KR102487821B1 - Composition for three-dimensional lamination, electrode comprising the same, and method for manufacturing electrode - Google Patents

Abstract

The present invention is a composition for three-dimensional stacking comprising a metal-organic framework (MOF) precursor including a solvent, an organic ligand and a metal precursor, wherein the metal-organic framework has organic ligands attached to metal ions of the metal precursor. It relates to a composition for 3D stacking characterized in that it is coordinated, an electrode including the composition for 3D stacking, a method for manufacturing the same, and an electronic device including the electrode.

Description

Composition for 3-dimensional lamination, electrode including the same, and manufacturing method thereof

The present invention relates to a composition for 3D stacking, in particular, a metal-organic framework (which can be applied to anode materials for batteries for 3D printing electrode materials, catalysts, gas sensors, mobile IT devices, electric vehicles (EV), and energy storage devices (ESS)). It relates to a composition for three-dimensional layering based on MOF), an electrode including the same, and a manufacturing method thereof.

Lithium secondary batteries are used in small home appliances such as smartphones and laptops, as well as medium and large-sized energy storage devices for electric vehicles. In addition, since the Paris Climate Agreement in 2015, more than 200 countries, including developing countries, have been obligated to reduce greenhouse gas emissions, and Germany (after 2030), the United Kingdom, and France (after 2040) will limit new vehicle sales of internal combustion engine vehicles. The ban is expected to increase the global demand for electric vehicles. As of 2016, the cathode and anode materials market was $6.3 billion, and is expected to reach $15 billion in 2020.

Metal-organic frameworks (MOFs), porous crystalline materials made by coordination bonding of metal ions and organic linkers, have attracted much attention as pioneers in developing stable nanoparticles for catalysis, gas storage, sensors, and energy-related applications.

Due to the discovery of more than 20,000 Metal-Organic Frameworks (MOFs) with a vast array of advanced functions, building blocks such as various metal nodes and organic linkers Numerous studies on the synthesis of MOFs have been conducted over the past decades by a rich variety of building blocks. In this regard, the basic synthesis protocol of the MOF is by self-assembly of building blocks such as metal nodes and organic interconnects, and has a relatively simple synthesis method.

Ni-based metal-organic frameworks have high electrical conductivity and uniform micropore size, and thus are attracting attention as next-generation electrode materials. The technology of the present patent invention is to design an electrode of a desired shape by utilizing a metal-organic framework precursor solution as a 3D printing solution. Electrodes designed in a specific shape by 3D printing can be used as energy storage electrodes, electrochemical catalysts, and sensors due to the high electrical conductivity and uniform pore size of the metal-organic framework.

The present invention has been made to solve the above problems, and one aspect of the present invention is a composition for 3D stacking that can design an electrode of a desired shape by using a metal organic framework (MOF) precursor solution as a 3D printing solution. to provide.

In addition, another embodiment of the present invention provides a method for manufacturing an electrode comprising the step of forming an electrode by discharging the composition for three-dimensional stacking using a 3D printer.

In addition, another embodiment of the present invention provides an electrode manufactured by the above manufacturing method.

Another embodiment of the present invention provides an electronic device including the electrode.

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned technical problem, and other technical problems not mentioned are clearly understood by those skilled in the art from the description below. It could be.

As a technical means for achieving the above-described technical problem, one aspect of the present invention,

A composition for three-dimensional stacking comprising a metal-organic framework (MOF) precursor including a solvent, an organic ligand and a metal precursor, wherein the metal-organic framework is a metal ion of the metal precursor coordinated with an organic ligand. Characterized in that, it provides a composition for three-dimensional lamination.

The organic ligand may be characterized by being represented by any one of Formulas 1 to 4 below.

[Formula 1]

In Formula 1, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are They may be the same as or different from each other.

[Formula 2]

In Formula 2, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are They are the same as or different from each other, and n may be an integer from 0 to 5.

[Formula 3]

In Formula 3, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are are the same as or different from each other, and R1 to R6 are each independently hydrogen, straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain of C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

[Formula 4]

In Formula 4, X1 to X6 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X5 and X6 are are the same as each other, X1, X3 and X5 are the same as or different from each other, and Y1 to Y6 may each independently represent carbon or nitrogen.

The metal precursor is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, A metal selected from the group consisting of Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub, and combinations thereof. can

The composition for 3D stacking may further include an additive.

The composition for 3D stacking may further include at least one first additive selected from the group consisting of lithium-metal oxide and activated carbon (AC).

The composition for 3D stacking may further include at least one second additive selected from the group consisting of a binder, a conductive material, and a reaction initiator.

The lithium-metal oxide is one selected from the group consisting of lithium titanate (LTO), lithium vanadium oxide (LVO), lithium-vanadium phosphate (LVP), and mixtures thereof can be characterized.

1 to 50 parts by weight of a solvent based on 100 parts by weight of the composition for 3D stacking; 20 to 65 parts by weight of an organic ligand; 15 to 60 parts by weight of a metal precursor; 0 to 30 parts by weight of the first additive; And 0 to 20 parts by weight of the second additive; can be characterized by comprising a.

In addition, another aspect of the present invention,

discharging the composition for three-dimensional lamination according to claim 1 using a 3D printer; and forming a metal-organic framework (MOF) by heat-treating the ejected composition for 3D lamination, wherein the heat treatment is carried out after or after the step of discharging the 3D lamination composition. It provides a method for producing an electrode, characterized in that it proceeds simultaneously with.

The heat treatment may be performed at a temperature of 100 ° C to 120 ° C.

The heat treatment may be performed for 2.5 to 4 hours.

The electrode may be formed to be patterned in an interdigitated structure.

It may be characterized in that the inner diameter of the nozzle of the 3D printer for discharging the three-dimensional layering composition is 300 μm or less.

It may be characterized in that the composition for three-dimensional lamination is discharged and laminated in 10 or more layers.

In addition, another aspect of the present invention,

An electrode manufactured by the method for manufacturing the electrode is provided.

In addition, another aspect of the present invention,

An electronic device including the electrode is provided.

According to one aspect of the present invention, an electrode of a desired shape can be designed by using a precursor solution of a metal-organic framework (MOF) as a composition for 3-dimensional stacking, and an electrode designed in a specific shape by 3D printing is metal-organic Due to the high electrical conductivity and uniform pore size of the skeletal body, it can be used as an electrode, electrochemical catalyst, sensor, etc.

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

1 shows a composition for three-dimensional stacking according to an embodiment of the present invention.
2 shows an electrode manufactured by 3D printing according to an embodiment of the present invention.
3 shows XRD data of a 3D printed material using a composition for 3D stacking prepared according to an embodiment of the present invention.
4 shows half-cell charge/discharge test results using an electrode manufactured according to an embodiment of the present invention.
5 shows half-cell CV (Cyclic Voltammogram) test results using an electrode manufactured according to an embodiment of the present invention.
6 shows half-cell charge/discharge test and CV test results of a 3-dimensional metal-organic framework (MOF) and a 2-dimensional metal-organic framework prepared according to an embodiment of the present invention.
FIG. 7 shows capacitance characteristics of an electrode 3D printed with activated carbon containing Ni-MOF (right) compared to an electrode 3D printed only with activated carbon (left) manufactured by the method according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention can be implemented in many different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In the entire specification of the present invention, 'include' a certain element means that other elements may be further included without excluding other elements unless otherwise stated.

The first aspect of the present application is,

A composition for 3D stacking comprising a solvent, an organic ligand and a metal precursor, characterized in that an organic ligand is coordinated with ions of the metal.

Hereinafter, the composition for three-dimensional lamination according to the first aspect of the present disclosure will be described in detail.

In one embodiment of the present application, the organic ligand may be characterized by being represented by any one of Formulas 1 to 4 below.

[Formula 1]

In Formula 1, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are They may be the same as or different from each other.

[Formula 2]

In Formula 2, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are They are the same as or different from each other, and n may be an integer from 0 to 5.

[Formula 3]

In Formula 3, X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X1 and X3 are are the same as or different from each other, and R1 to R6 are each independently hydrogen, straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched chain of C2-C10 alkenyl, straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.

[Formula 4]

In Formula 4, X1 to X6 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxyl group (OH), X1 and X2 are the same, X3 and X4 are the same, and X5 and X6 are are the same as each other, X1, X3 and X5 are the same as or different from each other, and Y1 to Y6 may each independently represent carbon or nitrogen.

In one embodiment of the present application, in Formulas 1 to 3, X1 to X4 may preferably be an amine group (NH2), and in Formula 3, R1 to R6 are each independently preferably hydrogen, linear or branched C1 -C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched C2-C10 alkenyl or straight or branched C2-C10 alkynyl. More preferably, in Formula 3, R1 to R6 may each independently be hydrogen or a straight-chain or branched-chain C1-C10 alkyl, and even more preferably, in Formula 3, R1, R3, R4, and R6 are hydrogen, and R2 and R5 can be tert-alkyl.

In one embodiment of the present application, the metal precursor is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, selected from the group consisting of Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub and combinations thereof It may contain a precursor of a metal, preferably Ni. Meanwhile, the metal precursor may be provided in the form of a salt, and the salt may include chloride, fluoride, bromide, iodide, or triflate. , BF ₄ , PF ₆ , NO ^3- , SO ₄ ^2- , ClO ₄ ^- and combinations thereof.

In one embodiment of the present application, the weight mixing ratio of the organic ligand and the metal precursor may be 1: 1 to 6, preferably 1: 2 to 5, more preferably 1: 3 to 5 It could be 4.

In one embodiment of the present application, each of the organic ligands may include an aryl core and a substituent capable of coordinating with the metal as shown in Chemical Formulas 1 to 4, and the substituents included in the organic ligand may be combined with the metal precursor. Each may form a coordinate bond. That is, as shown in Chemical Formulas 1 to 3, X1 to X4 of the organic ligands and X1 to X6 of the organic ligands of Chemical Formula 4 may form coordinate bonds with the metal precursor, respectively.

In one embodiment of the present application, the metal precursor may include a substituted or unsubstituted heteroaryl having an element capable of coordinating with the metal. That is, the metal precursor may be mixed with an organic ligand in the form of a heteroaryl coordinated with a metal. In this case, a coordination bond may be formed between a substituent included in the organic ligand and the metal on both sides of the organic ligand, and a heteroaryl coordinated with the metal may be positioned in a direction opposite to that of the organic ligand. That is, since the metal forms a coordination bond with two substituents of the organic ligand and two elements included in the heteroaryl, it may have a 4 coordination bond. As described above, since the mixture produced by mixing the organic ligand and the metal precursor contains substituted or unsubstituted heteroaryl on both sides, the heteroaryl serves as a protective cap so that the organic ligand in the subsequent step can be specified. It may be that the coordination bond is possible only at the position.

In one embodiment of the present application, the solvent may be characterized in that a salt is mixed with an organic solvent. At this time, the organic solvent is EG (Ethylene Glycol), ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), DMC (Dimethyl carbonate), DEC (Diethyl carbonate), EMC (Ethylmethyl carbonate), DME (1 ,2-dimethoxyethane), GBL (γ-butrolactone), MF (methyl formate), MP (methyl propionate), DMF (dimethylformamide), DMA (dimethylamide), dimethyl sulfoxide (DMSO), and combinations thereof. It may include a material selected from the group consisting of, and preferably may be DMA, DMF, DMSO, or EG. The salt may be NH ₄ OH or NaCH ₃ COO, but it may include conventional cation and anion salts as non-limiting examples.

In one embodiment of the present application, the composition for 3D stacking may further include at least one first additive selected from the group consisting of lithium-metal oxide and activated carbon (AC), In addition, the composition for 3D stacking may further include at least one second additive selected from the group consisting of a binder, a conductive material, and a reaction initiator.

In one embodiment of the present application, as a non-limiting example, PVdf, PTFE, PVdf-PTFE copolymer may be used as the binder.

In one embodiment of the present application, the conductive material means a material added in a small amount to improve conductivity between material particles or with a metal current collector and to prevent the binder from acting as an insulator, and as a non-limiting example, activated carbon (activated carbon) carbon), graphene, and carbon black (Super-P) can be used.

In one embodiment of the present application, when activated carbon is used as an electrode active material based on porosity, it performs a function of improving the efficiency of ion movement, and any commercially available activated carbon can be used without limitation.

In one embodiment of the present application, the lithium-metal oxide is lithium titanate (LTO), lithium vanadium oxide (LVO), lithium-vanadium phosphate (LVP), and mixtures thereof It may be characterized in that it is one selected from the group consisting of.

In one embodiment of the present application, the solvent may be 1 part by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and 50 parts by weight or less with respect to 100 parts by weight of the composition for 3D stacking. , preferably 45 parts by weight or less, more preferably 40 parts by weight or less, even more preferably 35 parts by weight or less. In addition, with respect to 100 parts by weight of the 3D layering composition, the organic ligand may be 10 parts by weight or more, preferably 15 parts by weight or more, more preferably 20 parts by weight or more, and still more preferably 30 parts by weight or more. 70 parts by weight or less, preferably 65 parts by weight or less, more preferably 60 parts by weight or less, and even more preferably 50 parts by weight or less. In addition, with respect to 100 parts by weight of the 3D stacking composition, the metal precursor may be 10 parts by weight or more, preferably 15 parts by weight or more, more preferably 20 parts by weight or more, and even more preferably 30 parts by weight or more. 70 parts by weight or less, preferably 65 parts by weight or less, more preferably 60 parts by weight or less, and even more preferably 55 parts by weight or less. In addition, with respect to 100 parts by weight of the 3D stacking composition, the first additive is 0 parts by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and even more preferably 15 parts by weight or more. 45 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 25 parts by weight or less. In addition, with respect to 100 parts by weight of the 3D stacking composition, the second additive is 0 parts by weight or more, preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more. 30 parts by weight or less, preferably 25 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 15 parts by weight or less. By satisfying the above content range, it will be possible to have viscoelasticity suitable for use in 3D printing work.

The second aspect of the present application is,

discharging the composition for three-dimensional lamination according to claim 1 using a 3D printer; and forming a metal-organic framework (MOF) by heat-treating the ejected composition for 3D lamination, wherein the heat treatment is carried out after or after the step of discharging the 3D lamination composition. It provides a method for producing an electrode, characterized in that it proceeds simultaneously with.

Detailed descriptions of portions overlapping with those of the first aspect of the present application have been omitted, but the contents described for the first aspect of the present application can be equally applied even if the description is omitted from the second aspect.

Hereinafter, the manufacturing method of the electrode according to the second aspect of the present application will be described in detail.

First, in one embodiment of the present application, a step of discharging the composition for 3D lamination according to claim 1 using a 3D printer is included. In this case, the current collector, the positive electrode, and the negative electrode constituting the energy storage device may all be formed by 3D printing, or only the active material may be formed using a 3D printer on a current collector such as a prepared metal foil. In this case, the collector metal ink is discharged with a 3D printer to form a collector pattern in a desired shape, which may include a process of printing and forming metal anodes and cathodes capable of 3D printing with a 3D printer. .

In one embodiment of the present application, since the electrode is formed by 3D printing, the type of substrate is not particularly limited. Therefore, compared to the conventional manufacturing method in which the manufacturing process is complicated and expensive equipment is used and the manufacturing cost is very high, when the present invention is applied, the manufacturing process is very simple and the manufacturing cost is reduced.

Next, in one embodiment of the present application, a step of forming a metal-organic framework (MOF) by heat-treating the discharged composition for 3D stacking may be included. This is because it may be preferable to synthesize a composition for 3D stacking composed of a metal-organic framework (MOF) precursor into MOF and apply a heat treatment process to remove the solvent included in the ink. The heat treatment method can be used without limitation as long as it is a means of applying heat, but may preferably use infrared rays. The heat treatment may be characterized in that it is made at a temperature of 40 ° C or higher, preferably 60 ° C or higher, more preferably 75 ° C or higher, still more preferably 90 ° C or higher, and still more preferably 100 ° C or higher, The temperature of the heat treatment may be characterized in that it is made at a temperature of 150 ° C or less, preferably 140 ° C or less, more preferably 130 ° C or less, and even more preferably 120 ° C or less. In addition, the heat treatment may be characterized in that it is made for 0.5 to 8 hours, preferably 1.0 to 6 hours, more preferably 2.5 to 4 hours. The heat treatment may be performed after the step of discharging the composition for 3D stacking or concurrently with the step.

In one embodiment of the present application, since the electrode is formed using a 3D printer, there is no limit to its shape, and various structures for increasing the surface area of the electrode can be applied. Therefore, the electrode may be characterized in that it is formed to be patterned. The shape of the pattern is not limited to any shape applied to increase the surface area of a conventional electrode, but may preferably have an interdigitated structure. If the shape of the electrode is complicated, in the conventional manufacturing method, there was a problem that manufacturing was difficult or the manufacturing cost increased. However, since the present invention applies a 3D printer, the structure of the electrode having a very complicated structure but high efficiency can be applied. .

In one embodiment of the present application, the inner diameter of the nozzle of the 3D printer for discharging the composition for 3D stacking may be determined without limitation as long as the ejection can be performed well. Preferably, it may be 20 μm or more, 30 μm or more, or 50 μm or more, and preferably 500 μm or less, 400 μm or less, or 300 μm or less.

In one embodiment of the present application, in the process of forming the anode and the cathode using a 3D printer, the thickness of the electrode is increased by stacking at least two or more layers to increase the volume for accommodating the electrolyte, and the laminated structure can be can A 3D printer is a device for producing a three-dimensional three-dimensional structure. It manufactures a three-dimensional three-dimensional structure by laminating raw materials into a plurality of layers according to a design drawing. In this embodiment, a 3D printer capable of repeatedly stacking raw materials A thick (or high) electrode may be formed by repeatedly stacking electrode constituent materials using the characteristics of the printer. Preferably, the composition for three-dimensional lamination may be discharged and stacked in 10 or more layers.

As described above, since the thickness (height) of the electrode is thicker than the width of the thin electrode wall in the energy storage device manufactured by the method according to the embodiment of the present invention, the electrolyte material is filled between the anode and the cathode manufactured in a small size. There is an excellent effect of increasing the amount of electricity and greatly increasing the amount of electrical energy stored in one cell.

The third aspect of the present application,

An electrode manufactured by the method for manufacturing the electrode is provided.

Although detailed descriptions of portions overlapping with the first and second aspects of the present application have been omitted, the contents described for the first and second aspects of the present application can be equally applied even if the description is omitted in the third aspect.

Hereinafter, the electrode according to the third aspect of the present application will be described in detail.

In one embodiment of the present application, the electrode active material may be used for a secondary battery or a supercapacitor, and since the metal-organic framework has high porosity and excellent electrical conductivity, energy density and output characteristics of the devices can be improved. it may be improving Specifically, the total pore volume of the metal-organic framework may be 0.01 cm ³ /g to 5.0 cm ³ /g, and the metal-organic framework includes pores having an average diameter of 0.5 Å to 5.0 Å it could be In addition, the metal-organic framework may have an electrical conductivity of 0.01 S·cm ⁻¹ or more.

In one embodiment of the present application, the electrode active material may be formed on an electrode current collector. In this case, the type of the electrode current collector may not be significantly limited as long as it has conductivity without causing chemical change of the device. For example, the electrode current collector may include stainless steel, aluminum, nickel, titanium, calcined carbon, or a material in which carbon, nickel, titanium, silver, or the like is surface-treated on the surface of aluminum or stainless steel. Meanwhile, the electrode current collector may have a thickness of about 3 μm to 500 μm, and fine irregularities may be formed on the surface of the current collector to increase adhesion of the electrode active material. That is, it may be usable in various forms such as films, sheets, foils, nets, porous bodies, foams, and non-woven fabrics.

In one embodiment of the present application, the electrode active material may further include a conductive material and a binder in addition to the active material. In this case, the conductive material is used to impart conductivity to the electrode, and may be any material that has electrical conductivity without causing a chemical change in the device. For example, the conductive material is graphite such as natural graphite or artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, summer black, carbon-based materials such as carbon fiber, copper, nickel, aluminum , metal powder or metal fibers such as silver, conductive whiskey such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide or conductive polymers such as polyphenylene derivatives, and combinations thereof. it may be Meanwhile, the conductive material may be used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode active material.

In addition, the binder may serve to improve adhesion between particles of the electrode active material and adhesion between the electrode active material and the current collector. Specifically, the binder may be, for example, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, Carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), alcohol It may include a material selected from the group consisting of phonated-EPDM, styrene butadiene rubber (SBR), fluororubber, or various copolymers thereof and combinations thereof. Meanwhile, the binder may be typically used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the electrode active material.

In addition, the supercapacitor may preferably be a hybrid supercapacitor, and the hybrid supercapacitor may specifically include: an anode; cathode; It may include a separator and an electrolyte interposed between the positive electrode and the negative electrode. In this case, the electrode active material may be preferably used as an active material of the negative electrode, and activated carbon may be used as a positive electrode active material of the positive electrode.

In one embodiment of the present application, the electrolyte used in the hybrid supercapacitor may be a mixture of a salt and an additive in an organic solvent. At this time, the organic solvent is ACN (Acetonitrile), EC (Ethylene carbonate), PC (Propylene carbonate), DMC (Dimethyl carbonate), DEC (Diethyl carbonate), EMC (Ethylmethyl carbonate), DME (1,2-dimethoxyethane), It may include a material selected from the group consisting of γ-butrolactone (GBL), methyl formate (MF), methyl propionate (MP), and combinations thereof. In addition, the salt is used in an amount of 0.8 to 2 M, and may be a mixture of a lithium (Li) salt and a non-lithium salt. The lithium (Li) salt accompanies an intercalation/desorption reaction into the structure of the anode active material, that is, the metal-organic framework, and its types include LiBF ₄ , LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiAlCl ₄ , LiCF ₃ SO ₃ , LiN(SO ₂ CF ₃ ) ₂ , LiC(SO ₂ CF ₃ ) ₃ , lithium bis(oxalato)borate (LiBOB), and combinations thereof. In addition, the non-lithium salt accompanies an adsorption/desorption reaction on the surface area of the carbon material additive, and may be used by mixing 0 to 0.5 M with the lithium salt. In this case, the non-lithium salt includes a material selected from the group consisting of TEABF ₄ (Tetraethylammonium tetrafluoroborate), TEMABF ₄ (Triethylmethylammonium tetrafluoroborate), SBPBF ₄ (spiro-(1,1′)-bipyrrolidium tetrafluoroborate), and combinations thereof it may be In addition, the carbon material additive may include a material selected from the group consisting of vinyl carbonate (VC), vinyl ethylene carbonate (VEC), fluoroethylene carbonate (FEC), and combinations thereof.

In one embodiment of the present application, the separator is positioned between the positive electrode and the negative electrode to prevent the positive electrode and the negative electrode from being in physical contact with each other and electrically shorted, and a porous material may be used. For example, the separator may include a material selected from the group consisting of polypropylene, polyethylene, polyolefin, and combinations thereof.

In one embodiment of the present application, the hybrid supercapacitor having the above configuration has high electrical conductivity because it uses a metal-organic framework as an anode active material, and has improved capacity due to the high specific surface area of the carbon material additive, resulting in high energy density. And it may have an output characteristic. That is, a carbon material additive may be inserted into a plurality of spaces formed in the metal-organic framework, and a hybrid supercapacitor including the additive may exhibit excellent electrical conductivity, capacitance, and output characteristics.

The fourth aspect of the present application,

It provides an electronic device including the electrode according to the third aspect of the present application.

Detailed descriptions of portions overlapping with the first to third aspects of the present application have been omitted, but the contents described for the first to third aspects of the present application can be equally applied even if the description is omitted in the fourth aspect. .

In one embodiment of the present application, the metal-organic framework prepared from the composition for 3D stacking is a catalyst for water purification, an anticancer drug, a treatment for immunodeficiency virus, a treatment for fungal and bacterial infections, and malaria in addition to an electrode active material for a supercapacitor or a secondary battery. Since it can be applied in various fields such as therapeutic agents, various drug delivery materials, photocatalysts, sensors, and aerospace materials, it can be used as a commercially very useful material.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

Preparation Example 1: Preparation of composition slurry for 3D stacking

Activated carbon ink for 3D printing and 3D Ni-MOF precursor ink were prepared and mixed, and a composition slurry for 3D stacking was prepared. The activated carbon ink for 3D printing was prepared by mixing 4.15 g of MSP-20, 0.50 g of Super-p, 1.75 g of PVdF 8 wt% solution and 2 mL of NMP, and the 3D Ni-MOF precursor ink was prepared by mixing 1.837 mL of HITP solution and Ni/ It was prepared by mixing 2.755 mL of NH4OH solution.

Preparation Example 2: Electrode manufacturing by 3D printing output

Using the composition slurry for 3D stacking prepared in Preparation Example 1 as an ink, it was transferred to a dispenser-type 3D printer-specific syringe attached with a metal needle (250 μm in diameter, SNA-26G), and at a pressure of 30 kPa, 0.070 Electrodes were formed by 3D printing output in an interdigitated structure as shown in FIG. 2 with a printing interval of mm. Heat treatment was performed at 65 °C for 3.5 hours. Electrodes may be formed in a multi-layered structure in consideration of capacitance.

Experimental Example 1: XRD data analysis of three-dimensionally stacked MOFs

XRD analysis of the 3D printed and heat-treated electrode in Preparation Example 2 was performed. Referring to FIG. 3, when compared with Ni-HITP prepared by heat-treating the 3D-printed Ni-MOF precursor and Ni-HITP produced by the conventional hydrothermal synthesis method, the 2-theta values were 4.72, 9.52, 12.54, 16.48, 17.12, Considering that peak values appeared at 27.12 and 42.18, it was found that MOF was formed after 3D printing of the composition for 3D stacking.

Experimental Example 2: Half-cell charge/discharge test including three-dimensionally stacked MOF electrodes

A half cell was formed using the composition slurries for 3D stacking prepared in Preparation Examples 1 and 2 as an electrode active material, and a charge/discharge test was performed. The results are shown in Figure 4.

- Working electrode: 3D Ni-MOF/AC on Cu foil (18 ㎛, 14 Φ)

- Counter, Reference electrode: Li foil (14 Φ)

- Electrode weight: 0.44 mg (active material: conductive material: binder = 83 wt%: 10 wt%: 7 wt%)

- Electrolyte: 1M LiPF6 (EC:DMC = 1:1)

- Separator: glass filter (625 ㎛)

- Potential range: 0 - 3.0 V

- Current density: 0.9 A/g (5 C), 1.8 A/g (20 C), 4.5 A/g (75 C), 9.0 A/g (270 C)

As shown in FIG. 4, it was confirmed that characteristics such as specific capacity according to charge/discharge rate, stability according to cycle, and coulombic efficiency were excellent.

Experimental Example 3: Half-Cell CV (Cyclic Voltammogram) test including three-dimensionally stacked MOF electrodes

A CV test was performed by constructing a half cell using the composition slurries for 3D stacking prepared in Preparation Examples 1 and 2 as an electrode active material. Results are shown in FIG. 5 .

- Working electrode: 3D Ni-MOF/AC on Cu foil (18 μm, 14 Φ)

- Counter, Reference electrode: Li foil (14 Φ)

- Electrode weight: 0.44 mg (active material: conductive material: binder = 83 wt%: 10 wt%: 7 wt%)

- Electrolyte: 1M LiPF6 (EC : DMC = 1 : 1)

- Separator: glass filter (625 ㎛)

- Potential range: 0 - 3.0 V

- Scan rates: 1, 5, 10, 20, 30, 50, 70, 100 mV/s

As shown in FIG. 5, it was observed that the 3D printed activated carbon and the Ni-MOF mixed electrode material showed a reversible electrochemical reaction in the CV profile showing the electrode reactivity. It was found that this electrode material had electrochemical properties as a negative electrode material.

Experimental Example 4: Comparison of half-cell charge/discharge and CV (Cyclic Voltammogram) test results including a three-dimensionally stacked MOF electrode and an electrode made of a two-dimensional MOF.

An electrode using the three-dimensionally stacked MOF electrode prepared in Preparation Example 2 and the Ni-MOF surface-coated with a doctor blade as an electrode active material was prepared, and each half cell was configured to charge and discharge and CV (Cyclic Voltammogram) tests were performed, The results are shown in FIG. 6 .

As shown in FIG. 6, it was confirmed that the 3D printed Ni-MOF/AC electrode showed an improved capacitance value at the same current density compared to the case of the 2D Ni-MOF. It was confirmed that this was due to the improved efficiency of ion migration due to the 3D printing structure and the porosity and conductivity of the activated carbon incorporated into the ink.

Experimental Example 5: Comparison of half-cell charge/discharge test results including 3-dimensionally stacked MOF + AC electrode and 3-dimensionally stacked AC electrode.

An electrode using the three-dimensionally stacked MOF + AC electrode prepared in Preparation Example 2 and the three-dimensionally stacked AC electrode made only of AC (activated carbon) as an active material was prepared, and each half cell was configured to perform a charge/discharge test. is shown in Figure 7.

As shown in FIG. 7, it was confirmed that the 3D-printed Ni-MOF/AC electrode showed about 2 times improved capacity value at a similar current density compared to the case of the 3D-printed electrode with only activated carbon. It was confirmed that this was due to the improved efficiency of ion migration due to the 3D printing structure and the porosity and conductivity of the activated carbon incorporated into the ink.

Claims (15)

discharging a composition for 3D stacking using a 3D printer having a nozzle inner diameter of 300 μm or less; and
forming a metal-organic framework (MOF) by heat-treating the discharged composition for 3D stacking; including,
The composition for 3D stacking includes a metal-organic framework (MOF) precursor including a solvent, an organic ligand, and a metal precursor, wherein the metal-organic framework has organic ligands coordinated to metal ions of the metal precursor. combined, and the composition for three-dimensional stacking further includes at least one first additive selected from the group consisting of lithium-metal oxide and activated carbon (AC),
The method of manufacturing an electrode, characterized in that the heat treatment is performed after the step of discharging the composition for three-dimensional stacking or concurrently with the step, and is performed at a temperature of 40 ° C to 150 ° C.
According to claim 1,
The organic ligand is a method for producing an electrode, characterized in that represented by any one of the following formulas (1) to (4).
[Formula 1]

(In Formula 1 above,
X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH),
X1 and X2 are equal to each other, X3 and X4 are equal to each other, and X1 and X3 are equal to or different from each other.)

[Formula 2]

(In Formula 2 above,
X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH),
X1 and X2 are the same as each other, X3 and X4 are the same as each other, X1 and X3 are the same as or different from each other,
n is an integer from 0 to 5.)

[Formula 3]

(In Formula 3,
X1 to X4 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH),
X1 and X2 are the same as each other, X3 and X4 are the same as each other, X1 and X3 are the same as or different from each other,
R1 to R6 are each independently hydrogen, straight or branched C1-C10 alkyl, straight or branched C1-C10 alkoxy, straight or branched C1-C10 aminoalkyl, straight or branched C2-C10 alkenyl , straight or branched C2-C10 alkynyl, C3-C10 cycloalkyl, C6-C10 aryl or C1-C10 alkylcarbonyl.)

[Formula 4]

(In Chemical Formula 4,
X1 to X6 are each independently an amine group (NH2), a carboxy group (COOH) or a hydroxy group (OH),
X1 and X2 are equal to each other, X3 and X4 are equal to each other, X5 and X6 are equal to each other,
X1, X3 and X5 are the same as or different from each other,
Y1 to Y6 are each independently carbon or nitrogen.)
According to claim 1,
The metal precursor is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Characterized in that it comprises a metal selected from the group consisting of Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Cn and combinations thereof , Method of manufacturing an electrode.
delete According to claim 1,
The method for producing an electrode, characterized in that the composition for three-dimensional stacking further comprises at least one second additive selected from the group consisting of a binder, a conductive material, and a reaction initiator.
According to claim 1,
The lithium-metal oxide is one selected from the group consisting of lithium titanate (LTO), lithium vanadium oxide (LVO), lithium-vanadium phosphate (LVP), and mixtures thereof Characterized in, a method for manufacturing an electrode.
The method of claim 5, based on 100 parts by weight of the three-dimensional layering composition,
1 to 50 parts by weight of a solvent;
20 to 65 parts by weight of an organic ligand;
15 to 60 parts by weight of a metal precursor;
0 to 30 parts by weight of the first additive; and
0 to 20 parts by weight of the second additive; characterized in that it comprises a method for producing an electrode.
delete delete The method of claim 1, wherein the heat treatment is performed for 2.5 to 4 hours.
According to claim 1,
The method of manufacturing an electrode, characterized in that the electrode is formed to be patterned in an interdigitated structure.
delete ◈Claim 13 was abandoned when the registration fee was paid.◈ According to claim 1,
Method for producing an electrode, characterized in that by discharging the composition for three-dimensional stacking and stacking in 10 or more layers.
An electrode manufactured by the method according to any one of claims 1 to 3, 5 to 7, 10, 11 and 13.
An electronic device comprising the electrode according to claim 14 .

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