WO2023047861A1 - 導電性２次元粒子含有組成物、導電性膜、および導電性２次元粒子含有組成物の製造方法 - Google Patents

導電性２次元粒子含有組成物、導電性膜、および導電性２次元粒子含有組成物の製造方法 Download PDF

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WO2023047861A1
WO2023047861A1 PCT/JP2022/031424 JP2022031424W WO2023047861A1 WO 2023047861 A1 WO2023047861 A1 WO 2023047861A1 JP 2022031424 W JP2022031424 W JP 2022031424W WO 2023047861 A1 WO2023047861 A1 WO 2023047861A1
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conductive
water
containing composition
dimensional
dispersion medium
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French (fr)
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雅史 小柳
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to US18/610,748 priority patent/US12509592B2/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present disclosure relates to a conductive two-dimensional particle-containing composition, a conductive film, and a method for producing a conductive two-dimensional particle-containing composition.
  • MXene has attracted attention as a new conductive material.
  • MXene is a type of so-called two-dimensional material, which is a layered material having the form of one or more layers, as described below.
  • MXenes generally have the form of particles (which may include powders, flakes, nanosheets, etc.) of such layered materials.
  • Non-Patent Document 1 shows that MXene has unique structural and electronic properties by using one of O, Cl, S, Se, and Te as the surface functional group of MXene. ing.
  • Non-Patent Document 2 also shows that (Ti 3 C 2 T x )MXene is applied to functional compositions that can be used in various fields such as electrochemical energy storage, smart electronics, and healthcare. ing. Specifically, inks in which the above (Ti 3 C 2 T x )MXene is dispersed in EtOH, DMSO, DMF, or NMP are shown.
  • Non-Patent Document 1 has a structure that is easily oxidized in the air. Therefore, for example, when a conductive film is formed, the conductive film exhibits high conductivity and maintains high conductivity for a long period of time.
  • Non-Patent Document 2 discloses a composition in which MXene is dispersed in DMSO or the like, but the conductivity of a conductive film formed using this composition significantly decreases after 6 months. ing.
  • the present disclosure has been made in view of the above circumstances, and an object thereof is, for example, when a conductive film is formed, the conductive film exhibits high conductivity and maintains high conductivity for a long period of time.
  • Conductive two-dimensional particles of a layered material comprising one or more layers and a dispersion medium having a dielectric constant greater than that of water;
  • the one or more layers have the formula: M m X n (wherein M is at least one Group 3, 4, 5, 6, 7 metal; 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) and a modification or termination T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body represented by and
  • a conductive two-dimensional particle-containing composition is provided in which the conductive two-dimensional particles contain elemental fluorine and elemental oxygen.
  • M is at least one Group 3, 4, 5, 6, 7 metal; X is a carbon atom, a nitrogen atom, or a combination thereof; A is at least one Group 12, 13, 14, 15, 16 element; n is 1 or more and 4 or less, m is greater than n and less than or equal to 5) preparing a precursor represented by (b) performing an etching treatment using an etchant to remove at least some A atoms from the precursor; (c) washing the etched product obtained by the etching treatment with water to obtain a water-washed product; (d) performing an intercalation treatment of the intercalation compound, which includes stirring a mixed solution of the water-washed product and the intercalation compound of the water-washed product; (e) forming a composition by mixing the intercalated product obtained by the intercalation treatment with delamination and a dispersion medium having a dielectric constant greater than that of water; A method of
  • a conductive two-dimensional particle-containing composition is formed of a predetermined layered material (also referred to herein as “MXene”), and has conductive two-dimensional particles containing elemental fluorine and elemental oxygen; and a dispersion medium having a dielectric constant greater than that of water, thereby containing MXene, exhibiting high conductivity, and being able to maintain high conductivity for a long period of time.
  • MXene predetermined layered material
  • An electrically conductive two-dimensional particle-containing composition is provided.
  • FIG. 1 is a schematic cross-sectional view showing MXene, which is a layered material that can be used for a conductive two-dimensional particle-containing composition in one embodiment of the present disclosure, where (a) shows single-layer MXene and (b) shows multi-layer (illustratively bilayer) MXene is shown.
  • Embodiment 1 Composition containing conductive two-dimensional particles
  • a conductive two-dimensional particle-containing composition according to one embodiment of the present disclosure will be described in detail below, but the present disclosure is not limited to such an embodiment.
  • the conductive two-dimensional particle-containing composition in the present embodiment is Conductive two-dimensional particles of a layered material comprising one or more layers and a dispersion medium having a dielectric constant greater than that of water;
  • the one or more layers have the formula: M m X n (wherein M is at least one Group 3, 4, 5, 6, 7 metal; 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) and a modification or termination T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body represented by and the conductive two-dimensional particles have elemental fluorine and elemental oxygen.
  • the conductive two-dimensional particle-containing composition contains the conductive two-dimensional particles and a dispersion medium having a dielectric constant higher than that of water, so that, for example, the initial conductivity is high and the conductivity is not deteriorated over time.
  • a suppressed conductive film can be formed.
  • the layered material may be understood as a layered compound, also denoted as "M m X n T s ", where s is any number, conventionally x or z may be used instead of s. Typically n can be 1, 2, 3 or 4, but is not so limited.
  • M is preferably at least one selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and Mn, and from Ti, V, Cr and Mo At least one selected from the group consisting of is more preferable.
  • M can be titanium or vanadium and X can be a carbon or nitrogen atom.
  • MXene's precursor MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 Ts (in other words, M is Ti, X is C, n is 2 and m is 3).
  • MXene may contain a relatively small amount of residual A atoms, for example, 10% by mass or less relative to the original A atoms.
  • the residual amount of A atoms can be preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of A atoms exceeds 10% by mass, there may be no problem depending on the application and usage conditions of the electrode.
  • the conductive two-dimensional particles (also referred to as "MXene particles") in the conductive two-dimensional particle-containing composition according to this embodiment will be described below with reference to FIG.
  • the conductive two-dimensional particles of the present embodiment are aggregates containing one layer of MXene 10a (single layer MXene) schematically illustrated in FIG. 1(a). More specifically, the MXene 10a includes a layer main body (M m X n layer) 1a represented by M m X n and a surface of the layer main body 1a (more specifically, at least two surfaces facing each other in each layer). MXene layer 7a with modifications or terminations T3a, 5a present on one side). Therefore, the MXene layer 7a is also expressed as "M m X n T s ", where s is any number.
  • a layered material particle according to the present embodiment can include a plurality of layers as well as a single layer.
  • a multi-layer MXene includes a two-layer MXene 10b as schematically shown in FIG. 1(b), but is not limited to these examples.
  • 1b, 3b, 5b and 7b in FIG. 1(b) are the same as 1a, 3a, 5a and 7a in FIG. 1(a) described above.
  • Two adjacent MXene layers (eg 7a and 7b) of a multi-layer MXene are not necessarily completely separated and may be in partial contact.
  • the MXene 10a exists in one layer with the multilayer MXene 10b separated individually, and the multilayer MXene 10b that is not separated may remain and be a mixture of the single-layer MXene 10a and the multilayer MXene 10b. Even when the multi-layered MXene is included, the multi-layered MXene is preferably MXene with a small number of layers obtained through a delamination treatment.
  • the phrase “the number of layers is small” means, for example, that the number of layers of MXene is 10 or less.
  • this "multilayer MXene with a small number of layers" may be referred to as a "small layer MXene".
  • the thickness of the small-layer MXene in the stacking direction is preferably 15 nm or less, more preferably 10 nm or less.
  • single-layer MXene and small-layer MXene may be collectively referred to as "single-layer/small-layer MXene".
  • the particles of the layered material according to the present embodiment preferably contain a large amount of single-layer/small-layer MXene.
  • the specific surface area of the MXene can be made larger than that of the multilayer MXene, and as a result, deterioration of electrode characteristics over time can be further suppressed, as shown in Examples described later.
  • the number of MXene layers to be laminated is 10 layers or less and the thickness is 15 nm or less, preferably 10 nm or less. % or more, more preferably 90 volume % or more, and still more preferably 95 volume % or more.
  • the volume of the monolayer MXene is larger than the volume of the few-layer MXene. Since the true densities of these MXenes do not vary greatly depending on the form of existence, it can be said that it is more preferable that the mass of single-layer MXenes is larger than the mass of small-layer MXenes. When these relationships are satisfied, the specific surface area can be further increased, and deterioration of conductivity with time can be further suppressed.
  • the particles of the layered material according to this embodiment are formed only of monolayer MXene.
  • each MXene layer (corresponding to the MXene layers 7a and 7b described above) can be, for example, 1 nm or more and 30 ⁇ m or less, for example, 1 nm or more and 5 nm or less, Furthermore, it may be 1 nm or more and 3 nm or less (mainly, it may vary depending on the number of M atomic layers included in each layer).
  • the interlayer distance (or gap dimension, indicated by ⁇ d in FIG. 1(b)) is, for example, ⁇ 0.8 nm and ⁇ 10 nm, especially ⁇ 0.8 nm and ⁇ 5 nm. Below, more particularly about 1 nm, the total number of layers can be from 2 to 20,000.
  • the conductive two-dimensional particles have a fluorine element and an oxygen element on the surface. Having elemental fluorine and elemental oxygen means that these elements are bound and adsorbed on the surface of MXene in the form of ions, for example.
  • Conductive two-dimensional particles have elemental fluorine and elemental oxygen with small atomic radii. For example, the presence of elemental oxygen and elemental fluorine with small atomic radii on the surface of the layer body constituting MXene narrows the interlayer distance. As a result, the structure is stable, the oxidation resistance is enhanced, and moisture absorption due to intercalation of water molecules between layers is suppressed, and high moisture absorption resistance can be realized.
  • the existence of the fluorine atoms and oxygen atoms in the conductive two-dimensional particles can be confirmed by the XPS method as described later.
  • the modification or termination T contains a chlorine atom, or M and at least one selected from the group consisting of PO 4 3 ⁇ , I and SO 4 2 ⁇ in the layer. may be combined.
  • the chlorine atoms, PO 4 3 ⁇ , I and SO 4 2 ⁇ may be derived from raw materials used in the production process of the conductive two-dimensional particles.
  • the chlorine atoms, I may be present in ionic form.
  • modification or termination T contains a chlorine atom, or M of the layer is bonded to at least one selected from the group consisting of PO 4 3 ⁇ , I and SO 4 2 ⁇
  • a composition containing more single-layer/small-layer MXene as the conductive two-dimensional particles is obtained.
  • a conductive film having higher conductivity can be obtained as a conductive film formed using the composition, which is preferable.
  • the presence of these chlorine atoms and the like on the surface of the conductive two-dimensional particles can be confirmed by the XPS method as described later.
  • the ratio of the conductive two-dimensional particles (MXene content) contained in the conductive two-dimensional particle-containing composition is not particularly limited. It can be 1% by mass or more.
  • the conductive two-dimensional particles are difficult to disperse and it is difficult to form a composition, according to the conductive two-dimensional particle-containing composition according to the present embodiment, the conductive two-dimensional particles are Conductive two-dimensional particles can form compositions with high dispersities because they are readily dispersed in larger dispersion media. By using a composition having such a high dispersion ratio for film formation, for example, a conductive film that needs to be thick, such as for electrodes, can be produced with good productivity.
  • the proportion of the conductive two-dimensional particles can also be 0.01% by mass or more in terms of solid content. Further, the proportion of the conductive two-dimensional particles may be 1.5% by mass or more in terms of solid content. Considering the dispersibility of the conductive two-dimensional particles, the upper limit of the above ratio is, for example, 10% by mass in terms of solid content.
  • a dispersion medium having a dielectric constant higher than that of water is used as a dispersion medium for dispersing the conductive two-dimensional particles.
  • a dispersion medium having a dielectric constant higher than that of water the charge of the conductive two-dimensional particles (MXene particles) becomes more stable, resulting in higher dispersibility.
  • a conductive two-dimensional particle-containing composition in which the conductive two-dimensional particles (MXene particles) are dispersed at a high content rate can be realized without aggregation.
  • a conductive film having high orientation and high conductivity can be realized.
  • the dielectric constant of water is 80.4 at 20.degree.
  • a dispersion medium having a dielectric constant of more than 80, or even 100 or more can be used.
  • a dispersion medium having a dielectric constant higher than that of water may be referred to as a "high dielectric constant dispersion medium”.
  • Examples of dispersion media having a dielectric constant greater than that of water include N-methylformamide (NMF, dielectric constant: 171) and N-methylacetamide (NMAc, dielectric constant: 179). can be used.
  • NMF N-methylformamide
  • NMAc N-methylacetamide
  • a mixed dispersion medium of a high relative dielectric constant dispersion medium and another dispersion medium may be used as long as the relative dielectric constant is higher than that of water.
  • Preferred dispersion media include those containing at least one of N-methylformamide and N-methylacetamide, which are high dielectric constant dispersion media. More preferably, the dispersion medium contains at least one of N-methylformamide and N-methylacetamide in an amount of 50% by volume or more.
  • Other dispersion media include dispersion media having a dielectric constant of 10 or more, such as aqueous dispersion media and organic dispersion media.
  • the aqueous dispersion medium is typically water, and optionally an aqueous solution containing water and a relatively small amount of other liquid substances (e.g., 30% by mass or less, preferably 20% by mass or less, based on the total amount). .
  • acetonitrile (relative dielectric constant: 38), N,N-dimethylacetamide (relative dielectric constant: 38), N,N-dimethylformamide (relative dielectric constant: 37), DMSO (relative dielectric constant: 47), DMF (relative dielectric constant: 37), NMP (relative dielectric constant: 32), acetone (relative dielectric constant: 20), 2-methyl 2-propanol (relative dielectric constant: 10), isopropyl alcohol (relative dielectric constant : 18), alcohols including ethanol (relative permittivity: 25) and methanol (relative permittivity: 33).
  • the dispersion medium having a dielectric constant higher than that of water preferably contains NMF having a high dielectric constant, and most preferably, the dispersion medium is composed of NMF.
  • the conductive two-dimensional particle-containing composition according to the present embodiment includes, in addition to the conductive two-dimensional particles and the dispersion medium, amines such as tetramethylammonium hydroxide, hexylamine, and octylamine, polyphosphoric acid, sodium ascorbate, and the like. may contain additives.
  • the proportion of the additive in the composition is not particularly limited, but from the viewpoint of increasing the concentration of the conductive two-dimensional particles, the proportion of the additive in the composition may be suppressed to, for example, 10% by mass or less.
  • Examples of the conductive two-dimensional particle-containing composition according to this embodiment include ink, paste, slurry, and the like.
  • the paste is a conductive paste of a composite material containing a polymer.
  • the mass ratio of conductive two-dimensional particles (layered material particles) in the conductive paste is, for example, 50% or more.
  • the polymer include a hydrophilic polymer (including a hydrophobic polymer mixed with a hydrophilic auxiliary agent to exhibit hydrophilicity, and a hydrophobic polymer whose surface has been subjected to a hydrophilic treatment).
  • the polymer is one or more selected from the group consisting of polysulfone, cellulose acetate, regenerated cellulose, polyethersulfone, water-soluble polyurethane, polyvinyl alcohol, sodium alginate, acrylic acid-based water-soluble polymer, polyacrylamide, polyaniline sulfonic acid, and nylon. is more preferably included.
  • the hydrophilic polymer is more preferably a hydrophilic polymer having a polar group, and the polar group is a group that forms a hydrogen bond with the modification or termination T of the layer.
  • the polymer for example, one or more polymers selected from the group consisting of water-soluble polyurethane, polyvinyl alcohol, sodium alginate, acrylic acid-based water-soluble polymer, polyacrylamide, polyaniline sulfonic acid, and nylon are preferably used.
  • one or more polymers selected from the group consisting of water-soluble polyurethane, polyvinyl alcohol, and sodium alginate are more preferable.
  • a polymer having a urethane bond having both properties of a hydrogen bond donor and a hydrogen bond acceptor is preferable, and from that point of view, the water-soluble polyurethane is particularly preferable.
  • the method for producing a conductive two-dimensional particle-containing composition of the present embodiment includes: (a) the following formula: M m AX n (wherein M is at least one Group 3, 4, 5, 6, 7 metal; X is a carbon atom, a nitrogen atom, or a combination thereof; A is at least one Group 12, 13, 14, 15, 16 element; n is 1 or more and 4 or less, m is greater than n and less than or equal to 5) preparing a precursor represented by (b) performing an etching treatment using an etchant to remove at least some A atoms from the precursor; (c) washing the etched product obtained by the etching treatment with water to obtain a water-washed product; (d) performing an intercalation treatment of the intercalation compound, which includes stirring a mixed solution of the water-washed product and the intercalation compound of the water-washed product; (e) forming a composition by performing delamination and mixing a dispersion medium having a dielectric constant greater than that of water using the
  • a predetermined precursor that can be used in this embodiment is the MAX phase, which is a precursor of MXene, The formula below: M m AX n (wherein M is at least one Group 3, 4, 5, 6, 7 metal; X is a carbon atom, a nitrogen atom, or a combination thereof; A is at least one Group 12, 13, 14, 15, 16 element; n is 1 or more and 4 or less, m is greater than n and less than or equal to 5) is represented by
  • A is at least one Group 12, 13, 14, 15, 16 element, usually a Group A element, typically Groups IIIA and IVA, more particularly Al, Ga, In, It may contain at least one selected from the group consisting of Tl, Si, Ge, Sn, Pb, P, As, S and Cd, preferably Al.
  • a MAX phase is a crystal in which a layer composed of A atoms is located between two layers denoted by M m X n (each X may have a crystal lattice located in an octahedral array of M). have a structure.
  • the MAX phase can be produced by a known method. For example, TiC powder, Ti powder and Al powder are mixed in a ball mill, and the resulting mixed powder is fired in an Ar atmosphere to obtain a fired body (block-shaped MAX phase). After that, the obtained sintered body can be pulverized with an end mill to obtain a powdery MAX phase for the next step.
  • Etching is performed using an etchant to remove at least some A atoms from the precursor.
  • the etchant preferably contains one or more of HF, H3PO4 , HCl, HI and H2SO4 .
  • the etchant more preferably contains at least one of HF (hydrofluoric acid) and H 3 PO 4 (phosphoric acid).
  • HF hydrofluoric acid
  • H 3 PO 4 phosphoric acid
  • etching with an etchant containing phosphoric acid are more preferable than the MILD method because particles of a flake-like layered material (MXene particles) having a large planar area and a number average Feret diameter of preferably 3 ⁇ m or more can be obtained easily.
  • Other etching conditions are not particularly limited, and known conditions can be adopted.
  • the etchant a mixture of the above acid and, for example, pure water as a solvent may be used.
  • the etching solution has an HF concentration of 1.5 M or more and 14 M or less, an H3PO4 concentration of 5.5 M or more, an HCl concentration of 6.0 M or more , an HI concentration of 5.0 M or more, and an H2SO4 concentration of
  • An etchant that satisfies at least one selected from the group consisting of 5.0M or more can be used.
  • the etching of the A atoms along with the A atoms, optionally part of the M atoms can also be selectively etched.
  • An example of the etching product obtained by the above etching is slurry.
  • the etched product obtained by the etching is washed with water.
  • the acid and the like used in the etching can be sufficiently removed.
  • the amount of water to be mixed with the etched material and the cleaning method are not particularly limited.
  • water may be added, followed by stirring, centrifugation, and the like.
  • Stirring methods include handshake, automatic shaker, shear mixer, pot mill, and the like.
  • the degree of stirring such as stirring speed and stirring time may be adjusted according to the amount, concentration, etc. of the object to be treated.
  • the washing with water may be performed once or more. Washing with water is preferably carried out multiple times.
  • Intercalation of the intercalation compound is carried out, including the step of stirring a mixed solution obtained by mixing the treated material (water-washed material) obtained by the water washing with the intercalation compound of the water-washed material.
  • the compound for interlayer insertion of the treated water is not particularly limited as long as it is a compound that can be inserted between the layers of the treated water and can be separated into layers in the next step (e) delamination.
  • Alkali metal compounds and alkaline earth metal compounds are preferable as the intercalation compound.
  • Li-containing compounds are more preferred.
  • an ionic compound in which Li ions and cations are combined can be used. Examples include halides including iodides, chlorides and fluorides of Li ions, hydroxides, phosphates, sulfide salts including sulfates, nitrates, acetates and carboxylates of Li ions.
  • the content of the intercalation compound in the intercalation compound is preferably 0.001% by mass or more.
  • the above content is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.
  • the content of the intercalation compound is preferably 10% by mass or less, more preferably 1% by mass or less.
  • the specific method of intercalation is not particularly limited, and for example, the intercalation compound may be mixed with the water medium clay of MXene, stirred, or allowed to stand still.
  • stirring at room temperature is mentioned.
  • the stirring method include a method using a stirrer such as a stirrer, a method using a stirring blade, a method using a mixer, and a method using a centrifugal device.
  • the stirring time can be set according to the manufacturing scale of the electrode, and can be set, for example, between 12 and 24 hours.
  • a composition is formed by performing delamination using the intercalated product obtained by the intercalation treatment in step (d) and mixing with a dispersion medium having a dielectric constant higher than that of water.
  • the stirring method includes handshake, stirring using an automatic shaker, and the like.
  • the degree of stirring such as stirring speed and stirring time may be adjusted according to the amount, concentration, etc. of the material to be treated.
  • ultrasonic treatment is not performed as delamination.
  • the particles of the layered material have a large plane parallel to the layer of the particles, that is, a single layer with a large number average Feret diameter. Fewer MXenes can be obtained.
  • the dispersion medium with a dielectric constant higher than that of water used for mixing is as described above for the dispersion medium with a dielectric constant higher than that of water contained in the conductive two-dimensional particle-containing composition.
  • step (d) and step (e) include the following aspects (I) and (II) as a plurality of aspects. or (III). Aspects (I), (II) and (III) are described below.
  • step (d) the mixture of the water-washed product and the intercalation compound of the water-washed product was acidified, and in step (e), the intercalated product was delaminated. After that, the delamination-treated material obtained by delamination is mixed with a dispersion medium having a dielectric constant higher than that of water to form a composition.
  • step (III) in step (d) the mixed solution of the water-washed product and the intercalation compound of the water-washed product is acidified; By mixing with a dispersion medium having a larger dielectric constant than water, delamination and mixing with a dispersion medium having a dielectric constant larger than that of water are performed together.
  • the mixture of the water-washed material and the intercalation compound of the water-washed material in step (d) should be alkaline.
  • the pH may be in the range of 8-14.
  • the method for making the mixed solution alkaline is not limited.
  • the intercalation compound may be a hydroxide, preferably a mixed solution containing lithium hydroxide as the Li-containing compound.
  • a mixed solution containing an interlayer intercalating compound and a pH adjuster such as a hydroxide such as ammonia, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, or the like may be used.
  • the intercalated product and a dispersion medium having a dielectric constant higher than that of water are mixed to perform delamination and a dielectric constant higher than that of water.
  • Mixing of a large dispersion medium is also carried out. For example, as shown in Examples described later, an intercalation-treated product and a dispersion medium having a dielectric constant higher than that of water are mixed to obtain a mixture for stirring.
  • the mixture for stirring has a ratio of 0.1 g or more and 10 g or less of the solid content of the intercalated product to 1 mL or more and 100 mL or less of the dispersion medium (on a manufacturing scale, this ratio is the dispersion medium and the intercalation treatment It is sufficient if the solid content of the product is increased).
  • the stirring mixture is stirred at 20-25° C. (room temperature).
  • the agitated material obtained by agitation is, for example, further agitated using a handshake, an automatic shaker, a stirrer, an agitating blade, or the like, then centrifuged in a centrifuge to collect the supernatant liquid, and then After centrifuging the resulting supernatant, the supernatant is discarded and the remaining precipitate is obtained as a composition containing highly dispersed conductive two-dimensional particles.
  • the mixture of the water-washed product and the intercalating compound in the water-washed product in step (d) may be acidic.
  • the pH may be in the range of 0 or more and 6 or less.
  • the method for acidifying the mixed liquid is not limited.
  • the intercalation compound is a chloride
  • the Li-containing compound is preferably a mixture containing lithium chloride.
  • a mixed solution containing an interlayer intercalating compound and an inorganic acid such as hydrochloric acid, phosphoric acid, or sulfuric acid as a pH adjuster may be used.
  • step (e) after delamination of the intercalation treatment product using an aqueous dispersion medium, the delamination treatment product obtained by delamination and the relative dielectric constant of and a large dispersion medium to form a composition.
  • the above delamination includes stirring the treated product obtained by the intercalation in step (d) in an aqueous dispersion medium such as pure water.
  • an aqueous dispersion medium such as pure water.
  • pure water is added to the remaining precipitate, and then, for example, handshaking or stirring with an automatic shaker is performed, and then centrifugation is performed.
  • the delamination-treated material is stirred in a dispersion medium having a dielectric constant higher than that of water.
  • the stirred product obtained by stirring is further stirred using, for example, a handshake, an automatic shaker, a wet disperser, ultrasonic waves, etc., and then centrifuged by a centrifuge to collect the supernatant, Next, after centrifuging the obtained supernatant, the supernatant is discarded, and the remaining precipitate is obtained as a highly dispersed conductive two-dimensional particle-containing composition.
  • This embodiment includes a conductive film obtained using a composition containing conductive two-dimensional particles.
  • a conductive film formed from a composition containing conductive two-dimensional particles has high orientation and exhibits high conductivity.
  • the conductive film formed from the conductive two-dimensional particle-containing composition of the present embodiment is measured with a micrometer, a scanning electron microscope (SEM), or a stylus profilometer.
  • SEM scanning electron microscope
  • the conductivity obtained by substituting the thickness of the conductive film and the surface resistivity of the conductive film measured by the four-probe method into the following formula can achieve, for example, 5000 S / cm or more. .
  • Conductivity [S/cm] 1/(thickness of conductive film [cm] ⁇ surface resistivity of conductive film [ ⁇ / ⁇ ])
  • the method of forming the conductive film is not limited, and includes filtration, coating, immersion, and the like.
  • Filtration methods include, for example, suction filtration of the composition.
  • a filter for suction filtration for example, a membrane filter (manufactured by Merck Ltd., Durapore, pore size 0.45 ⁇ m) can be used.
  • the coating method includes, for example, a single-fluid nozzle, a two-fluid nozzle, a nozzle such as an airbrush, a spray coat for spray coating, a table coater, a comma coater, a slit coat using a bar coater, screen printing, and a metal mask. Examples of coating methods include printing, spin coating, immersion, brushing, and dropping.
  • the above coating and drying may be repeated multiple times as necessary until a conductive film with a desired thickness is obtained. Drying and curing can be performed at a temperature of 80° C. or higher and 400° C. or lower using, for example, a normal pressure oven or a vacuum oven.
  • the resulting conductive film should maintain high conductivity (reduce initial conductivity loss and prevent oxidation), e.g., electrodes or electromagnetic shielding (EMI shielding) in any suitable electrical device.
  • the electrode is not particularly limited, but may be, for example, a capacitor electrode, a battery electrode, a biosignal sensing electrode, a sensor electrode, an antenna electrode, or the like.
  • Examples 1 to 5 Preparation of monolayer MXene [Examples 1 to 5]
  • precursor (MAX) preparation (2) precursor etching, (3) post-etching cleaning, (4) Li intercalation, ( 5) Delamination and mixing of a dispersion medium with a high dielectric constant were performed in order to prepare an MXene-containing composition. That is, in Examples 1 to 5, the dispersion medium was replaced from water with a prescribed dispersion medium before the monolayer formation of MXene.
  • Precursor (MAX) preparation TiC powder, Ti powder and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls at a molar ratio of 2:1:1. mixed for 24 hours. The obtained mixed powder was fired at 1350° C. for 2 hours in an Ar atmosphere. The resulting sintered body (block-shaped MAX) was pulverized with an end mill to a maximum dimension of 40 ⁇ m or less. This gave Ti 3 AlC 2 particles as a precursor (powdered MAX).
  • the stirred material was transferred to a 50 mL centrifuge tube, centrifuged at 3500 G for 5 minutes using a centrifuge, and then the supernatant was discarded. Then, (i) add 35 mL of pure water to the remaining precipitate, (ii) stir by handshaking, (iii) centrifuge at 3500 G for 5 minutes, and (iv) remove the supernatant. . The steps (i) to (iv) were repeated 5 times in total. Finally, after centrifuging at 3500 G for 5 minutes using a centrifuge, the supernatant was discarded to obtain a water-washed product.
  • Example 6-9 In Examples 6-9, (1) Precursor (MAX) preparation, (2) Precursor etching, (3) Post-etch cleaning, (4) Li intercalation, (5) ) delamination and (6) mixing of a dispersion medium with a high dielectric constant were carried out in this order to prepare an MXene-containing composition. That is, in Examples 6 to 9, the dispersion medium was replaced from water by a prescribed dispersion medium after the monolayer formation of MXene.
  • Precursor (MAX) preparation TiC powder, Ti powder and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls at a molar ratio of 2:1:1. mixed for 24 hours. The obtained mixed powder was fired at 1350° C. for 2 hours in an Ar atmosphere. The resulting sintered body (block-shaped MAX) was pulverized with an end mill to a maximum dimension of 40 ⁇ m or less. This gave Ti 3 AlC 2 particles as a precursor (powdered MAX).
  • etching is performed under the following etching conditions to form a solid-liquid mixture (slurry) containing a solid component derived from the Ti 3 AlC 2 powder.
  • the stirred product is transferred to a 50 mL centrifuge tube, centrifuged at 3500 G for 5 minutes using a centrifuge, then the supernatant is discarded and the Li intercalated product (MXene clay ).
  • Comparative Examples 1 and 2 In Comparative Examples 1 and 2, (1) preparation of precursor (MAX), (2) etching of precursor, (3) etching The subsequent washing and (4) replacement of the dispersion medium were performed in order to prepare an MXene-containing composition.
  • Precursor (MAX) preparation TiC powder, Ti powder and Al powder (all manufactured by Kojundo Chemical Laboratory Co., Ltd.) were placed in a ball mill containing zirconia balls at a molar ratio of 2:1:1. mixed for 24 hours. The obtained mixed powder was fired at 1350° C. for 2 hours in an Ar atmosphere. The resulting sintered body (block-shaped MAX) was pulverized with an end mill to a maximum dimension of 40 ⁇ m or less. This gave Ti 3 AlC 2 particles as a precursor (powdered MAX).
  • etching is performed under the following etching conditions to form a solid-liquid mixture (slurry) containing a solid component derived from the Ti 3 AlC 2 powder.
  • Comparative Example 3 In Comparative Example 3, (1) precursor (MAX) preparation, (2) precursor etching, (3) post-etching cleaning, (4) Li intercalation, and (5) delamination in Example 6 to obtain a monolayered MXene-containing clay in an aqueous dispersion medium. This monolayered MXene-containing clay in a water dispersion medium was used for the production of the MXene film described later.
  • compositional analysis of surface groups of MXene particles The composition of the surface groups of the MXene particles was determined by XPS measurement under the following conditions using a VersaProbe X-ray photoelectron spectrometer manufactured by Ulvac-Phi. Table 4 shows the results. (XPS measurement conditions) Incident X-ray: monochromatic AlK ⁇ X-ray output: 25.6W Measurement area: diameter 100 ⁇ m Photoelectron capture angle: 45.0 degrees Pass energy: 23.50 eV
  • MXene film The composition obtained in each example was subjected to suction filtration. After filtration, vacuum drying was performed at 200° C. for 24 hours to prepare an MXene film. A membrane filter (manufactured by Merck Ltd., Durapore, pore size 0.45 ⁇ m) was used as a filter for suction filtration. The supernatant contained 0.05 g of MXene two-dimensional particles as a solid content and 40 mL of pure water. The density and conductivity of the resulting MXene films were measured as follows.
  • the initial conductivity of the resulting MXene film was determined.
  • the surface resistivity was measured at three points per sample, and this was defined as R 0 ( ⁇ ).
  • a simple low resistivity meter Mitsubishi Chemical Analytic Co., Loresta AX MCP-T370
  • the thickness was measured at three points per sample.
  • a micrometer (MDH-25MB manufactured by Mitutoyo Co., Ltd.) was used for thickness measurement.
  • the volume resistivity was obtained from the surface resistivity and film thickness, and the initial conductivity (S/cm) was calculated by taking the reciprocal of the value.
  • the average value ( ⁇ 0 ) of the initial conductivity at the three locations was adopted. Table 4 shows the results.
  • the MXene film was also tested in a hermetically sealed manner similar to the test apparatus shown in Figure 5c of the document: Pristine Titanium Carbide MXene Films with Environmentally Stable Conductivity and Superior Mechanical Strength (Adv. Funct. Mater. 2020, 30, 1906996). Put a small amount of water in the bottom of the desiccator, place the MXene film so that it does not come into direct contact with the water, hold it in a humid environment saturated with room temperature and humidity for 7 days, and then, in the same manner as above, 1 sample The surface resistivity was measured at three points per , and the electrical conductivity (S/cm) was calculated from the film thickness. The average value ( ⁇ ) of the conductivity after 7 days at the three locations was adopted.
  • ( ⁇ / ⁇ 0 ) ⁇ 100 (%) was obtained as the ratio of the average value ( ⁇ ) of the conductivity after 7 days to the average value ( ⁇ 0 ) of the initial conductivity.
  • Table 4 shows the results.
  • ( ⁇ / ⁇ 0 ) ⁇ 100(%) was 70% or more, it was evaluated as having high moisture absorption resistance and high reliability.
  • the ( ⁇ / ⁇ 0 ) ⁇ 100(%) is preferably 80% or more.
  • Table 4 shows the following. That is, the compositions of Examples 1 to 5 according to the present embodiment have a MXene content of 1.0% by mass or more and a high dispersion rate, and a conductive film obtained using this composition had an initial conductivity of 5000 S/cm or more, and a change in conductivity after 7 days of 70% or more, and the initial conductivity was almost maintained. Further, preferably modified or terminated T contains a chlorine atom, or M of said layer is bonded to at least one selected from the group consisting of PO 4 3- , I and SO 4 2- . 6 to 9 had a higher initial conductivity of 6000 S/cm or more, and the change in conductivity after 7 days was as high as 85% or more, and a conductive film with higher hygroscopic resistance was obtained.
  • Comparative Examples 1 and 2 are examples in which DMSO and DMF were used as the dispersion medium, but in these examples, the dispersibility of the MXene particles was poor and aggregated.
  • the initial conductivity of the formed conductive film was considerably low, and the conductivity after 7 days also decreased to about half of the initial conductivity. The reason for this is thought to be that the conductive film formed using the poorly dispersible composition was not dense, and that moisture penetrated into the conductive film, resulting in significant deterioration over time.
  • Comparative Example 3 is an example using water as a dispersion medium. In this example, the initial conductivity was high, but after 7 days the conductivity dropped significantly.
  • the dispersion media DMSO and DMF used in Comparative Examples 1 and 2 are the same organic dispersion media as NMF, but the dispersibility of MXene particles is clearly different.
  • the conductivity and moisture absorption resistance (reliability) of the conductive film formed in is also greatly affected, and by making the composition containing the dispersion medium according to the present embodiment, excellent conductivity and excellent moisture absorption resistance It was found that a conductive film having both (reliability) can be obtained.
  • the disclosure content of this specification may include the following aspects.
  • ⁇ 1> Containing conductive two-dimensional particles of a layered material containing one or more layers and a dispersion medium having a dielectric constant greater than that of water,
  • the one or more layers have the formula: M m X n (wherein M is at least one Group 3, 4, 5, 6, 7 metal; 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) and a modification or termination T (T is at least one selected from the group consisting of a hydroxyl group, a fluorine atom, a chlorine atom, an oxygen atom and a hydrogen atom) present on the surface of the layer body represented by and A conductive two-dimensional particle-containing composition, wherein the conductive two-dimensional particles contain elemental fluorine and elemental oxygen.
  • the modification or termination T contains a chlorine atom, or at least M of the layer is selected from the group consisting of PO 4 3 ⁇ , I and SO 4 2 ⁇
  • ⁇ 3> The conductive two-dimensional particles according to ⁇ 1> or ⁇ 2>, wherein the dispersion medium having a dielectric constant higher than that of water contains at least one of N-methylformamide and N-methylacetamide. Containing composition.
  • ⁇ 4> The conductive two-dimensional particle-containing composition according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the conductive two-dimensional particles is 1% by mass or more.
  • ⁇ 5> The conductive two-dimensional particle-containing composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a polymer.
  • ⁇ 6> A conductive film having a conductivity of 5000 S/cm or more, formed from the conductive two-dimensional particle-containing composition according to any one of ⁇ 1> to ⁇ 5>.
  • the conductive two-dimensional particle-containing composition of the present disclosure is useful for forming a conductive film with high initial conductivity and suppressed deterioration of conductivity over time.
  • the conductive film formed using the conductive two-dimensional particle-containing composition can be used for any appropriate application, such as electromagnetic shielding (EMI shielding), electrodes for capacitors, electrodes for batteries, and biosignal sensing electrodes. , a sensor electrode, an antenna electrode, and the like.

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WO2025225525A1 (ja) * 2024-04-26 2025-10-30 株式会社村田製作所 導電性粒子、フィルム、ペースト、コンポジット材料、および導電性粒子の製造方法

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