WO2022153890A1 - 導電性膜およびその製造方法 - Google Patents

導電性膜およびその製造方法 Download PDF

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Publication number
WO2022153890A1
WO2022153890A1 PCT/JP2022/000039 JP2022000039W WO2022153890A1 WO 2022153890 A1 WO2022153890 A1 WO 2022153890A1 JP 2022000039 W JP2022000039 W JP 2022000039W WO 2022153890 A1 WO2022153890 A1 WO 2022153890A1
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Prior art keywords
mxene
film
conductive film
group
atom
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English (en)
French (fr)
Japanese (ja)
Inventor
匡矩 阿部
武志 部田
淑子 島▲崎▼
宙樹 坂本
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Priority to JP2022575535A priority Critical patent/JP7626146B2/ja
Priority to CN202280009193.XA priority patent/CN116745864B/zh
Publication of WO2022153890A1 publication Critical patent/WO2022153890A1/ja
Priority to US18/349,593 priority patent/US12476019B2/en
Anticipated expiration legal-status Critical
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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
    • H01B1/06—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
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure

Definitions

  • the present disclosure relates to a conductive membrane and a method for producing the same.
  • MXene has been attracting attention as a new material with conductivity.
  • MXene is a kind of so-called two-dimensional material, and is a layered material having the form of one or a plurality of layers as described later.
  • MXene has the form of particles of such layered material (also referred to as MXene particles, which may include powders, flakes, nanosheets, etc.).
  • Patent Document 1 proposes to increase the strength of MXene by containing metal nanoparticles such as nanoparticles, nanocopper particles, nanoaluminum particles, and nanomagnesium particles on the surface and between layers of MXene powder. ing.
  • Non-Patent Document 1 Li cations are present in the interlayer space of MXene due to LiCl used for chemical etching, and Li cations are exchanged with other metal ions to obtain powder. It is stated that structural changes occur.
  • Patent Document 1 and Non-Patent Document 1 Has not been shown to enhance these properties.
  • the present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a conductive film having high initial conductivity and exhibiting stable conductivity, and a method for producing the same.
  • the layer has the following formula: Mm Xn (In the formula, 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 represented by and the modification or termination T existing on the surface of the layer body (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).
  • 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).
  • the layer has the following formula: Mm Xn (In the formula, 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 represented by and the modification or termination T existing on the surface of the layer body (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).
  • a precursor film containing the above is prepared, and (b1) one or more selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y on the precursor film.
  • a method for producing a conductive film comprises applying a solution containing the transition element of the above as an ion in a solvent.
  • a conductive film is formed of a predetermined layered material (also referred to herein as "MXene") from Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y.
  • a conductive film containing one or more transition elements selected from the above group, which contains MXene, has high initial conductivity, and has excellent conductivity stability.
  • (a1) a predetermined precursor film is prepared, and (b1) the precursor film is coated with Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y.
  • the conductive film can be produced by applying a solution containing one or more transition elements selected from the above group as ions in a solvent.
  • FIG. 6 is a schematic schematic cross-sectional view showing MXene, which is a layered material that can be used for a conductive film in one embodiment of the present invention, in which FIG. Layer) MXene is shown. It is a schematic explanatory drawing of the mechanism of exhibiting the adsorption resistance of the conductive film of this invention, (a) is the conventional MXene film which does not have a transition element, (b) is MXene film (conductive film) which contains a transition element. Is shown. It is a figure explaining the interlayer distance in the transition element containing MXene particles which concerns on this invention.
  • the conductive film in this embodiment is A conductive film containing particles of a layered material containing one or more layers.
  • the layer has the following formula: Mm Xn (In the formula, 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 represented by and the modification or termination T existing on the surface of the layer body (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). Including and It contains one or more transition elements selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y.
  • the conductive film of the present embodiment in order to distinguish the conductive film of the present embodiment from the MXene film containing no transition element, it may be referred to as a "transition element-containing MXene film” or a “transition element ion-bearing MXene film”.
  • the MXene film containing no transition element is referred to as a "precursor film”.
  • the layered material constituting the precursor film is referred to as "MXene”
  • the particles thereof are referred to as “MXene particles”
  • the particles of the layered material constituting the conductive film of the present embodiment are referred to as "transition element-containing MXene particles”.
  • the layered material can be understood as a layered compound, also expressed as " MmXnTs ", where s is any number, and conventionally, x or z may be used instead of s.
  • n can be 1, 2, 3 or 4, but is not limited to this.
  • 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. More preferably, it is at least one selected from the group.
  • M can be titanium or vanadium and X can be a carbon or nitrogen atom.
  • the MAX phase is Ti 3 AlC 2 and MXene is Ti 3 C 2 T s (in other words, M is Ti, X is C, n is 2, and m is 3). Is).
  • MXene may contain a relatively small amount of residual A atom, for example, 10% by mass or less with respect to the original A atom.
  • the residual amount of A atom can be preferably 8% by mass or less, more preferably 6% by mass or less. However, even if the residual amount of A atom exceeds 10% by mass, there may be no problem depending on the use and usage conditions of the conductive film.
  • the transition element-containing MXene particles according to the present embodiment have a structure corresponding to the skeleton, except that the transition element is contained and the interlayer distance of the layered material is increased accordingly. It is the same as a particle.
  • the structure corresponding to the skeleton of the transition element-containing MXene particles is described, and the transition element is not shown in FIG.
  • the MXene particles are an aggregate containing one layer of MXene 10a (monolayer MXene) schematically illustrated in FIG.
  • the MXene 10a is more specifically 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, at least two surfaces facing each other in each layer).
  • M m X n layer a layer body 1a represented by M m X n
  • a surface of the layer body 1a more specifically, at least two surfaces facing each other in each layer.
  • MXene layer 7a with modifications or terminations T3a and 5a present in. Therefore, the MXene layer 7a is also expressed as "MM X n T s ", and s is an arbitrary number.
  • the MXene particles may contain a plurality of layers together with one layer.
  • the plurality of layers of MXene include, but are not limited to, two layers of MXene10b, as schematically shown in FIG. 1 (b). 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 multilayer MXene may not necessarily be completely separated, but may be partially in contact with each other.
  • the MXene10a may be a mixture of the single-layer MXene10a and the multilayer MXene10b, in which the multilayer MXene10b is individually separated and exists in one layer, and the unseparated multilayer MXene10b remains.
  • each layer of MXene is, for example, 0.8 nm or more and 5 nm or less, particularly 0.8 nm or more and 3 nm or less. (Mainly, it may vary depending on the number of M atomic layers contained in each layer).
  • the interlayer distance or void size, indicated by ⁇ d in FIG. 1B is, for example, 0.8 nm or more and 10 nm or less, particularly 0.8 nm or more and 5 nm.
  • the total number of layers can be 2 or more and 20,000 or less.
  • the MXene particles are preferably MXene having a small number of layers obtained by delaminating the multilayer MXene.
  • the "small number of layers” means, for example, that the number of layers of MXene is 6 or less.
  • the thickness of the multilayer MXene having a small number of layers in the stacking direction is preferably 10 nm or less.
  • this "multilayer MXene with a small number of layers” may be referred to as "small layer MXene”.
  • the single layer MXene and the small layer MXene may be collectively referred to as "single layer / small layer MXene”.
  • the MXene particles preferably include a single layer MXene and a small layer MXene, that is, a single layer / small layer MXene.
  • the ratio of the single layer / small layer MXene having a thickness of 10 nm or less may be 50% by volume or more, further 70% by volume or more, further 90% by volume or more, and further. May be 95% by volume or more.
  • the conductive film of the present embodiment contains one or more transition elements selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y. It is known that MXene interacts with the d-orbital of metal, but among them, the electrons of the d-orbital of these transition elements easily interact with the ⁇ electron of MXene, and the action of retaining the layer and layer of MXene. It is considered that it contributes to the improvement of the stability of the conductivity because it is easy to secure. In addition, it can contribute to the improvement of the strength of the conductive film by exerting the action of holding the MXene layer and the layer.
  • the transition element may be the same as or different from the elements constituting MXene.
  • the ions of the transition element are supported on MXene. That is, the transition element-containing MXene particles are preferably transition element-supported MXene particles.
  • the term "supporting" means that the transition element does not constitute MXene itself, and a transition metal ion or a transition metal inorganic acid salt is present between layers of MXene.
  • the inorganic acid salt can be, for example, an inorganic acid salt used in the step (b1) or the step (d2) in the method for producing a conductive film.
  • titanium sulfate for example, as the inorganic acid salt, titanium ions may exist between layers of MXene in a state of being bound to sulfate ions which are counter ions.
  • one or more of Ti, Cr and Y is preferable, and Ti is most preferable.
  • the transition element is preferably present between the layers.
  • the transition element is, for example, Ti, as schematically illustrated in FIG. 2B
  • the transition element particularly the ion (Ti ion 41 in the case of FIG. 2)
  • the water molecules 40 easily invade between the layers 7c and the layers 7c, and the decrease in conductivity due to the presence of the water molecules 40, that is, the deterioration of the conductivity due to moisture absorption with time can be suppressed.
  • the transition element-containing MXene particles 10d as shown in FIG. 2B, the invasion of water molecules 40 into the layers was suppressed, and the deterioration of conductivity due to moisture absorption over time could be suppressed, and the initial stage. It is considered that high conductivity can be maintained without significantly lowering the conductivity.
  • transition element ions anchor the layer 7d and the layer 7d of the transition element-containing MXene particles 10d, thereby contributing to ensuring the strength of the MXene film. Furthermore, as a guess, it is considered that the interaction of transition element ions with MXene promotes the movement of electrons as described above, which may contribute to the achievement of high initial conductivity.
  • the MXene film as a reference used for comparison of moisture absorption resistance is a MAX phase preparation step including a firing step and a crushing step, and an etching treatment step. It is assumed that the delamination step and the concentration step are the same as the method for producing the conductive film according to the present invention, and Li is contained in the MXene film in some form.
  • the layers in the multilayer MXene (particles) have been described as an example, but the “between layers” of the transition element-containing MXene particles in the present embodiment is not limited to this, for example, simply. It also refers between a layer MXene (particles) and another single layer MXene (particles), and between a single layer MXene (particles) and a multilayer MXene (particles).
  • the conductive film of the present embodiment preferably has transition element ions between the layers constituting MXene, and the distance between the layers constituting MXene is the MXene film not containing the transition element. Shorter than.
  • the above-mentioned “distance between layers constituting MXene” means that when Mm Xn is Ti 3 C 2 O 2 (O-term) represented by Ti 3 C 2 , the crystal structure is shown in FIG. As schematically shown (in FIG. 3, 50 is a titanium atom, 51 is an oxygen atom, and other elements are omitted), and refers to the distance indicated by the double arrow in FIG.
  • the distance can be determined by the position of a low-angle peak of 11 ° (deg) or less corresponding to the (002) plane of MXene in the XRD profile obtained by X-ray diffraction measurement.
  • the peak refers to the peak top.
  • the X-ray diffraction measurement may be performed under the conditions shown in Examples described later.
  • Examples of the position of the low-angle peak include a range of 5 to 11 °, and among them, for example, 6.2 ° or more, and further 6.3 ° or more.
  • the profile obtained by X-ray diffraction measurement of the conductive film is 52 °.
  • Ti is carried as a transition element in addition to Ti forming the skeleton of MXene.
  • the angle difference between the two peaks that is, the difference in angle (unit deg) obtained by (the angle of the peak located at 52 ° or more and 58 ° or less)-(the angle of the peak having 45 ° or more and 49 ° or less). Can be in the range of 7 ° or more and 10 ° or less.
  • the peaks in the XRD profile particularly the peaks located at 52 ° or more and 58 ° or less and the peaks having 45 ° or more and 49 ° or less, have higher numerical values than the measurement points of one point before and after (that is, positive).
  • the portion (having an extreme value) is regarded as the peak apex, the height when a perpendicular line is drawn from the peak apex to the baseline is taken as the peak height, and the peak height is 1/500 or more of the peak corresponding to the (002) plane. It means something that is.
  • the initial conductivity of the conductive film of the present embodiment is measured by measuring the thickness of the conductive film with a micrometer, measuring with a scanning electron microscope (SEM), or measuring with a stylus type surface shape measuring device.
  • the thickness of the conductive film and the surface resistance of the conductive film measured by the 4-probe method are obtained by substituting into the following equation, and can be 5000 S / cm or more.
  • Conductivity [S / cm] 1 / (Thickness of conductive film [cm] x Surface resistivity of conductive film [ ⁇ / ⁇ ])
  • the measurement with the micrometer may be used when the thickness of the conductive film is thin. It may be used when the thickness of the conductive film is 5 ⁇ m or more.
  • the measurement with the stylus type surface shape measuring device is when the thickness of the conductive film is 400 ⁇ m or less, and the measurement with the scanning electron microscope is when the thickness of the conductive film is 200 ⁇ m or less. It is used when it is not possible to measure with the stylus type surface shape measuring device.
  • the measurement magnification may be determined according to the film thickness.
  • the measurement is performed using a Dektak (registered trademark) measuring device manufactured by Veeco Instruments Inc. The thickness of the conductive film is calculated as an average value.
  • excellent conductivity means that the conductivity after 4 weeks in an environment of temperature 25 ° C. and humidity 99% is 10% or more of the initial conductivity. , Preferably 20% or more.
  • the conductive membrane of this embodiment can be used for any suitable application.
  • suitable application such as electrodes and electromagnetic shields (EMI shields) in any suitable electrical device.
  • EMI shields electromagnetic shields
  • the electrode is not particularly limited, but may be, for example, a capacitor electrode, a battery electrode, a biological signal sensing electrode, a sensor electrode, an antenna electrode, or the like.
  • a capacitor electrode a battery electrode
  • a biological signal sensing electrode a sensor electrode
  • an antenna electrode or the like.
  • the capacitor can be an electrochemical capacitor.
  • An electrochemical capacitor is a capacitor that utilizes the capacity developed by a physicochemical reaction between an electrode (electrode active material) and an ion (electrolyte ion) in an electrolytic solution, and is a device (storage) that stores electrical energy. Can be used as a device).
  • the battery can be a chemical cell that can be recharged and discharged repeatedly.
  • the battery can be, for example, a lithium ion battery, a magnesium ion battery, a lithium sulfur battery, a sodium ion battery, and the like, but is not limited thereto.
  • the biological signal sensing electrode is an electrode for acquiring a biological signal.
  • the biological signal sensing electrode can be, for example, an electrode for measuring EEG (electroencephalogram), ECG (electrocardiogram), EMG (electromyogram), EIT (electrical impedance tomography), but is not limited thereto.
  • the sensor electrode is an electrode for detecting a target substance, state, abnormality, etc.
  • the sensor may be, for example, a gas sensor, a biosensor (a chemical sensor utilizing a molecular recognition mechanism of biological origin), or the like, but is not limited thereto.
  • the antenna electrode is an electrode for radiating electromagnetic waves into space and / or receiving electromagnetic waves in space.
  • the method for producing one conductive film of the present embodiment is as follows.
  • the layer has the following formula: Mm Xn (In the formula, 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 represented by and the modification or termination T existing on the surface of the layer body (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).
  • a precursor film containing the above is prepared, and (b1) one or more selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y on the precursor film.
  • (b1) one or more selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y on the precursor film.
  • Another method for producing a conductive film (second manufacturing method) of the present embodiment is (A2) The following formula: M m AX n (In the formula, 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)
  • 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
  • (C2) Performing an intercalation treatment of monovalent metal ions, which comprises a step of mixing the etched product obtained by the etching treatment with a metal compound containing monovalent metal ions.
  • (D2) The monovalent metal ion intercalated product obtained by the monovalent metal ion intercalation treatment, Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Performing a transition element intercalation treatment comprising mixing a solution containing one or more transition elements selected from the group consisting of Y as ions in a solvent, and (e2) the transition element intercurry.
  • a conductive film containing the above transition element can also be produced by this production method.
  • a predetermined dry MXene membrane is prepared as a precursor membrane.
  • the production of the precursor film is not limited, and for example, when a precursor film is obtained by spraying using a slurry containing MXene (particles) in a liquid medium, it can be produced by the following method.
  • MXene particles particles of a predetermined layered material
  • Such MXene particles can be synthesized by selectively etching (removing and optionally layering) A atoms (and optionally a portion of M atoms) from the MAX phase.
  • the MAX phase is expressed by the following formula: M m AX n (In the formula, M, X, n and m are as described above, A is at least one group 12th, 13th, 14th, 15th and 16th element, usually a group A element, representatively.
  • Is a group IIIA and a group IVA may include at least one selected from the group consisting of Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, S and Cd.
  • a layer composed of A atoms is located between two layers represented by and represented by M m X n (each X may have a crystal lattice located in an octahedral array of M). It has a crystal structure.
  • M m X n n
  • one layer of X atoms is arranged between each layer of M atoms of n + 1 layer (these are also collectively referred to as “MM X n layer”). It has a repeating unit in which a layer of A atoms (“A atom layer”) is arranged as a layer next to the n + 1th layer of M atoms, but is not limited to this.
  • the MAX phase can be produced by a known method. For example, TiC powder, Ti powder and Al powder are mixed by a ball mill, and the obtained mixed powder is fired in an Ar atmosphere to obtain a fired body (block-shaped MAX phase). Then, the obtained fired body can be pulverized with an end mill to obtain a powdery MAX phase for the next step.
  • the A atom layer (and possibly part of the M atom) is removed by selectively etching (removing and possibly layering) the A atom (and possibly part of the M atom) from the MAX phase.
  • etching solution usually, but not limited to, an aqueous solution of fluoroacid is used. It is modified to terminate such surfaces.
  • the etching can be carried out using an etching solution containing F ⁇ , and may be, for example, a method using a mixed solution of lithium fluoride and hydrochloric acid, a method using hydrofluoric acid, or the like.
  • the etching solution contains a metal compound containing monovalent metal ions, and even if the monovalent metal ions are intercalated at the same time as the etching. good.
  • the content of the metal compound containing the monovalent metal ion in the etching solution can be the same as the step (b2) of the second production method described later.
  • the layer separation of MXene is promoted by any appropriate post-treatment (for example, sonication, handshake or automatic shaker) as appropriate. May be good.
  • monovalent including a step of mixing the etched product obtained by the etching treatment with a metal compound containing a monovalent metal ion under the same conditions as the step (c2) of the second manufacturing method described later.
  • the metal ion of the above may be intercalated. In the ultrasonic treatment, the shearing force is too large and the MXene can be destroyed.
  • a slurry S containing MXene (particles) in a liquid medium is prepared.
  • the concentration of particles of the layered material in the slurry S can be, for example, 5 mg / mL or more, but in particular, the particles can be disaggregated / overlapped and, in some cases, layer-separated, so that the concentration of the particles is 30 mg / mL without causing nozzle clogging. It can be more than mL.
  • the higher the concentration of particles of the layered material in the slurry S the shorter the time required to produce a film having a desired thickness, which is suitable for industrial mass production.
  • the upper limit of the particle concentration of the layered material can be appropriately selected, and can be, for example, 200 mg / mL or less.
  • the concentration of particles of the layered material is understood as the solid content concentration in the slurry S, and the solid content concentration can be measured by using, for example, a heat-drying weight measuring method, a freeze-drying weight measuring method, a filtration weight measuring method, or the like.
  • the slurry S may be a dispersion liquid and / or a suspension containing particles 10a and / or 10b of the layered material in a liquid medium.
  • the liquid medium can be an aqueous medium and / or an organic medium, preferably an aqueous medium.
  • the aqueous medium is typically water, and in some cases, contains other liquid substances in addition to water in a relatively small amount (for example, 30% by mass or less, preferably 20% by mass or less based on the whole aqueous medium). May be good.
  • the organic medium may be, for example, N-methylpyrrolidone, N-methylformamide, N, N-dimethylformamide, ethanol, methanol, dimethyl sulfoxide, ethylene glycol, acetic acid and the like.
  • a precursor film is produced by spraying as follows.
  • the liquid component derived from the liquid medium of the slurry S may remain or may not be substantially present.
  • the precursor film does not have to contain a so-called binder.
  • a slurry (fluid) containing particles of a layered material in a liquid medium and a gas (another fluid) are separately discharged from the nozzle 20 and collided with each other outside the nozzle 20.
  • a method of (mixing) and depositing particles of the layered material on the base material 31 to form the precursor film 30 will be described.
  • the nozzle 20 that can be used in this embodiment is a nozzle called an external mixing type multi-fluid nozzle.
  • FIG. 5 shows an example of an external mixing type multi-fluid nozzle.
  • the nozzle 20 preferably has a configuration in which the slurry and the gas collide with each other in a vortex flow outside the nozzle 20.
  • the external mixing type multi-fluid nozzle 20c is an external mixing type multi-fluid nozzle having a configuration in which the slurry S and the gas G collide with each other in a vortex flow outside the nozzle 20c. More specifically, the external mixing type multi-fluid nozzle 20c has a head portion H configured to discharge the slurry S and separately collide with the gas G discharged as a eddy current (preferably a high-speed swirling eddy current). For example, by using the nozzle 20c, the mist M containing the particles of the layered material can be sprayed from the mixed fluid of the slurry S and the gas G as follows.
  • the gas G is passed through one or more spiral grooves (not shown) provided in the swivel member (not shown) incorporated in the head portion H, and the gas discharge port (not shown) is passed.
  • a high-speed swirling vortex of gas G is generated by discharging from.
  • the slurry S is introduced into the fluid supply pipe inside the nozzle 20c provided for the slurry S by the negative pressure of the high-speed swirling vortex flow by the gas G, and is discharged from the fluid discharge port (not shown) at the tip of the fluid supply pipe. Slurry.
  • the external mixing type multi-fluid nozzle 20c may be an external mixing vortex type multi-fluid nozzle (for example, Atmax nozzle manufactured by Atmax Co., Ltd.).
  • the nozzle 20c discharges the slurry S containing the particles of the layered material in the liquid medium and the gas G separately from the nozzle 20c and causes them to collide with each other outside the nozzle 20c, thereby causing the slurry S.
  • a strong shearing force can be applied to the particles of the layered material.
  • the agglomeration can be released, and when the particles of the layered material are overlapped, the overlap can be released.
  • layer separation delamination
  • the slurry S may be supplied to the nozzle 20c by either a pressure method or a suction method.
  • the gas G is not particularly limited, and may be, for example, air, nitrogen gas, or the like.
  • the pressure of the gas G can be appropriately set, and may be, for example, 0.05 to 1.0 MPa (gauge pressure).
  • the particle size of mist M can be adjusted as appropriate, and may be, for example, 1 ⁇ m or more and 15 ⁇ m or less.
  • the mist M sprayed from the nozzle 20 is supplied (applied) (spray coated) on the surface of the base material 31, and particles of the layered material are deposited on the base material 31 to form the precursor film 30.
  • the liquid component contained in the mist M (derived from the liquid medium of the slurry S) can be removed at least partially, preferably entirely, by drying while and / or after being fed onto the substrate 31.
  • the base material is not particularly limited and may consist of any suitable material.
  • the base material may be, for example, a resin film, a metal foil, a printed wiring board, a mountable electronic component, a metal pin, a metal wiring, a metal wire, or the like.
  • drying Even if the drying is performed under mild conditions such as natural drying (typically placed in an air atmosphere under normal temperature and pressure) or air drying (blowing air), warm air drying (spraying heated air) is performed. ), Heat drying, and / or vacuum drying may be performed under relatively active conditions.
  • mild conditions such as natural drying (typically placed in an air atmosphere under normal temperature and pressure) or air drying (blowing air), warm air drying (spraying heated air) is performed. ), Heat drying, and / or vacuum drying may be performed under relatively active conditions.
  • Spraying and drying from the nozzle 20 may be repeated as appropriate until a desired film thickness is obtained.
  • the combination of spraying and drying may be repeated a plurality of times.
  • a slurry containing MXene particles 10a and / or 10b at a relatively high concentration can be used, so that only one spray (and optionally drying) is required to carry out a relatively thick film (and optionally drying).
  • a thickness of 0.5 ⁇ m or more) can be obtained, and the number of sprays (and optionally drying) performed until a desired film thickness is obtained can be reduced.
  • the precursor film is produced as the precursor film 30.
  • the precursor film 30 contains particles 10a and / or 10b of the layered material, and the liquid component derived from the liquid medium of the slurry S may remain or may not be substantially present.
  • the precursor film 30 does not contain a so-called binder.
  • the precursor film may be prepared by suction filtration of the supernatant liquid containing MXene particles obtained by the above slurry or the above delamination. Further, the precursor film by spraying may be produced by using a nozzle other than the external mixing type multi-fluid nozzle.
  • a solution containing one or more transition elements selected from the group consisting of Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y as ions in a solvent is applied to the precursor film. ..
  • a compound containing the transition element can be used for preparing a solution containing the transition element as an ion in the solvent.
  • the compound for example, it is preferable to use one or more inorganic acid salts selected from the group consisting of sulfates, nitrates, acetates, and phosphates of the transition elements. More preferably, it is one or more inorganic acid salts of sulfate and acetate.
  • the concentration of the compound contained in the solution is not particularly limited, and can be, for example, in the range of 0.001 M or more and 0.1 M or less.
  • concentration of the compound contained in the solution is preferably in the range of 0.001 M or more and 0.1 M or less.
  • concentration of the compound contained in the solution is preferably in the range of 0.01 M or more and 0.1 M or less.
  • the counter anion source the above-mentioned inorganic acid salt may be used, but the acid may not be essential.
  • water for example, purified water such as distilled water or deionized water
  • lower alcohol having about 2 to 4 carbon atoms for example, ethanol, isopropanol, butanol, etc.
  • hexane acetone and other organic solvents
  • the coating includes commonly used coating methods such as immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, die coater, and electrostatic coating.
  • the post-coating step is not particularly limited.
  • the coated product by immersion is withdrawn from the solution, washed with water and then dried, for example, dried at 70 to 90 ° C. for 1 to 2 hours, and further 120 to 160. Examples include drying at ° C.
  • the MAX phase can be produced by a known method. For example, TiC powder, Ti powder and Al powder are mixed by a ball mill, and the obtained mixed powder is fired in an Ar atmosphere to obtain a fired body (block-shaped MAX phase). Then, the obtained fired body can be pulverized with an end mill to obtain a powdery MAX phase for the next step.
  • etching process is performed using an etching solution to remove at least a part of A atoms from the MAX phase.
  • the etching treatment conditions are not particularly limited, and known conditions can be adopted.
  • it can be carried out using an etching solution containing F ⁇ , and may be, for example, a method using a mixed solution of lithium fluoride and hydrochloric acid, a method using hydrofluoric acid, or the like.
  • the etching solution contains a metal compound containing monovalent metal ions, and the monovalent metal ions are intercalated at the same time as the etching, instead of the following step (c2) or together with the following step (c2). You may.
  • the content of the metal compound containing monovalent metal ions in the etching solution is preferably 0.001% by mass or more.
  • the content is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.
  • the content of the metal compound containing monovalent metal ions in the etching solution is preferably 10% by mass or less, more preferably 1% by mass or less.
  • An intercalation treatment of monovalent metal ions is performed, which includes a step of mixing the etched product obtained by the etching treatment with a metal compound containing monovalent metal ions.
  • the monovalent metal ion constituting the metal compound containing the monovalent metal ion include alkali metal ions such as lithium ion, sodium ion and potassium ion, copper ion, silver ion and gold ion.
  • the metal compound containing the monovalent metal ion include an ionic compound in which the metal ion and a cation are bonded.
  • Examples thereof include iodides, phosphates, sulfide salts including sulfates, nitrates, acetates and carboxylates of the above metal ions.
  • the monovalent metal ion lithium ion is preferable as described above, and as the metal compound containing a monovalent metal ion, a metal compound containing lithium ion is preferable, an ionic compound of lithium ion is more preferable, and a lithium ion iodine is preferable. More preferably, one or more of the compounds, phosphates and sulfide salts. If lithium ions are used as the metal ions, it is considered that water hydrated with lithium ions has the most negative dielectric constant, so that it is easy to form a single layer.
  • the content of the metal compound containing the monovalent metal ion in the compound for intercalation treatment of the monovalent metal ion is preferably 0.001% by mass or more.
  • the content is more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more.
  • the content of the metal compound containing monovalent metal ions is preferably 10% by mass or less, more preferably 1% by mass or less.
  • stirring may be performed or the mixture may be allowed to stand.
  • 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 centrifuge device.
  • ⁇ Process (d2) It is composed of an intercalated product of monovalent metal ions obtained by the intercalation treatment of monovalent metal ions, and Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W and Y.
  • a solution containing one or more transition elements selected from the group as ions in the solvent is mixed.
  • the type and concentration of the transition element compound contained in the solution are as described in the step (b1) of the first production method.
  • stirring may be performed or the mixture may be allowed to stand.
  • Examples of 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 centrifuge device.
  • the solvent is at least partially removed from the transition element intercalation-treated product obtained by the transition element intercalation treatment to obtain a conductive film.
  • the method for removing the solvent at least partially is not particularly limited, and examples thereof include filtration, heating, and vacuum distillation.
  • suction filtration of the supernatant liquid or clay obtained after washing the transition element intercalated product with water can be mentioned.
  • vacuum drying at 80 ° C. for 24 hours can be performed to prepare a conductive film.
  • a membrane filter manufactured by Merck Co., Ltd., Durapore, pore diameter 0.45 ⁇ m
  • the conductive film and the method for producing the conductive film according to the embodiment of the present invention have been described in detail above, but various modifications are possible.
  • the conductive film of the present invention may be produced by a method different from the production method in the above-described embodiment, and the method for producing the conductive film of the present invention is the conductive film in the above-described embodiment. Please note that you are not limited to what you offer.
  • Example 1 [Manufacture of MXene film containing transition elements]
  • Example 1 a Ti ion-supported MXene film was prepared as a sample (conductive film).
  • Ti 3 AlC 2 particles were prepared as MAX particles by a known method.
  • the Ti 3 AlC 2 particles (powder) were added to 9 mol / L hydrochloric acid together with LiF (1 g of Ti 3 AlC 2 particles to 10 mL of 9 mol / L hydrochloric acid), and at 35 ° C. with a stirrer. Stirring for 24 hours gave a solid-liquid mixture (suspension) containing solid components derived from Ti 3 AlC 2 particles.
  • the operation of washing with pure water and separating and removing the supernatant using a centrifuge is repeated about 10 times. did. Then, the mixture obtained by adding pure water to the sediment is stirred with an automatic shaker for 15 minutes, and then centrifuged with a centrifuge for 5 minutes to separate the supernatant into the sediment, and the supernatant is separated by centrifugal dehydration. Removed. As a result, the remaining sediment excluding the supernatant was diluted by adding pure water to obtain a crudely purified slurry.
  • the crudely purified slurry may contain single-layer MXene and multi-layer MXene that has not been monolayered due to insufficient layer separation (delamination) as MXene particles, and further contains impurities other than MXene particles (unreacted MAX particles and unreacted MAX particles). It is understood to include crystals of by-products derived from the etched A atom (eg, crystals of AlF 3 ) and the like.
  • the crudely purified slurry obtained above was placed in a centrifuge tube and centrifuged at a relative centrifugal force (RCF) of 2600 ⁇ g for 5 minutes using a centrifuge. As a result, the centrifuged supernatant was recovered to obtain a purified slurry. It is understood that the purified slurry contains a large amount of single-layer MXene as MXene particles. The remaining sediment, excluding the supernatant, was subsequently not used.
  • RCF relative centrifugal force
  • the purified slurry obtained above was placed in a centrifuge tube and centrifuged at 3500 ⁇ g of RCF for 120 minutes using a centrifuge. As a result, the centrifuged supernatant was separated and removed. The separated supernatant was not used thereafter. A clay-like substance (clay) was obtained as the remaining sediment after removing the supernatant. As a result, Ti 3 C 2 T s -aqueous dispersion clay was obtained as MXene clay. The MXene clay and pure water were mixed in an appropriate amount to prepare an MXene aqueous dispersion having a MXene solid content concentration of 75 mg / mL.
  • MXene spray film was prepared as follows.
  • an external mixing vortex type multi-fluid (two-fluid) nozzle (manufactured by Atmax Co., Ltd., Atmax nozzle AM12 type) was used.
  • the slurry (solid content concentration 84 mg / mL) prepared above was placed in a plastic syringe and set in a syringe pump (YSP-101 manufactured by YMC Co., Ltd.).
  • the extrusion speed of the syringe pump was set to 5.0 mL / min, and the discharge port of the plastic syringe was connected to the liquid material (slurry) supply port of the external mixing type multi-fluid nozzle.
  • the gas supply port of the external mixing type multi-fluid nozzle is connected to the compressed air supply source (compressed air line in the factory) via a plastic hose, and the gas discharge pressure from the nozzle becomes 0.45 MPa (gauge pressure). Adjusted as follows.
  • the MXene solid content concentration 15 mg / mL aqueous dispersion and gas (air) are discharged from an external mixing type multi-fluid nozzle and sprayed on the surface of a base material made of gold-coated glass (manufactured by Waki Laboratory Co., Ltd.). did. After spraying, it was dried overnight in a vacuum oven at 80 ° C. to obtain a spray MXene film as a precursor film.
  • Example 1 (conductive membrane).
  • Example 2 In Example 2, a Cr ion-supported MXene film was prepared as a sample (conductive film).
  • Example 3 a Y ion-supported MXene film was prepared as a sample (conductive film).
  • Example 1 (Formation of precursor film)
  • a spray MXene film was obtained in the same manner as in Example 1 except that the film was sprayed on a substrate made of a polyimide film (manufactured by Toray DuPont Co., Ltd.).
  • a transition element ion-bearing MXene film was obtained by immersing a precursor film (MXene film) in an aqueous solution containing a transition element, but this is a method for producing a transition element ion-bearing MXene film.
  • the transition element intercalation treatment by mixing the monovalent metal ion intercalation treated product and the transition element ion-containing solution, for example, from the transition element intercalation treated product by filtration or the like.
  • the transition element ion-bearing MXene film may be obtained by removing at least a part of the solvent.
  • Comparative Example 1 an Al ion-supported MXene film was prepared as a sample. First, as precursor membranes, a filtered MXene membrane and a spray MXene membrane were obtained in the same manner as in Example 1.
  • Comparative Example 2 In Comparative Example 2, a MXene membrane (precursor membrane) without ion support was prepared as a sample. As the precursor membrane, a filtered MXene membrane and a spray MXene membrane were obtained in the same manner as in Example 1. In Comparative Example 2, the filtered MXene membrane and the spray MXene membrane were not immersed in the transition element-containing solution, and the filtered MXene membrane and the spray MXene membrane, that is, the precursor membrane were used as samples of Comparative Example 2. In the following evaluation, Comparative Example 2 is shown as Control.
  • the sample was held at room temperature (about 25 ° C.) in an environment of 99% humidity, and the conductivity was measured one day after the start of holding, and then at intervals of one week from the start of holding until the fifth week. The conductivity was measured. The conductivity was measured at three locations including the vicinity of the center of the film per sample. A low resistance conductivity meter (Loresta AX MCP-T370 manufactured by Mitsubishi Chemical Analytical Corporation) was used for measuring the conductivity. The thickness of the sample (dry film) was measured using a micrometer (MDH-25MB manufactured by Mitutoyo Co., Ltd.). The results showing the time course of the conductivity of Examples 1, 2 and 5 and Comparative Examples 1 and 2 are shown in FIG.
  • the “conductivity change rate” on the vertical axis of FIG. 6 shows the initial conductivity as 100% and the subsequent conductivity as a ratio (%) to the initial conductivity.
  • the initial conductivity was 6044 S / cm in Example 1, 13514 S / cm in Example 2, 15707 S / cm in Example 3, 6305 S / cm in Comparative Example 1, and 4454 S / cm in Comparative Example 2.
  • Example 2 which is the result of the MXene film (precursor film) without ion support
  • the conductivity after one day was significantly reduced from the initial conductivity, and the conductivity was continued thereafter.
  • the result was that the stability of the conductivity was significantly inferior.
  • Example 1 although the initial conductivity was high and the conductivity decreased after one day, the decrease in conductivity was sufficiently suppressed as compared with Comparative Example 2, and the conductivity was stable. Further, in Examples 2 and 3, as in Example 1, the initial conductivity is high and the conductivity drops once, but the decrease in conductivity is sufficiently suppressed as compared with Comparative Example 2, and the conductivity is stable. ..
  • the Cr ion-supported MXene film of Example 2 and the Y ion-supported MXene film of Example 3 also joined the layers of the MXene film in the same manner as the Ti ion-supported MXene film of Example 1, and water molecules were less likely to enter. As mentioned above, it is considered that the conductivity is stable.
  • Example 2 The same as in Example 2 except that a 0.01 M chromium acetate aqueous solution or a 0.001 M chromium acetate aqueous solution was used instead of the 0.1 M chromium acetate aqueous solution in the immersion in the transition element-containing solution in Example 2.
  • a spray MXene film (dry film) formed in the above manner was also prepared separately, and the above-mentioned change in conductivity with time was measured. As a result, it was confirmed that even when the transition element concentration in the transition element-containing solution used in the production of the spray MXene film was changed, the same tendency as in Example 2 was exhibited.
  • Example 3 in the immersion in the transition element-containing solution in Example 3, the same as in Example 3 except that a 0.01 M yttrium acetate aqueous solution or a 0.001 M yttrium acetate aqueous solution was used instead of the 0.1 M yttrium acetate aqueous solution.
  • a spray MXene film (dry film) formed in the above manner was also prepared separately, and the above-mentioned change in conductivity with time was measured. As a result, it was confirmed that even when the transition element concentration in the transition element-containing solution used in the production of the spray MXene film was changed, the same tendency as in Example 3 was exhibited.
  • Example 1 and Comparative Examples 1 and 2 were Using the samples of Example 1 and Comparative Examples 1 and 2 in which a spray MXene film was formed on the surface of a base material made of gold-coated glass (manufactured by Waki Laboratory Co., Ltd.), the strength of the sample film was as follows. A tape peeling test was performed and evaluated.
  • Two tape peeling tests were performed based on the standard (IPC-TM-650).
  • a 3M Brand 600 1 / 2inch tape manufactured by 3M was prepared, and the roll-shaped tape was peeled off in the first week and used for the test from the second lap.
  • the tape was pulled out by 5 cm or more and attached to the spray MXene membrane as the first tape, and the tape and the spray MXene membrane were brought into close contact with each other so as to remove all the air.
  • the first tape was peeled off at once from the spray MXene film in a direction of about 90 °, and the film state was observed.
  • the time for applying the tape was set to 1 minute or less. The result is shown in FIG.
  • FIG. 7 was taken with the base material after the test and the deposits on the peeled first tape facing up.
  • 7 (a) is the result of Example 1
  • FIG. 7 (b) is the result of Comparative Example 1
  • FIG. 7 (c) is the result of Comparative Example 2.
  • FIG. 8 (a) is the result of Example 1
  • FIG. 8 (b) is the result of Comparative Example 1
  • FIG. 8 (c) is the result of Comparative Example 2.
  • Example 1 From the result of FIG. 7 (a) above, in Example 1, the spray MXene film was peeled off from the surface of the golden base material, but from FIG. 8 (a) which is the result of the tape peeling test again, the left side is almost affixed tape. Only, the spray MXene film remained stuck to the first tape on the right side. That is, peeling in the spray MXene film, that is, cohesive peeling did not occur. From this, it can be seen that the spray MXene film is strengthened by supporting Ti ions.
  • Comparative Example 1 the adhesion between the gold slide glass (base material) and the spray MXene film was weak, and the gold-colored substrate (gray in FIG. 7B) was wide in the first tape peeling test. It was observed.
  • Comparative Example 1 in the first tape peeling test, the cohesive peeling that peeled in the spray MXene film did not occur as much as in Comparative Example 2 below, but in the second tape peeling test, it was applied to the second tape on the left side. The MXene film was transferred and coagulation peeling occurred.
  • FIG. 9 shows FIG. 9, FIG. 10 in which the range of 2 ° to 9 ° in FIG. 9 is enlarged, and FIG. 11 in which the range of 35 ° to 55 ° in FIG. 9 is enlarged.
  • the peak position of the (002) plane in the range of 6 to 10 ° represents the distance between the nanosheets of the MXene film (interlayer distance), and the more the peak is located on the higher angle side. It is known that the interlayer distance of MXene becomes small.
  • the Ti ion-supported MXene film had a peak on the high angle side as compared with the precursor film without ion support. That is, it is considered that the nanosheets were anchored by Ti ions and the interlayer distance of MXene was narrowed. Further, in the case of the Al ion-supported MXene film of Comparative Example 1, it is considered that the nanosheets were not connected as much as Ti, and the interlayer distance of MXene was wider than that of Ti.
  • Example 2 The same as in Example 1 except that a 0.01 M titanium sulfate aqueous solution or a 0.1 M titanium sulfate aqueous solution was used instead of the 0.002 M titanium sulfate aqueous solution in the immersion in the transition element-containing solution in Example 1.
  • a spray MXene film (dry film) formed in the above manner was also prepared separately, and XRD measurement was performed.
  • the resulting two-dimensional X-ray diffraction image (profile) is shown in FIG. From FIG. 12, there is almost no effect on the structure due to the difference in the concentration of the transition element-containing solution during production, and the two-dimensional X-ray diffraction image (profile) of the Ti ion-bearing MXene film shown in FIG. 12 is shown in the above figure. It was almost the same as the two-dimensional X-ray diffraction image (profile) of the Ti ion-bearing MXene film of No. 9.
  • Comparative Example 1 in which Al ions were supported instead of Ti ions, as shown in FIG. 10, the peak was on the higher angle side than the precursor film, but on the lower angle side than the Ti ion-supported MXene film. Came out. From this, even when Al ions were used, the nanosheets were tied together and narrowed, but the MXene nanosheet holding function was not as effective as Ti. As a result, it was confirmed that even in Comparative Example 1, the decrease in conductivity due to moisture absorption was suppressed and the film had strength, but the performance was inferior to that of the Ti ion-supported MXene film.
  • Comparative Example 2 which is a precursor film, a peak appeared on the highest angle side. This suggests that the metal ions did not intercalate and the layers expanded due to the insertion of water molecules. As a result, in Comparative Example 2, the transition metal did not have the MXene nanosheet holding function, the conductivity was remarkably lowered, and the film strength was also the weakest.
  • the conductive film of the present invention can be used in any suitable application, for example, as an electrode or electromagnetic shield in an electric device, as an electrode, for example, a large-capacity capacitor, a battery, a low-impedance biometric signal sensing electrode, a high-sensitivity sensor, etc.
  • an antenna and an electromagnetic shield for example, it can be particularly preferably used for a highly shielded EMI shield.

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WO2020136864A1 (ja) * 2018-12-28 2020-07-02 株式会社アドマテックス ＭＸｅｎｅ粒子材料、スラリー、二次電池、透明電極、ＭＸｅｎｅ粒子材料の製造方法
CN110698847A (zh) * 2019-10-21 2020-01-17 西北工业大学 水性聚氨酯-MXene电磁屏蔽仿生纳米复合材料膜及制备方法

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WO2023120069A1 (ja) * 2021-12-23 2023-06-29 株式会社村田製作所 積層体、物品、および物品の製造方法
KR20240048600A (ko) * 2022-10-06 2024-04-16 연세대학교 산학협력단 재적층된 무기 나노시트 및 이의 제조방법
KR102923353B1 (ko) 2022-10-06 2026-02-06 연세대학교 산학협력단 재적층된 무기 나노시트 및 이의 제조방법

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