WO2019117360A1 - Procédé de revêtement de métal en nanofibres utilisant un effet de réduction de sel métallique, et procédé de fabrication d'électrode transparente - Google Patents

Procédé de revêtement de métal en nanofibres utilisant un effet de réduction de sel métallique, et procédé de fabrication d'électrode transparente Download PDF

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WO2019117360A1
WO2019117360A1 PCT/KR2017/014724 KR2017014724W WO2019117360A1 WO 2019117360 A1 WO2019117360 A1 WO 2019117360A1 KR 2017014724 W KR2017014724 W KR 2017014724W WO 2019117360 A1 WO2019117360 A1 WO 2019117360A1
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nanofibers
nanofiber
spinning solution
present
transparent electrode
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PCT/KR2017/014724
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English (en)
Korean (ko)
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안치원
김영태
한희
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/30—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/32—Filling or coating with impervious material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/48—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances fibrous materials

Definitions

  • the present invention relates to a nanofiber metal coating method and a transparent electrode manufacturing method using the metal salt reducing effect, and more particularly, to a nanofiber metal coating method and a transparent electrode manufacturing method that reduce a metal coating process on a nanofiber, simplify a nanofiber manufacturing process, And a method of manufacturing a transparent electrode using the same.
  • Nanofibers are ultrafine fibers having a very small diameter of about 1 ⁇ m or less and have many applications such as medical materials, filters, MEMS, and nano devices. Nanofibers have a very large surface area per unit mass, are flexible, have many micro spaces, and have a large number of fibers per unit area, so that they can be blended with other materials and exhibit a large dispersion in external stress.
  • the electrospinning device used in the electrospinning method is composed of a spinning tip from which the solution comes out, a high voltage device, and a collector which collects the nanofibers.
  • a high voltage is applied to the spinning tip to charge the droplets discharged from the discharging portion to jet the stream from the droplet by electrostatic repulsion, thereby forming nanofibers on the collecting plate.
  • Nanofibers can also be fabricated using microfluidic techniques. A device consisting of an injection tube and a collection tube is used. When the middle fluid and the outer fluid are different and are pushed to the external pressure, the core shell structure ≪ / RTI >
  • the plated nanofibers can be used for various purposes by performing plating on the nanofibers as described above.
  • a heat treatment process for carbonization of nanofibers is required to perform electroplating on nanofibers. Or to perform plating on nanofibers, a catalytic process for nanofibers, and an activation treatment process.
  • Korean Patent No. 10-1079775 (entitled Electrospinning Electrolytic Nanofiber Fabrication Method Through Electrolytic Plating), a) an electrospinning solution containing a polymer capable of forming a fiber and an electroless plating catalyst, Producing; b) electrospinning the electrospinning liquid to produce nanofibers having a diameter of 10 nm to 5 ⁇ in size; and c) electroless plating the nanofibers.
  • the method of manufacturing the metal-coated nanofibers of the present invention includes the steps of:
  • an object of the present invention is to provide a method for preparing an electrospinning solution, which comprises adding a metal salt to induce a reducing effect in a solution, forming nanoparticles in a solution through an aging process, Can be continuously and uniformly performed simultaneously with the electrospinning so that the metal coating process can be performed.
  • An object of the present invention is to produce a transparent electrode with high efficiency by forming copper-plated nanofibers on a transparent substrate.
  • a method of manufacturing a spinning solution comprising: i) preparing a spinning solution by mixing an organic reducing solvent, a metal salt, and a carbon fiber precursor; ii) aging the spinning solution at an aging temperature; iii) electrospinning the spinning solution to form nanofibers; iv) injecting the nanofibers into an electroless copper plating solution to perform copper plating on the nanofibers; And v) drying the plated nanofibers at a drying temperature.
  • the metal in the step iii), may be precipitated on the surface of the nanofiber by the reducing effect of the solvent.
  • the carbon fiber precursor may be polyacrylonitrile (PAN).
  • the carbon fiber precursor may be 5 to 20% by weight based on 100% by weight of the spinning solution.
  • the metal salt may be 1 to 80% by weight based on 100% by weight of the spinning solution.
  • the aging temperature may be lower than the boiling point of the organic reducing solvent.
  • the spinning solution is radiated to a target cathode
  • the cathode may be a roll, a plate, or a needle type.
  • the rotation speed of the roller may be 1000 to 2000 rpm.
  • the spinning liquid in the step ii), may be radiated to a cathode electrode formed of a conductive material.
  • the drying temperature may be 10 to 100 degrees Celsius.
  • the step iv) may be performed by injecting the nanofibers into the electroless copper plating solution at a concentration of 0.05 to 0.5 g / L and stirring the nanofibers.
  • a method of manufacturing a spinning solution comprising: i) preparing a spinning solution by mixing an organic reducing solvent, a metal salt, and a carbon fiber precursor; ii) aging the spinning solution at an aging temperature; iii) electrospinning the spinning solution on a substrate to form nanofibers; iv) dipping the substrate on which the nanofibers are formed in an electroless copper plating solution to perform copper plating on the nanofibers; And v) drying the substrate at a drying temperature.
  • the substrate may be formed of a transparent material.
  • the effect of the present invention according to the above structure is to reduce the metal coating process on the nanofibers to simplify the nanofiber manufacturing process and reduce the manufacturing cost.
  • the effect of the present invention is that the process of immersing the nanofibers in a solution is omitted so that the multifunctional multi-layer nanofibers (a combination of metal-coated nanofibers or non-metal-coated nanofibers) can be formed, It is possible to form a metal coated nanofiber by a simple process which is capable of metal coating after transfer and can be used for a large area continuous process and which does not require heat treatment or vacuum process.
  • the effect of the present invention is that a transparent electrode can be produced by forming the plated nanofibers on a transparent substrate, and having a low sheet resistance and generating a high heat even with a small electric power.
  • FIG. 1 is a schematic diagram of a state change of a nanofiber according to an embodiment of the present invention.
  • FIG. 2 is an FIB image of plated nanofibers according to one embodiment of the present invention.
  • FIG 3 is an FIB image of plated nanofibers according to one embodiment of the present invention.
  • 5 is a SEM image of nanofibers according to an embodiment of the present invention.
  • FIG 6 is an SEM image of nanofibers according to an embodiment of the present invention.
  • FIG 9 is an SEM image of nanofibers after being electrospun in accordance with another embodiment of the present invention.
  • FIG. 10 is an SEM image of a copper-plated nanofiber according to another embodiment of the present invention.
  • FIG. 11 is a graph showing transmittance of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • FIG. 12 is a graph illustrating sheet resistance of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • FIG. 13 is a graph showing sheet resistance of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • FIG. 14 is a graph illustrating heating of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • 15 is a graph showing changes in sheet resistance with respect to folding of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • Preferred embodiments of the present invention include: i) preparing a spinning solution by mixing an organic reducing solvent, a metal salt and a carbon fiber precursor; ii) aging the spinning solution at an aging temperature; iii) electrospinning the spinning solution to form nanofibers; iv) injecting the nanofibers into an electroless copper plating solution to perform copper plating on the nanofibers; And v) drying the plated nanofibers at a drying temperature.
  • FIG. 1 is a schematic diagram of a state change of a nanofiber according to an embodiment of the present invention.
  • FIG. FIG. 1 (a) shows a nanofiber formed by electrospinning.
  • FIG. 1 (b) shows a state where silver is precipitated on the surface of the nanofiber.
  • FIG. 1 (c) shows a state where silver is precipitated on the surface of the nanofiber.
  • the nanofiber metal coating method of the present invention can be performed in the following steps.
  • a spinning solution can be prepared by mixing an organic reducing solvent, a metal salt, and a carbon fiber precursor.
  • the organic reducing solvent may be formed of dimethylformamide (DMF).
  • the metal salt may be silver nitrate (AgNO 3 ).
  • the carbon fiber precursor may be polyacrylonitrile (PAN).
  • the carbon fiber precursor may be 5 to 20% by weight based on 100% by weight of the spinning solution.
  • the concentration of the carbon fiber precursor in the spinning solution can not be sufficiently formed and the formation rate of nanofibers due to electrospinning may be lowered.
  • the thickness variation of the nanofibers formed by electrospinning increases and the proportion of the carbon fibers having diameters of 1 ⁇ or more increases, The formation ratio of the nanofibers may be lowered.
  • the metal salt may be 1 to 80% by weight based on 100% by weight of the spinning solution.
  • the concentration of silver (Ag + ) in the spinning solution can not be sufficiently formed and the amount of silver particles precipitated on the surface of the nanofiber And the proportion of nanofibers without silver particles may increase.
  • silver nitrate (AgNO 3 ) When silver nitrate (AgNO 3 ) is contained in an amount of more than 80% by weight based on 100% by weight of the spinning solution, the concentration of silver (Ag + ) in the spinning solution is excessive and silver particles precipitated on the surface of the nanofiber It is not evenly distributed in the nanofibers, and a phenomenon that a part of the particles are precipitated out may be generated.
  • the spinning solution can be aged at the aging temperature.
  • the aging temperature may be lower than the boiling point of the organic reducing solvent.
  • nanoparticles formed by the carbon fiber precursor may not be uniformly generated and distributed in the solvent.
  • the spinning solution can be electrospun to form nanofibers.
  • the metal by the metal salt may be precipitated on the surface of the nanofiber by the reducing effect of the solvent.
  • the metal by the metal salt may be silver (Ag).
  • the silver nanoparticles produced by the reduction effect of the solvent can be adjusted according to the aging time and temperature, and the nanoparticles can be used as a catalyst when electroless plating the nanofibers after electrospinning the spinning solution.
  • the amount or size (surface area per particle) of silver nanoparticles deposited on the surface of the nanofibers can be controlled.
  • the spinning liquid is radiated to the target cathode, and the cathode may be roll, plate or needle type.
  • the rotation speed of the roll may be 1000 to 2000 rpm.
  • the angle at which the spinning liquid is radiated to the roll is referred to as an orientation angle.
  • the rotation speed of the roll is 1000 to 2000 rpm, the orientation angle is maintained and the nanofibers can be formed. Namely, when the rotation speed of the roll is less than 1000 rpm or exceeds 2000 rpm, the nanofiber is generated in a state in which the orientation angle is not constant and the diameter of the nanofiber is not uniformly formed, When a voltage is applied after forming a network, electricity may not be conducted.
  • the spinning solution may be radiated to a cathode electrode formed of a conductive material.
  • the spinning solution When the spinning solution is radiated to the cathode electrode, the spinning solution may be radiated toward the cathode electrode while changing the position or the spraying angle of the syringe for spraying the spinning solution.
  • the nanofibers can be injected into the electroless copper plating solution to perform copper plating on the nanofibers.
  • the nanofibers can be injected into the electroless copper plating solution at 0.05 to 0.5 g / L and stirred.
  • nanofibers are injected into the electroless copper plating solution and then stirred.
  • nanofibers may be injected into the electroless copper plating solution without stirring.
  • nanofibers When nanofibers are injected into the electroless copper plating solution in an amount of less than 0.5 g / L or more than 0.5 g / L, copper plating may not be performed on some nanofibers.
  • the plated nanofibers can be dried at the drying temperature.
  • the drying temperature may be 10 to 100 degrees Celsius.
  • drying temperature is less than 10 degrees, drying on the plated nanofibers may not be performed properly.
  • the drying temperature exceeds 100 ° C., the plated copper may peel off due to rapid drying.
  • the nanofibers may be frequently broken due to the surface tension during immersing the nanofibers in the solution for the catalyst treatment. Accordingly, there is a problem in that it is difficult to commercialize a product using nanofibers because it is difficult to mass-produce a product using nanofibers or other additional processes.
  • the process of immersing the nanofibers in a solution is omitted, thereby making it possible to manufacture large-sized products using the nanofibers.
  • the nanofiber composite material having copper-plated nanofibers can be prepared using the nanofiber metal coating method of the present invention.
  • the carbon fiber precursor polyacrylonitrile (PAN)
  • PAN polyacrylonitrile
  • DMF dimethylformamide
  • AgNO 3 silver nitrate
  • the spinning solution was electrospun with a roller rotating at 1500 rpm in an electric field of 20 kV to form nanofibers.
  • FIGS. 2 and 3 are FIB images of plated nanofibers according to [Example 1] of the present invention.
  • FIG. 2 (a) is an image of a plated nanofiber dried at room temperature (RT) for 10 seconds at a magnification x 25000 and x 1750 of an FIB (ion microscope), and Fig. 2 (b) RT) at a magnification of x 2500 and x 250 of FIB (ion microscope) for plated nanofibers dried for 1 minute.
  • FIG. 3 (a) is an image of a plated nanofiber dried at room temperature (RT) for 5 minutes at a magnification x10000 and x2500 of FIB (ion microscope), and Fig. 3 (b) ) With a magnification of x12500 and x2500 of FIB (ion microscope) for plated nanofibers dried for 10 minutes.
  • FIG. 4 (a) is an image of a nanofiber formed with a pre-copper plating diameter of 0.964 to 1.1 micrometers ( ⁇ ), image taken at a magnification x50000 of an SEM (electron microscope), and Fig. 4 (b) Is an image picked up at a magnification x50000 of an SEM (electron microscope) on a nanofiber formed with a diameter of 1.2 to 1.6 micrometers (mu m) after copper plating. It can be confirmed that the thickness of the copper metal layer is formed to 0.1 to 0.5 micrometer (mu m) by comparing the diameter of the pre-plating nanofiber of FIG. 4 (a) and the diameter of the post-plating nanofiber of FIG. 4 (b).
  • FIG. 5 (a) is an image of a nanofiber formed with a copper pre-plating diameter of 0.696 to 0.916 micrometers ( ⁇ ), image taken at SEM (electron microscope) magnification x50000, and FIG. 5 And an image picked up at a magnification x50000 of an SEM (electron microscope) on a nanofiber formed with a diameter of 1.1 to 1.16 micrometers (mu m) after copper plating. It can be confirmed that the thickness of the copper metal layer is formed in the range of 0.4 to 0.65 micrometer (mu m) by comparing the pre-plating nanofiber diameter in Fig. 5 (a) and the post-plating nanofiber diameter in Fig. 5 (b).
  • FIG. 6 (a) is an image of a nanofiber formed with a pre-copper plating diameter of 0.778 to 1.03 micrometer ( ⁇ ⁇ ) at a magnification x25000 of an SEM (electron microscope), and Fig. 6 The image was taken at a magnification x50000 of an SEM (electron microscope) on a nanofiber formed with a diameter of 1.53 micrometers ( ⁇ ) after copper plating. It can be confirmed that the thickness of the copper metal layer is formed to be 0.5 to 0.76 micrometer (mu m) by comparing the diameter of the pre-plating nanofiber of FIG. 6 (a) with that of the post-plating nanofiber of FIG. 6 (b).
  • FIG. 7 (a) is an image taken at a magnification x50000 of an SEM (electron microscope) for a nanofiber formed with a copper pre-plating diameter of 0.827 to 1.26 micrometers ( ⁇ ⁇ ), and FIG. Is an image of a nanofiber formed with a diameter of 1.32 to 1.56 micrometers ( ⁇ ⁇ ) after copper plating at a magnification x 25000 of an SEM (electron microscope). It can be confirmed that the thickness of the copper metal layer is formed to 0.3 to 0.5 micrometer (mu m) by comparing the diameter of the pre-plating nanofiber of Fig. 7 (a) with that of the post-plating nanofiber of Fig. 7 (b).
  • the copper metal layer may be formed to a thickness of 0.1 to 0.76 micrometers ( ⁇ ⁇ ).
  • the nanofiber metal coating method of the present invention it is possible to reduce the metal coating process on the nanofibers, simplify the nanofiber manufacturing process, and reduce the manufacturing cost.
  • multifunctional multi-layer nanofibers a combination of metal-coated nanofibers or non-metal-coated nanofibers
  • transfer the nanofibers to the substrate
  • metal coated nanofiber by a simple process which does not require a heat treatment or a vacuum process.
  • a metal electrode plated nanofiber can be formed on a transparent substrate to produce a transparent electrode that has low sheet resistance and generates high heat even at low electric power.
  • a transparent electrode having copper-plated nanofibers can be manufactured using the nanofiber metal coating method of the present invention.
  • a spinning solution can be prepared by mixing a solvent, a metal salt, and a carbon fiber precursor formed of an organic reducing solvent.
  • the spinning solution can be aged at the aging temperature.
  • the spinning solution can be electrospun onto the substrate to form nanofibers.
  • the substrate may be formed of a transparent material.
  • the substrate may be formed of synthetic resin, glass, and silicon.
  • the substrate is formed of the above-described material, but the present invention is not limited thereto.
  • the substrate on which the nanofibers are formed can be immersed in an electroless copper plating solution to perform copper plating on the nanofibers.
  • the substrate can be dried at the drying temperature.
  • the transparent electrode manufacturing method of the present invention is characterized in that unlike the above-described nanofiber metal coating method of the present invention, electrospinning is performed on a substrate as a target without using a roller as a target, It can be immersed in a copper plating solution to perform copper plating on the nanofibers.
  • the remaining matters may be the same as those of the nanofiber metal coating method of the present invention described above.
  • PAN Polyacrylonitrile
  • a carbon fiber precursor was dissolved in a solvent composed of dimethylformamide (DMF) in an amount of 8% by weight, dissolved in 10% by weight of silver nitrate (AgNO 3 )
  • DMF dimethylformamide
  • AgNO 3 silver nitrate
  • the spinning solution was subjected to electrospinning for 10 seconds on a 2.5 cm x 2.5 cm 2 PC film (PolyCabonate film) to form nanofibers on the PC film.
  • PAN Polyacrylonitrile
  • a carbon fiber precursor was dissolved in a solvent composed of dimethylformamide (DMF) in an amount of 8% by weight, dissolved in 10% by weight of silver nitrate (AgNO 3 )
  • DMF dimethylformamide
  • AgNO 3 silver nitrate
  • the spinning solution by electrospinning 30 seconds target the PC film (PolyCabonate film) of 2.5X2.5cm 2, thereby forming the nanofibers on a PC film.
  • PAN Polyacrylonitrile
  • a carbon fiber precursor was dissolved in a solvent composed of dimethylformamide (DMF) in an amount of 8% by weight, dissolved in 10% by weight of silver nitrate (AgNO 3 )
  • DMF dimethylformamide
  • AgNO 3 silver nitrate
  • the spinning solution was electrospun for 60 seconds to a 2.5 cm x 2.5 cm 2 PC film (polyCabonate film) to form nanofibers on the PC film.
  • FIG. 8 is a TEM image of nanofibers according to another embodiment of the present invention
  • FIG. 9 is an SEM image of nanofibers after electrospun according to another embodiment of the present invention
  • 10 is an SEM image of copper-plated nanofibers according to another embodiment of the present invention.
  • Figs. 8 to 10 are images of the transparent electrode of [Example 2]. Fig.
  • FIG. 8 (a) is an image taken in 100 nanometers (nm)
  • FIG. 8 (b) is an image taken in 20 nanometers (nm).
  • nanoparticles of 2.35 to 3.05 nanometers (nm) were generated, and it was confirmed that silver (Ag) particles were well dispersed on the surface of the nanofibers during electrospinning.
  • Such silver (Ag) particles can be used as a catalyst for copper electroless plating.
  • Fig. 9 (a) is an image taken at a magnification x20000 of an SEM with respect to nanofibers after electrospinning
  • Fig. 9 (b) is an image obtained at a magnification x100000 of an SEM with respect to nanofibers after electrospinning.
  • the nanofiber formed on the PC film according to Example 2 has a diameter of 350 to 400 nanometers (nm).
  • FIG. 10 (a) is an image taken at a magnification x20000 of an SEM for a copper-plated nanofiber
  • Fig. 10 (b) is an image at a magnification x100000 of an SEM for a copper-plated nanofiber.
  • the transparent electrode of [Example 2] has copper-plated nanofibers having a diameter of 800 to 910 nanometers (nm).
  • the diameter of the copper-plated nanofibers increases by at least two times the diameter of the pre-copper-coated nanofibers, and thus the silver (Ag ) Particles are remarkably catalytic.
  • FIG. 11 is a graph showing transmittance of a transparent electrode using nanofibers according to another embodiment of the present invention. Specifically, it is a graph showing the transmittance with respect to the wavelength of light in each of the transparent electrodes of [Example 2] - [Example 4].
  • a graph is a graph showing the transparent electrode transmittance of [Example 2]
  • a graph b is a graph showing the transparent electrode transmittance of [Example 3]
  • a graph c is a transparent electrode transmittance of [Example 4] Fig.
  • the transparent electrode transmittance of [Example 2] was formed to be 94% on average, the transparent electrode transmittance of [Example 3] was formed to be 70% on average, The electrode transmittance may be formed to be 58%.
  • the spinning liquid is spun on the transparent PC film to form the nanofiber on the PC film, and the PC film on which the nanofiber is formed,
  • a PC film having copper-plated nanofibers is obtained by dipping in a plating solution, a transparent electrode having excellent transmittance can be formed.
  • FIG. 12 is a graph showing sheet resistance of a transparent electrode using nanofibers according to another embodiment of the present invention
  • FIG. 13 is a graph illustrating sheet resistance of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • FIG. 12 is for a transparent electrode of [Example 3]
  • FIG. 13 is for a transparent electrode of [Example 4].
  • the unit of sheet resistance is AVRRES ⁇ / sq.
  • the sheet resistance of the transparent electrode of [Example 3] can be measured to be 2.61 AVRRES? / Sq.
  • the sheet resistance of the transparent electrode of [Example 4] can be measured at 1AVRRES? / Sq.
  • FIG 14 is a graph illustrating heating of the transparent electrode using nanofibers according to another embodiment of the present invention.
  • a graph a shows the transparent electrode temperature (temperature) of Example 4 according to time (sec) when a voltage of 1 V is applied to the transparent electrode of Example 4, and the graph b shows [ (Temperature) of [Example 4] according to time (sec) when a voltage of 1.5 V is applied to the transparent electrode of Example 4.
  • the above-mentioned heating experiment was carried out by shortening the time required for the characteristics of the substrate formed of the PC film.
  • the substrate is formed of glass (quartz glass)
  • the heating time can be increased and the experiment can be performed at a considerably high temperature have.
  • the transparent electrode according to another embodiment of the present invention can obtain a transparent electrode which is excellent in heating performance and low in sheet resistance, so that a high-performance heating can be performed even with a small amount of electric power.
  • the transparent electrode of the present invention can be applied to a place where transparency and heating are required, in particular, a windshield for a vehicle, and the like.
  • 15 is a graph showing changes in sheet resistance with respect to folding of a transparent electrode using nanofibers according to another embodiment of the present invention.
  • a graph a shows the change in sheet resistance ( ⁇ R / R) versus the number of times the transparent electrode of Example 3 was folded (bending cycle)
  • the transparent electrode of the present invention can be applied to wearable devices because the change in sheet resistance is maintained at a constant level even when the shape changes.
  • the transparent electrode of the present invention is provided on the clothes, so that clothes that are heated even at a low electric power can be manufactured.
  • It can also be attached to an object of complex shape.
  • a nanofiber transparent electrode having a high transmittance and a low sheet resistance, by preparing a nanofiber including a catalyst uniformly dispersed at one time during electrospinning.

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Abstract

Un mode de réalisation de la présente invention concerne un procédé de dépôt autocatalytique de nanofibres permettant de réduire un processus de dépôt autocatalytique pour une nanofibre, ce qui permet de simplifier le processus de fabrication de nanofibres et de réduire les coûts de fabrication. Le procédé de dépôt autocatalytique de nanofibres utilisant un effet de réduction d'argent, selon un mode de réalisation de la présente invention, comprend les étapes consistant à : i) produire une solution de filage par mélange d'un solvant de réduction organique, d'un sel métallique et d'un précurseur de fibre de carbone; ii) faire vieillir la solution de filage à une température de vieillissement; iii) former une nanofibre par électrofilage de la solution de filage; iv) réaliser un placage de cuivre sur la nanofibre par injection de la nanofibre dans une solution de cuivrage autocatalytique; et v) sécher la nanofibre plaquée à une température de séchage.
PCT/KR2017/014724 2017-12-14 2017-12-14 Procédé de revêtement de métal en nanofibres utilisant un effet de réduction de sel métallique, et procédé de fabrication d'électrode transparente WO2019117360A1 (fr)

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KR102619550B1 (ko) * 2021-06-25 2023-12-29 나재훈 나노구리 면상발열체 제조 장치 및 방법

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