WO2022114714A1 - Composite hybride comprenant une structure organométallique (mof) et une feuille bidimensionnelle - Google Patents

Composite hybride comprenant une structure organométallique (mof) et une feuille bidimensionnelle Download PDF

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WO2022114714A1
WO2022114714A1 PCT/KR2021/017228 KR2021017228W WO2022114714A1 WO 2022114714 A1 WO2022114714 A1 WO 2022114714A1 KR 2021017228 W KR2021017228 W KR 2021017228W WO 2022114714 A1 WO2022114714 A1 WO 2022114714A1
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metal
carbide
oxide
formula
group
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김태우
김현욱
유정준
변세기
한성옥
이학주
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재단법인 파동에너지 극한제어 연구단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/04—Nickel compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present invention relates to a hybrid composite including a metal-organic framework (MOF) and a two-dimensional sheet, wherein the two-dimensional sheet includes a metal oxide sheet or a metal carbide sheet.
  • MOF metal-organic framework
  • MOFs Metal-Organic Frameworks
  • Numerous studies on the synthesis of MOFs have been conducted over the past few decades due to the abundance of different types of building blocks.
  • 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.
  • MOF metal-organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic ligand-containing organic a gas storage material because of its very wide specific surface area.
  • the combinations of metal precursors and organic ligands included in MOF are very diverse, thousands of crystal structures are registered in the database, and various functional groups can also be included, so it is spotlighted as a promising material in various industries. have.
  • electrochemicals due to the low conductivity of the MOF itself, its utility is falling, and research for synthesizing the MOF having conductivity is being actively conducted.
  • a super capacitor is a capacitor with a very large capacitance, and is called an ultra capacitor or an ultra-high-capacitance capacitor in Korean. In scientific terms, it is called an electrochemical capacitor to distinguish it from the conventional electrostatic or electrolytic capacitors. Unlike a battery that uses a chemical reaction, a supercapacitor uses a simple movement of ions to the electrode and electrolyte interface or a charging phenomenon by a surface chemical reaction. Accordingly, it is receiving attention as a next-generation energy storage device that can be used as a substitute for an auxiliary battery or battery due to its rapid charge/discharge capability, high charge/discharge efficiency, and semi-permanent cycle life characteristics.
  • Supercapacitors have been commercialized since the 1980s and have a relatively short history of development, but their development is due to the development of hybrid-type product design technology that uses asymmetric electrodes and new electrode materials such as metal oxides and conductive polymers, including activated carbon, which have been traditionally used. The speed is very fast. Some of the recently announced products have energy density that exceeds that of Ni-MH batteries.
  • Supercapacitors a next-generation energy storage device, can quickly store and take out large-capacity electricity, have 100 times higher output than secondary batteries, and can be used semi-permanently, so there are various application fields such as mobile phones, digital camera flashes, and hybrid vehicles. do.
  • supercapacitors are important as renewable energy storage devices such as solar power, wind power, and hydrogen fuel cells, which are eco-friendly, clean alternative energy that does not emit carbon dioxide by replacing petroleum.
  • the carbon-based electrode material mainly stores energy in the electric double layer, so it has a relatively high output characteristic, but has a disadvantage in that the energy storage amount is low.
  • the advantage of showing high storage capacity it has many problems such as the disadvantage of being difficult to use in mass production because the material is expensive. Therefore, in order to improve the energy density and power density of the supercapacitor, it is urgent to develop an electrode having high porosity and electrical conductivity, which is inexpensive and has high electrical conductivity.
  • the present inventors prepared a hybrid composite in which a plurality of metal-organic frameworks (MOFs) and a plurality of two-dimensional metal oxide or metal carbide sheets were randomly mixed while studying to solve the above problems, When applied as an electrode of a supercapacitor or a secondary battery, it was confirmed that the performance of a supercapacitor or a secondary battery can be improved due to the characteristic high porosity and electrical conductivity characteristics of the hybrid composite, thereby completing the present invention.
  • MOFs metal-organic frameworks
  • the hybrid complex is applied in various fields, such as a catalyst for water purification, an anticancer agent, an immunodeficiency virus treatment, a treatment for fungal and bacterial infections, a treatment for malaria, various drug delivery materials, photocatalysts, sensors, and aerospace materials, in addition to supercapacitors or secondary batteries. As this is possible, it can be used as a commercially very useful material.
  • Korean Patent Laid-Open No. 10-2019-0013629 discloses an antibacterial agent containing MOF and an antibacterial filter containing the same.
  • the present invention has been devised to solve the above problems, and an embodiment of the present invention provides a hybrid composite including a plurality of metal-organic frameworks (MOFs) and a plurality of two-dimensional metal oxide or metal carbide sheets.
  • MOFs metal-organic frameworks
  • another embodiment of the present invention provides an electrode active material including the hybrid composite.
  • one aspect of the present invention is,
  • MOFs metal-organic frameworks
  • two-dimensional nanosheets a two-dimensional nanosheet selected from the group consisting of a metal oxide sheet, a metal carbide sheet, and a metal hydroxide sheet, wherein the metal-organic framework has a three-dimensional shape, and the plurality of It provides a hybrid composite, characterized in that the two-dimensional nanosheet is laminated on the surface of the metal-organic framework.
  • the metal-organic framework may include a structure of Formula 1 below.
  • M is a metal
  • L is an organic ligand and includes any one of the structures of Chemical Formulas 2 to 4 below.
  • 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 as each other, X3 and X4 are the same as each other, and X1 and X3 are same or different from each other
  • 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 as each other, X3 and X4 are the same as each other, and X1 and X3 are They are the same as or different from each other, and n is an integer from 0 to 5.
  • 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 as each other, X3 and X4 are the same as each other, and X5 and X6 are are identical to each other, X1, X3 and X5 are the same as or different from each other, and Y1 to Y6 are each independently carbon or nitrogen.
  • M is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf, Ta, W, Re , Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub, and may be one containing a metal selected from the group consisting of combinations thereof.
  • the metal oxide sheet is manganese oxide, cobalt oxide, rubidium oxide, titanium oxide, vanadium oxide, iron oxide, nickel oxide ( nickel oxide, copper oxide, zinc oxide, zirconium dioxide, molybdenum oxide, tantalum oxide and a metal oxide selected from the group consisting of combinations thereof.
  • the metal carbide sheet is titanium carbide, aluminum carbide, chromium carbide, zinc carbide, copper carbide, magnesium carbide, zirconium carbide ( zirconium carbide, molybdenum carbide, vanadium carbide, niobium carbide, iron carbide, manganese carbide, cobalt carbide, nickel carbide (nickel carbide), tantalum carbide (tantalum carbide), and may include a metal carbide selected from the group consisting of combinations thereof.
  • the metal hydroxide sheet may be a peeled metal double layer hydroxide (LDH) nanosheet, and the peeled metal double layer hydroxide nanosheet may be a compound represented by the following [Formula 5]:
  • M II is selected from the group consisting of Ca 2+ , Mg 2+ , Zn 2+ , Ni 2+ , Mn 2+ , Co 2+ , Fe 2+ , Cu 2+ and mixed metals thereof
  • M III is selected from the group consisting of Fe 3+ , Al 3+ , Cr 3+ , Mn 3+ , Ga 3+ , Co 3+ , Ni 3+ and mixed metals thereof
  • a n- is a hydroxide ion ( OH - ), nitrate ions (NO 3 - ), PO 4 3- , HPO 4 2- , H 2 PO 4 - and combinations thereof, 0 ⁇ x ⁇ 1, and z is 0.1 to 15 may be a mistake in
  • the metal-organic framework and the two-dimensional nanosheet each include a plurality of nanopores, and the size of the nanopores may be 0.5 nm to 20 nm.
  • the content of the two-dimensional nanosheet relative to 100 parts by weight of the metal-organic framework may be 10 parts by weight to 300 parts by weight.
  • the porosity of the hybrid composite may be 30 vol% to 70 vol%.
  • the electrical conductivity of the hybrid composite may be 0.01 S ⁇ cm ⁇ 1 or more.
  • Another aspect of the present invention provides a catalyst including the hybrid complex.
  • Another aspect of the present invention provides an electrode for a device including the hybrid composite.
  • the hybrid composite includes both the characteristic porosity of the metal-organic framework (MOF) and the characteristic porosity of the metal oxide sheet or metal carbide sheet, and the metal-organic framework (MOF) and the metal oxide or metal carbide sheet may have very high porosity because they also include three-dimensional pores that are randomly mixed. Therefore, since the hybrid composite has high porosity and excellent electrical conductivity, when it is used in electrodes such as supercapacitors or secondary batteries, energy density and output characteristics of the device can be improved.
  • MOF metal-organic framework
  • the metal oxide or metal carbide sheet may have very high porosity because they also include three-dimensional pores that are randomly mixed. Therefore, since the hybrid composite has high porosity and excellent electrical conductivity, when it is used in electrodes such as supercapacitors or secondary batteries, energy density and output characteristics of the device can be improved.
  • the hybrid composite is relatively easy to manufacture, it can be mass-produced and thus can be highly useful industrially.
  • FIG. 1 is a schematic diagram showing a manufacturing process of a hybrid composite according to an embodiment of the present invention.
  • FIG. 2 is a schematic diagram showing a metal-organic framework (MOF) according to an embodiment of the present invention.
  • MOF metal-organic framework
  • FIG 3 shows an SEM image of a metal-organic framework (MOF) according to an embodiment of the present invention.
  • FIG. 4 is a schematic diagram showing a manufacturing process of a metal oxide sheet according to an embodiment of the present invention.
  • FIG. 5 is a schematic diagram showing a manufacturing process of a metal carbide sheet according to an embodiment of the present invention.
  • FIG. 6 is a schematic diagram showing a manufacturing process of a metal hydroxide sheet according to an embodiment of the present invention.
  • FIG. 7A is a photograph showing a solution including a metal oxide sheet prepared according to an embodiment of the present invention
  • FIG. 7B is a TEM image of a metal oxide nanosheet prepared according to an embodiment of the present invention.
  • FIG. 8 is a schematic diagram (FIG. 8a) showing a two-dimensional Mxene structure according to an embodiment of the present invention and XRD data (FIG. 8b) of a metal carbide sheet manufactured according to an embodiment of the present invention, an embodiment of the present invention TEM and SAED patterns showing bulk metal carbide (FIG. 8c), expanded metal carbide (FIG. 8d) and exfoliated metal carbide sheet (FIG. 8e) according to the example, and a photograph showing a solution containing the prepared metal carbide sheet ( 8f).
  • FIG. 9A is a photograph showing a solution including a metal hydroxide sheet prepared according to an embodiment of the present invention
  • FIG. 9B is a TEM image of the exfoliated metal hydroxide nanosheet prepared according to an embodiment of the present invention will be.
  • FIG. 10 is a photograph showing a manufacturing process of a hybrid composite according to an embodiment of the present invention.
  • FIG. 12 is an SEM photograph showing a Ni-MOF (top) and a hybrid composite (bottom) prepared according to an embodiment of the present invention.
  • FIG 13 shows electron mapping of the Ni-MOF/MnO2 hybrid composite prepared according to an embodiment of the present invention.
  • Ni-HITP powder which is Ni-MOF
  • Ni-MOF Ni-HITP powder
  • FIG. 2 A photograph of the metal-organic framework SEM image obtained through the above preparation method is shown in FIG. 2 . Referring to FIG. 2 , it can be confirmed that a porous MOF is formed.
  • a metal oxide sheet according to the present invention In order to prepare a metal oxide sheet according to the present invention, first, bulk K 0.45 MnO 2 having a two-dimensional structure was synthesized by solid-state synthesis. Thereafter, K+ ions in the layer were removed by treatment with 1M HCl three or more times. Then, the acid-treated sample was reacted with TBAOH to obtain a MnO2 nanosheet colloid. The dose of TBAOH applied in relation to the amount of exchangeable protons H at 0.13 MnO*0.7H 2 O. That is, the molar ratio of TBA+/H+ was changed to about 3 by changing the concentration of TBA hydroxide. Laminated manganese dioxide (MnO 2 ) was prepared, and each manganese dioxide layer was exfoliated by swelling the stacked manganese dioxide to obtain an exfoliated manganese dioxide sheet.
  • MnO 2 Laminated manganese dioxide
  • FIG. 7 is a photograph (FIG. 7A) showing a solution containing a metal oxide sheet according to an embodiment of the present invention, and a photograph and graph (FIG. 7B) showing the characteristics of the prepared metal oxide sheet.
  • FIG. 7A it can be seen that the Tyndall phenomenon appears, and it can be confirmed that the manganese oxide nanosheets are well dispersed, and referring to FIG. 7B , it can be confirmed that the exfoliated nanosheets of manganese oxide are well formed.
  • a high-purity Ti 3 AlC 2 block was prepared by pressureless sintering.
  • An initial powder of TiH 2 , Al, and TiC in a 1:1.1:2 ratio was ball milled for 12 hours, treated at 1400 °C for 2 hours in an argon atmosphere, and then the block was crushed and passed through a 325-mesh sieve. Then, 1 g of Ti 3 AlC 2 powder was added to the HF solution and the mixture was stirred at 60 °C for a predetermined time.
  • Ti 3 AlC 2 after acid treatment is put in a solution such as Formamide, Di-water, Methanol, Dimethyformamide and dispersed.
  • Formamide solution + Ti 3 C 2 and methanol solution + Ti 3 C 2 with the best dispersion were analyzed through TEM analysis.
  • FIG. 8f A photograph of the solution including the obtained Ti 3 C 2 nanosheet is shown in FIG. 8f .
  • the SEM photograph of Ti 3 AlC 2 in the bulk form is shown in FIG. 8c
  • the SEM image of Ti 3 C 2 in the expanded bulk form is shown in FIG. 8d
  • the SEM of the finally obtained Ti 3 C 2 nanosheet A photograph is shown in FIG. 8E .
  • FIGS. 8c to 8e it was confirmed that the bulk of Ti 3 AlC 2 was expanded between layers during HF treatment, which was confirmed that Al in the layer was removed and expanded due to the electrical repulsive force between the layers.
  • the gap between each sheet was widened to have a layered structure.
  • the finally obtained Ti 3 C 2 nanosheet exhibited a peeled sheet shape.
  • the pH was slowly adjusted to 5.5 ⁇ 0.5 using a 2M NaOH solution, and N2 gas was continuously flowed to prevent the synthesis of carbonate-type LDH.
  • the temperature of the solution was maintained at 60° C. and stirred vigorously for 24 hours.
  • the purple sample was separated through a centrifuge and washed several times with distilled water to remove unreacted remaining ions. The separated wet powder was dried in an oven at 60° C. for one day to obtain a final Zn-Cr LDH powder.
  • Figure 9a is a photograph showing a solution containing a metal hydroxide sheet prepared according to an embodiment of the present invention
  • Figure 9b is a TEM image of the exfoliated metal oxide nanosheet prepared according to an embodiment of the present invention will be.
  • FIG. 9A it can be seen that the Tyndall phenomenon of the colloidal colloid of ZrCr-LDH exfoliated ZnCr-LDH can be confirmed, and it can be seen that the metal hydroxide nanosheet is well dispersed.
  • FIG. 9B the exfoliated ZnCr - It can be confirmed that the LDH nanosheet was well formed.
  • the XRD analysis of the bulk Ti 3 AlC 2 and Ti 3 C 2 nanosheet metal carbide of Preparation Example 3 was performed and the results are shown in FIG. 8b, from below, simulated Ni-MOF, Ni-MOF synthesized by reflux method , layered bulk K 0.45 MnO 2 , exfoliated MnO 2 nanosheets, and Ni-MOF/MnO 2 XRD analysis of the hybrid composite was performed, and the results are shown in FIG. 11 .
  • FIG. 8b the peaks of Ti 3 AlC 2 and Ti 3 C 2 nanosheets in the bulk form of Preparation Example 3 were confirmed, and it was confirmed that they were consistent with the theoretical peaks.
  • FIG. 8b the peaks of Ti 3 AlC 2 and Ti 3 C 2 nanosheets in the bulk form of Preparation Example 3 were confirmed, and it was confirmed that they were consistent with the theoretical peaks.
  • FIG. 8b the peaks of Ti 3 AlC 2 and Ti 3 C 2 nanosheets in the bulk form of Preparation Example 3 were confirmed
  • the SEM photograph of the obtained hybrid composite is shown in FIG. 12 (below), and as shown in FIG. 12, the hybrid composite is randomly mixed in a porous metal-organic framework with a metal oxide or metal carbide sheet covering the surface. It was confirmed that it has a three-dimensional porous structure.
  • FIG. 13 shows electron mapping of the Ni-MOF/MnO2 hybrid composite prepared according to an embodiment of the present invention
  • FIG. 14 is an EDS spectrum of the Ni-MOF/MnO2 hybrid composite prepared according to an embodiment of the present invention. is shown.
  • FIG. 15 and 16 show the charging/discharging performance results according to the current for the Ni-MOF/MnO2 hybrid composite prepared according to an embodiment of the present invention.
  • FIG. 15 shows the charging/discharging performance results according to the current of the Ni-MOF (0.05 g)/MnO 2 composite
  • FIG. 16 is the charging/discharging performance according to the current of the Ni-MOF (0.1 g)/MnO 2 composite.
  • the results are shown.
  • 17 shows a comparison of the performance of the Ni-MOF/MnO 2 hybrid composite prepared according to an embodiment of the present invention with respect to the current density of Ni-MOF
  • FIG. 18 is prepared according to an embodiment of the present invention It shows the cycle performance results for the Ni-MOF / MnO 2 hybrid composite (Ni-MOF (0.05 g) / MnO 2 ).
  • the first aspect of the present application is a first aspect of the present application.
  • MOFs metal-organic frameworks
  • two-dimensional nanosheets a two-dimensional nanosheet selected from the group consisting of a metal oxide sheet, a metal carbide sheet, and a metal hydroxide sheet, wherein the metal-organic framework has a three-dimensional shape, and the plurality of It provides a hybrid composite, characterized in that the two-dimensional nanosheet is laminated on the surface of the metal-organic framework.
  • the hybrid composite includes a plurality of metal-organic frameworks (MOFs) and a plurality of two-dimensional metal oxide or metal carbide sheets as shown in FIG. 1 .
  • the hybrid composite includes both the characteristic porosity of the metal-organic framework (MOF) (see the SEM image of FIG. 2 ) and the characteristic porosity of the metal oxide sheet or metal carbide sheet, and the metal-organic framework
  • the sieve (MOF) and the metal oxide or metal carbide sheet may have very high porosity because they also include three-dimensional pores that are randomly mixed.
  • the metal-organic framework has a three-dimensional shape, and the plurality of two-dimensional nanosheets are randomly stacked on the surface of the metal-organic framework to form a core-shell (Core-). shell) structure.
  • the metal-organic framework may have a one-dimensional, two-dimensional, or three-dimensional form, and may specifically include the structure of Formula 1 below.
  • M is a metal
  • L is an organic ligand
  • the metal represented by M is Ni, Cu, Fe, Sc, Ti, V, Cr, Mn, Co, Zn, Y, Zr, Nb, Mo, Tc, Rh, Pd, Ag, Cd, Lu, Hf , Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg, Uub, and combinations thereof. and may preferably include Ni or Cu.
  • the metal-organic framework (MOF) may have semiconducting properties, and electrons may move through the metal part and the ligand part. have.
  • the organic ligand represented by L in Formula 1 may include any one of the structures of Formulas 2 to 4 below.
  • 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 as each other, X3 and X4 are the same as each other, and X1 and X3 are may be the same or different from each other.
  • 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 as each other, X3 and X4 are the same as each other, and X1 and X3 are The same or different from each other, n may be an integer of 0 to 5.
  • 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 as each other, X3 and X4 are the same as each other, and X5 and X6 are may be the same as each other, X1, X3 and X5 may be the same as or different from each other, and Y1 to Y6 may each independently be carbon or nitrogen.
  • X1 to X4 may preferably be an amine group (NH2)
  • X1 to X6 may preferably be an amine group (NH2)
  • the compound represented by Formula 3 may include an ortho-diamine group.
  • the organic ligand may include an aryl core and a substituent capable of coordinating with a metal as shown in Formulas 1 to 3, and the substituent included in the organic ligand is each coordinated with the metal. It may be to form a bond. That is, X1 to X4 of Formulas 1 and 2 or X1 to X6 of Formula 3 may form a coordination bond with a metal, respectively.
  • the organic ligand (first organic ligand) represented by Formula 1 or 2 and the organic ligand (second organic ligand) represented by Formula 3 cross-coordinate with the metal.
  • the metal-organic framework may be one in which the first organic ligand and the second organic ligand form a coordination bond on both sides of one metal as the center, and the structure is expanded by having the structure as a repeating unit may be to have
  • the electrical conductivity of the metal-organic framework may be 0.01 S ⁇ cm -1 or more.
  • the electrical conductivity of the metal-organic framework may be measurable in the form of polycrystalline pellets or polycrystalline films.
  • the electrical conductivity of the metal-organic framework pellets may be 0.01 S ⁇ cm -1 or more, preferably 0.01 S ⁇ cm -1 to 10 S ⁇ cm -1 , more preferably 1 S ⁇ cm -1 to 5 S ⁇ cm -1 may be.
  • the electrical conductivity of the metal-organic framework film may be 10 S ⁇ cm -1 or more based on an average film thickness of 500 nm, preferably 0.01 S ⁇ cm -1 to 100 S ⁇ cm -1 , more preferably For example, it may be 0.01 S ⁇ cm -1 to 50 S ⁇ cm -1 .
  • the organic ligand of the metal-organic framework may have high electrical conductivity because it has pi-back bonding.
  • the pi back bonding is a chemical concept in which electrons move from an atomic orbital of one atom to a ⁇ * anti-bonding orbital of another atom or ligand. Specifically, by an aryl group included in an organic ligand The bonding may be formed.
  • 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 has an average diameter of 0.5 nm to 20 nm. It may include pores. That is, since the metal-organic framework has a high porosity and average pore diameter, when a hybrid composite including the same is used as an electrode active material of an electrochemical device such as a secondary battery or a supercapacitor, the occlusion and desorption of the electrolyte is easy. The electrochemical properties of the electrochemical device may be improved.
  • the hybrid composite is a plurality of two-dimensional nanosheets, and may include a two-dimensional nanosheet selected from the group consisting of a metal oxide sheet, a metal carbide sheet, and a metal hydroxide sheet.
  • the metal oxide sheet is manganese oxide, cobalt oxide (cobalt oxdie), rubidium oxide (rubidium oxide), titanium oxide (titanium oxide), vanadium oxide (vanadium oxide), iron oxide (iron oxide), nickel Nickel oxide, copper oxide, zinc oxide, zirconium dioxide, molybdenum oxide, tantalum oxide and a metal oxide selected from the group consisting of combinations thereof, and preferably may include manganese oxide or cobalt oxide.
  • the metal oxide sheet may be any metal oxide that can be manufactured into a two-dimensional nanosheet that can be manufactured according to the manufacturing process shown in FIG. 4 .
  • a mixture of tert-butyl alcohol (TBA) and amine is treated on a metal oxide in a laminated form, and the mixture is inserted between the metal oxide layers, followed by ultrasonic treatment ( Sonication) may be to obtain a metal oxide sheet by exfoliating each metal oxide layer by swelling (swelling).
  • the metal carbide sheet is titanium carbide (titanium carbide), aluminum carbide (aluminum carbide), chromium carbide (chromium carbide), zinc carbide (zinc carbide), copper carbide (copper carbide), magnesium carbide (magnesium carbide), zirconium Carbide (zirconium carbide), molybdenum carbide (molybdenum carbide), vanadium carbide (vanadium carbide), niobium carbide (niobium carbide), iron carbide (iron carbide), manganese carbide (manganese carbide), cobalt carbide (cobalt carbide) It may include a metal carbide selected from the group consisting of nickel carbide, tantalum carbide, and combinations thereof, and may preferably include titanium carbide.
  • the metal carbide sheet may be manufactured according to the manufacturing process shown in FIG. 5 . Specifically, first, the bulk metal carbide having a layered crystal structure in the bulk form is treated with HF, etc. to obtain expanded metal carbide with each metal carbide layer separated, and fluoroamphetamine (FA) is added to the expanded metal carbide. ) or by treatment with dimethylformamide (DMF) or the like to obtain a peeled metal carbide sheet.
  • FFA fluoroamphetamine
  • DMF dimethylformamide
  • the metal hydroxide sheet is a peeled metal double layer hydroxide (LDH) nanosheet
  • the peeled metal double layer hydroxide nanosheet is a compound represented by the following [Formula 5], characterized in that may be doing:
  • M II is selected from the group consisting of Ca 2+ , Mg 2+ , Zn 2+ , Ni 2+ , Mn 2+ , Co 2+ , Fe 2+ , Cu 2+ and mixed metals thereof
  • M III is selected from the group consisting of Fe 3+ , Al 3+ , Cr 3+ , Mn 3+ , Ga 3+ , Co 3+ , Ni 3+ and mixed metals thereof
  • a n- is a hydroxide ion ( OH - ), nitrate ions (NO 3 - ), PO 4 3- , HPO 4 2- , H 2 PO 4 - and combinations thereof, 0 ⁇ x ⁇ 1, and z is 0.1 to 15 may be a mistake in
  • FIG. 6 is a schematic diagram showing a manufacturing process of a metal hydroxide sheet according to an embodiment of the present invention.
  • the metal double layer hydroxide (LDH) nanosheet represented by Formula 1 is co-precipitated, and then the metal double layer hydroxide salt is prepared by adding 1-butanol, 1-hexanol, 1-octanol ( 1-octanol), 1-decanol (1-decanol), CCl4, xylene formamide (HCONH2; formamide), and dimethylformamide (dimethylformamide, DMF) reaction with one or more solvents selected from the group consisting of It can be prepared in the form of a nanosheet through the step of dissolving (exfoliation) in the form of a metal double-layer hydroxide salt having a cationic surface charge.
  • the type of the solvent is not limited as long as it can dissolve the metal double layer hydroxide salt.
  • the two-dimensional nanosheet may each include a plurality of nanopores, wherein the size of the nanopores may be 0.5 nm to 20 nm.
  • the content of the two-dimensional nanosheet relative to 100 parts by weight of the metal-organic framework may be 10 parts by weight to 300 parts by weight.
  • the content of the two-dimensional nanosheet relative to 100 parts by weight of the metal-organic framework may be 30 parts by weight to 200 parts by weight.
  • a hybrid complex can be obtained by reacting the metal-organic framework to contain about 0.01 to 0.2 g of the metal-organic framework per 10 ml of the dispersed solution including the two-dimensional nanosheet, but this is not limited This is merely an example, and is not limited thereto.
  • the porosity of the hybrid composite may be 30 vol% to 70 vol%. That is, the hybrid composite includes both the specific porosity of the metal-organic framework (MOF) and the specific porosity of the metal oxide sheet or metal carbide sheet, and the metal-organic framework (MOF) and the metal oxide Alternatively, the metal carbide sheet may have a very high porosity because it also includes three-dimensional pores that are randomly mixed and generated.
  • MOF metal-organic framework
  • the metal carbide sheet may have a very high porosity because it also includes three-dimensional pores that are randomly mixed and generated.
  • the electrode active material may be used in a secondary battery or a supercapacitor, etc., and since the hybrid composite has high porosity and excellent electrical conductivity, the energy density and output characteristics of the devices are improved.
  • the porosity of the hybrid composite may be 30 vol% to 70 vol%, and the electrical conductivity may be 0.01 S ⁇ cm ⁇ 1 or more.
  • the electrode active material may be formed on the electrode current collector.
  • the electrode current collector may include stainless steel, aluminum, nickel, titanium, sintered carbon, or a material in which carbon, nickel, titanium, silver, or the like is surface-treated on the surface of aluminum or stainless steel.
  • the electrode current collector may have a thickness of about 3 ⁇ m to 500 ⁇ m, and may be to form fine irregularities on the surface of the current collector to increase the adhesion of the electrode active material. That is, it may be used in various forms, such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven body.
  • the electrode active material may further include a conductive material and a binder in addition to the active material.
  • the conductive material is used to impart conductivity to the electrode, and as long as it has electrical conductivity without causing a chemical change in the device, there may be no restriction on the type of the conductive material.
  • the conductive material may include 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 , a metal powder or metal fiber such as silver, a conductive whiskey such as zinc oxide and potassium titanate, a conductive metal oxide such as titanium oxide or a conductive polymer such as a polyphenylene derivative, and a material selected from the group consisting of combinations thereof may be doing Meanwhile, the conductive material 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.
  • the binder may serve to improve adhesion between the electrode active material particles and adhesion between the electrode active material and the current collector.
  • the binder is, for example, polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile (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 ponylated-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 supercapacitor may preferably be a hybrid supercapacitor, and the hybrid supercapacitor may specifically include a positive electrode; cathode; It may include a separator and an electrolyte interposed between the positive electrode and the negative electrode.
  • the electrode active material may be preferably used as the active material of the negative electrode, and activated carbon may be used as the positive active material of the positive electrode.
  • the electrolyte used in the hybrid supercapacitor may be used by mixing a salt and an additive in an organic solvent.
  • 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 GBL ( ⁇ -buthrolactone), MF (Methyl formate), MP (Methyl propionate), and combinations thereof.
  • the lithium (Li) salt is accompanied by an insertion/desorption reaction into the structure of the anode active material, that is, the hybrid composite, 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 , LiBOB (Lithium bis(oxalato)borate), and combinations thereof may be included.
  • the non-lithium salt is accompanied by 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.
  • the non-lithium salt contains a material selected from the group consisting of TEABF 4 (Tetraethylammonium tetrafluoroborate), TEMABF 4 (Triethylmethylammonium tetrafluorborate), SBPBF 4 (spiro-(1,1′)-bipyrrolidium tetrafluoroborate) and combinations thereof.
  • the carbon material additive may include a material selected from the group consisting of VC (Vinylene Carbonate), VEC (Vinyl ethylene carbonate), FEC (Fluoroethylene carbonate), and combinations thereof.
  • 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 from being electrically shorted, and a material having a porosity may be used.
  • the separator may include a material selected from the group consisting of polypropylene-based, polyethylene-based, polyolefin-based, and combinations thereof.
  • the hybrid supercapacitor having the above configuration has high electrical conductivity because the hybrid composite is used as the negative electrode active material, and the capacity is improved due to the high specific surface area of the carbon material additive, so that high energy density and output characteristics may be to have That is, a carbon material additive is inserted into a plurality of spaces formed in the hybrid composite, and a hybrid supercapacitor including the same may exhibit excellent electrical conductivity, capacitance, and output characteristics.
  • the hybrid complex is a catalyst for water purification, anticancer agent, immunodeficiency virus treatment agent, fungal and bacterial infection treatment agent, malaria treatment agent, various drug delivery materials, photocatalyst, sensor, Since it can be applied in various fields such as aerospace materials, it can be used as a commercially very useful material.

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Abstract

L'invention concerne un composite hybride comprenant une structure organométallique (MOF) et une feuille bidimensionnelle. Le composite hybride présente une porosité élevée et une excellente conductivité, et peut donc être utilisé dans une électrode d'un supercondensateur ou d'une cellule secondaire pour améliorer ses caractéristiques de densité d'énergie et d'émission et analogues.
PCT/KR2021/017228 2020-11-24 2021-11-23 Composite hybride comprenant une structure organométallique (mof) et une feuille bidimensionnelle WO2022114714A1 (fr)

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CN116351473A (zh) * 2023-02-27 2023-06-30 北京工业大学 金属有机框架-二氧化锰复合材料及分解臭氧的应用

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