KR102353597B1 - electrode material comprising metal-organic unimolecular and Mxene, Preparing method of the same - Google Patents

Abstract

The electrode material according to the present invention includes a maxine (MXene) layer having a terminal group; and a metal-organic monomolecule intercalated between the terminal groups of the aforementioned MXene layer. In this case, the above-mentioned maxine layer may be a laminate of unit maxine (Unit MXene) represented by the following formula (1).
[Formula 1]
M _n+1 X _n T _x
In the above-mentioned formula 1,
M is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), chromium (Cr), manganese (Mn), scandium (Sc), molybdenum (Mo), niobium (Nb) , is a transition metal selected from tantalum (Ta) or a combination thereof,
X is carbon (C), nitrogen (N), or a combination thereof,
n is an integer from 1 to 3,
T _x is a terminal group of the unit maxine, oxygen (O), hydroside (OH), epoxide, alkoxide having 1-5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

Description

Electrode material comprising metal-organic monomolecules and maxine, and manufacturing method thereof

The present invention relates to an electrode material and a method for manufacturing the same, and more particularly, to an electrode material containing maxine having an increased interlayer distance by a metal-organic single molecule and a method for manufacturing the same.

Graphene is a single atomic layer material composed of carbon atoms having a honeycomb structure. Because of its excellent physical properties such as very high electrical conductivity and mechanical strength, graphene is an electronic material, optoelectronic material, energy generation and storage, chemical sensor, physiological It is the most studied as an electrode material for applied devices. However, there are many difficulties in mass synthesizing high-quality graphene that is economical and consistent, and the degree of industrial application is low. Accordingly, studies on two-dimensional materials similar to graphene are being actively conducted.

MXene, one of the two-dimensional materials, has the mechanical strength and electrical conductivity similar to that of graphene, but has the advantage of being able to apply a solution process and thus can be mass-produced. are receiving However, the transition metal included in Maxine easily forms a transition metal oxide in an aqueous electrolyte, so that electrical activity is deteriorated. Therefore, in order to commercialize an electrode material including maxine, a technology capable of effectively preventing the oxidation of transition metal contained in maxine should be preceded.

Republic of Korea Patent Publication No. 10-2020-0052597

An object of the present invention is to provide an electrode material capable of providing a high capacitance by preventing oxidation of the electrode material and having improved electrical activity, and a method for manufacturing the same.

The present invention is a maxine (MXene) layer with end groups; It includes an electrode material including a metal-organic monomolecule intercalated between the terminal groups of the aforementioned MXene layer. In this case, the above-mentioned maxine layer may be a laminate of unit maxine (Unit MXene) represented by the following formula (1).

[Formula 1]

M _n+1 X _n T _x

In the above-mentioned formula 1,

M is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), chromium (Cr), manganese (Mn), scandium (Sc), molybdenum (Mo), niobium (Nb) , is a transition metal selected from tantalum (Ta) or a combination thereof,

X is carbon (C), nitrogen (N), or a combination thereof,

n is an integer from 1 to 3,

T _x is a terminal group of the unit maxine, oxygen (O), hydroside (OH), epoxide, alkoxide having 1-5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

The interlayer distance (d-spacing) of the electrode material according to an aspect of the present invention is calculated from the peak of the (002) plane on the X-ray diffraction pattern using CuKα ray, and may satisfy Equation 1 below.

(Equation 1)

(In Equation 1, D ₁ is the interlayer distance of the maxine layer before the metal-organic monomolecules are intercalated, and D ₂ is the interlayer distance of the maxine layer in which the metal-organic monomolecules are intercalated.)

In the electrode material according to an aspect of the present invention, the above-described electrode material maxine layer: metal-organic monomolecular weight ratio of 1: 0.05 to 2 may be.

In the electrode material according to an aspect of the present invention, the above-described metal-organic monomolecular organic monomolecule may include an amine group.

In the electrode material according to an aspect of the present invention, the above-described metal-organic monomolecular metal is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), zinc (Zn), cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), ruthenium (Ru) or these can be selected from a combination of

In addition, the present invention includes an energy storage device containing the above-described electrode material.

Furthermore, the present invention includes a method for manufacturing the electrode material described above.

In detail, the method of manufacturing an electrode material according to an aspect of the present invention comprises the steps of mixing a metal precursor, an organic single molecule containing an amine group, a maxine layer, and a solvent; and heat-treating after adding a reducing agent to the mixture of the mixing step.

In the method for manufacturing an electrode material according to an aspect of the present invention, the above-described maxine layer: metal precursor: the weight ratio of the organic monomer containing an amine group may be 1: 0.03 to 0.3: 0.01 to 0.05.

In the method of manufacturing an electrode material according to an aspect of the present invention, the above-described metal precursor is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au) ), nickel (Ni), zinc (Zn), cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), ruthenium (Ru), or combinations thereof It may include at least one selected from the group consisting of halogen salts, phosphates, nitrates, sulfates, ammonium salts, acetates and carbonates of a metal selected from

In the method for manufacturing an electrode material according to an aspect of the present invention, the organic monomolecules including the above-described amine group may be organic monomolecules represented by the following Chemical Formula 2 or salts thereof.

[Formula 2]

Ar-[NH ₂ ] _n

In Formula 2,

Ar is C6 to C30 aryl, specifically C6 to C12 aryl, more specifically phenyl, naphthyl, or a combination thereof;

n is an integer corresponding to the number of substituents in Ar, specifically, an integer of 4 or more.

In the method of manufacturing an electrode material according to an aspect of the present invention, the above-described reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ), hydrogen iodide (HI), hydrogen sulfide (H ₂ S), dimethylhydrazine, hydroquinone, sulfuric acid (H ₂ SO ₄ ), aluminum powder, and combinations thereof may be selected from the group consisting of.

In the method of manufacturing an electrode material according to an aspect of the present invention, the above-described solvent is formamide (FA), N-methylformamide (NMFA), N,N-dimethylformamide (DMF), acetamide (AA) , N-methylacetamide (NMAA), N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), propylene carbonate (Propylene carbonate), or a mixture thereof.

In the method of manufacturing an electrode material according to an aspect of the present invention, the above-described heat treatment may be performed in a temperature range of 15 to 150 °C.

The electrode material according to the present invention contains maxine having an increased interlayer distance by a metal-organic monomolecule, and thus can have improved electrical conductivity, thereby providing an energy storage device having a remarkably improved capacitance.

1 is a result of analyzing the physical properties of an electrode material according to the present invention by X-ray photoelectron spectroscopy (XPS).
2 is a scanning electron microscope (SEM) image showing the microstructure of the electrode material according to the present invention.
3 is an X-ray diffraction analysis (XRD) result of the electrode material according to the present invention.
4 is a graph showing a cyclic voltage and current curve of a capacitor using the electrode material according to the present invention as an electrode.

Hereinafter, an electrode material and a manufacturing method thereof of the present invention will be described in detail with reference to the accompanying drawings. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, if there is no other definition in the technical terms and scientific terms used, it has the meaning commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the summary of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted. Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise. In this specification and the appended claims, the units used without special mention are based on weight, and in one example, the unit of % or ratio means weight % or weight ratio.

The present invention is a maxine (MXene) layer with end groups; It includes an electrode material including a metal-organic monomolecule intercalated between the terminal groups of the maxine layer described above. In detail, the electrode material according to the present invention may include a maxine layer having an increased interlayer distance (d-spacing) by metal-organic monomolecules. When an electrode material containing a maxine layer having an increased interlayer distance by such metal-organic monomolecules is used as an electrode of an energy storage device such as a capacitor, oxidation of the electrode material can be prevented, thereby providing excellent electrical activity It is good that it can have a significantly increased storage capacity.

In this case, the above-mentioned maxine layer may be a laminate of unit maxine (Unit MXene) represented by the following formula (1).

[Formula 1]

M _n+1 X _n T _x

In the above-mentioned formula 1,

M is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), chromium (Cr), manganese (Mn), scandium (Sc), molybdenum (Mo), niobium (Nb) , is a transition metal selected from tantalum (Ta) or a combination thereof,

X is carbon (C), nitrogen (N), or a combination thereof,

n is an integer of 1 or more, specifically an integer of 1 to 3,

T _x is a terminal group bonded to the transition metal M of the unit maxine, oxygen (O), hydroside (OH), epoxide, alkoxide having 1-5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br) ), iodide (I), or a combination thereof.

That is, the maxine layer according to an aspect of the present invention may be one in which the _{unit maxine (Unit MXene) of the M n+1} X _n T _x structure is laminated in at least 10 layers, specifically 10 to 500 layers, but the present invention However, the present invention is not limited thereto, and a laminate in which at least 10 units of the maxine of the _{M n+1} X _n T _{x structure are stacked is sufficient.}

In one non-limiting example, the above-described unit maxin is Ti ₂ CT _x , (Ti _0.5 , Nb _0.5 ) ₂ CT _x , Sc ₂ CT _x , V ₂ CT _x , Nb ₂ CT _x , Mo ₂ CT _x , Ti ₃ C ₂ T _x , Ti ₃ CNT _x , Zr ₃ C ₂ T _x , Hf ₃ C ₂ T _x , Ti ₄ N ₃ T _x , Nb ₄ C ₃ T _x , Ta ₄ C ₃ T _x , Mo ₂ TiC ₂ T _x , Cr ₂ TiC ₂ T _x and Mo ₂ Ti ₂ C ₃ T _{x It} may be one or more selected from the group consisting of, but is not limited thereto, and a two-dimensional transition metal nitride or a two-dimensional transition metal carbide is sufficient.

In a non-limiting example, the diameter of the maxine layer described above may be 50 nm to 20 μm, specifically 100 nm to 10 μm, and the thickness of the maxine layer may be 0.1 to 10 nm, specifically 0.5 to 5 nm, but , but is not limited thereto.

In one embodiment, the metal-organic single molecule contained in the electrode material according to the present invention may be a complex in which a metal and an organic single molecule are coordinated.

In one embodiment, the above-described organic monomolecules may be organic monomolecules represented by the following Chemical Formula 2 or salts thereof. In this case, the above-mentioned salt may be an acid salt, but is not limited thereto.

[Formula 2]

Ar-[NH ₂ ] _n

In the above-mentioned formula 2,

Ar is C6 to C30 aryl, specifically C6 to C12 aryl, more specifically phenyl, naphthyl, or a combination thereof;

n is an integer corresponding to the number of substituents in Ar, specifically, an integer of 4 or more.

In this case, Ar, which is the central organic molecule of the above-described organic monomolecule, may include nitrogen of the above-described amine group as a coordination atom, but may have at least two or more coordination atoms on the same plane.

As a non-limiting example, the above-described organic monomolecules may be 1,2,4,5-Benzenetetramine tetrahydrochloride (BTA), 1,2,4,5-benzenetetrathiol, 1,2,4,5-benzenetetrol, etc. It is not limited thereto.

The above-mentioned metal is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), zinc (Zn), cobalt (Co) , chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), may be selected from ruthenium (Ru) or a combination thereof, but is not limited thereto, and if a metal having conductivity enough

In one embodiment, the maxine layer contained in the electrode material according to the present invention: the weight ratio of the metal-organic monomolecule is 1: 0.05 to 2, preferably 1: 0.05 to 0.5, more preferably 1: 0.08 to 0.2. have. When the electrode material contains the maxine layer and the metal-organic monomolecules in this weight ratio, the interlayer distance of the maxine layer may be constantly increased by the metal-organic monomolecules. However, if the content of metal-organic monomolecules is high compared to the content (weight) of the maxine layer, the transition metal and metal-organic monomolecular metal in the maxine layer are oxidized, and there is a risk of collapsing the two-dimensional layered structure of the electrode material. , it is preferable to include a small amount of metal-organic monomolecules compared to the maxine layer. In detail, when the content of metal-organic monomolecules is small compared to the content of the maxine layer, the maxine layer has an interlayer distance that is constantly increased by the metal-organic monomolecules, and the two-dimensional layered structure can be maintained without collapsing. good to have

Looking at the X-ray photoelectron spectroscopy (XPS) analysis result of FIG. 1, the electrode material according to the present invention has metal peaks (Ni and Ti) combined with oxygen on Ni 2p, Ni 1s, and Ti 2p spectra. may not exist. In the case of the electrode material including the conventional maxine layer, it is vulnerable to oxidation, and the transition metal present on the surface of the maxine layer is changed to a transition metal oxide, so that the structure and characteristics are changed, so there is a problem in that the storage capacity is lowered. Therefore, in the case of the conventional electrode material, a separate antioxidant, etc. is added to prevent oxidation of the transition metal in the maxine layer, but the antioxidant has a disadvantage in reducing the intrinsic properties of the maxine layer. However, in the case of the electrode material according to the present invention, it is possible to maintain the two-dimensional layered structure without oxidation of the surface of the maxine layer, even though it does not contain many additives such as antioxidants, so it can have improved storage capacity and stable performance. good.

In one embodiment, the interlayer distance of the maxine layer contained in the electrode material means the distance between the terminal groups of the maxine layer, and the above-described interlayer distance is (002) on the X-ray diffraction analysis (XRD) pattern using CuKα ray. _{) plane peak, specifically, the interplanar distance (D 1} ) calculated from the peak appearing at 2θ of 8 to 10° on the XRD pattern of the maxine layer in which the metal-organic monomolecules are not intercalated and the metal-organic monomolecules are intercalated _{It is calculated from the interplanar distance (D 2} ) calculated from the peak appearing at 2θ of 5 to 7° on the XRD pattern of the maxine layer, and may satisfy Equation 1 below.

(Equation 1)

However, in terms of maintaining a stable two-dimensional structure and not oxidizing the surface of the maxine layer having an increased interlayer distance by the metal-organic monomolecules, the interlayer distance ratio according to Equation 1 is 3 or less, specifically 2 or more, more specifically may be less than or equal to 1.8. As a practical example, the interlayer distance ratio according to Equation 1 may be 1.3 to 1.73, and more specifically, 1.4 to 1.5.

In addition, the present invention includes an energy storage device containing the above-described electrode material, specifically, a capacitor. Accordingly, when an electrode material containing a maxine layer having an increased interlayer distance by a metal-organic monomolecule is used as an electrode for a capacitor, it can have a significantly increased storage capacity than when a conventional maxine layer is used as an electrode.

Furthermore, the present invention includes a method for manufacturing the electrode material described above.

In detail, the method for manufacturing an electrode material according to an aspect of the present invention comprises the steps of: a) mixing a metal precursor, an organic monomolecule containing an amine group, a maxine layer, and a solvent; and b) adding a reducing agent to the mixture of the mixing step and then heat-treating the mixture.

In one embodiment, the method of manufacturing an electrode material according to the present invention is a three-dimensional inorganic compound, Max (MAX, where M is a transition metal, A is a group 13 or group 14 element, X, before performing step a) may further comprise the step of preparing a maxine layer from carbon or nitrogen). In detail, by introducing MAX into a strong acid solution containing a fluorine compound, it may be prepared by selectively removing the A layer from the MAX.

At this time, the aforementioned Ti ₂ CdC, Sc ₂ InC, Ti ₂ AlC, Ti ₂ GaC, Ti ₂ InC, Ti ₂ TIC, V ₂ AlC, V ₂ GaC, Cr ₂ GaC, Ti ₂ AlN, Ti ₂ GaN, Ti ₂ InN, V ₂ GaN, Cr ₂ GaN, Ti ₂ GeC, Ti ₂ SnC, Ti ₂ PbC, V ₂ GeC, Cr ₂ AlC, Cr ₂ GeC, V ₂ PC, V ₂ AsC, Ti ₂ SC, Zr ₂ InC, Zr ₂ TlC, Nb ₂ AlC, Nb ₂ GaC, Nb ₂ InC, Mo ₂ GaC, Zr ₂ InN, Zr ₂ TlN, Zr ₂ SnC, Zr ₂ PbC, Nb ₂ SnC, Nb ₂ PC, Nb ₂ AsC, Zr ₂ SC, Nb2SC, Hf ₂ InC, Hf ₂ TlC, Ta ₂ AlC, Ta ₂ GaC, Hf ₂ SnC, Hf ₂ PbC, Hf ₂ SnN, Hf ₂ SC; Ti ₃ AlC ₂ , V ₃ AlC ₂ , Ti ₃ SiC ₂ , Ti ₃ GeC ₂ , Ti ₃ SnC ₂ , Ta ₃ AlC ₂ ; One or more of Ti ₄ AlN ₃ , V ₄ AlC ₃ , Ti ₄ GaC ₃ , Ti ₄ SiC ₃ , Ti ₄ GeC ₃ , Nb ₄ AlC ₃ , and Ta ₄ AlC ₃ may be selected, but is not limited thereto.

In addition, the above-described fluorine compound is lithium fluoride (LiF), sodium fluoride (NaF), magnesium fluoride (MgF ₂ ), strontium fluoride (SrF ₂ ), beryllium fluoride (BeF ₂ ), calcium fluoride (CaF ₂ ), ammonium fluoride ( NH ₄ F), _{ammonium difluoride (NH 4} HF ₂ ) and ammonium hexafluoroaluminate ((NH ₄ ) ₃ AlF ₆ ) may be any one or a mixture of two or more selected from, and the strong acid solution is chlorohydrofluoric acid ( HF), hydrochloric acid (HCl), sulfuric acid (HSO ₄ ) may be any one or a mixture of two or more selected from an aqueous solution, but is not limited thereto.

That is, as the maxine layer of step a) was prepared using a strong acid solution containing MAX and a fluorine compound, the prepared maxine layer has transition metal M on the surface of oxygen (O), hydroside (OH), and epoxide. Bonds with a _{terminal group (T x} ) containing side, an alkoxide having 1 to 5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br), iodide (I), or a combination thereof may be in the form of Accordingly, the above-described maxine layer may be a laminate of unit maxine (Unit MXene) represented by the following formula (1).

[Formula 1]

M _n+1 X _n T _x

In the above-mentioned formula 1,

M is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), chromium (Cr), manganese (Mn), scandium (Sc), molybdenum (Mo), niobium (Nb) , is a transition metal selected from tantalum (Ta) or a combination thereof,

X is carbon (C), nitrogen (N), or a combination thereof,

n is an integer from 1 to 3,

T _x is a terminal group bonded to the transition metal M of the unit maxine, oxygen (O), hydroside (OH), epoxide, alkoxide having 1-5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br) ), iodide (I), or a combination thereof.

That is, the above-described maxine layer may be one in which at least 10 or more, specifically, 10- to 500-layered unit maxine _{of the M n+1} X _n T _{x structure is laminated, but the present invention is not limited thereto.} , M _n+1 X _n T _{x A} laminate in which at least 10 units of the maxine structure are stacked is sufficient.

In one non-limiting example, the above-described unit maxin is Ti ₂ CT _x , (Ti _0.5 , Nb _0.5 ) ₂ CT _x , Sc ₂ CT _x , V ₂ CT _x , Nb ₂ CT _x , Mo ₂ CT _x , Ti ₃ C ₂ T _x , Ti ₃ CNT _x , Zr ₃ C ₂ T _x , Hf ₃ C ₂ T _x , Ti ₄ N ₃ T _x , Nb ₄ C ₃ T _x , Ta ₄ C ₃ T _x , Mo ₂ TiC ₂ T _x , Cr ₂ TiC ₂ T _x and Mo ₂ Ti ₂ C ₃ T _{x It} may be one or more selected from the group consisting of, but is not limited thereto, and a two-dimensional transition metal nitride or a two-dimensional transition metal carbide is sufficient.

In one embodiment, the metal precursor of step a) is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), Halogen salt of a metal selected from zinc (Zn), cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), ruthenium (Ru), or a combination thereof , phosphate, nitrate, sulfate, ammonium salt, acetate, and may include one or more selected from the group consisting of carbonate, but is not limited thereto.

In one embodiment, the organic monomolecule including the amine group in step a) may be an organic monomolecule represented by the following Chemical Formula 2 or a salt thereof. In this case, the above-mentioned salt may be an acid salt, but is not limited thereto.

[Formula 2]

Ar-[NH ₂ ] _n

In the above-mentioned formula 2,

Ar is C6 to C30 aryl, specifically C6 to C12 aryl, more specifically phenyl, naphthyl, or a combination thereof;

n is an integer corresponding to the number of substituents in Ar, specifically, an integer of 4 or more.

In this case, Ar, which is the central organic molecule of the above-described organic monomolecule, may include nitrogen of the above-described amine group as a coordination atom, but may have at least two or more coordination atoms on the same plane.

As a non-limiting example, the above-described organic monomolecules may be 1,2,4,5-Benzenetetramine tetrahydrochloride (BTA), 1,2,4,5-benzenetetrathiol, 1,2,4,5-benzenetetrol, etc. It is not limited thereto.

In step a), the above-described maxine layer: metal precursor: the weight ratio of the organic monomer containing an amine group is 1: 0.01 to 1.2: 0.01 to 0.5, preferably 1: 0.03 to 0.3: 0.01 to 0.05, more preferably 1: 0.05 to 0.12: It may be 0.02 to 0.04. When the above-described weight ratio is satisfied, the maxine layer contained in the electrode material may have an interlayer distance constantly increased by the metal-organic monomolecules. However, if the content of the metal precursor and organic monomolecules is high compared to the content (weight) of the maxine layer, the transition metal in the maxine layer and the metal in the metal-organic monomolecular intercalated between layers are oxidized, and the two-dimensional layered structure of the electrode material collapses Since there is a risk of becoming a layer, it is preferable to include a small amount of metal precursors and organic monomolecules compared to the maxine layer. When the content (weight) of the metal precursor and the organic monomolecules is small compared to the maxine layer, the maxine layer can have an interlayer distance that is constantly increased by the metal-organic monomolecules, and can prevent surface oxidation of the electrode material. It is good that the layered structure can be maintained as it is without collapsing.

As a non-limiting example, the solvent of step a) is a polar solvent, specifically formamide (FA), N-methylformamide (NMFA), N,N-dimethylformamide (DMF), acetamide (AA), N -Methylacetamide (NMAA), N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), propylene carbonate (Propylene carbonate) or a mixture thereof may be used. However, the present invention is not limited thereto, and any polar solvent generally used in the field of manufacturing electrode materials is sufficient.

In one embodiment, the heat treatment of step b) may be performed in a temperature range of 15 to 150 °C, preferably in a temperature range of 30 to 100 °C, more preferably in a temperature range of 30 to 50 °C. However, when the temperature range of 30 to 100 ℃ is satisfied, the oxidation reaction of the metal (including the transition metal) in the electrode material is not induced, so the maxine layer has an increased interlayer distance due to the metal-organic monomolecules, and the two-dimensional The layered structure can be maintained as it is.

At this time, the sphere heat treatment time is not limited, but may be performed for 1 to 50 hours, specifically 10 to 40 hours, and more specifically 20 to 30 hours.

As a non-limiting example, the reducing agent of step b) is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ), hydrogen iodide (HI), hydrogen sulfide (H ₂ S), dimethylhydrazine, hydroquinone, sulfuric acid (H ₂ SO ₄ ), may be selected from the group consisting of aluminum powder and combinations thereof, but is not limited thereto.

Hereinafter, the present application will be described in more detail using examples, but the following examples are only illustrative to help the understanding of the present application, and the content of the present application is not limited to the following examples.

(Example 1)

Step 1: Ti ₃ C ₂ T _x Produce

First, _{1 g of Ti 3} AlC ₂ (Khantal, Sweden, 325 mesh) was slowly added to a Teflon flask containing 50 mL of a 50 wt.% hydrofluoric acid solution for about 30 minutes, followed by stirring at room temperature for 5 hours. Next, the resultant (Ti ₃ C ₂ T _x ) obtained after stirring was washed with 500 mL of distilled water and then centrifuged to remove the remaining hydrofluoric acid and residues. Finally, after filtering using 100 mL of ethanol until the pH of the material obtained through centrifugation reached 4-6, it was dried in a vacuum oven at 120° C. for 1 day to obtain _{Ti 3} C ₂ T _{x .} .

Step 2: Ti ₃ C ₂ T _x @Ni-BTA manufacturing

_{Ti 3} C ₂ T _x 100 mg obtained in Preparation Example 1, nickel nitrate hexahydrate (Nickel nitrate hexahydrate, Ni(NO ₃ ) ₂ .6H ₂ O)) 90 mg, 1,2,4,5-benzenetetra After mixing 35 mg of amine tetrahydrochloride (1,2,4,5-Benzenetetramine tetrahydrochloride; BTA, C ₆ H ₂ (NH ₂ ) ₄ .4HCl) in 100 mL of dimethylformamide (DMF), the mixture To the aqueous ammonia (Ammonium hydroxide, NH ₄ OH) 1 mL was slowly added for about 1 minute, and reacted at 25 ℃ for 24 hours. Next, the solid powder obtained after the reaction was washed several times with acetone and water, dried in a vacuum oven at 80 ° C. for 1 hour, and Ti ₃ C ₂ T _x (Ti ₃ C _{2 ) intercalated with Ni-BTA.} T _x @NI-BTA).

(Example 2)

In Example 1, except that the reaction temperature was 40 °C, the same method as in Example 1 was used.

(Example 3)

In Example 1, except that the reaction temperature was 80 °C, the same method as in Example 1 was used.

(Example 4)

In step 2 of Example 1, Ni(NO ₃ ) ₂ ·6H ₂ O and BTA were used by changing the weights of 9 mg and 3.5 mg, respectively, except that the same method as in Example 1 was used.

(Example 5)

In Example 4, except that the reaction temperature was 40 °C, the same method as in Example 4 was used.

(Example 6) Method for preparing Mxene in which Ni-BTA was synthesized

In Example 4, except that the reaction temperature was 80 °C, the same method as in Example 4 was used.

(Comparative Example 1)

_{Ti 3} C ₂ T _x prepared in step 1 of Example 1 was used as Comparative Example 1.

(Comparative Example 2) Ni-BTA preparation

First, after mixing 90 mg of Ni(NO ₃ ) ₂ .6H ₂ O and 35 mg of BTA in 100 mL of DMF, _{1 mL of NH 4} OH was slowly added to the mixture for about 1 minute, and at 80° C. for 24 hours. reacted. Next, the solid powder obtained after the reaction was washed several times with acetone and water, and then dried in a vacuum oven at 80° C. for 1 hour to obtain Ni-BTA.

1 is a result of analyzing the physical properties of an electrode material according to the present invention by X-ray photoelectron spectroscopy (XPS). First, looking at the results of Ni 2p and Ni 1s, which are metals derived from metal-organic monomolecules, NiO peaks are observed in Examples 1 to 3, in which the content (weight) of metal-organic monomolecules is high compared to the maxine layer. On the other hand, it can be seen that the NiO peak was not observed in Examples 4 to 6, in which the content (weight) of metal-organic monomolecules was low compared to the maxine layer. In addition, looking at the results of Ti 2p, which is a transition metal derived from the maxine layer, in Examples 1 to 3, TiO ₂ peaks (in the figure, ^{corresponding to Ti 4+} peaks) are observed, whereas those of Examples 4 to 6 In this case, it can be seen that _{the TiO 2 peak is not observed.} As can be seen from the results, as the content (weight) of the metal-organic monomolecules is lower than that of the maxine layer, only the metal-organic monomolecules are selectively formed without oxidation of the metal, and the surface oxidation of the transition metal in the maxine layer is reduced. can be seen to be prevented.

2 is a scanning electron microscope (SEM) image showing the microstructure of the electrode material according to the present invention. As shown, in Examples 1 to 3 (maxine layer: weight ratio of metal-organic monomolecule = 1:1.25) having a high content (weight) of metal-organic monomolecules compared to the maxine layer, oxides were observed on the surface of the maxine, , it can be seen that the two-dimensional layered structure is collapsed. On the other hand, in the case of Examples 4 to 6 (maxine layer: weight ratio of metal-organic monomolecule = 1: 0.125) in which the content (weight) of metal-organic monomolecules compared to the maxine layer is very low, without surface oxidation of the electrode material, It can be observed that the two-dimensional layered structure is maintained as it is. This is considered to be because Examples 4 to 6 contained a smaller amount of Ni than Examples 1 to 3.

In more detail, the microstructure of the electrode material was analyzed through X-ray diffraction analysis (XRD). 3 is an X-ray diffraction analysis (XRD) result of the electrode material according to the present invention. From the XRD analysis result of FIG. 3 , the interlayer distance of Maxine was calculated through the peak for the (002) plane. As a result, the interlayer distance of Comparative Example 1, which is pure maxine, is 0.9 nm, and the interlayer distance of Example 1 (Maxine layer: weight ratio of metal-organic monomolecules = 1: 1.25, heat treatment temperature = 25 ° C.) is 1.57 nm, Example 5 (Maxine layer: weight ratio of metal-organic monomolecules = 1: 0.125, heat treatment temperature = 40 ° C.), the interlayer distance was 1.42 nm, Example 6 (Maxine layer: weight ratio of metal-organic monomolecules = 1: 0.125, heat treatment temperature = 80° C.) and the interlayer distance is 1.42 nm. As can be seen from the results, it can be seen that the interlayer distance of Examples is increased by about 1.5 times or more than Comparative Example 1. On the other hand, Example 2 (maxine layer: weight ratio of metal-organic monomolecules = 1: 1.25, heat treatment temperature = 40 ° C) and Examples having the same weight ratio as Example 1 but having a higher reaction temperature (heat treatment temperature) than Example 1 In the case of 3 (maxine layer: metal-organic monomolecular weight ratio = 1: 1.25, heat treatment temperature = 80 °C), a peak for the (002) plane cannot be observed. Through this, it can be seen that the higher the heat treatment temperature, the more the metal (Ni) derived from the metal-organic monomolecules is oxidized and the two-dimensional layered structure is collapsed. On the other hand, Example 5 (Maxine layer: weight ratio of metal-organic monomolecules = 1: 0.125, heat treatment temperature = 40 °C) and Example 6 (Maxine layer: weight ratio of metal-organic monomolecules = 1: 0.125, heat treatment temperature) = 80 ° C), although the heat treatment temperature is high as in Examples 2 and 3, a distinct peak for the (002) plane can be observed as the reaction temperature increases. Through this, it can be seen that when the metal-organic monomolecule is included less than that of the maxine layer, the oxidation reaction of the metal-organic monomolecule is not induced and the two-dimensional structure is maintained despite the high heat treatment temperature.

4 is a graph showing a cyclic voltage and current curve of a capacitor using the electrode material according to the present invention as an electrode. In detail, Fig. 4 (a) is _{a cyclic voltage current curve of a capacitor using pure Ti 3} C ₂ T _x of Comparative Example 1 as an electrode, and Fig. 4 (b) is a pure Ni-BTA of Comparative Example 2 as an electrode. It is a cyclic voltage current curve of the capacitor used, and FIG. 4(c) shows Example 1 (Ti ₃ C ₂ T _x @Ni-BTA, maxine layer: metal-organic monomolecular weight ratio = 1: 1.25, heat treatment temperature = 25 ℃) is a cyclic voltage and current curve of a capacitor using an electrode material as an electrode, and FIG. 4 (d) is Example 2 (Ti ₃ C ₂ T _x @Ni-BTA, maxine layer: metal-organic monomolecular weight ratio) = 1: 1.25, heat treatment temperature = 40 ℃) is a cyclic voltage and current curve of a capacitor using an electrode material as an electrode, Figure 4 (e) is Example 3 (Ti ₃ C ₂ T _x @Ni-BTA, Maxine layer: - a cyclic voltammetry curve of the capacitor using the electrode material according to 1.25, the heat treatment temperature = 80 ℃) as an electrode, (f) of Figure 4 example 4 (Ti ₃ C metal organic monomolecular weight ratio = 1 ₂ T _x @Ni-BTA, maxine layer: metal-organic monomolecular weight ratio = 1: 0.125, heat treatment temperature = 25 ° C.) is a cyclic voltage and current curve of a capacitor using an electrode material as an electrode, ) is the cycle voltage of the capacitor using the electrode material according to Example 5 (Ti ₃ C ₂ T _x @Ni-BTA, maxine layer: metal-organic monomolecular weight ratio = 1: 0.125, heat treatment temperature = 40 ° C) as an electrode It is a current curve, and (h) of FIG. 4 is an electrode according to Example 6 (Ti ₃ C ₂ T _x @Ni-BTA, maxine layer: metal-organic monomolecular weight ratio = 1: 0.125, heat treatment temperature = 80 ° C) This is the cyclic voltage and current curve of a capacitor using a material as an electrode. At this time, the cyclic voltammetry curve was analyzed in the range of -0.5-0.5 V with a scan rate of 1 to 100 mV/s through the two-electrode system. As shown, it can be seen that Comparative Examples 2, 1, 2, and 3 had low current densities, and the shape of the cyclic voltammetry curve was not suitable as an electrode for an energy storage device. That is, Comparative Example 2, Example 1, Example 2, and Example 3 have low application potential as electrodes for energy storage devices. On the other hand, in Examples 4, 5 and 6, it can be seen that the cyclic voltammetry curve has a shape that is relatively closer to a rectangle than that of Comparative Example 1. Through this, it can be seen that Examples 4 to 6, in which the content of metal-organic monomolecules is very low compared to the maxine layer, have excellent capacitance even at a high scan speed.

As described above, the present invention has been described with reference to specific matters and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (13)

MXene layer with end groups; It comprises a metal-organic monomolecule intercalated between the terminal groups of the MXene layer,
The metal-organic monomolecules of the organic monomolecules include an amine group,
The maxine layer is a laminate of the unit maxine (Unit MXene) represented by the following formula (1), an electrode material.
[Formula 1]
M _n+1 X _n T _x
In Formula 1,
M is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), chromium (Cr), manganese (Mn), scandium (Sc), molybdenum (Mo), niobium (Nb) , is a transition metal selected from tantalum (Ta) or a combination thereof,
X is carbon (C), nitrogen (N), or a combination thereof,
n is an integer from 1 to 3,
T _x is a terminal group of the unit maxine, oxygen (O), hydroside (OH), epoxide, alkoxide having 1-5 carbon atoms, fluoride (F), chloride (Cl), bromide (Br), iodide (I), or a combination thereof. According to claim 1,
The interlayer distance (d-spacing) of the electrode material is calculated from the peak of the (002) plane on the X-ray diffraction analysis pattern using CuKα ray, and satisfies Equation 1 below.
(Equation 1)

(In Equation 1, D ₁ is the interlayer distance of maxine before the metal-organic monomolecules are intercalated, and D ₂ is the interlayer distance of maxine in which the metal-organic monomolecules are intercalated.) According to claim 1,
The maxine layer: the weight ratio of the metal-organic single molecule is 1: 0.05 to 0.5, the electrode material. delete According to claim 1,
The metal of the metal-organic monomolecule is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), zinc (Zn) , selected from cobalt (Co), chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), ruthenium (Ru), or a combination thereof, the electrode material. An energy storage device comprising the electrode material according to any one of claims 1 to 3 and 5. mixing a metal precursor, an organic monomer containing an amine group, a Mxene layer, and a solvent; and heat-treating after adding a reducing agent to the mixture of the mixing step. 8. The method of claim 7,
The maxine layer: the metal precursor: the weight ratio of the organic monomer containing an amine group is 1: 0.03 to 0.3: 0.01 to 0.05, the method of manufacturing an electrode material. 8. The method of claim 7,
The metal precursor is silver (Ag), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), zinc (Zn), cobalt (Co) , chromium (Cr), manganese (Mn), iron (Fe), rhodium (Rh), palladium (Pd), ruthenium (Ru) or a combination thereof halogen salt, phosphate, nitrate, sulfate, ammonium salt, A method of manufacturing an electrode material comprising at least one selected from the group consisting of acetate and carbonate. 8. The method of claim 7,
The method for producing an electrode material, wherein the organic monomolecules containing the amine group are organic monomolecules represented by the following Chemical Formula 2 or salts thereof.
[Formula 2]
Ar-[NH ₂ ] _n
In Formula 2,
Ar is C6 to C30 aryl, specifically C6 to C12 aryl, more specifically phenyl, naphthyl, or a combination thereof;
n is an integer corresponding to the number of substituents in Ar, specifically, an integer of 4 or more. 8. The method of claim 7,
The reducing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH ₄ OH), sodium borohydride (NaBH ₄ ), hydrazine (N ₂ H ₄ ), hydrogen iodide (HI), hydrogen sulfide (H ₂ S) ), dimethylhydrazine, hydroquinone, sulfuric acid (H ₂ SO ₄ ), aluminum powder, and a method of manufacturing an electrode material that is selected from the group consisting of combinations thereof. 8. The method of claim 7,
The solvent is formamide (FA), N-methylformamide (NMFA), N,N-dimethylformamide (DMF), acetamide (AA), N-methylacetamide (NMAA), N-dimethylacetamide ( DMA), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), propylene carbonate (Propylene carbonate), or a mixture thereof, a method of manufacturing an electrode material. 8. The method of claim 7,
The heat treatment is performed in a temperature range of 15 to 150 ℃, the method of manufacturing an electrode material.

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