WO2023112778A1 - ２次元粒子、導電性膜、導電性ペーストおよび複合材料 - Google Patents

２次元粒子、導電性膜、導電性ペーストおよび複合材料 Download PDF

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WO2023112778A1
WO2023112778A1 PCT/JP2022/044947 JP2022044947W WO2023112778A1 WO 2023112778 A1 WO2023112778 A1 WO 2023112778A1 JP 2022044947 W JP2022044947 W JP 2022044947W WO 2023112778 A1 WO2023112778 A1 WO 2023112778A1
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component
particles
dimensional
mxene
less
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French (fr)
Japanese (ja)
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章麿 ▲柳▼町
匡矩 阿部
直規 一条
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Murata Manufacturing Co Ltd
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Priority to CN202280082647.6A priority Critical patent/CN118382599A/zh
Priority to JP2023567718A priority patent/JP7729403B2/ja
Publication of WO2023112778A1 publication Critical patent/WO2023112778A1/ja
Priority to US18/739,780 priority patent/US20240327227A1/en
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    • 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
    • C01B32/914—Carbides of single elements
    • C01B32/921—Titanium carbide
    • 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
    • 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
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01B5/16—Non-insulated conductors or conductive bodies characterised by their form comprising conductive material in insulating or poorly conductive material, e.g. conductive rubber
    • 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
    • C01P2002/08—Intercalated structures, i.e. with atoms or molecules intercalated in their structure
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to two-dimensional particles, conductive films, conductive pastes and composite materials.
  • 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 can include powders, flakes, nanosheets, etc.) of such layered materials.
  • MXene Various researches are currently being conducted to apply MXene to various electrical devices. For the above applications, materials containing MXene are required to have higher conductivity and moisture resistance. As part of the study, a cleaning treatment method for MXene is being studied.
  • Non-Patent Document 1 describes that Li + can be removed by washing MXene in the presence of acid.
  • An object of the present disclosure is to provide two-dimensional particles capable of realizing a conductive film having high conductivity and moisture resistance. Another object of the present disclosure is to provide a conductive film, a conductive paste, and a conductive composite material using such two-dimensional particles.
  • the disclosure includes: [1] A two-dimensional particle having one or more layers, containing Li atoms,
  • the layer has the following 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 Li atoms include a first component and a second component having a larger chemical shift as measured by 7 Li NMR than the first component, Two-dimensional particles, wherein the ratio of the first component in the total of the first component and the second component is 17 atomic % or more and 70 atomic % or less.
  • the chemical shift of the first component measured by the 7 Li NMR is less than 0.6 ppm, and the chemical shift of the second component measured by the 7 Li NMR is 0.6 ppm or more and 2.0 ppm or less.
  • [3] The two-dimensional particle of [1] or [2], containing a phosphorus atom.
  • [5] The two-dimensional particle according to any one of [1] to [4], wherein the phosphorus atom is in the form of PO 4 3- .
  • [6] The two-dimensional particle according to any one of [1] to [5], which has an average thickness of 1 nm or more and 10 nm or less.
  • a conductive film comprising the two-dimensional particles according to any one of [1] to [6].
  • a conductive paste containing the two-dimensional particles according to any one of [1] to [6].
  • a conductive composite material comprising the two-dimensional particles according to any one of [1] to [6] and a resin.
  • the present disclosure it is possible to provide two-dimensional particles capable of realizing a conductive film having high conductivity and moisture resistance. Also, the present disclosure can provide a conductive film, a conductive paste, and a conductive composite material using such two-dimensional particles.
  • FIG. 1 is a schematic cross-sectional view showing MXene particles of a layered material in one embodiment of the present disclosure, where (a) shows a monolayer MXene particle and (b) shows a multi-layer (illustratively bi-layer) MXene particle; . 1 is a schematic cross-sectional view showing a conductive film in one embodiment of the present disclosure; FIG.
  • a two-dimensional particle in this embodiment is a two-dimensional particle of a layered material having one or more layers and contains Li atoms.
  • the above layer has the following 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) (the layer body may have a crystal lattice in which each X is located in an octahedral array of M) and a surface of the layer body (more particularly, the surfaces of the layer bodies facing each other a modification or termination T (T is at least one selected from the group consisting of hydroxyl groups, fluorine atoms, chlorine atoms, oxygen atoms and hydrogen atoms) present on at least one of the two surfaces that Li atoms include a first component and a second component having a larger chemical shift than the first component as measured by 7 Li NMR (nuclear magnetic resonance), The proportion of the first component in the total of the first component and the second component is 17 atomic % or more and
  • the conductive film obtained using the two-dimensional particles of the present disclosure has high conductivity and good moisture resistance.
  • moisture resistance means the ability to maintain electrical conductivity even when placed under high humidity conditions for a long period of time.
  • electrodes comprising such conductive films can be used in applications where high conductivity and high moisture resistance are required, such as electrodes for antennas, especially as electrodes for RFID (radio frequency identifier).
  • the oxidation number of the element is not limited to 0, and may be any number within the range of possible oxidation numbers of the element.
  • 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.
  • 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.
  • MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 T s (in other words, M is Ti, X is C, n is 2, m is 3 is).
  • MXene may contain A atoms derived from the MAX phase of the precursor in a relatively small amount, 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 two-dimensional particles.
  • the layer may be referred to as an MXene layer, and the two-dimensional particles may be referred to as MXene two-dimensional particles or MXene particles.
  • the two-dimensional particles of the present embodiment are aggregates containing one layer of MXene particles (hereinafter simply referred to as "MXene particles") 10a (single-layer MXene particles) schematically illustrated in FIG. 1(a).
  • MXene particles 10a include a layer body (M m X n layer) 1a represented by M m X n and a surface of the layer body 1a (more specifically, two surfaces facing each other in each layer). (at least one of) is the MXene layer 7a with modifications or terminations T3a, 5a present in the . Therefore, the MXene layer 7a is also denoted as "M m X n T s ", where s is any number.
  • the two-dimensional particles of this embodiment may contain one or more layers.
  • multiple layers of MXene particles include two layers of MXene particles 10b as schematically shown in FIG. 1(b), but are 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-layered MXene particle are not necessarily completely separated and may be in partial contact.
  • the above-mentioned MXene particles 10a are those in which the above-mentioned multi-layered MXene particles 10b are individually separated and exist in one layer. may be a mixture of
  • the thickness of each layer (corresponding to the MXene layers 7a and 7b described above) contained in the MXene particles is, for example, 0.8 nm or more and 5 nm or less, particularly 0.8 nm or more and 3 nm or less. Yes (mainly depending on the number of M atomic layers included in each layer).
  • the interlayer distance or pore size, indicated by ⁇ d in FIG. 1(b) is for example 0.8 nm or more and 10 nm or less, especially 0.8 nm or more and 5 nm or less. , more particularly about 1 nm, and the total number of layers can be greater than or equal to 2 and less than or equal to 20,000.
  • the multilayered MXene particles that can be contained are preferably MXene particles with a small number of layers obtained through a delamination process.
  • the phrase “the number of layers is small” means, for example, that the number of MXene layers to be stacked is 6 or less.
  • the thickness of the multi-layered MXene particles having a small number of layers in the stacking direction is preferably 15 nm or less, more preferably 10 nm or less.
  • this "multilayer MXene particle with a small number of layers” may be referred to as "small layer MXene particle”.
  • single-layer MXene particles and low-layer MXene particles are sometimes collectively referred to as "single-layer/low-layer MXene particles.”
  • the two-dimensional particles of the present embodiment preferably include single-layer MXene particles and low-layer MXene particles, ie, single-layer/low-layer MXene particles.
  • the ratio of single-layer/small-layer MXene particles having a thickness of 15 nm or less is preferably 90% by volume or more, more preferably 95% by volume or more.
  • the Li atoms include a first component and a second component having a larger chemical shift than the first component as measured by 7 Li NMR, and the first component in the total of the first component and the second component is 17 atomic % or more and 70 atomic % or less. Thereby, a conductive film having high conductivity and moisture resistance can be realized.
  • the proportion of the first component in the sum of the first component and the second component can be measured by 7 Li NMR.
  • 7 Li NMR the proportion of the first component in the total
  • the integration delay time for the 7 Li NMR measurement is 4 seconds.
  • the first component is bound by water and exists in a state with a low degree of freedom
  • the second component is loosely adsorbed on the layer surface of the two-dimensional particles and has a degree of freedom is considered to exist at a relatively high level.
  • the degrees of freedom of the first component and the second component can be confirmed, for example, by comparing the T2 relaxation time (spin-spin relaxation time).
  • T2 relaxation time spin-spin relaxation time
  • the T2 relaxation time of the first component is shorter than the T2 relaxation time of the second component, for example, the T2 relaxation time of the first component is 0.6 ms or less, and the T2 relaxation time of the second component is 1.2 ms or more. is.
  • a comparison of the T2 relaxation times of the first component and the second component suggests that the first component interacts more strongly with the substance than the second component.
  • the chemical shift of the first component as measured by 7 Li NMR can be for example less than 0.6 ppm, even -0.2 ppm to 0.55 ppm, especially -0.15 ppm to 0.5 ppm.
  • the chemical shift of the second component measured by 7 Li NMR can be, for example, 0.6 ppm or more and 2.0 ppm or less, and further 0.7 ppm or more and 1.7 ppm or less.
  • the reference material for 7 Li NMR measurements is Li in a 1 mol/L LiCl aqueous solution.
  • the chemical shift of the first component measured by 7 Li NMR represents the chemical shift value of the peak assigned to the first component in the 7 Li NMR spectrum.
  • the chemical shift of the second component measured by 7 Li NMR represents the chemical shift value of the peak assigned to the second component in the 7 Li NMR spectrum.
  • the chemical shift of the second component is larger than the chemical shift of the first component measured by 7 Li NMR, and the peak attributed to the second component is relative to the peak attributed to the first component by the 7 Li NMR Located on the low-field side of the spectrum.
  • the peak attributed to the first component overlaps with the peak attributed to the second component, the peaks may be separated by regression using the Lorenz curve.
  • the Li atoms are typically present on the layer. That is, it may be in contact with the layer or may exist on the layer via another element.
  • the content of Li atoms in the two-dimensional particles is, for example, 0.1% by mass or more and 20% by mass or less, further 0.1% by mass or more and 10% by mass or less, especially It may be 0.2% to 5% by mass, particularly 0.2% to 3% by mass.
  • the Li atom content can be measured by, for example, inductively coupled plasma atomic emission spectrometry (ICP-AES).
  • ICP-AES inductively coupled plasma atomic emission spectrometry
  • the two-dimensional particles contain phosphorus atoms. It is thought that the inclusion of phosphorus atoms facilitates the presence of Li atoms of the second component, thereby facilitating the manifestation of high electrical conductivity and high moisture resistance.
  • the phosphorus atom content can be, for example, 0.1% by mass or more and 14% by mass or less, further 0.15% by mass or more and 5% by mass or less, and particularly 0.15% by mass or more and 1% by mass or less.
  • Said phosphorus atoms can be present, for example, in the form of anions containing phosphorus atoms, especially in the form of PO 4 3- .
  • An anion containing a phosphorus atom may be attached to M in the layer.
  • the ratio of (average length of two-dimensional surface of two-dimensional particles)/(average thickness of two-dimensional particles) is 1.2 or more, preferably 1.5 or more, more preferably 2 That's it.
  • the average major diameter of the two-dimensional surfaces of the two-dimensional particles and the average thickness of the two-dimensional particles may be obtained by the method described later.
  • the average value of the long diameters of the two-dimensional surfaces is 1 ⁇ m or more and 20 ⁇ m or less.
  • the average value of the major diameters of the two-dimensional surfaces may be referred to as "average flake size”.
  • the average value of the long axis of the two-dimensional surface is preferably 1.5 ⁇ m or more, more preferably 2.5 ⁇ m or more.
  • the average value of the major axis of the two-dimensional surface is 20 ⁇ m or less, preferably 15 ⁇ m or less, and more preferably 10 ⁇ m or less.
  • the major axis of the two-dimensional surface refers to the major axis of each MXene particle approximated to an elliptical shape in an electron micrograph, and the average value of the major axis of the two-dimensional surface is 80 particles or more. The number average of the above major diameters. Scanning electron microscope (SEM) and transmission electron microscope (TEM) photographs can be used as electron microscopes.
  • the average value of the major diameters of the two-dimensional particles of the present embodiment may be measured by dissolving a conductive film containing the two-dimensional particles in a solvent and dispersing the two-dimensional particles in the solvent. Alternatively, it may be measured from the SEM image of the conductive film.
  • the average thickness of the two-dimensional particles of the present embodiment is preferably 1 nm or more and 15 nm or less.
  • the thickness is preferably 10 nm or less, more preferably 7 nm or less, and even more preferably 5 nm or less.
  • the lower limit of the thickness of two-dimensional particles can be 1 nm.
  • the average value of the thickness of the two-dimensional particles is obtained as a number average dimension (for example, number average of at least 40 particles) based on an atomic force microscope (AFM) photograph or a transmission electron microscope (TEM) photograph.
  • AFM atomic force microscope
  • TEM transmission electron microscope
  • the method for producing two-dimensional particles of this embodiment includes: (a) providing a predetermined precursor; (b) performing an etching treatment using an etchant to remove at least some A atoms from the precursor; (c) performing a water washing treatment, including a step of washing the etched product obtained by the etching treatment with water; (d) performing an intercalation treatment including a step of mixing the water-washed product obtained by the water washing with a metal-containing compound; (e) obtaining two-dimensional particles by performing a delamination process, including the step of stirring the intercalated product obtained by the intercalation process;
  • the etching solution contains phosphorus atoms,
  • the metal-containing compound contains at least Li atoms.
  • 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.
  • step (b) an etching treatment is performed using an etchant to remove at least some of the A atoms from the precursor.
  • the etchant contains a phosphorus atom, especially an anion containing a phosphorus atom.
  • a phosphorus atom such as a phosphorus atom, especially a phosphorus atom
  • the etchant contains a phosphorus atom, especially an anion containing a phosphorus atom.
  • an anion containing a phosphorus atom such as a phosphorus atom, especially a phosphorus atom
  • the inclusion of phosphorus atoms in the etching solution facilitates the presence of Li atoms of the second component.
  • a sufficient etching process becomes possible, and it becomes easy to intercalate Li atoms in the subsequent intercalation process.
  • the form of existence of the anion containing the phosphorus atom is not particularly limited. good too.
  • Anions containing phosphorus atoms include PO 4 3- .
  • the etching solution preferably contains H 3 PO 4 and may further contain HF.
  • a specific example of the etching solution is a mixed solution of an aqueous solution of HF and an aqueous solution of H3PO4 .
  • the etchant may further contain HCl and LiF.
  • the concentration of anions containing phosphorus atoms, particularly PO 4 3- is, for example, 2 mol/L or more and 20 mol/L or less, further 2.5 mol/L or more and 18 mol/L or less, and particularly 3 mol/L or more and 15 mol/L.
  • concentration of anions containing phosphorus atoms, particularly PO 4 3- is, for example, 2 mol/L or more and 20 mol/L or less, further 2.5 mol/L or more and 18 mol/L or less, and particularly 3 mol/L or more and 15 mol/L.
  • the concentration of HF can be, for example, 2 mol/L or more and 20 mol/L or less, further 2.5 mol/L or more and 18 mol/L or less, and particularly 2.5 mol/L or more and 15 mol/L or less.
  • the sum of the concentration of the anion containing the phosphorus atom and the concentration of HF is, for example, 7 mol/L or more and 30 mol/L or less, further 7.5 mol/L or more and 27 mol/L or less, especially 8 mol/L or more and 25 mol/L. /L or less.
  • the etched product obtained by the above etching treatment is washed with water.
  • the acid and the like used in the etching process 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 acid-treated material to be treated.
  • the washing with water may be performed once or more. It is preferable to wash with water several times.
  • An intercalation treatment is performed, which includes a step of mixing the water-washed product obtained by the water washing with a metal-containing compound containing metal ions. This intercalates the metal ions between the layers.
  • the above metal ions include monovalent metal ions, specifically alkali metal ions such as lithium ions, sodium ions and potassium ions, copper ions, silver ions, and gold ions.
  • alkali metal ions such as lithium ions, sodium ions and potassium ions
  • copper ions such as silver ions, and gold ions.
  • metal-containing compounds containing the above metal ions include iodides, phosphates, sulfide salts including sulfates, nitrates, acetates, and carboxylates of the above metal ions.
  • the metal ions include at least lithium ions.
  • the metal-containing compound preferably contains a metal compound containing lithium ions, more preferably contains an ionic compound of lithium ions, and is one of iodide, phosphate, and sulfide salts of lithium ions. It is more preferable to include the above, and it is particularly preferable to include a lithium ion phosphate.
  • the resulting two-dimensional particles can contain Li atoms.
  • the content of the metal-containing compound in the intercalation treatment compound when the water-washed product and the metal-containing compound are mixed is, for example, 0.001% by mass or more and 10% by mass or less, and further 0.01% by mass. It may be 0.1% by mass or more and 1% by mass or less, especially 0.1% by mass or more and 1% by mass or less. When the content of the metal-containing compound is within the above range, the dispersibility in the compound for intercalation treatment is good.
  • the specific method of the intercalation treatment is not particularly limited.
  • a metal-containing compound may be mixed with the water-washed product, and the mixture may be 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.
  • step (e) delamination treatment is performed, including a step of stirring the intercalated product obtained by performing the intercalation treatment.
  • delamination treatment MXene particles can be formed into a single layer or a small layer.
  • the conditions for the delamination treatment are not particularly limited, and can be performed by a known method.
  • stirring methods include ultrasonic treatment, handshake, and stirring using an automatic shaker.
  • 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. For example, after centrifuging the slurry after the intercalation and discarding the supernatant liquid, pure water is added to the remaining precipitate, and the layers are separated by, for example, handshaking or stirring with an automatic shaker. mentioned.
  • the removal of unexfoliated matter includes a step of centrifuging, discarding the supernatant, and washing the remaining precipitate with water.
  • phosphorus atoms may coexist during delamination.
  • Such phosphorus atoms may be present in the form of anions containing phosphorus atoms and may be present in the form of PO 4 3- .
  • the pure water added to the precipitate may be an aqueous solution of phosphoric acid.
  • the pH of such an aqueous solution of phosphoric acid may be, for example, 2-5, or 2.5-4.5.
  • the phosphorus atoms may coexist only during layer separation, and the phosphorus atoms may not coexist during washing.
  • an aqueous phosphoric acid solution is used instead of the pure water added to the remaining precipitate, and pure water is added in the operation of (i).
  • phosphorus atoms may coexist during layer separation and washing.
  • an aqueous phosphoric acid solution is used instead of the pure water added to the remaining precipitate, and the pure water added in the operation of (i)
  • An aqueous solution of phosphoric acid may be used instead of .
  • the delaminated material obtained by stirring can be used as it is as two-dimensional particles containing single-layer/small-layer MXene particles, and may be washed with water if necessary.
  • Electrode 3 Conductive film
  • Applications of the two-dimensional particles of the present embodiment include conductive films containing two-dimensional particles.
  • a conductive film has high electrical conductivity, high moisture resistance, and high smoothness.
  • the conductive film of this embodiment will be described with reference to FIG.
  • FIG. 2 illustrates the conductive film 30 obtained by stacking only the two-dimensional particles 10, the present invention is not limited to this.
  • the conductive film may contain additives such as a binder added during film formation, if necessary.
  • the proportion of the additive in the conductive film (dry) is preferably 30% by volume or less, more preferably 10% by volume or less, even more preferably 5% by volume or less, and most preferably 0% by volume. .
  • the supernatant liquid containing the two-dimensional particles obtained by the delamination is subjected to suction filtration, or the two-dimensional particles are mixed with a dispersion medium.
  • a conductive film can be produced by performing the step of removing the dispersion medium by drying or the like after spraying in the form of a slurry having an appropriate concentration, one or more times.
  • the method of spraying may be, for example, an airless spray method or an air spray method, and specific examples include a method of spraying using a nozzle such as a one-fluid nozzle, a two-fluid nozzle, and an airbrush.
  • Dispersion media that can be contained in the slurry include water; organic media such as N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, methanol, ethanol, dimethylsulfoxide, ethylene glycol and acetic acid.
  • organic media such as N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, methanol, ethanol, dimethylsulfoxide, ethylene glycol and acetic acid.
  • binder examples include acrylic resins, polyester resins, polyamide resins, polyolefin resins, polycarbonate resins, polyurethane resins, polystyrene resins, polyether resins, and polylactic acid.
  • the conductivity of the conductive film is preferably 2,000 S/cm or more, more preferably 5,000 S/m or more, still more preferably 10,000 S/cm or more, for example 100,000 S/cm or less, or It may be 50,000 S/cm or less.
  • the conductivity of the conductive film of this embodiment is 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 equation.
  • Conductivity [S / cm] 1 / (thickness of conductive film [cm] ⁇ surface resistivity of conductive film [ ⁇ / sq.])
  • Electrodiment 4 Conductive paste and conductive composite material
  • Other applications using the two-dimensional particles of the present embodiment include a conductive paste containing the two-dimensional particles and optionally a resin or additive (dispersion medium, viscosity modifier, etc.), the two-dimensional particles and and a conductive composite material containing a resin. These are also suitable for applications that require the ability to maintain high conductivity even under high humidity conditions.
  • Examples of resins that can be contained in the conductive paste and conductive composite material include the same resins that can be contained in the conductive film.
  • Dispersion media that can be contained in the conductive paste include water; organic media such as N-methylpyrrolidone, N-methylformamide, N,N-dimethylformamide, methanol, ethanol, dimethylsulfoxide, ethylene glycol, and acetic acid. is mentioned.
  • the electrode according to this embodiment includes the conductive film.
  • Such an electrode may be formed only from the conductive film, or may include the conductive film and, for example, a substrate.
  • Electrodes include those in a solid state to those in a flexible soft state.
  • the conductive film may be exposed to the outside air so as to be in direct contact with the object to be measured, or may be covered with a base material or the like.
  • the conductive film and the base material may be in direct contact.
  • the material of the substrate is not particularly limited, and may be, for example, an inorganic material such as ceramic or glass, or an organic material. Examples of such organic materials include flexible organic materials, and specific examples include thermoplastic polyurethane elastomers (TPU), PET films, polyimide films, and the like.
  • the material of the base material may be a fibrous material such as paper or cloth (for example, a sheet-like fibrous material).
  • Electrodes of the present embodiments may be utilized for any suitable application. Examples include counter electrodes and reference electrodes for electrochemical measurements, electrodes for electrochemical capacitors, electrodes for batteries, bio-electrodes, electrodes for sensors, and electrodes for antennas. It can also be used in applications where maintaining high conductivity (reducing initial conductivity loss and preventing oxidation) is required, such as electromagnetic shielding (EMI shielding). Details of these applications are described below.
  • EMI shielding electromagnetic shielding
  • the electrodes are not particularly limited, but may be, for example, capacitor electrodes, battery electrodes, biosignal sensing electrodes, sensor electrodes, antenna electrodes, and the like.
  • capacitor electrodes capacitor electrodes
  • battery electrodes biosignal sensing electrodes
  • sensor electrodes sensor electrodes
  • antenna electrodes and the like.
  • the capacitor can be an electrochemical capacitor.
  • An electrochemical capacitor is a capacitor that utilizes the capacity that is generated due to the physicochemical reaction between an electrode (electrode active material) and ions in an electrolyte (electrolyte ion). device).
  • the battery can be a chemical cell that can be repeatedly charged and discharged.
  • the battery can be, for example, but not limited to, a lithium ion battery, a magnesium ion battery, a lithium sulfur battery, a sodium ion battery, and the like.
  • a biosignal sensing electrode is an electrode for acquiring biosignals.
  • the biosignal sensing electrodes can be, but are not limited to, electrodes for measuring EEG (electroencephalogram), ECG (electrocardiogram), EMG (electromyography), EIT (electrical impedance tomography), for example.
  • the sensor electrode is an electrode for detecting the target substance, state, abnormality, etc.
  • the sensor can be, for example, a gas sensor, a biosensor (a chemical sensor that utilizes a biogenic molecular recognition mechanism), or the like, but is not limited thereto.
  • the antenna electrode is an electrode for radiating electromagnetic waves into space and/or receiving electromagnetic waves in space.
  • the antenna formed by the antenna electrode is an antenna for mobile communication such as a mobile phone (so-called 3G, 4G, 5G antenna), an RFID antenna, or an NFC (Near Field Communication) antenna. Not limited.
  • the electrode of this embodiment is preferably used as an antenna electrode.
  • An electrode including the conductive film has high electrical conductivity and high moisture resistance, and has high smoothness as a conductive film. Electrodes having such characteristics can be advantageously used to extend the communication distance.
  • the two-dimensional particles in one embodiment of the present disclosure have been described in detail above, various modifications are possible.
  • the two-dimensional particles of the present disclosure may be produced by a method different from the production method in the above-described embodiment, and the two-dimensional particle production method of the present disclosure is the same as the two-dimensional particles in the above-described embodiment. Note that you are not limited to just what you provide.
  • Example 1-8, Comparative Examples 1-2 [Preparation of two-dimensional particles]
  • (1) Precursor (MAX) preparation, (2) Precursor etching, (3) Cleaning, (4) Intercalation, (5) Delamination and (6) water washing were performed in order to prepare two-dimensional particles.
  • 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 1,350° C. for 2 hours in an Ar atmosphere. The obtained sintered body (block) was pulverized with an end mill to a maximum size of 40 ⁇ m or less. As a result, Ti 3 AlC 2 particles were obtained as a precursor (MAX).
  • Ti 3 C 2 T s - water-borne clay (MXene after washing): 0.5 g solids ⁇ Metal-containing compound: 0.68 g of Li 3 PO 4 ⁇ Intercalation container: 100 mL eyeboy ⁇ Temperature: 20°C or higher and 25°C or lower (room temperature) ⁇ Time: 24 hours ⁇ Stirrer rotation speed: 700 rpm
  • the slurry obtained by performing delamination intercalation was put into a 50 mL centrifuge tube, centrifuged for 5 minutes at 3,500 G using a centrifuge, and then the supernatant was recovered. . Furthermore, after adding 35 mL of an aqueous solution of phosphoric acid adjusted to pH 3.5, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a monolayer MXene particle-containing liquid. This was repeated several times to obtain a supernatant containing monolayer MXene particles. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Example 9 After the preparation of the precursor (MAX), the etching step, the washing step and the delamination step were performed in the same manner as in Example 1, the following step (5) was performed to prepare two-dimensional particles (single-layer MXene particles). A clay was made.
  • Precursor (MAX) preparation same as Examples 1-8
  • Precursor etching same as Examples 1-8
  • Cleaning same as Example 1
  • intercalation The slurry obtained by performing the same (5) delamination intercalation as in Examples 1 to 8 was put into a 50 mL centrifuge tube, and centrifuged at 3500 G for 5 minutes using a centrifuge. A supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Example 10 After the preparation of the precursor (MAX), the etching step, the washing step and the delamination step were performed in the same manner as in Example 1, the following step (5) was performed to prepare two-dimensional particles (single-layer MXene particles). A clay was made.
  • Precursor (MAX) preparation same as Examples 1-8
  • Precursor etching same as Examples 1-8
  • Cleaning same as Example 1
  • intercalation The slurry obtained by performing the same (5) delamination intercalation as in Examples 1 to 8 was put into a 50 mL centrifuge tube and centrifuged at 3,500 G for 5 minutes using a centrifuge.
  • the supernatant was collected to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, after adding 35 mL of pure water and stirring with a shaker for 15 minutes, centrifugation was performed at 3,500 G for 5 minutes, and the supernatant liquid was recovered as a monolayer MXene particle-containing liquid. I got the liquid. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Example 11 After the preparation of the precursor (MAX), the etching step, the washing step and the delamination step were performed in the same manner as in Example 1, the following step (5) was performed to prepare two-dimensional particles (single-layer MXene particles). A clay was made.
  • Precursor (MAX) preparation same as Examples 1-8
  • Precursor etching same as Examples 1-8
  • Cleaning same as Example 1
  • intercalation The slurry obtained by performing the same (5) delamination intercalation as in Examples 1 to 8 was put into a 50 mL centrifuge tube and centrifuged at 3,500 G for 5 minutes using a centrifuge.
  • the supernatant was collected to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated twice. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Example 12 After the preparation of the precursor (MAX), the etching step, the washing step and the delamination step were performed in the same manner as in Example 1, the following step (5) was performed to prepare two-dimensional particles (single-layer MXene particles). A clay was made.
  • Precursor (MAX) preparation same as Examples 1-8
  • Precursor etching same as Examples 1-8
  • Cleaning same as Example 1
  • intercalation The slurry obtained by performing the same (5) delamination intercalation as in Examples 1 to 8 was put into a 50 mL centrifuge tube and centrifuged at 3,500 G for 5 minutes using a centrifuge.
  • the supernatant was collected to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated three times. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Example 13 After the preparation of the precursor (MAX), the etching step, the washing step and the delamination step were performed in the same manner as in Example 1, the following step (5) was performed to prepare two-dimensional particles (single-layer MXene particles). A clay was made.
  • Precursor (MAX) preparation same as Examples 1-8
  • Precursor etching same as Examples 1-8
  • Cleaning same as Example 1
  • intercalation The slurry obtained by performing the same (5) delamination intercalation as in Examples 1 to 8 was put into a 50 mL centrifuge tube and centrifuged at 3,500 G for 5 minutes using a centrifuge.
  • the supernatant was collected to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated four times. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • a clay containing two-dimensional particles (monolayer MXene particles) was obtained. Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated four times. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • etching and intercalation conditions ⁇ Precursor: Ti 3 AlC 2 (through a 45 ⁇ m sieve) ⁇ Etching liquid composition: LiF 3 g HCl (9M) 30 mL ⁇ Precursor input amount: 3.0 g ⁇ Etching container: 100 mL eyeboy ⁇ Etching temperature: 35 ° C. ⁇ Etching time: 24h ⁇ Stirrer rotation speed: 400 rpm (3) Washing: The same as in Example 1 (5) Delamination The slurry obtained by performing intercalation is put into a 50 mL centrifuge tube and centrifuged at 3,500 G for 5 minutes using a centrifuge.
  • the supernatant was recovered to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated four times. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • the supernatant was collected to obtain a clay containing two-dimensional particles (single-layer MXene particles). Furthermore, the operation of adding 35 mL of pure water, stirring with a shaker for 15 minutes, centrifuging at 3,500 G for 5 minutes, and recovering the supernatant as a liquid containing monolayer MXene particles was repeated four times. A containing supernatant was obtained. Furthermore, after centrifuging the supernatant using a centrifuge at 4,300 G for 2 hours, the supernatant was discarded to obtain a clay containing two-dimensional particles (single-layer MXene particles). rice field.
  • Clays containing two-dimensional particles (single-layer MXene particles) obtained in Examples 1-13 and Comparative Examples 1-6 were subjected to suction filtration. After filtration, vacuum drying was performed at 80° C. for 24 hours to prepare a conductive film containing two-dimensional particles.
  • a membrane filter manufactured by Merck Ltd., Durapore, pore size 0.45 ⁇ m was used as a filter for suction filtration.
  • the supernatant liquid contained 0.05 g of solid content of two-dimensional particles and 40 mL of pure water.
  • the conductive film containing the obtained two-dimensional particles was measured by X-ray photoelectron spectroscopy (XPS) to measure the content of phosphorus atoms contained in the two-dimensional particles.
  • Quantum 2000 manufactured by ULVAC-PHI was used for the XPS measurement.
  • the content of phosphorus atoms contained in the two-dimensional particles was 0.20% by mass in Example 1, 0.25% by mass in Example 2, 0.32% by mass in Example 3, and 0.34% in Example 4. % by mass, Comparative Example 1 was 0.14 mass %, Comparative Example 2 was 0.18 mass %, Comparative Example 5 was 0.20 mass %, and Comparative Example 6 was 0.34 mass %.
  • the content of Li atoms contained in the two-dimensional particles was 0.30% by mass in Example 1.
  • Two-dimensional particles (single-layer MXene particles) and dried Al 2 O 3 powder were mixed at a mass ratio of 1:9 in a glove box in an Ar atmosphere (dew point less than ⁇ 60° C.) and pulverized in an agate mortar. to obtain a mixed powder.
  • the mixed powder was packed in a zirconia sample tube for solid NMR with an outer diameter of 4 mm in the glove box, capped with a Kel-F cap, and used as a sample for NMR measurement.
  • a Bruker AVANCE III 400 (magnetic field strength: 9.4 T, resonance frequency of 7 Li nucleus: 155.455 MHz) was used.
  • PH MAS 400S1 BL4 NP/H VTN manufactured by Bruker was used.
  • the ratio of the first component to the total of the first component and the second component was in the range of 17 atomic % or more and 70 atomic % or less.
  • the phosphoric acid aqueous solution was used during delamination, while in Examples 9 to 13, only pure water was used during delamination without using the phosphoric acid aqueous solution. Since Examples 4 and 5 and Examples 9 to 13 have different etching conditions, the state of the surface group of the MXene layer is different. It is considered that two-dimensional particles were obtained in which the ratio of the first component to the total of the second component was 17 atomic % or more and 70 atomic % or less.
  • the relative area of each echo was plotted against the refocus time for the real component after phase correction was applied to the obtained time domain data. Regression is performed on this echo attenuation profile by the sum of exponential functions in which the relative areas of the first component and the second component obtained in the above quantitative measurement are fixed as a coefficient ratio, and the respective time constants (T2 relaxation times) are obtained. rice field.
  • the T2 relaxation time of the first component was 0.47 ms, and the T2 relaxation time of the second component was 1.7 ms.
  • the T2 relaxation time of the first component was 0.36 ms, and the T2 relaxation time of the second component was 2 ms.
  • the T2 relaxation time of the first component was 0.56 ms, and the T2 relaxation time of the second component was 1.5 ms.
  • the T2 relaxation time of the first component was 0.44 ms, and the T2 relaxation time of the second component was 1.2 ms.
  • the T2 relaxation time of the first component is shorter than the T2 relaxation time of the first component, and it is considered that the first component interacts strongly with the substance.
  • Conductive composite film preparation method 1 Polyurethane solution (manufactured by Dainichiseika Kogyo Co., Ltd., non-volatile content concentration 35% by mass) was added to 50 g of the two-dimensional particle dispersion liquid of Example 5 (two-dimensional particle (MXene solid content) concentration: 6.4% by mass) in pure water. 52.750 g of a 100-fold diluted solution was added to form a composite. Thereafter, the composite was stirred for 15 minutes using an automatic shaker (SK550 manufactured by F&FM).
  • SK550 automatic shaker manufactured by F&FM
  • the resulting composite spray film had a thickness of 4.4 ⁇ m and an initial conductivity of 17,668 S/cm as measured by the conductivity measurement method described later.
  • the electrical conductivity measured in the same manner after a humidity resistance test of 99% humidity at room temperature for 14 days was 8,127 S/cm, and the rate of change from the initial electrical conductivity was 46%.
  • Polyurethane solution (manufactured by Dainichi Seika Kogyo Co., Ltd., non-volatile content concentration 35% by mass) was added to 25.221 g of the two-dimensional particle dispersion liquid (two-dimensional particle (MXene solid content) concentration: 3.25% by mass) of Comparative Example 3. 14.779 g of a solution diluted 100 times with pure water was added to prepare a composite. After that, the composite was stirred for 15 minutes using an automatic shaker (SK550 manufactured by F&FM).
  • SK550 automatic shaker manufactured by F&FM
  • the resulting composite spray film had a film thickness of 3.2 ⁇ m and an initial conductivity of 10,269 S/cm as measured by the conductivity measurement method described later, which is lower than that of the two-dimensional particles of Example 5. result. Further, after the humidity resistance test was conducted for 14 days under normal temperature humidity of 99%, the electrical conductivity measured in the same manner was 3,081 S/cm, and the rate of change from the initial electrical conductivity was 30%.
  • the conductive composite film containing the two-dimensional particles of Example 5 had high initial conductivity and good moisture resistance.
  • the ratio of the first component to the total of the first component and the second component exceeds 70 atomic %, and the initial conductivity and moisture resistance are not sufficiently satisfactory. rice field.
  • the conductive film containing two-dimensional particles obtained in Example 4 had a film density of 3.6 g/cm 3 and an electrical conductivity of 14,000 S/cm.
  • the conductive film containing two-dimensional particles obtained in Example 6 had a film density of 3.7 g/cm 3 , a conductivity of 15,700 S/cm, and a conductivity change rate of 95%.
  • the conductive film containing two-dimensional particles obtained in Example 7 had a film density of 3.2 g/cm 3 , a conductivity of 13,600 S/cm, and a conductivity change rate of 94%.
  • the conductive film containing two-dimensional particles obtained in Comparative Example 3 had a film density of 2 g/cm 3 , a conductivity of 9,000 S/cm, and a conductivity change rate of 78%.
  • the conductive film containing two-dimensional particles obtained in Comparative Example 4 had a film density of 2 g/cm 3 , a conductivity of 6,000 S/cm, and a conductivity change rate of 23%.
  • Method 2 for producing a conductive film The clay containing the two-dimensional particles (single-layer MXene particles) obtained in Examples 1 to 13 was coated on a polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror) to a thickness of 120 ⁇ m or less. Then, it was air-dried to obtain a conductive film by coating. The film thickness of the obtained conductive film was 1 ⁇ m.
  • the film density, conductivity, and conductivity change rate of the conductive film were measured by the following methods.
  • Film density measurement method A film having a diameter of 12 mm ⁇ was punched out from the film, the weight was measured with an electronic balance, and the thickness was measured with a height gauge. Film density was calculated from the values obtained.
  • the conductivity of the obtained conductive film containing two-dimensional particles was determined.
  • the electrical conductivity was measured at three points per sample for resistivity ( ⁇ ) and thickness ( ⁇ m), and the electrical conductivity (S/cm) was calculated from these measurements. The average value of the ratio was adopted.
  • a simple low resistivity meter Mitsubishi Chemical Analytic Co., Ltd., Loresta AX MCP-T370
  • a micrometer MDH-25MB manufactured by Mitutoyo Co., Ltd.
  • the volume resistivity was obtained from the obtained surface resistance and the thickness of the conductive film, and the reciprocal of the obtained value was obtained to obtain the conductivity, which was defined as E 0 .

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CN113209933A (zh) * 2021-04-15 2021-08-06 中国工程物理研究院材料研究所 一种MXene气凝胶的制备方法及其对磷和铀酰的吸附应用
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