less, 10 hours or less, 8 hours or less, 6 hours or less, 4 hours or less, 2 hours or less, 1 hour or less, 0.9 hours or less, or 0.7 hours or less.

[0163] In one implementation example, after step (3), a step of adjusting the concentration of the organic solution may be included (step (4)). The concentration of the organic solution may be adjusted by concentrating it through a natural evaporation method, a rotary vacuum evaporation method, a centrifugation method, etc., or by diluting it through the addition of a solvent, and the replacement of the organic solvent may be performed through a centrifuge, a sequential concentration and dilution method, a dialysis method, etc.

[0164]

[0165] In another aspect, the present invention may relate to a MXene organic ink containing a two-dimensional MXene surface-modified with an organic material, wherein the two-dimensional MXene is dispersed in an organic solvent.

[0166] In one embodiment, the organic solvent may be an industrial organic solvent.

[0167] In one embodiment, the industrial organic solvent may include, but is not limited to, one or more selected from 2-methoxy ethanol (2ME), propylene glycol methyl ether (PGME), tetrahydrofuran (THF), propyleneglycol monomethyl ether (PGME), chloroform, toluene, 1,2-dichlorobenzene, and methyl ethyl ketone (MEK).

[0168] The two-dimensional MXene or MXene organic ink surface-modified with an organic material manufactured in this way has significantly improved oxidation stability compared to the existing MXene aqueous solution, thereby greatly enhancing long-term storage stability, and can be used more efficiently in various solution coating processes such as spray coating, spin coating, bar coating, roll-to-roll coating, gravure coating, and inkjet printing. In particular, the two-dimensional MXene surface-modified with a metal-organic network according to one embodiment of the present invention can be stably dispersed not only in polar organic solvents but also in industrial non-polar organic solvents essential for various EHD (electrohydrodynamic) printing, 3D printing businesses, or polymer complexation, and at the same time has high electrical conductivity, so that it can be efficiently applied in various fields. In addition, it is very advantageous in forming complexes with various organic monomers or organic polymer materials having hydrophobicity, and can be easily applied to the production of films and coatings having high electrical conductivity applicable to flexible electrodes, conductive adhesives / bonds, electromagnetic shielding, flexible heaters, sensors, energy storage electrodes, light-emitting diode displays, etc.

[0169] For example, a film formed with a uniform thickness on a substrate can be manufactured by evenly applying a MXene organic ink containing a surface-modified two-dimensional MXene according to one embodiment of the present invention onto a substrate and evaporating the solvent.

[0170]

[0171] In other embodiments, the above-described maxine organic ink may contain other particles and / or polymers in addition to the surface-modified two-dimensional maxine.

[0172] The above other particles include, but are not limited to, metals including Ag, Au, Cu, Pd, and Pt; metal oxides including SiO2 and ITO; nitrides; carbides; semiconductors including Si, GaAs, and InP; glasses such as silica or boron-based glasses; liquid crystals such as poly(3,4-ethylenedioxythiophene); organic and inorganic porous materials; and organic polymers.

[0173] The polymers include, for example, epoxy resins, polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE), polyetherimide (PEI), acrylate resins, polyamide (PA), acrylonitrile-butadiene-styrene resins (ABS), polyamideimide (PAI), polybenzimidazole (PBI), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyoxymethylene (POM), polyether ketone (PEK), polyether ether ketone (PEEK), polyarylether ketone (PAEK), liquid crystal polymer (LCP), polyimide (PI), polycarbonate (PC), self-reinforced polyphenylene (SPR), (meth)acrylate polymers, urethane (meth)acrylate polymers, polystyrene (PS), polyurethane, and Polysiloxanes, etc., but are not limited thereto.

[0174] In one embodiment, the above-mentioned MXene organic ink may be a dispersion of the surface-modified two-dimensional MXene in the organic solvent at a concentration of 1 to 100 mg / mL. More specifically, the above-mentioned MXene organic ink may be one in which the surface-modified two-dimensional MXene is dispersed in the organic solvent at a concentration of 1 mg / mL or more, 3 mg / mL or more, 5 mg / mL or more, 7 mg / mL or more, 10 mg / mL or more, 15 mg / mL or more, 20 mg / mL or more, 30 mg / mL or more, 40 mg / mL or more, 50 mg / mL or more, 60 mg / mL or more, 70 mg / mL or more, 80 mg / mL or more, or 90 mg / mL or more, or the above-mentioned MXene organic ink may be one in which the surface-modified two-dimensional MXene is dispersed in the organic solvent at a concentration of 100 mg / mL or less, 90 mg / mL or less, 80 mg / mL or less, 70 mg / mL or less, 60 mg / mL or less, 50 mg / mL or less, 40 mg / mL or less, 30 mg / mL or less, 20 mg / mL or less, 15 mg / mL or less, or It may be dispersed in the organic solvent at a concentration of 10 mg / mL or less.

[0175]

[0176] In another aspect, the present invention may relate to an electrically conductive film comprising the above-described MXene organic ink.

[0177] In one embodiment, the film can be manufactured through various solution coating processes such as spray coating, spin coating, inkjet printing, filtration, multilayer coating or dip coating using the above-described maxine organic ink.

[0178] In one embodiment, the coating or film comprising the surface-modified two-dimensional MXene or the MXene organic ink containing the surface-modified two-dimensional MXene has an electrically conductive surface of at least 0.01 S / cm, more specifically, at least 100 S / cm, 500 S / cm, 1,000 S / cm, 1,500 S / cm, 2,000 S / cm, 2,500 S / cm, and preferably at least 3,000 S / cm.

[0179] In one embodiment, the thickness of the coating may be 1 to 999 nm, for example, the thickness of the coating may be 1 nm or more, 5 nm or more, 10 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 550 nm or more, 600 nm or more, 700 nm or more, or 800 nm or more, and further, the thickness of the coating may be 999 nm or less, 950 nm or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm It may be less than, 200 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less.

[0180] In one embodiment, the thickness of the film may be 1 to 500 microns (μm), for example, the thickness of the film may be 1 micron or more, 2 microns or more, 3 microns or more, 4 microns or more, 5 microns or more, 6 microns or more, 7 microns or more, 7.5 microns or more, 8 microns or more, 9 microns or more, 10 microns or more, 10.5 microns or more, 11 microns or more, 12 microns or more, 12.5 microns or more, 13 microns or more, 14 microns or more, 15 microns or more, 20 microns or more, 30 microns or more, 40 microns or more, 50 microns or more, 100 microns or more, 150 microns or more, 200 microns or more, 250 microns or more, 300 microns or more, 350 microns or more, 400 microns or more or It may be 450 microns or more, and further, the thickness of the film may be 500 microns or less, 470 microns or less, 420 microns or less, 370 microns or less, 320 microns or less, 270 microns or less, 230 microns or less, 170 microns or less, 120 microns or less, 60 microns or less, 50 microns or less, 40 microns or less, 30 microns or less, 20 microns or less, 15 microns or less, 14 microns or less, 13 microns or less, 12 microns or less, 11.5 microns or less, 11 microns or less, 10.5 microns or less, 10 microns or less, 9 microns or less, 8.5 microns or less, 8 microns or less, 7 microns or less, 6 microns or less, 5 microns or less, 4 microns or less, 3 microns or less, or 2 microns or less.

[0181]

[0182] In another aspect, the present invention may relate to an electrically conductive polymer composite or an electromagnetic shielding composite comprising the above-described maxine organic ink.

[0183] The above surface-modified two-dimensional maxene is very advantageous in forming complexes with various organic monomers or organic polymer materials having hydrophobicity, and thus can be applied to flexible electrodes, conductive adhesives / bonds, electromagnetic shielding, flexible heaters, sensors, energy storage, conversion, generation electrodes, and light-emitting diode displays.

[0184] In one embodiment, the electrically conductive polymer composite and the electromagnetic shielding composite may contain particles and / or polymers other than the MXene organic ink, examples of which are as detailed above.

[0185] In one embodiment, the electrically conductive polymer composite has an electrically conductive surface of at least 0.01 S / cm, and more specifically, may have a surface conductivity of at least 100 S / cm, 105 S / cm, 110 S / cm, 115 S / cm, and preferably at least 150 S / cm.

[0186]

[0187] Hereinafter, the present invention will be described in more detail through examples and test examples. However, these examples and test examples are provided merely to facilitate understanding of the present invention, and the scope of the present invention is not limited to these examples and test examples. Modifications, substitutions, and insertions commonly known in the art may be performed, and such modifications are also included within the scope of the present invention.

[0188]

[0189] <Example 1> Surface modification of two-dimensional MXene using electrophilic organic substance benzoic acid and preparation of MXene organic ink (BA-MXene)

[0190] Exfoliated MXene (Ti3C2T) prepared by treating Ti3AlC2 powder (average particle size ≤ 40 μm) with LiF (Alfa Aesar, 98.5%)-HCl (DAEJUNG, 35-37%) x) was diluted to 1 mg / mL in NMP to prepare 30 mL. 30 μL of a 1.0 M toluene solution of LiHMDS (Lithium bis(trimethylsilyl)amide) was mixed with 5 mL of NMP solution, added to the MXene dispersion, and stirred at room temperature for about 5 minutes. At the same time, 3 mg of benzoic acid (electrophilic organic substance) was mixed with 5 mL of NMP and completely dissolved. The surface was Ti-O by LiHMDS. - (Ti-O - After adding a benzoic acid solution to the MAXene dispersion transformed into ethanol (Enolate), the reaction was carried out by stirring at room temperature for about 1 to 3 hours. After an appropriate reaction time, stirring was stopped, and the reaction product was washed with ethanol 2 to 3 times through a centrifuge, and the MAXene surface-modified with benzoic acid was separated through the final centrifuge process. Then, in the final step, the MAXene was dispersed in the organic solvent to be substituted (THF, Chloroform, Chlorobenzene, MEK, or Toluene) to produce the MAXene organic ink. For the versatility of this technology, even if the MAX company or etching process used is various, high-quality MAXene organic ink that can be stably dispersed in organic solvents such as THF, Chloroform, Chlorobenzene, MEK, and Toluene can be produced by mixing a small amount of ethanol. As mentioned above, the amount of ethanol may vary depending on the MAX company or etching method used.

[0191] The appearance of the organic ink of the MXene, in which the two-dimensional MXene surface-modified with an organic material according to Example 1 is dispersed in an industrial organic solvent (THF, Chloroform, 1,2-Dichlorobenzene, MEK, toluene, etc.), is shown in Fig. 2.

[0192] As shown in Fig. 2, it was confirmed that the two-dimensional MXene BA-MXene surface-modified with an organic material according to Example 1 was stably dispersed in various industrial organic solvents.

[0193] As shown in Fig. 3, it was confirmed that the two-dimensional MXenes Bu-MXene and p-Tosyl-MXene, surface-modified with organic materials according to Examples 2 and 3, were stably dispersed in THF.

[0194] In addition, as shown in Fig. 4, when a two-dimensional MXene surface-modified with an organic substance (benzoic acid) was dispersed in EtOH and UV-Vis analysis was performed, it was confirmed that the original characteristics of the two-dimensional MXene were maintained even after surface modification with an organic substance, as shown in Fig. 3.

[0195] As illustrated in Fig. 5, the two-dimensional MXene surface-modified with an organic material (benzoic acid) according to Example 1 showed an increased inter-sheet distance compared to the MXene before surface modification through X-ray diffraction analysis (XRD). This confirms that the organic material was successfully modified on the surface of the MXene.

[0196] As shown in FIG. 6, the two-dimensional MXene surface-modified with an organic substance (benzoic acid) according to Example 1 showed a weight difference of about 5.1 wt.% before and after surface modification as shown in a thermogravimetric analyzer (TGA), confirming that about 5.1 wt.% of the organic substance (benzoic acid) was present on the two-dimensional MXene surface after surface modification, indicating that the surface modification was successful.

[0197]

[0198] <Example 2> Surface modification of two-dimensional MXene using alkyl halides and preparation of MXene organic ink (Bu-MXene)

[0199] The method is the same as Example 1, but the electrophilic organic material used was prepared using bromobutane.

[0200]

[0201] <Example 3> Surface modification of two-dimensional MXene using p-toluene sulfonic acid and preparation of MXene organic ink (p-Tosyl-MXene)

[0202] The method is the same as Example 1, but the electrophilic organic material used was prepared using p-toluene sulfonic acid.

[0203]

[0204] <Manufacturing Example 1> Manufacturing of a two-dimensional MXene BA-MXene film surface-treated with an organic material

[0205] The two-dimensional maxine solution surface-modified with the organic material (benzoic acid) prepared in Example 1 above could be easily manufactured into a film by vacuum filtration using a PVDF membrane (pore size: 47 μm).

[0206] As illustrated in Fig. 7, the surface-modified two-dimensional MXene solution according to Example 1 with an organic material (benzoic acid) was easily fabricated into a film by vacuum filtration using a PVDF membrane (pore size: 47 μm). The surface-modified two-dimensional MXene film fabricated in this manner was confirmed to have an electrical conductivity of approximately 4,120 S / cm.

[0207]

[0208] <Manufacturing Example 2> Manufacturing of a 2D MXene Butyl-MXene Film Surface-Treated with Organic Materials

[0209] The surface-modified two-dimensional MXene solution prepared in Example 2 above with an organic compound (Bromobutane) was easily fabricated into a film by vacuum filtration using a PVDF membrane (pore size: 47 μm). The surface-modified two-dimensional MXene film thus prepared was confirmed to have an electrical conductivity of approximately 3,819 S / cm.

[0210]

[0211] <Manufacturing Example 3> Manufacturing of a two-dimensional MXene Tosyl-MXene film surface-treated with an organic material

[0212] The surface-modified two-dimensional MXene solution prepared in Example 3 above with an organic compound (p-toluene sulfonic acid) was easily fabricated into a film by vacuum filtration using a PVDF membrane (pore size: 47 μm). The surface-modified two-dimensional MXene film thus prepared was confirmed to have an electrical conductivity of approximately 4,002 S / cm.

[0213]

[0214] <Manufacturing Example 4> Manufacturing of BA-MXene / PDMS composite sheet

[0215] 100 mg of the two-dimensional MXene surface-modified with an organic material (benzoic acid) prepared in Example 1, 900 mg of PDMS (Beca Corporation, CAS#63148-62-9), and 100 mg of a curing agent were mixed in a THF solution and stirred for 40 o 90 after C heat curing (3 hours) o C After thermal curing (3-5 hours), a highly stretchable MXene-PDMS composite sheet with excellent elastic recovery can be manufactured. The obtained conductive MXene@PDMS composite was confirmed to have an electrical conductivity of approximately 0.5 S / cm, which is higher than that of conventional non-conductive PDMS (Fig. 10). Based on the confirmed electrical conductivity values, it is expected to be used in various applications such as pressure sensors. For reference, the resistance and conductivity measurement equipment used was the CMT-SR200N model from Advanced Instrument Technology (AIT).

[0216]

[0217] <Manufacturing Example 5> Manufacturing of Bu-MXene / PDMS composite sheet

[0218] The method is the same as that used in Manufacturing Example 5, but the Maxine used was that used in Example 2. It was confirmed that it was easy to manufacture a composite sheet with a very uniform shape.

[0219]

[0220] <Manufacturing Example 6> Manufacturing of p-Tosyl-MXene / PDMS composite sheet

[0221] The method is the same as that used in Manufacturing Example 5, but the Maxine used was that used in Example 3. It was confirmed that it was easy to manufacture a composite sheet with a very uniform shape.

[0222]

[0223] As shown in Fig. 9, the two-dimensional MXene surface-modified with an organic material (benzoic acid) according to Example 1 can be manufactured in the form of a MXene / PDMS polymer ink with a very uniform shape as shown in Fig. 8 when mixed with a PDMS polymer based on its stable dispersion characteristics in a THF solvent, and it was confirmed that this can be cured to manufacture a Bu-MXene / PDMS composite of excellent quality.

[0224] FIG. 10 is a scanning electron microscope (SEM) image result of a MXene-PDMS composite made using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention.

[0225] Figure 11 shows the results showing the electrical conductivity of a Bu-A-MXene / PDMS composite produced using a surface-modified two-dimensional MXene organic ink according to Example 1 of the present invention. It was confirmed that the surface-modified two-dimensional MXene film produced in this way had an electrical conductivity characteristic of approximately 0.5 S / cm.

[0226]

[0227] <Manufacturing Example 7> Manufacturing of BA-MXene / Epoxide composite sheet

[0228] 100 mg of the two-dimensional MXene surface-modified with an organic material (benzoic acid) prepared in Example 1 and 1,000 mg of a one-component epoxy resin (Sytape, CAS#24969-06-0) were mixed in a THF solution and stirred at 90 o C heat curing (1-3 hours) allows the production of a MXene-epoxide composite sheet with a uniform distribution of conductive MXene while maintaining the rigid properties of conventional epoxy materials. These materials are expected to find diverse industrial applications as conductive composites that possess both rigid properties and thermal conductivity, heat diffusion, and electromagnetic shielding properties.

[0229]

[0230] FIG. 12 is an image of a maxine-epoxy composite pad made using a surface-modified two-dimensional maxine organic ink according to Example 1 of the present invention and a general-purpose epoxy resin.

[0231]

[0232] <Manufacturing Example 8> Manufacturing of BA-MXene / TPU composite sheet

[0233] 100 mg of the two-dimensional MXene surface-modified with an organic material (benzoic acid) prepared in Example 1 and 1,000 mg of TPU (Songwon Industrial, CAS#9009-54-5) were mixed in a THF solution and stirred at 70 o C heat curing (12 hours) allows the production of a Maxene@TPU composite sheet that maintains the elastic properties of conventional TPU materials while exhibiting electrical conductivity and electromagnetic shielding properties not found in conventional TPU materials. This is expected to be applied in various fields, such as wearable electronics, in the future.

[0234]

[0235] FIG. 13 is an image of a maxine-TPU composite pad made using a surface-modified two-dimensional maxine organic ink and a high-elastic polymer, TPU, according to one embodiment of the present invention.

[0236]

[0237] Electrical Conductivity (S / cm) Electromagnetic Shielding SE (dB) Note Manufacturing Example 14,12060 Pristine BA-MXene Manufacturing Example 23,81957 Pristine Bu-MXene Manufacturing Example 34,00259 Pristine p-Tosyl-MXene Manufacturing Example 40.512 PDMS Composite Manufacturing Example 50.249 PDMS Composite Manufacturing Example 60.4410 PDMS Composite Manufacturing Example 88731 TPU Composite

[0238] In addition, the devices and methods described above are not limited to the configurations and methods of the embodiments described above, and the embodiments may be configured by selectively combining all or part of each embodiment so that various modifications can be made.

Claims

As a 1.2-dimensional maxine, A two-dimensional MXene surface-modified with an organic / inorganic base, which is modified to have nucleophilic properties by deprotonating the two-dimensional MXene using an organic / inorganic base.

2. In paragraph 1, The above organic / inorganic bases are MO-OH groups on the surface of Maxene - A two-dimensional maxene surface-modified with an organic / inorganic base, which can be converted into a base.

3. In paragraph 2, A two-dimensional MXene surface-modified with an organic / inorganic base, wherein the organic / inorganic base is at least one selected from Ammonia solution, Triethylamine, Pyridine, LiHMDS, NaHMDS, KHMDS, LiOH, NaOH, KOH, LiOEt, NaOEt, KOEt, or NaH.

4. In paragraph 1, The above two-dimensional maxine, which is the target of surface modification, is M n+1 X n A two-dimensional array of crystal cells having an empirical formula of at least one layer, Each X is located within an octahedral array of multiple Ms, M is at least one metal selected from the group consisting of Group IIIB metals, Group IVB metals, Group VB metals and Group VIB metals, Each X is C, N or a combination thereof, Two-dimensional maxene surface-modified with organic / inorganic bases, where n is 1, 2, 3, or 4.

5. In paragraph 1, The above two-dimensional maxine, which is the target of surface modification, is M'2M" n X n+1 A two-dimensional array of crystal cells having an empirical formula of at least one layer, Each X is located within an octahedral array of multiple M' and M", M' and M" are different metals selected from the group consisting of Group IIIB metals, Group IVB metals, Group VB metals and Group VIB metals, Each X is C, N or a combination thereof, Two-dimensional maxene surface-modified with organic / inorganic bases, where n is 1 or 2. As a 6.2-dimensional organic magnetron, An organic surface-modified two-dimensional maxine surface, the surface of which is modified with an electrophilic organic substance that binds to the two-dimensional maxine surface according to any one of claims 1 to 5.

7. In paragraph 6, The above electrophilic organic material is MO on the two-dimensional MXene surface - A two-dimensional maxene with organic surface modification covalently bonded to .

8. In paragraph 7, An organic surface-modified two-dimensional MXene, wherein the organic substance comprises at least one selected from a carbonyl group (-CO), a carboxylic acid group (-CO2H), an aldehyde group (-CHO), an ester group (-COC-), a halogen group (-F, -Cl, -Br, -I), a phosphorous acid (-PO3H3), a sulfonyl group (-SO2R, R=alkyl, aryl), a sulfonic acid group (-SO3H), a silyl group (-SiR3, R=alkyl, aryl), and an isocyanate (-NCO) directly or indirectly connected to an aryl group, an alkyl group, or a heterocyclic compound.

9. In paragraph 6, The above organic surface-modified two-dimensional maxine is an organic surface-modified two-dimensional maxine represented by at least one of the following chemical formulas 1 to 10: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] Here, R1 to R3 are each independently an alkyl group or an allyl group within C1 to C20, L is a linker that connects oxygen and substituent A, and substituent A can be selected from (C6-C30) aryl and (C4-C30) heteroaryl or can be connected to each other to form a ring. The above heteroaryl and heteroarylene contain one or more heteroatoms selected from B, N, O, S, P(=O), Si and P.

10. In paragraph 6, The organic material is a surface-modified two-dimensional maxine, which is comprised of compounds represented by at least one of the following structures:

11. A MXene organic ink comprising a two-dimensional MXene surface-modified with an organic material according to Article 6 dispersed in an organic solvent.

12. A MXene-polymer composite comprising a MXene organic ink and a polymer according to Article 13.

13. A method for manufacturing a two-dimensional maxine surface-modified with an organic material according to Article 6, (1) The surface is MO by dispersing the 2D MXene with an organic / inorganic base in an aprotic organic solvent. - A step of preparing a two-dimensional maxine organic dispersion having a shape; (2) A step of preparing an electrophilic organic substance and dispersing it in an organic solvent to prepare an organic substance dispersion; and (3) A method for manufacturing an organic surface-modified two-dimensional maxine, comprising a step of mixing and stirring the organic dispersion and the two-dimensional maxine organic dispersion to modify the two-dimensional maxine surface with an organic material.

14. In paragraph 13, A method for manufacturing a two-dimensional maxine by surface modification of an organic material, wherein the mixture of the organic / inorganic base and the organic material is a mixture of the organic / inorganic base and the organic material in a volume ratio of 1:1 to 10.

15. A method for manufacturing Maxine organic ink, A step of manufacturing a two-dimensional maxine with an organic surface modification using a manufacturing method according to Article 13; and A method for manufacturing a MXene organic ink, comprising a step of dispersing the above organic surface-modified two-dimensional MXene in an organic solvent.

16. In paragraph 15, The above-mentioned solvent is an industrial organic solvent, and the method for manufacturing Maxine organic ink.

17. In paragraph 15, The above industrial organic solvents are, A method for producing a MXene organic ink, comprising at least one selected from 2-methoxy ethanol (2ME), propylene glycol methyl ether (PGME), tetrahydrofuran (THF), dimethylformamide, propyleneglycol monomethyl ether acetate (PGME), chloroform, diethylene glycol monobutyl ether, chlorobenzene, 1,2-dichlorobenzene, 1,2-dichloroethane, toluene, cyclohexanone, and methyl ethyl ketone (MEK).

18. In paragraph 15, A method for manufacturing a MXene organic ink, which is applied to at least one of an electrically conductive film, an electromagnetic shielding film, a MXene-polymer composite, an electromagnetic shielding MXene-polymer composite, an electromagnetic shielding MXene-polymer fiber, and a bioelectronic material.

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