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WO2016129774A1 - Procédé de préparation d'agrégats de nanotubes de carbone alignés verticalement - Google Patents

Procédé de préparation d'agrégats de nanotubes de carbone alignés verticalement Download PDF

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Publication number
WO2016129774A1
WO2016129774A1 PCT/KR2015/011383 KR2015011383W WO2016129774A1 WO 2016129774 A1 WO2016129774 A1 WO 2016129774A1 KR 2015011383 W KR2015011383 W KR 2015011383W WO 2016129774 A1 WO2016129774 A1 WO 2016129774A1
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carbon nanotube
zirconium
metal
vertically aligned
forming
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Korean (ko)
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김준형
유홍
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SK Innovation Co Ltd
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SK Innovation Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for producing vertically aligned carbon nanotube assemblies, and more particularly, to a method for producing vertically aligned carbon nanotube assemblies with high productivity.
  • Carbon nanotubes are carbon structures in which an atomic layer of graphite has a cylindrical shape, and its length is very long compared to its diameter.
  • CNTs are conductive, extremely high in strength, and chemically stable, they are prepared in the form of powders, pastes, yarns, thin films, and sheets, and exhibit excellent properties when applied to electrical, electronic, electrochemical, and energy related devices.
  • the manufacturing method of CNT is divided into a technique of making a powder form which does not have a large degree of orientation and a technique of making a form oriented vertically on a substrate.
  • a representative technique for making powder forms is the fluidized bed chemical vapor deposition method.
  • a thin layer of catalyst material is formed using a silicon or metal substrate on which a ceramic buffer layer is formed, and the catalyst layer is a dry coating method applied in a vacuum state using sputtering or e-beam, and a solution containing a catalyst element.
  • the spin coating method (dip coating) and dip coating method (dip coating) is mainly used as a coating method.
  • Vertically oriented CNTs can be broadly divided into two types. One is that when a part of vertically oriented CNTs are pulled horizontally on the substrate surface, the surrounding CNTs are collectively connected and drawn so that they can be made into a thin, high-transmittance CNT sheet. Some drawable CNTs can be drawn and they cannot be drawn to form CNT sheets or CNT yarns.
  • Drawable CNTs have the advantage of making CNT sheets and CNT yarns easy to dry, which is very advantageous for applications.
  • the thicknesses of the buffer layer and the catalyst layer should be applied uniformly and thinly, and until now, they are manufactured by a sputtering method or a dry process using e-beam, which requires high vacuum, and thus the manufacturing cost is high.
  • a sputtering method or a dry process using e-beam which requires high vacuum, and thus the manufacturing cost is high.
  • Non-Patent Document 1 Xavier Lepro et al., “Spinnable carbon nanotube forests grown on thin, flexible metallic substrates”, CARBON 48 (2010) 3621-3627)
  • An object of the present invention is to provide a method for producing a vertically aligned carbon nanotube aggregate through a wet method of high productivity.
  • A applying a buffer layer-forming solution containing a metal compound containing zirconium and an organic solvent to at least one side of the substrate to form a buffer layer;
  • B preparing a solution for forming a catalyst layer comprising an organic solvent and a catalyst precursor compound comprising at least one metal selected from the group consisting of iron, cobalt and nickel;
  • C coating the catalyst layer forming solution on the buffer layer to form a catalyst layer;
  • D forming a vertically aligned carbon nanotube aggregate on the catalyst layer.
  • the metal compound comprising zirconium is a metal organic compound comprising zirconium, a metal salt comprising zirconium or a mixture thereof.
  • zirconium-containing metal compound is zirconium pentanedionate, zirconium acetate, zirconium acrylate, zirconium acetylacetonate and zirconium acetylacetonate At least one selected from the group consisting of zirconium hydroxide, a method for producing a vertically aligned carbon nanotube aggregate.
  • step (A) further comprises a heat treatment step after application of the buffer layer forming solution.
  • step (A) is a layer containing amorphous zirconium oxide.
  • the catalyst precursor compound is a metal organic compound, a metal salt or a mixture thereof comprising at least one metal selected from the group consisting of iron, cobalt and nickel. .
  • catalyst precursor compound according to item 1 wherein the catalyst precursor compound is at least one selected from the group consisting of pentanedionate, nitrate, sulfate, hydrochloride, acetate and formate selected from the group consisting of iron, cobalt and nickel , Method for producing vertically aligned carbon nanotube aggregates.
  • the molar ratio of item 10, wherein the molar ratio of at least one metal of iron, cobalt and nickel of the catalyst precursor compound to a metal comprising aluminum or zirconium of the compound for forming the catalyst carrier is 1: 5 to 5: 1.
  • step (C) further comprises a heat treatment step after application of the catalyst layer forming solution.
  • step (D) is performed by chemical vapor deposition.
  • the manufacturing method of the present invention can produce vertically aligned carbon nanotube aggregates by wet method, for example, spin coating method or dip coating method, under atmospheric pressure, it is possible to introduce them into continuous processes such as roll-to-tol process.
  • Productivity allows the production of vertically aligned carbon nanotube assemblies.
  • the carbon nanotubes when a portion of the vertically aligned carbon nanotubes is pulled in a horizontal direction on the substrate surface, the carbon nanotubes are collectively connected and drawn to form a thin, high transmittance carbon nanotube sheet. It can be made into, and can be made into carbon nanotube yarns by giving rotation upon drawing.
  • the carbon nanotube sheet and the carbon nanotube seal have high electrical conductivity and high strength, and thus may be very useful for transparent electrodes, battery current collectors, supercapacitors, and the like.
  • FIG. 1 is a view schematically showing a substrate, a buffer layer, a catalyst layer, and a vertically aligned CNT aggregate according to the manufacturing method of the present invention.
  • Example 2 is a scanning electron micrograph of the surface of the buffer layer according to Example 1;
  • FIG. 3 is a scanning electron micrograph of the vertically aligned CNT aggregate prepared according to Example 1.
  • Example 4 is a scanning electron micrograph of a CNT yarn prepared by drawing while rotating the vertically oriented CNT aggregate prepared according to Example 1.
  • FIG. 5 is a photograph of a CNT sheet prepared by drawing a portion of the vertically oriented CNT aggregate prepared according to Example 1.
  • the present invention comprises the steps of: (A) applying a buffer layer-forming solution containing a metal compound containing zirconium and an organic solvent to at least one surface of the substrate to form a buffer layer; (B) preparing a solution for forming a catalyst layer comprising an organic solvent and a catalyst precursor compound comprising at least one metal selected from the group consisting of iron, cobalt and nickel; (C) coating the catalyst layer forming solution on the buffer layer to form a catalyst layer; And (D) forming a carbon nanotube aggregate on the catalyst layer, to which a wet process can be applied.
  • a buffer layer forming solution containing a metal compound containing zirconium and an organic solvent is applied to at least one surface of a substrate to form a buffer layer ((A) step).
  • the substrate may be used without particular limitation as long as it has the durability to withstand the process of forming the buffer layer, the catalyst layer and the carbon nanotube aggregate, and it may be desirable to be able to maintain the shape even at a high temperature of about 800 ° C.
  • Such substrates include, for example, glass, polymers, other organic-inorganic thin films, metals, and the like.
  • polymers silicon, quartz, glass, mica, graphite, diamond, ceramics, iron, nickel, chromium, Molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, indium, antimony, and the like. It can be used in the form of alloys above.
  • the flexible thin film may be used.
  • the metal compound containing zirconium contained in the buffer layer forming solution is a main component for forming the buffer layer, which allows the buffer layer to be stably formed by a wet method, and the vertically aligned carbon nanotubes formed thereafter may be horizontally drawn.
  • It may be a metal organic compound containing zirconium, a metal salt containing zirconium, or a mixture thereof, and more specifically, zirconium pentanedionate, zirconium acetate, zirconium acrylate, zirconium acrylate For example, at least one selected from the group consisting of zirconium acetylacetonate and zirconium hydroxide.
  • the organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving / dispersing a metal compound containing zirconium.
  • organic solvent capable of dissolving / dispersing a metal compound containing zirconium.
  • alcohol, acetone, dimethylformamide, n-methylpyrrolidone, etc. may be used alone or in combination of two or more. It can be mixed and used.
  • the metal cation concentration of the solution for buffer layer formation is 0.01-0.2M.
  • the buffer layer can be formed to a suitable thickness.
  • the thickness of a buffer layer is 2-30 nm. The thickness of the buffer layer can be adjusted by adjusting the application rate, the number of application, etc. in addition to the concentration of the buffer layer forming solution.
  • the buffer layer according to the present invention is formed through a wet method in which the above-mentioned buffer layer forming solution is applied to a substrate.
  • the method of applying the buffer layer forming solution to the substrate is not particularly limited as long as it is a wet coating process known in the art, and examples thereof include spin coating or dip coating, but are not limited thereto.
  • the buffer layer forming solution is applied to the substrate, the buffer layer is formed through a heat treatment process in which natural drying or predetermined heat is applied.
  • the zirconium-containing metal compound is thermally decomposed so that the buffer layer includes amorphous zirconium oxide, which may be more preferable in terms of productivity of the carbon nanotubes, stability of the buffer layer, and the like.
  • the condition of the heat treatment is not particularly limited as long as it can produce amorphous zirconium oxide, for example, may be performed for 5 to 30 minutes at a temperature of 250 to 500 °C.
  • step (B) a solution for forming a catalyst layer comprising a catalyst precursor compound and an organic solvent including at least one metal selected from the group consisting of iron, cobalt and nickel is prepared (step (B)).
  • the catalyst precursor compound forms a catalyst for growing vertically aligned carbon nanotubes
  • the present invention employs metal organic compounds, metal salts or mixtures thereof comprising at least one metal selected from the group consisting of iron, cobalt and nickel. .
  • At least one pentanedionate, nitrate, sulfate, hydrochloride, acetate, formate, etc. selected from the group consisting of iron, cobalt and nickel may be used alone or in combination of two or more. have.
  • the organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving / dispersing the catalyst precursor compound.
  • an alcohol, acetone, dimethylformamide, n-methylpyrrolidone, or the like may be used alone or in combination of two or more thereof. Can be.
  • the catalyst layer forming solution may further include a compound for forming a catalyst carrier, which is a metal organic compound or metal salt containing aluminum or zirconium.
  • the catalyst carrier may be more desirable for uniform growth of vertically oriented carbon nanotubes, as it prevents agglomeration of the catalyst and helps uniform dispersion.
  • More specific examples of the compound for forming the catalyst carrier may be used alone or in combination of two or more of pentanedionate, nitrate, sulfate, hydrochloride, acetate, formate, and the like of aluminum or zirconium.
  • the molar ratio of at least one metal of iron, cobalt and nickel of the catalyst precursor compound and the metal including aluminum or zirconium of the compound for forming the catalyst carrier is 1: 5 to It is preferable to mix so that it becomes 5: 1. Dispersion of the catalyst in the above range can be performed most effectively.
  • the metal cation concentration of the solution for catalyst layer formation is 0.01-0.2M. Within this concentration, the catalyst layer can be formed to a suitable thickness. At this time, the metal cation includes both the metal of the catalyst precursor compound and the metal of the catalyst carrier. It is preferable that the thickness of a catalyst layer is 2-30 nm. The thickness of the catalyst layer may be adjusted by adjusting the coating speed, the number of coating, etc., in addition to the concentration of the catalyst layer forming solution.
  • step (C) the catalyst layer forming solution is applied onto the buffer layer to form a catalyst layer.
  • the catalyst layer according to the present invention is formed through a wet method in which the above-described solution for forming a catalyst layer is applied onto the buffer layer in the same manner as the buffer layer.
  • the applicable wet coating process is also not particularly limited, and for example, spin coating or dip coating, but is not limited thereto.
  • the catalyst layer forming solution is applied onto the buffer layer
  • the catalyst layer is formed by a natural drying or a heat treatment process in which a predetermined heat is applied.
  • the conditions of the heat treatment are not particularly limited, but may be performed, for example, for 5 to 30 minutes at a temperature of 100 to 800 ° C.
  • step (D) To form a vertically aligned carbon nanotube aggregate on the catalyst layer (step (D)).
  • Forming the vertically aligned carbon nanotube aggregate on the catalyst layer can be used without particular limitation the methods known in the art, preferably chemical vapor deposition method can be used.
  • the heating rate may be performed at 40 to 700 ° C. per minute.
  • 1 is a schematic view showing a complete layer, a catalyst layer, and grown CNTs on a metal substrate.
  • the vertically aligned carbon nanotube aggregates prepared according to the production method of the present invention may be produced as carbon nanotube thin films (paper, sheet, film) through a method known in the art.
  • the vertically aligned carbon nanotube assembly according to the present invention is capable of drawing in the horizontal direction, the sheet produced by drawing or the yarn produced by rotation during drawing has a high electrical conductivity and high strength transparent electrode, battery current collector, It can be very useful for supercapacitor.
  • Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol to a metal cation concentration of 0.09 mole.
  • a 100 ⁇ m thick STS 304 stainless steel thin film was immersed in the solution and maintained for 5 seconds, and was pulled up at a pulling speed of 6 cm / min at 25 ° C.
  • the substrate was heat-treated at 300 ° C. for 10 minutes and cooled to room temperature to prepare a metal substrate coated with a buffer layer.
  • the heat-treated substrate had a stable buffer layer applied to the surface even after several months.
  • the scanning electron micrograph of the surface of the completed layer thus prepared is shown in FIG. 2.
  • the growth furnace was heated to 750 ° C. in 2 minutes while simultaneously injecting 450 sccm of argon gas, 10 sccm of hydrogen gas, and 120 sccm of ethylene gas. After growing for 5 minutes, the atmosphere in the growth furnace was changed to argon and cooled to room temperature to prepare a vertically oriented CNT aggregate. Scanning electron micrographs of the CNTs thus prepared are shown in FIG. 3.
  • the scanning electron micrograph of the CNT yarn prepared by rotating the prepared vertically oriented CNT aggregate is shown in FIG. 4.
  • FIG. 5 A photograph of a CNT sheet prepared by drawing a portion of the prepared vertically oriented CNT aggregate is shown in FIG. 5.
  • Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol to a metal cation concentration of 0.09 mole.
  • a 100 ⁇ m thick STS 304 stainless steel thin film was immersed in the solution and maintained for 5 seconds, and was pulled up at a pulling speed of 6 cm / min at 25 ° C.
  • the substrate was heat-treated at 400 ° C. for 10 minutes and cooled to room temperature to prepare a metal substrate coated with a buffer layer.
  • the heat-treated substrate had a stable buffer layer applied to the surface even after several months.
  • the growth furnace was heated to 770 ° C in 20 minutes while simultaneously injecting 450 sccm of argon gas, 150 sccm of hydrogen gas, and 60 sccm of ethylene gas. After the growth was maintained at 750 ° C. for 1 minute, the atmosphere in the growth furnace was changed to argon, and then cooled to room temperature to prepare a vertically aligned CNT aggregate.
  • Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol so that the metal cation concentration was 0.1 mole. After immersing the 100 mm thick STS 304 stainless steel thin film in the solution and maintained for 5 seconds, it was pulled up at a pulling speed of 6 cm / min at 25 °C room temperature. After coating, the substrate was heat-treated at 400 ° C. for 10 minutes and cooled to prepare a metal substrate having a buffer layer applied thereto.
  • the growth furnace was heated to 750 ° C. in 10 minutes while simultaneously injecting 450 sccm of argon gas, 100 sccm of hydrogen gas, and 50 sccm of ethylene gas. After growing for 2 minutes at 760 °C, the atmosphere in the growth furnace was changed to argon and then cooled to room temperature to prepare a vertically aligned CNT aggregate.
  • Zirconium acetate was dissolved in a 200 cc solution of methyl alcohol to a metal cation concentration of 0.09 mole. After immersing the 100 mm thick STS 304 stainless steel thin film in the solution and maintained for 5 seconds, it was pulled up at a pulling speed of 6 cm / min at 25 °C room temperature. After the coating, the substrate was heat-treated at 300 ° C. for 10 minutes and cooled to room temperature to prepare a metal substrate coated with a buffer layer. The heat-treated substrate had a stable buffer layer applied to the surface even after several months.
  • zirconium pentanedionate and cobalt nitrate were weighed so that the atomic ratio of zirconium and cobalt was 1: 2, and dissolved in an ethyl alcohol solution so that the cation concentration was 0.05 mole (mole) to prepare a solution for forming a catalyst layer.
  • the solution was maintained for 5 seconds and then pulled up at a pulling rate of 6 cm / min at 25 ° C. using a dip coater.
  • the substrate was heat-treated at 300 ° C. for 10 minutes and cooled to room temperature to prepare a metal substrate coated with a catalyst layer.
  • the heat-treated substrate was stable in the catalyst layer applied to the surface even after several months.
  • the growth furnace was heated to 750 ° C. in 2 minutes while simultaneously injecting 450 sccm of argon gas, 20 sccm of hydrogen gas, and 120 sccm of ethylene gas, and then 750 ° C. After growing for 5 minutes, the atmosphere in the growth furnace was changed to argon and cooled to room temperature to prepare a vertically oriented CNT aggregate.
  • catalyst layer 140 vertically aligned carbon nanotube assembly

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Abstract

La présente invention concerne un procédé de préparation d'agrégats de nanotubes de carbone alignés verticalement, et plus spécifiquement, un procédé de préparation d'agrégats de nanotubes de carbone alignés verticalement, le procédé permettant l'application d'un procédé par voie humide et comprenant les étapes consistant à : (A) former une couche tampon par revêtement, sur au moins une surface d'un substrat, d'une solution, qui comprend un solvant organique et un composé métallique contenant du zirconium, pour la formation d'une couche tampon ; (B) préparer une solution destinée à la formation d'une couche de catalyseur, comprenant un solvant organique, et un composé précurseur de catalyseur contenant au moins un métal choisi dans le groupe constitué par le fer, le cobalt et le nickel ; (C) former une couche de catalyseur par revêtement, sur la couche tampon, de la solution pour la formation d'une couche de catalyseur ; et (D) former des agrégats de nanotubes de carbone sur la couche de catalyseur.
PCT/KR2015/011383 2015-02-12 2015-10-27 Procédé de préparation d'agrégats de nanotubes de carbone alignés verticalement Ceased WO2016129774A1 (fr)

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KR101869805B1 (ko) 2016-09-29 2018-07-24 전자부품연구원 리튬 이차 전지용 음극, 이의 제조 방법 및 이를 이용한 리튬 이차 전지
KR101893933B1 (ko) 2016-10-07 2018-09-03 전자부품연구원 리튬 이차 전지용 음극, 이의 제조 방법 및 이를 이용한 리튬 이차 전지
KR102651783B1 (ko) * 2018-09-20 2024-03-26 주식회사 엘지에너지솔루션 리튬 이차전지용 음극 및 이를 포함하는 리튬 이차전지
KR102822789B1 (ko) * 2020-02-24 2025-06-20 주식회사 엘지에너지솔루션 탄소 와이어 집전체를 포함하는 전극 및 이를 포함하는 이차전지
NO346078B1 (en) * 2020-10-15 2022-02-07 Univ Of South Eastern Norway Direct growth cross-linked carbon nanotubes on microstructured metal substrate for supercapacitor application

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