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KR-20260065377-A - MANUFACTURING METHOD OF CARBON NANOFILM USING AIR-LIQUID INTERFACE TRANSFER OF NANOPARTICLES, AND CARBON NANOFILM

KR20260065377AKR 20260065377 AKR20260065377 AKR 20260065377AKR-20260065377-A

Abstract

The present invention relates to a method for manufacturing a carbon nanofilm through gas-liquid interface migration of nanoparticles and to a carbon nanofilm, and more specifically, to a method for manufacturing a carbon nanofilm through gas-liquid interface migration of nanoparticles using a Pickering emulsion of metal-supported carbon particles and to a carbon nanofilm obtained by said method.

Inventors

  • 구강희
  • 허지은
  • 서승환

Assignees

  • 울산과학기술원

Dates

Publication Date
20260508
Application Date
20241101

Claims (18)

  1. Step of preparing an aqueous solution of metal-supported carbon particles; A step of preparing a Pickering emulsion by mixing an oil-based perfluorocarbon compound with the above aqueous solution; A step of transferring the above Pickering emulsion onto a glass slice; A step of adding a hydrogen peroxide solution to a Pickering emulsion on the glass slice to suspend metal-supported carbon particles adsorbed with a perfluorocarbon compound, and forming a self-assembled thin film of metal-supported carbon particles adsorbed with a perfluorocarbon compound at the air-water interface; A step of slowly immersing a glass slice having the thin film formed thereon into a container filled with water and transferring the thin film to an air-water interface; and A method for manufacturing a carbon nanofilm, comprising the step of immersing a transfer substrate in the above-mentioned container and lifting it up to transfer the thin film onto the transfer substrate.
  2. In paragraph 1, A method for manufacturing a carbon nanofilm, wherein the above-mentioned transfer substrate is plasma-treated to have a hydrophilic surface.
  3. In paragraph 1, A method for manufacturing a carbon nanofilm, wherein the total process time of the steps of forming the self-assembled thin film, transferring the thin film to an air-water interface, and transferring the thin film is within 2 minutes.
  4. In paragraph 1, A method for manufacturing a carbon nanofilm, wherein the aqueous solution of hydrogen peroxide above contains 1% to 30% hydrogen peroxide.
  5. In paragraph 1, The above self-assembled thin film is assembled into a jamming network structure between metal-supported carbon particles, and A method for manufacturing a carbon nanofilm, wherein the thickness of the self-assembled thin film is at least twice the size of the metal-supported carbon particles.
  6. In paragraph 1, The above metal-supported carbon particles are metal-supported carbon particles, and The above metal is at least one metal particle among Pt, Au, Ag, Co, Cu, Ni, Ru, Fe, Ir, and Pd, the oxide particles thereof, or the alloy particles thereof, and The metal is 1% to 60% by weight of the metal-supported carbon particles, and A method for manufacturing a carbon nanofilm, wherein the metal-supported carbon particles have a size of 10 nm to 100 nm.
  7. In paragraph 1, The above perfluorinated carbon compound is a perfluorinated alkylamine, and A method for preparing a carbon nanofilm, wherein the ratio (ml/mg) of a perfluorocarbon compound to metal-supported carbon particles in the Pickering emulsion is 1:2 to 10.
  8. In paragraph 1, The above transfer substrate has a smooth surface, a porous surface, or a curved surface structure, The above transfer substrate is a plate substrate or a substrate with a three-dimensional shape, Method for manufacturing carbon nanofilms.
  9. In paragraph 1, The above transfer substrate is a film, mesh, perforated substrate, glass substrate, semiconductor substrate, or three-dimensional structure, and A method for manufacturing a carbon nanofilm, wherein the transfer substrate comprises a sponge, rubber, plastic, metal oxide, silicon wafer, fiber, hydrogel, paper, cloth, metal foil, or alloy.
  10. In paragraph 1, The above transfer substrate is a stretchable substrate or a flexible substrate, and A method for manufacturing a carbon nanofilm, wherein the stretchable substrate is used for transfer in a pre-stretched state.
  11. The through-hole area is 1% or less of the total area, and Carbon nanofilm, a self-assembled chain of metal-supported carbon particles.
  12. Manufactured by the method of any one of paragraphs 1 to 10, and A carbon nanofilm that is a self-assembled metal-supported carbon particle assembled into a jamming network structure.
  13. In Paragraph 12, The carbon nanofilm above is a carbon nanofilm that is a single layer or a multilayer.
  14. In Paragraph 12, The carbon nanofilm described above comprises one or a mixture of two or more metal-supported carbon particles.
  15. In Paragraph 12, The above carbon nanofilm is, Metal coating layer; Includes more, A carbon nanofilm in which the metal coating layer is coated on the surface of metal-supported carbon particles and the self-assemblies of metal-supported carbon particles.
  16. Listing; and A carbon nanofilm layer of claim 12 transferred to at least a portion of the surface of the above-described material; Includes, A structure in which the carbon nanofilm layer is a single layer or a multilayer of carbon nanofilms.
  17. In Paragraph 16, The above description is a planar body (2D) or a three-dimensional structure (3D), and The surface of the above-mentioned material has a smooth surface, a curved surface, or pores, A structure in which the carbon nanofilm layer is conformally transferred according to the surface shape of the substrate.
  18. In Paragraph 17, The above structure is an electrode, a membrane, or a catalyst plate.

Description

Manufacturing Method of Carbon Nanofilm Using Air-Liquid Interface Transfer of Nanoparticles and Carbon Nanofilm The present invention relates to a method for manufacturing a carbon nanofilm through the migration of nanoparticles to a gas-liquid interface and to a carbon nanofilm. Carbon nanoparticles are widely utilized commercially due to their excellent mechanical, chemical, and electrical conductivity. For practical applications, the process of transferring them into thin films onto a substrate is essential, and various techniques such as Physical Vapor Deposition (PVD), Chemical Vapor Deposition (CVD), and Atomic Layer Deposition (ALD) have been developed for this purpose. However, these techniques have primarily focused on carbon nanotubes or graphene, which form network structures. Recently, techniques have been developed to form ultrathin structures through the self-assembly of nanoparticles at fluid interfaces; however, for amorphous carbon nanoparticles, which have high surface energy and heterogeneous sizes and shapes, severe aggregation occurs due to strong van der Waals forces and electrostatic interactions between particles, making it difficult to ensure structural stability and uniformity. Due to these problems, large-scale production of carbon nanoparticle thin films is extremely limited with existing technology, and due to the absence of a process that enables the formation of an independent and stable network structure of carbon nanoparticles and their mass production, there are significant limitations to their commercial use in various high-performance applications such as catalyst supports, functional membranes, and electrodes. FIG. 1 is a schematic diagram illustrating the process in which carbon nanoparticles move from an oil-water interface (Pickering emulsion) through an oxygen-water interface to an air-water interface to form an interconnected network, according to one embodiment. FIG. 2 illustrates the process of forming a carbon nanofilm through the air-water interface migration of carbon nanoparticles using a Pickering emulsion according to one embodiment. FIG. 3 shows optical microscope (OM), scanning electron microscope (SEM), and TEM images of a platinum-supported carbon thin film (Pt 5 /C film) with a double continuous network (jamming network) thin film structure according to one embodiment. FIG. 4 shows a side view of a porous double continuous network with a jamming structure and an SEM image of a thin film cross-section according to one embodiment. Here, in the SEM image showing the cross-section of the thin film, the inset is an image magnified to a higher magnification. Figure 5 shows a single-step process completed within 1 minute and optical microscope images over time according to one embodiment. FIG. 6 shows an image of a thin film transferred onto a substrate of different sizes using the process of 4a according to one embodiment. Figure 7 shows optical microscope images, height measurement results, and AFM height images of the thin film thickness according to the number of transfers, according to one embodiment. Figure 8 shows the results of CS-STEM EDS analysis and XPS analysis targeting C, F, and Pt elements on a platinum-supported carbon nanoparticle thin film according to one embodiment. Here, STEM images of the film with corresponding element mappings of carbon (red), fluorine (green), and platinum (blue) are shown, and XPS analysis of the Pt 5 /C film is shown, illustrating the spectra from left to right corresponding to the C 1s, F 1s, and Pt 4f peaks, respectively. FIG. 9 is a schematic diagram showing the manufacturing process of a dual-component catalyst thin film containing carbon nanoparticles supported with different metals according to one embodiment, and the optical microscope and SEM EDS analysis results of the corresponding thin film. FIG. 10 shows optical microscope images of a Pickering emulsion stabilized with carbon nanoparticles supported with different metals in the form of an alloy, and a corresponding thin film, according to one embodiment. Figure 11 shows optical microscope images illustrating the change in size of an oil-in-water Pickering emulsion stabilized with platinum-supported carbon particles according to the platinum loading amount, according to one embodiment. Here, the images are optical microscope photographs of Pickering emulsions (FC-40/water) stabilized with Pt/C particles (0%, 5%, 10%, 20%, 60%) having different percentages of Pt relative to carbon particles. The concentration of Pt/C particles in DI water is fixed at 1.5 mg/mL. The scale bar is 200 μm. FIG. 12 is a schematic diagram showing whether thin film transfer is possible depending on the water wettability of the substrate according to one embodiment. Here, it shows a schematic diagram of a process for transferring a Pt/C thin film to a substrate with low water wettability (left) and high water wettability (right) using lift-on technology. FIG. 13 shows thin film im