WO2021131643A1 - 導電性複合構造体およびその製造方法 - Google Patents

導電性複合構造体およびその製造方法 Download PDF

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WO2021131643A1
WO2021131643A1 PCT/JP2020/045508 JP2020045508W WO2021131643A1 WO 2021131643 A1 WO2021131643 A1 WO 2021131643A1 JP 2020045508 W JP2020045508 W JP 2020045508W WO 2021131643 A1 WO2021131643 A1 WO 2021131643A1
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base material
mxene
composite structure
metal base
conductive composite
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French (fr)
Japanese (ja)
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匡矩 阿部
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2021567168A priority Critical patent/JP7164055B2/ja
Priority to CN202080089834.8A priority patent/CN114901470B/zh
Publication of WO2021131643A1 publication Critical patent/WO2021131643A1/ja
Priority to US17/835,700 priority patent/US20220328843A1/en
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    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B2562/00—Details of sensors; Constructional details of sensor housings or probes; Accessories for sensors
    • A61B2562/12—Manufacturing methods specially adapted for producing sensors for in-vivo measurements
    • A61B2562/125—Manufacturing methods specially adapted for producing sensors for in-vivo measurements characterised by the manufacture of electrodes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products

Definitions

  • the present invention relates to a conductive composite structure, more specifically, a conductive composite structure including a metal base material and a conductive film provided on the surface of the metal base material, and a method for producing the same.
  • MXene has been attracting attention as a new material with conductivity.
  • MXene is a kind of so-called two-dimensional material, and is a layered material having the form of one or a plurality of layers as described later.
  • MXene is known to be usable as an electrode active material for electrochemical capacitors (particularly pseudocapacitors) and lithium ion batteries (see, for example, Patent Document 1 and the like).
  • An electrode using MXene as an electrode active material can be produced as a conductive film composed of a mixture containing MXene and a binder, and in some cases, can be produced as a conductive film composed of MXene only. Further, an electrode using MXene as an electrode active material can also be produced by forming such a conductive film on the surface of a current collector made of a metal base material.
  • a slurry containing the electrode active material MXene, a binder and an organic solvent can be prepared, applied onto a current collector, dried, and pressed to fix the slurry. (See paragraphs 0020, 0026, 0042, etc. of Patent Document 1.)
  • conductive films composed only of MXenes have a drawback that it is difficult to maintain the shape of the film by MXenes alone, cracks may occur when bent, and bending resistance is low.
  • a conductive film consisting of a mixture containing MXene and a binder has improved bending resistance, but the surface and / or layers of MXene can be hindered by the binder, thus providing sufficient electrical properties for MXene itself. It is difficult to obtain sufficiently high bending resistance while utilizing it.
  • a conductive composite structure including a metal base material and a conductive film provided on the surface of the metal base material.
  • the conductive film comprises a layered material comprising one or more layers.
  • the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, and X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5)
  • T is a hydroxyl group, an oxygen atom or a combination thereof
  • a conductive composite in which a balance derived from an organic compound having 2 to 8 carbon atoms having a hydroxyl group, a carbonyl group, or a combination thereof is bonded to each of the surface of the metal substrate and the surface of the layer body.
  • the structure is provided.
  • the layer has the following formula: M m X n (In the formula, M is at least one group 3, 4, 5, 6, 7 metal, and X is a carbon atom, a nitrogen atom or a combination thereof, n is 1 or more and 4 or less, m is greater than n and less than or equal to 5)
  • the layered material containing the layer body represented by and the modification or termination T (T is a hydroxyl group, an oxygen atom or a combination thereof) present on the surface of the layer body is a hydroxyl group, a carbonyl group or a combination thereof.
  • a production method comprising (b) applying the dispersion to the surface of a metal substrate and (c) subjecting the metal substrate to which the dispersion has been applied to a heat treatment is provided.
  • the conductive film is a predetermined layered material (the present specification). It is derived from an organic compound having 2 to 8 carbon atoms and having a hydroxyl group, a carbonyl group, or a combination thereof on the surface of the metal base material and the surface of the layer body of the layered material, respectively. The rest is bonded, which provides a conductive composite structure having high bending resistance and high bonding force between the conductive film and the metal substrate.
  • a dispersion liquid in which MXene is dispersed in a liquid medium containing an organic compound having 2 to 8 carbon atoms having a hydroxyl group, a carbonyl group or a combination thereof is provided.
  • a dispersion is applied to the surface of a metal base material and subjected to heat treatment, whereby the conductivity is high and the bonding force between the conductive film and the metal base material is high.
  • a sex composite structure can be produced.
  • FIG. 1 It is a schematic schematic cross-sectional view which shows the conductive composite structure in one Embodiment of this invention. It is a schematic schematic cross-sectional view which shows MXene which is a layered material which can be used for the conductive composite structure in one Embodiment of this invention. It is a figure which shows the evaluation result of the conductive composite structure produced in Example 1 of this invention, (a) shows the result of the axial center winding test, (b) shows the result of the acetone immersion test, ( c) shows the result of the tape peeling test.
  • the conductive composite structure 20 of the present embodiment includes a metal base material 11 and a conductive film 13 provided on the surface of the metal base material 11.
  • the method for manufacturing the conductive composite structure 20 of the present embodiment is as follows.
  • This includes (b) applying the dispersion liquid to the surface of a metal base material, and (c) subjecting the metal base material to which the dispersion liquid is applied to heat treatment.
  • a predetermined layered material is prepared.
  • the predetermined layered material that can be used in this embodiment is MXene and is defined as follows: A layered material comprising one or more layers, the layer having the following formula: M m X n (In the formula, M is at least one Group 3, 4, 5, 6, 7 metal, so-called early transition metals such as Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and It may contain at least one selected from the group consisting of Mn.
  • the layer body represented by may have a crystal lattice in which each X is located in an octahedral array of M) and the surface of the layer body (more specifically, the layer bodies are opposed to each other).
  • a modification or termination T T is a hydroxyl group, an oxygen atom or a combination thereof (in other words, a hydroxyl group and / or an oxygen atom), and optionally a fluorine atom and / or a fluorine atom) present on at least one of the two surfaces.
  • n can be 1, 2, 3 or 4, but is not limited to this.
  • MXene may have a hydroxyl group and / or an oxygen atom as a modification or termination T, preferably both a hydroxyl group and an oxygen atom. Hydroxyl groups and / or oxygen atoms present in MXene as modifications or terminations T contribute to the reactions described below.
  • M is preferably at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr and Mo.
  • Such MXene can be synthesized by selectively etching (removing and optionally layering) A atoms (and optionally a portion of M atoms) from the MAX phase.
  • the MAX phase is expressed by the following formula: M m AX n (In the formula, M, X, n and m are as described above, A is at least one group 12th, 13th, 14th, 15th and 16th element, usually a group A element, representatively.
  • Is a group IIIA and a group IVA and more particularly may include at least one selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S and Cd.
  • a layer composed of A atoms is located between two layers represented by and represented by M m X n (each X may have a crystal lattice located in an octahedral array of M).
  • M m X n a layer of X atoms between the layers of the M atoms are arranged layer by layer (Together these also referred to as "M m X n layer"), It has a repeating unit in which a layer of A atoms (“A atom layer”) is arranged as a layer next to the n + 1th layer of M atoms, but is not limited to this.
  • the A atom layer (and possibly part of the M atom) is removed by selectively etching (removing and possibly layering) the A atom (and possibly part of the M atom) from the MAX phase.
  • the etching liquid to the surface of the exposed M m X n layer a fluorine atom optionally (usually an aqueous solution of the fluorinated acid is used but not limited to) hydroxy groups and / or oxygen atom (further present in and / or A hydrogen atom, etc.) modifies and terminates such a surface.
  • the etching can be carried out using an etching solution containing F ⁇ , and may be, for example, a method using a mixed solution of lithium fluoride and hydrochloric acid, a method using hydrofluoric acid, or the like. Then, as appropriate, by any suitable post-treatment (eg sonication, handshake or automatic shaker, etc.), MXene layer separation (delamination, separating multi-layer MXene into single-layer MXene and / or low-layer MXene). May be promoted.
  • any suitable post-treatment eg sonication, handshake or automatic shaker, etc.
  • MXene layer separation delamination, separating multi-layer MXene into single-layer MXene and / or low-layer MXene. May be promoted.
  • the shearing force of the ultrasonic treatment is too large and the MXene particles can be destroyed, it is desired to obtain a two-dimensional MXene (preferably a single-layer MXene and / or a small-layer MXene) having a larger aspect ratio.
  • M can be titanium or vanadium and X can be a carbon or nitrogen atom.
  • X can be a carbon or nitrogen atom.
  • the MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 T s .
  • MXene may contain a relatively small amount of residual A atom, for example, 10% by mass or less with respect to the original A atom.
  • the residual amount of A atom can be preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of A atom exceeds 10% by mass, there may be no problem depending on the use and usage conditions of the conductive composite structure.
  • the MXene 10 synthesized in this way has one or more MXene layers 7a, 7b, 7c (three layers are exemplified in the figure, which are shown in the figure. It can be a layered material containing (but not limited to). More particularly, MXene layer 7a, 7b, 7c is, M m X n layer body represented by (M m X n layer) 1a, 1b, 1c and, the layer body 1a, 1b, 1c the surface (more specifically the Has modifications or terminations T 3a, 5a, 3b, 5b, 3c, 5c that are present on at least one of the two surfaces facing each other in each layer.
  • MXene layer 7a, 7b, 7c is, M m X n layer body represented by (M m X n layer) 1a, 1b, 1c and, the layer body 1a, 1b, 1c the surface (more specifically the Has modifications or terminations T 3a, 5a, 3b, 5b
  • MXene layer 7a, 7b, 7c is also denoted as "M m X n T s", s is an arbitrary number.
  • the MXene 10 is a laminate in which a plurality of MXene layers are laminated so as to be separated from each other, even if the MXene layers are individually separated and exist in one layer (single-layer structure, so-called single-layer MXene). It may be a multi-layer structure, so-called multi-layer MXene), or a mixture thereof.
  • MXene can be particles (also referred to as powders or flakes) as an aggregate composed of monolayer MXenes and / or multilayer MXenes. In the case of a multilayer MXene, two adjacent MXene layers (for example, 7a and 7b, 7b and 7c) do not necessarily have to be completely separated, and may be partially in contact with each other.
  • each layer of MXene is, for example, 0.8 nm or more and 5 nm or less, particularly 0.8 nm or more and 3 nm or less. (Mainly, it may vary depending on the number of M atomic layers contained in each layer), the maximum dimension in a plane parallel to the layer (two-dimensional sheet surface) is, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less. ..
  • the interlayer distance is, for example, 0.8 nm or more and 10 nm or less, particularly 0.8 nm or more and 5 nm. Below, it is more particularly about 1 nm, and the maximum dimension in a plane (two-dimensional sheet surface) perpendicular to the stacking direction is, for example, 0.1 ⁇ m or more and 100 ⁇ m or less, and particularly 1 ⁇ m or more and 20 ⁇ m or less.
  • the total number of layers may be 2 or more for each laminated body, for example, 50 or more and 100,000 or less, particularly 1,000 or more and 20,000 or less.
  • the thickness in the stacking direction is, for example, 0.1 ⁇ m or more and 200 ⁇ m or less, particularly 1 ⁇ m or more and 40 ⁇ m or less.
  • MXene When MXene is a laminated body (multilayer MXene), it may be MXene with a small number of layers.
  • the term "small number of layers” means, for example, that the number of layers of MXene is 6 or less.
  • the thickness of the multilayer MXene having a small number of layers in the stacking direction is preferably 10 nm or less. In the present specification, this "multilayer MXene with a small number of layers" (multilayer MXene in a narrow sense) is also referred to as "small layer MXene".
  • the MXene 10 may be particles (which may also be referred to as nanosheets), most of which are composed of a single layer MXene 10a and / or a small layer MXene.
  • the proportion of particles (single layer MXene and / or small layer MXene) having a thickness of 10 nm or less in the stacking direction in the entire MXene particles can be 50% by volume or more.
  • these dimensions described above are number average dimensions (for example, at least 40 number averages) or X-rays based on photographs of a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an atomic force microscope (AFM). It is obtained as a distance in real space calculated from the position of the (002) plane on the reciprocal lattice space measured by the diffraction (XRD) method.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • a liquid medium containing an organic compound having a hydroxyl group and / or a carbonyl group and having 2 to 8 carbon atoms (hereinafter, also simply referred to as “reactive organic compound”) is prepared.
  • the reactive organic compound has a hydroxyl group and / or a carbonyl group, and can typically have either a hydroxyl group or a carbonyl group.
  • the hydroxyl and / or carbonyl groups of the reactive organic compound contribute to the reactions described below.
  • the reactive organic compound has 2 or more and 8 or less carbon atoms, preferably 3 or more and / or 7 or less carbon atoms.
  • the number of carbon atoms is 2 or more, preferably 3 or more, it is possible to prevent the aggregation of MXenes in the dispersion liquid (before the heat treatment described later).
  • the number of carbon atoms is 8 or less, preferably 7 or less, when MXene is a laminated body (multilayer MXene), it can appropriately penetrate between the layers of the laminated body.
  • the reactive organic compound can be an alcohol or ketone having 2 or more and 8 or less carbon atoms. More specifically, the reactive organic compound can be at least one selected from the group consisting of isopropyl alcohol, N-methylpyrrolidone and methyl ethyl ketone, any one of these or any mixture of two or more. obtain.
  • the liquid medium is preferably composed of a reactive organic compound, but contains other organic compounds in a relatively small amount (for example, 30% by mass or less, preferably 20% by mass or less on an overall basis) in addition to the reactive organic compound. You may be.
  • the liquid medium may contain a very small amount of water (for example, 30% by mass or less, preferably 20% by mass or less on an overall basis), depending on the reactive organic compound used.
  • the MXene described above prepares a dispersion (also referred to as suspension or slurry) dispersed in such a liquid medium.
  • the dispersion method is not particularly limited, but can be typically stirring (share mixer, pot mill, etc.), sonication, shaking, or the like.
  • the reactive organic compound can come into contact with the surface of MXene, and when MXene is a laminate (multilayer MXene), it can come into contact with the outermost surface of the laminate and between the layers of the laminate. Can invade.
  • the content ratio of MXene in the dispersion liquid is not particularly limited, but may be, for example, 20 to 95% by mass.
  • the metal base material 11 may be a conductive member based on one or more kinds of metals.
  • the "metal-based conductive member” means that the metal content in the metal base material 11 (when two or more kinds of metals are contained, the total content of those metals) is 80% by weight or more, for example, 90% by weight. As mentioned above, it is preferably 95% by weight or more, and means a member which is conductive as a whole. Examples of the conductive substance other than the metal that can form the metal base material 11 include carbon and the like.
  • the metal base material 11 has a hydroxyl group, an oxygen atom or a combination thereof (in other words, a hydroxyl group and / or an oxygen atom) on the outermost surface thereof, and may preferably have both a hydroxyl group and an oxygen atom.
  • the hydroxyl groups and / or oxygen atoms present on the outermost surface of the metal substrate 11 contribute to the reaction described later.
  • the metal base material 11 can typically have a sheet-like shape. "Sheet-like”, as is generally understood, refers to a shape having two planes facing each other and a relatively small distance (thickness) between these planes, in addition to a sheet, a film or foil. It can also be called.
  • the metal substrate 11 is not limited to this, and may have any suitable form.
  • the metal base material 11 is not strictly composed entirely of metal atoms, even if it is a metal member.
  • the hydroxyl group and / or oxygen atom existing on the outermost surface of the metal base material 11 is a metal oxide film (more specifically, an amorphous metal oxide film) existing on the surface portion of the metal base material 11, so-called passivation. It may be present on the outermost surface of the film).
  • the metal base material 11 may be an aluminum base material, a copper base material, or a stainless steel base material (in other words, a conductive member based on aluminum, copper, or stainless steel), and more particularly, an aluminum member. , Copper member or stainless steel member.
  • the aluminum member has an alumina (possibly amorphous) film formed on its surface portion, and has a hydroxyl group and / or an oxygen atom, usually both a hydroxyl group and an oxygen atom, on the outermost surface of the alumina film. ..
  • a copper member has a copper oxide (which can be amorphous) film formed on its surface, with hydroxyl and / or oxygen atoms, usually both hydroxyl and oxygen atoms, on the outermost surface of the copper oxide film.
  • the stainless steel is a steel having a carbon content of 1.2% by mass or less and a chromium content of 10.5% by mass or more, and may contain an additive metal such as nickel in some cases.
  • the stainless steel may be, for example, SUS304, SUS316, SUS430, or the like.
  • the stainless steel member has a film of iron oxide and chromium oxide (which can be amorphous) formed on its surface, and has a hydroxyl group and / or oxygen atom on the outermost surface of the iron oxide-chromium oxide film, usually. Has both a hydroxyl group and an oxygen atom.
  • the metal base material 11 may have a conductive substance other than the metal as described above.
  • a carbon coat layer may be formed on a metal member (for example, an aluminum member, a copper member, or a stainless steel member).
  • Carbon has a hydroxyl group and / or an oxygen atom, usually both a hydroxyl group and an oxygen atom, on its outermost surface unless a special treatment such as a hydrophobic treatment is performed.
  • the dimensions of the metal base material 11 are not particularly limited, and can be appropriately selected depending on the use of the conductive composite structure 20.
  • the thickness of the metal base material 11 is preferably a bendable thickness, but this is not essential in applications where high bending resistance is not required.
  • the dispersion liquid prepared in the above step (a) is applied (more specifically, coated) to the surface of the metal base material 11.
  • the application method is not particularly limited, and for example, blade coating, knife coating, bar coating, screen printing, slit coating, die coating, roll coating, dip coating, spray coating, spin coating and the like can be used.
  • the thickness of the dispersion liquid applied to the surface of the metal base material 11 may vary depending on the composition of the dispersion liquid, the thickness desired for the conductive film 13, and the like.
  • Step (c) The metal base material 11 to which the dispersion liquid is applied in the above step (b) is subjected to heat treatment.
  • the reactive organic compound can be reacted with the metal base material 11 and with MXene 10. More specifically, the following reactions can proceed.
  • the hydroxyl group of the reactive organic compound can react with the oxygen atom existing on the outermost surface of the metal base material 11 to form a bond between them. Further, the hydroxyl group of the reactive organic compound can react with an oxygen atom existing on the surface of the layer bodies 1a, 1b and 1c of MXene 10 as a modification or a terminal T to form a bond between them.
  • these reactions can be, but are not limited to, a reaction that forms a hydrogen bond between the hydrogen atom of the hydroxyl group of the reactive organic compound and the oxygen atom of the metal substrate 11 / MXene10.
  • it may be accompanied by a reaction in which a hydrogen atom is eliminated from a reactive organic compound.
  • the reactive organic compound has a carbonyl group
  • the carbonyl group of the reactive organic compound can react with the hydroxyl group existing on the outermost surface of the metal substrate 11 to form a bond between them.
  • the carbonyl group of the reactive organic compound can react with a hydroxyl group existing as a modification or termination T on the surface of the layer bodies 1a, 1b and 1c of MXene 10 to form a bond between them.
  • these reactions may be reactions that form a hydrogen bond between the oxygen atom of the carbonyl group of the reactive organic compound and the hydrogen atom of the hydroxyl group of the metal substrate 11 / MXene10. Not limited. For example, it may be accompanied by a reaction in which a hydrogen atom is eliminated from a reactive organic compound.
  • reaction mechanism can be understood as schematically shown below.
  • the case where the reactive organic compound has a hydroxyl group the case where the isopropyl alcohol reacts with MXene and the case where the reactive organic compound reacts with a copper member, and the reactive organic compound has a carbonyl group.
  • N-methylpyrrolidone reacts with MXene and reacts with an aluminum member
  • methylethylketone reacts with an aluminum member
  • unreacted reactive organic compounds can be evaporated and removed by heat treatment.
  • the reaction and evaporation of the reactive organic compound proceed to allow MXene (whether in single-layer MXene or multi-layer MXene) to adhere to and agglomerate.
  • the heat treatment conditions may differ depending on the reactive organic compound used.
  • the heat treatment temperature can be, for example, 70 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 180 ° C. or lower.
  • the heat treatment time can be appropriately set, and can be, for example, 0.5 hours or more and 24 hours or less.
  • the heat treatment atmosphere can be a reduced pressure (or vacuum) atmosphere, an air atmosphere, a nitrogen atmosphere, or the like.
  • any appropriate post-step may be carried out after the heat treatment in step (c).
  • a post-step may be a step of cutting the conductive composite structure 20 into a desired shape (for example, punching) and / or a step of pressing the conductive composite structure 20.
  • the balance derived from the reactive organic compound is bonded to the surface of the metal base material 11, and the surfaces of the layer bodies 1a, 1b, and 1c of MXene (in other words, in other words). , MXene surface and / or interlayer) with the remainder derived from the reactive organic compound bonded.
  • the “residue derived from the reactive organic compound” means the residue of the reactive organic compound after the heat treatment. For example, as compared with the chemical formula of the original reactive organic compound, the "residue derived from the reactive organic compound" is desorbed from hydrogen atoms even if it is represented by the same chemical formula except for the hydrogen bond forming part.
  • the conductive film 13 can be understood as a dry film.
  • the conductive film 13 is provided on the surface of the metal base material 11 containing MXene and not containing a binder (binderless). Unless otherwise specified, the description in the manufacturing method of the present embodiment may be similarly applied to MXene and the metal base material in the conductive composite structure 20.
  • the bending resistance (particularly flexibility) is high, and the bonding strength between the conductive film 11 and the metal base material 13 (particularly, chemical stability with respect to an organic solvent). It is possible to manufacture the conductive composite structure 20 having high peel strength and the like). More specifically, even if the conductive composite structure 20 is bent, the conductive film 13 is less likely to crack, and even if the conductive composite structure 20 is immersed in an organic solvent or subjected to a tape peeling test. , The conductive film 13 is hard to peel off from the metal base material 11.
  • the conductive film 13 has a higher density of MXenes and a higher adhesion strength between MXenes (single-layer MXenes and / or multi-layer MXenes) as compared with a conventionally known conductive film composed only of MXenes (binder). It can be understood that this is due to the improved strength, shapeability and flexibility of the conductive film itself (even if it is less).
  • the reason why a high bonding force can be obtained between the conductive film 13 and the metal base material 11 is that there is a residue derived from the reactive organic compound on both the surface of MXene and the surface described in the metal. It can be understood that between the sex film 13 and the metal substrate 11, the balance derived from the reactive organic compound acts like an adhesive.
  • the conductive composite structure 20 of the present embodiment can be used for any suitable application. Since the conductive composite structure 20 of the present embodiment has a high MXene density in the conductive film 13 and can achieve desired electrical characteristics with smaller dimensions, the conductive composite structure 20 can be miniaturized, and thus the conductive composite structure 20 can be miniaturized. It can be preferably used when miniaturization of the product in which it is incorporated is required. Further, in the conductive composite structure 20 of the present embodiment, the conductive composite structure 20 is bent and stretched during use by the user of the final product into which the conductive composite structure is incorporated and / or during the manufacturing process until the conductive composite structure 20 is incorporated into the final product. It can be preferably used when it is required to withstand.
  • the conductive composite structure 20 of the present embodiment can be used as an electrode.
  • MXene of the conductive film 13 functions as an electrode active material (a substance that transfers electrons to and from electrolyte ions in the electrolytic solution), and the metal base material 11 Functions as a current collector.
  • the electrode is not particularly limited, but may be, for example, a capacitor electrode, a battery electrode, a bioelectrode, a sensor electrode, an antenna electrode, or the like.
  • a capacitor electrode a battery electrode
  • a bioelectrode a sensor electrode
  • an antenna electrode or the like.
  • the capacitor can be an electrochemical capacitor.
  • An electrochemical capacitor is a capacitor that utilizes the capacity developed by a physicochemical reaction between an electrode (electrode active material) and an ion (electrolyte ion) in an electrolytic solution, and is a device (storage) that stores electrical energy. Can be used as a device).
  • the battery can be a chemical cell that can be recharged and discharged repeatedly.
  • the battery can be, for example, a lithium ion battery, a magnesium ion battery, a lithium sulfur battery, a sodium ion battery, and the like, but is not limited thereto.
  • the electrodes may be required to be flexible enough to withstand bending and stretching, and the electrodes may be bent and placed within the capacitors and batteries, such applications.
  • the conductive composite structure 20 of the present embodiment can be suitably used as an electrode.
  • the bioelectrode is an electrode for acquiring a biosignal.
  • the bioelectrode can be, for example, an electrode for measuring EEG (electroencephalogram), ECG (electrocardiogram), EMG (electromyogram), EIT (electrical impedance tomography), but is not limited thereto.
  • the bioelectrode can be used by being attached to a living body (particularly the skin), and is required to have flexibility to withstand bending and stretching without peeling from the skin even if the skin expands and contracts.
  • the composite structure 20 can be suitably used as an electrode.
  • the sensor electrode is an electrode for detecting a target substance, state, abnormality, etc.
  • the sensor may be, for example, a gas sensor, a biosensor (a chemical sensor utilizing a molecular recognition mechanism of biological origin), or the like, but is not limited thereto.
  • a sensor electrode By using the conductive composite structure 20 of the present embodiment as a sensor electrode, it is possible to provide a sensor electrode having a high bonding force with a metal base material and being flexible as a whole.
  • the antenna electrode is an electrode for radiating electromagnetic waves into space and / or receiving electromagnetic waves in space.
  • the conductive composite structure 20 of the present embodiment as an antenna electrode, it is possible to provide an antenna electrode having a high bonding force with a metal base material and being flexible as a whole.
  • the conductive composite structure according to one embodiment of the present invention has been described in detail through its manufacturing method, but various modifications are possible.
  • the conductive composite structure of the present invention may be manufactured by a method different from the manufacturing method in the above-described embodiment, and the method for manufacturing the conductive composite structure of the present invention is in the above-described embodiment. It should be noted that it is not limited to those that provide a conductive composite structure.
  • Example 1 This example relates to an example in which a conductive composite structure is prepared by using isopropyl alcohol (IPA) as a reactive organic compound and copper foil as a metal base material.
  • IPA isopropyl alcohol
  • Ti 3 AlC 2 particles were prepared as MAX particles by a known method. 1 g of the Ti 3 AlC 2 particles (powder) is weighed, added to 10 mL of 9 mol / L hydrochloric acid together with 1 g of LiF, and stirred at 35 ° C. for 24 hours with a stirrer to obtain a solid derived from the Ti 3 AlC 2 powder. A solid-liquid mixture (suspension) containing the components was obtained.
  • the MXene-IPA dispersion liquid prepared above was used as a copper foil (stock) as the metal base material using a table coater (PI-1210 automatic coating device manufactured by Tester Sangyo Co., Ltd.). It was applied to the upper surface of Thunk Metal Co., Ltd. (thickness 10 ⁇ m).
  • a table coater PI-1210 automatic coating device manufactured by Tester Sangyo Co., Ltd.
  • Thunk Metal Co., Ltd. Thunk Metal Co., Ltd. (thickness 10 ⁇ m).
  • a variable blade (Baker applicator YBA-3 type manufactured by Yoshimitsu Seiki Co., Ltd.) set with a gap of 127 ⁇ m was used.
  • the copper foil coated with the MXene-IPA dispersion was placed in a vacuum oven (ETTAS vacuum dryer AVO-310SB, manufactured by AS ONE Corporation) in a vacuum (vacuum degree 0.1 kPa) at 120 ° C. for 3 hours. It was subjected to heat treatment. As a result, a structure in which a dry MXene film derived from the IPA dispersion (hereinafter referred to as "IPA-MXene film”) was formed on the upper surface of the copper foil was obtained as the conductive film.
  • IPA-MXene film dry MXene film derived from the IPA dispersion
  • Example 1 The conductive composite structure of Example 1 produced above was evaluated by subjecting it to a shaft core winding test, an acetone immersion test, and a tape peeling test.
  • the conductive composite structure was wound around an aluminum round bar having a diameter of 4 mm about two times, and the state was maintained to visually confirm the presence or absence of cracks and peeling. As a result, as shown in FIG. 3A, neither cracking in the IPA-MXene film nor peeling of the IPA-MXene film from the copper foil was observed.
  • the conductive composite structure was cut to obtain a 1 cm square test piece.
  • This test piece was immersed in acetone, which is one of the organic solvents, at room temperature for 1 minute, and the presence or absence of peeling was visually confirmed.
  • acetone which is one of the organic solvents
  • cellophane adhesive tape manufactured by Nichiban Co., Ltd., "Cellotape” (registered trademark)
  • IPA-MXene film was only sparsely peeled from the copper foil in a total of about 5% of the affixed area by the tape.
  • Example 2 This example relates to an example in which a conductive composite structure is prepared by using isopropyl alcohol (IPA) as a reactive organic compound and using aluminum foil as a metal base material. Unless otherwise specified, the same equipment as in Example 1 is used, and the same production conditions and evaluation methods are applied (the same applies to the following Examples and Comparative Examples).
  • IPA isopropyl alcohol
  • MXene powder obtained in the same manner as in Example 1 was freeze-dried, and the agglomerated dry powder was pulverized with a planetary ball mill. This gave a Ti 3 C 2 T s powder as MXene powder.
  • the MXene-IPA dispersion liquid prepared above was applied to the upper surface of an aluminum foil (manufactured by Thunk Metal Co., Ltd., thickness 10 ⁇ m) as a metal base material using a table coater.
  • IPA-MXene film a structure in which a dry MXene film derived from an IPA dispersion (hereinafter referred to as "IPA-MXene film") was formed on the upper surface of an aluminum foil was obtained.
  • Example 2 The conductive composite structure of Example 2 produced above was evaluated by subjecting it to a shaft core winding test, an acetone immersion test, and a tape peeling test in the same manner as in Example 1.
  • a shaft core winding test As a result of the axial winding test, as shown in FIG. 4A, neither crack in the IPA-MXene film nor peeling of the IPA-MXene film from the aluminum foil was observed.
  • the acetone immersion test as shown in FIG. 4 (b)
  • the IPA-MXene film maintained its original shape, and no peeling between the IPA-MXene film and the aluminum foil was observed.
  • the tape peeling test as shown in FIG. 4C, the IPA-MXene film was not peeled from the aluminum foil at all by the tape.
  • Example 2 showed the best results among Examples 1 to 4.
  • Example 3 This example relates to an example in which a conductive composite structure is prepared by using N-methylpyrrolidone (NMP) as a reactive organic compound and using aluminum foil as a metal base material.
  • NMP N-methylpyrrolidone
  • MXene powder obtained in the same manner as in Example 1 was freeze-dried, and the agglomerated dry powder was pulverized by a tube mill control (manufactured by IKA). This gave a Ti 3 C 2 T s powder as MXene powder.
  • the MXene-NMP dispersion liquid prepared above was applied to the upper surface of an aluminum foil (manufactured by Thunk Metal Co., Ltd., thickness 10 ⁇ m) as a metal base material using a table coater.
  • NMP-MXene film a structure in which a MXene dry film derived from an NMP dispersion (hereinafter referred to as "NMP-MXene film") was formed on the upper surface of an aluminum foil was obtained.
  • Example 3 The conductive composite structure of Example 3 produced above was evaluated by subjecting it to a shaft core winding test, an acetone immersion test, and a tape peeling test in the same manner as in Example 1.
  • a shaft core winding test As a result of the axial winding test, as shown in FIG. 5A, neither crack in the NMP-MXene film nor peeling of the NMP-MXene film from the aluminum foil was observed.
  • the acetone immersion test as shown in FIG. 5 (b)
  • the NMP-MXene film maintained its original shape, and no peeling between the NMP-MXene film and the aluminum foil was observed.
  • the tape peeling test as shown in FIG. 5C, the NMP-MXene film was not peeled from the aluminum foil at all by the tape.
  • Example 4 This example relates to an example in which a conductive composite structure is prepared by using methyl ethyl ketone (MEK) as a reactive organic compound and using aluminum foil as a metal base material.
  • MEK methyl ethyl ketone
  • the MXene-MEK dispersion liquid prepared above was applied to the upper surface of an aluminum foil (manufactured by Thunk Metal Co., Ltd., thickness 10 ⁇ m) as a metal base material using a table coater.
  • the aluminum foil coated with the MXene-MEK dispersion above is subjected to preliminary heat treatment (80 ° C., 10 minutes) on a hot plate, and then heated to 100 ° C. in a vacuum oven (vacuum degree 0.1 kPa). It was subjected to heat treatment for 10 hours.
  • a conductive film a structure in which a dry MXene film derived from the MEK dispersion (hereinafter referred to as “MEK-MXene film”) was formed on the upper surface of the aluminum foil was obtained.
  • Example 3 The conductive composite structure of Example 3 produced above was evaluated by subjecting it to a shaft core winding test, an acetone immersion test, and a tape peeling test in the same manner as in Example 1.
  • a shaft core winding test As a result of the axial winding test, as shown in FIG. 6A, neither crack in the MEK-MXene film nor peeling of the MEK-MXene film from the aluminum foil was observed.
  • the acetone immersion test as shown in FIG. 6 (b)
  • the MEK-MXene film maintained its original shape, and no peeling between the MEK-MXene film and the aluminum foil was observed.
  • the tape peeling test as shown in FIG. 6C, the MEK-MXene film was only peeled from the aluminum foil in a total of about 20% of the sticking area by the tape.
  • Comparative Example 1 This comparative example relates to an example in which a conductive composite structure is produced by using an aluminum foil as a metal base material without using a reactive organic compound.
  • Ti 3 AlC 2 particles were prepared as MAX particles by a known method. 1 g of the Ti 3 AlC 2 particles (powder) is weighed, added to 10 mL of 9 mol / L hydrochloric acid together with 1 g of LiF, and stirred at 35 ° C. for 24 hours with a stirrer to obtain a solid derived from the Ti 3 AlC 2 powder. A solid-liquid mixture (suspension) containing the components was obtained.
  • dispersion liquid 24.4 g of MXene clay (Ti 3 C 2 T s -aqueous dispersion clay) prepared above was stirred with a thin film swirl type high-speed mixer (manufactured by Primix Corporation, 40-L type) on the way. in further stirred by adding MXene powder (Ti 3 C 2 T s powder) 8.4 g, prepared in the same manner as in example 1 to obtain a MXene- aqueous dispersion. Stirring was carried out until a generally uniform MXene-aqueous dispersion was obtained.
  • Example 3 To the aluminum foil in the same manner as in Example 3 except that the MXene-aqueous dispersion liquid prepared above was used instead of the MXene-MEK dispersion liquid. The dispersion liquid was applied, heat-treated and pressed. As a result, the conductive composite structure of Comparative Example 1 was obtained.
  • the water-MXene film was peeled from the aluminum foil by the tape over a large area of more than about 70% of the sticking area, and the water-MXene film was peeled off from the aluminum foil. The bond between the membrane and the aluminum foil was low.
  • Comparative Example 2 This comparative example relates to an example in which dimethyl ether (DME) is used as the organic compound and aluminum foil is used as the metal base material.
  • DME dimethyl ether
  • the MXene-DME mixture obtained above is to be applied to the upper surface of an aluminum foil (manufactured by Thunk Metal Co., Ltd., thickness 10 ⁇ m) as a metal base material using a table coater. I tried. However, the MXene-DME mixture was difficult to apply. In addition, it peeled off from the aluminum foil after application.
  • the conductive composite structure of the present invention can be used for any suitable application, but can be preferably used for applications that are required to withstand miniaturization and / or bending and stretching, and can be particularly preferably used as an electrode, for example.

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