WO2025035652A1 - 一种涂炭集流体及其制备方法和应用 - Google Patents

一种涂炭集流体及其制备方法和应用 Download PDF

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Publication number
WO2025035652A1
WO2025035652A1 PCT/CN2023/136056 CN2023136056W WO2025035652A1 WO 2025035652 A1 WO2025035652 A1 WO 2025035652A1 CN 2023136056 W CN2023136056 W CN 2023136056W WO 2025035652 A1 WO2025035652 A1 WO 2025035652A1
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Prior art keywords
carbon
parts
current collector
carbon material
silicone oil
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English (en)
French (fr)
Inventor
余珊
宋启超
李学法
张国平
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Yangzhou Nanopore Innovative Materials Technology Ltd
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Yangzhou Nanopore Innovative Materials Technology Ltd
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    • 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
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • 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 embodiments of the present application relate to the technical field of lithium-ion batteries, for example, a carbon-coated current collector and a preparation method and application thereof.
  • a layer of conductive material is first coated on the surface of the current collector, and then the active material is directly coated on the surface of the current collector with conductive material when manufacturing the electrode.
  • the positive electrode active material coating of lithium-ion secondary batteries has gradually developed from the original oily system to the aqueous system; while the aqueous secondary batteries sodium-ion batteries developed in recent years, the positive and negative electrode active material coatings are both aqueous systems, and the water resistance requirements for the current collector coating are higher.
  • the water-resistant and hydrophobic binder currently used in lithium batteries is styrene-butadiene latex SBR.
  • SBR styrene-butadiene latex
  • the coating has a certain degree of water resistance when SBR is used as a binder to prepare the current collector carbon coating slurry, the SBR is unstable in the slurry and has a blue floating phenomenon, which will lead to poor coating consistency and weak water resistance.
  • CN113140706A provides a battery carbon coating process and a method for preparing a lithium-ion battery.
  • the battery carbon coating process includes the following steps: S1, preparing a carbon coating slurry, wherein the carbon coating slurry includes 10%-20% conductive carbon black, 70%-80% deionized water, 5%-10% styrene-butadiene rubber and 2%-4% dispersant by mass; S2, spraying the carbon coating slurry onto the inner surface of a small cylindrical steel shell or cylindrical aluminum shell of a lithium-ion battery.
  • the method for preparing a lithium-ion battery is to perform a carbon coating treatment on the inner surface of a small cylindrical steel shell or a small cylindrical aluminum shell battery, thereby improving the electronic conductivity of the current collector and the active material of the steel shell or aluminum shell, thereby reducing the internal resistance of the lithium-ion battery, increasing the capacity of the lithium-ion battery, and thus increasing the space utilization inside the lithium-ion battery.
  • CN110034302A discloses an ultra-thin carbon-coated current collector and a method for preparing the same, comprising the following steps: cleaning the current collector and then performing a positively charged treatment to obtain a current collector with a positive charge on the surface.
  • the carbon-coated current collector in the related art has problems such as poor water resistance, it is an urgent problem to be solved in the art to develop a carbon-coated current collector with good water resistance without using styrene-butadiene rubber latex binder.
  • the embodiment of the present application provides a carbon-coated current collector and its preparation method and application.
  • silicone oil is introduced into the binder, which contains alkoxy hydrolysis substituents to make it have a certain water resistance.
  • Fluorosilane is introduced into the modified conductive carbon material, which contains fluorinated hydrocarbons and can induce hydrophobicity, thereby further enhancing water resistance.
  • an embodiment of the present application provides a carbon-coated current collector, which includes a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating includes a combination of a modified conductive carbon material and a binder, and the raw materials for preparing the binder include, by weight: 40-60 parts of methyl isobutyl ketone, 25-30 parts of solvent, 20-25 parts of isobornyl methacrylate, 20-25 parts of methyl methacrylate, 20-25 parts of n-butyl acrylate, 20-25 parts of hydroxyethyl acrylate, 18-22 parts of silicone oil, and 50-55 parts of initiator; the modified conductive carbon material is a fluorosilane-modified carbon material.
  • the weight of the methyl isobutyl ketone is 40-60 parts, for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, and specific values between the above points are limited to space and for the sake of simplicity. Considering that, this application will no longer exhaustively list the specific point values included in the said range.
  • the weight proportion of the solvent is 25-30 parts, for example, 25 parts, 27 parts, 29 parts, 30 parts, and specific values between the above points. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the weight proportion of the isobornyl methacrylate is 20-25 parts, for example, it can be 20 parts, 22 parts, 23 parts, 25 parts, and specific values between the above points. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the weight parts of the methyl methacrylate is 20-25 parts, for example, it can be 20 parts, 22 parts, 23 parts, 25 parts, and specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the weight parts of the n-butyl acrylate is 20-25 parts, for example, it can be 20 parts, 22 parts, 23 parts, 25 parts, and specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the weight proportion of the hydroxyethyl acrylate is 20-25 parts, for example, 20 parts, 22 parts, 23 parts, 25 parts, and specific values between the above values. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific values included in the range.
  • the weight proportion of the silicone oil is 18-22 parts, for example, 18 parts, 20 parts, 22 parts, and specific values between the above values. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific values included in the range.
  • the weight proportion of the initiator is 50-55 parts, for example, it can be 50 parts, 51 parts, 52 parts, 53 parts, 55 parts, and specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the solvent comprises toluene.
  • the initiator comprises azobisisobutyronitrile.
  • the adhesive is synthesized by reacting isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinyl silane).
  • silicone oil triisopropoxyvinyl silane.
  • the silicone oil contains alkoxy hydrolyzed substituents, which makes it have a certain water resistance.
  • the silicone oil includes any one of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxy silicone oil, ethyl hydrogen silicone oil or hydroxy hydrogen silicone oil, or a combination of at least two thereof.
  • the fluorosilane comprises heptadecafluorodecyltrimethoxysilane
  • the fluorosilane includes organic silicon having less than 10 carbon atoms and more than 10 fluorine atoms.
  • the mass ratio of the fluorosilane to the carbon material is 1:(4-6), for example, it can be 1:4, 1:4.5, 1:5, 1:5.5, 1:6, and specific point values between the above point values. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • Fluorosilane contains fluorinated hydrocarbons that can induce hydrophobicity and also contains alkoxy hydrolysis substituents.
  • the modified conductive carbon material and the modified acrylic resin can form silanol through the hydrolysis reaction of their respective alkoxy groups, and then form new hydrogen bonds with the OH group, while forming covalent bonds on the surface of the carbon material, forming a highly cross-linked network structure, further enhancing water resistance.
  • the modified conductive coating material comprises, by weight: 5-10 parts of modified conductive carbon material, 7-22 parts of binder, and 3-20 parts of wetting agent.
  • the weight proportion of the modified conductive carbon material is 5-10 parts, for example, it can be 5 parts, 7 parts, 9 parts, 10 parts, and specific points between the above points. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the weight portion of the binder is 7-22 parts, for example, 7 parts, 10 parts, 15 parts, 20 parts, 22 parts, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application will no longer exhaustively list the specific point values included in the said range.
  • the weight proportion of the wetting agent is 3-20 parts, for example, 3 parts, 5 parts, 10 parts, 15 parts, 20 parts, and specific values between the above points. Due to limited space and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the carbon material includes any one of conductive carbon black, conductive graphite, carbon nanotubes, carbon nanofibers or graphene, or a combination of at least two of them.
  • the wetting agent includes any one of isopropyl alcohol, propylene glycol, n-octanol, polyethylene glycol or polyoxyethylene ether, or a combination of at least two thereof.
  • the foil material includes any one of aluminum foil, titanium foil or composite aluminum foil, or a combination of at least two of them.
  • This application avoids the use of SBR water-resistant binder, and prepares the binder by modifying the acrylic resin.
  • the generated alkoxy group ensures hydrophobicity; the conductive carbon material is silane-modified to prepare the slurry and carbon-coated current collector, and the carbon-coated current collector has super water resistance through the cross-linking reaction of the modified group.
  • an embodiment of the present application provides a method for preparing a carbon-coated current collector as described in the first aspect, the preparation method comprising:
  • methyl isobutyl ketone, a solvent, isobornyl methacrylate, methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate, silicone oil, and an initiator are mixed and reacted to obtain the binder; an alcohol solution of fluorosilane is mixed with a carbon material and modified to obtain the modified conductive carbon material;
  • step (2) mixing the binder obtained in step (1) with the modified conductive carbon material to obtain a modified conductive slurry
  • step (3) coating the modified conductive slurry obtained in step (2) on the surface of the foil and drying it to obtain the carbon-coated current collector.
  • the preparation method specifically comprises:
  • the alcohol solution of fluorosilane is mixed with the carbon material and modified, centrifuged, washed, and vacuum dried to obtain the modified conductive carbon material;
  • step (2) mixing the binder obtained in step (1) with the modified conductive carbon material to obtain a modified conductive slurry
  • step (3) coating the modified conductive slurry obtained in step (2) on the surface of the foil and drying it to obtain the carbon-coated current collector.
  • the temperature of the first insulation in step (1) is 75-85°C, for example, it can be 75°C, 80°C, 85°C, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the first insulation time is 1-3h, for example, it can be 1h, 1.5h, 2h, 3h, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the temperature of the second insulation is 75-85°C, for example, it can be 75°C, 80°C, 85°C, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the second insulation time is 2-4h, for example, it can be 2h, 2.5h, 3h, 4h, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the modification temperature is 40-60°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, and specific values between the above points. Due to space limitations and for the sake of brevity, this application will no longer exhaustively list the specific points included in the range.
  • the modification time is 4-6h, for example, 4h, 4.5h, 5h, 6h, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the cleaning comprises an ethanol cleaning.
  • the vacuum drying temperature is 50-60°C, for example, 50°C, 55°C, 60°C, and specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the vacuum drying time is 20-30h, for example, it can be 20h, 22h, 25h, 30h, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the mixing in step (2) is carried out under stirring.
  • the stirring rate is 10-5000 rpm, for example, it can be 10 rpm, 50 rpm, 100 rpm, 1000 rpm, 2000 rpm, 4000 rpm, 5000 rpm, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the mixing temperature is 15-30°C, for example, 15°C, 20°C, 25°C, 30°C, and specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the mixing time is 95-240 min, for example, 95 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 220 min, 240 min, and specific values between the above points. Due to space limitations and for the sake of simplicity, this application will no longer exhaustively list the range. Specific point values included.
  • the mixed material in step (2) also includes a wetting agent and a solvent.
  • the coating comprises dispersing using a homogenizer bar.
  • the coating rate is 60-120 m/min, for example, it can be 60 m/min, 80 m/min, 100 m/min, 120 m/min, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the drying temperature is 80-120°C, for example, it can be 80°C, 90°C, 100°C, 120°C, and specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the drying time is 30-60 min, for example, it can be 30 min, 35 min, 40 min, 50 min, 55 min, 60 min, and specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the specific preparation method of the carbon-coated current collector comprises the following steps:
  • the preparation method of the adhesive comprises: sequentially adding methyl isobutyl ketone and toluene solution into a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, heating to 75-85° C., sequentially adding isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinylsilane), adding 18% initiator azobisisobutyronitrile solution (the volume ratio of the initiator to the solvent is 1:35-40) of the mixed mass, keeping the temperature at 75-85° C.
  • the preparation method of the modified conductive carbon material comprises: adjusting water to a pH value of 4 to 5 with acetic acid, then adding an anhydrous ethanol solution containing 1 to 3% fluorosilane, stirring for 8 to 12 minutes, adding carbon material, stirring at high speed at 40 to 60° C. for 4 to 6 hours, then centrifuging, washing 1 to 3 times with an ethanol-water solution with a volume ratio of 1:(1 to 2), and finally Then, wash it with anhydrous ethanol for 1-3 times, put it into a vacuum oven and dry it at 50-60°C for 20-30 hours to obtain the modified conductive carbon material.
  • the method for preparing the carbon-coated current collector comprises:
  • the modified conductive slurry in the previous step is coated on the above foil through a coating machine, and then rolled up after drying to obtain a super water-resistant carbon-coated current collector.
  • the binder aqueous solution is stirred in a double planetary mixer at a speed of 10 to 30 rpm, a dispersion speed of 2000 to 4000 rpm, a temperature of 15 to 30° C., and a time of 15 to 30 min.
  • the modified conductive material is stirred in a double planetary mixer at a speed of 40 to 80 rpm, a dispersion speed of 3000 to 6000 rpm, a temperature of 15 to 30° C., and a time of 30 to 90 min.
  • the wetting agent is stirred in the double planetary mixer at a speed of 40 to 80 rpm, a dispersion speed of 3000 to 6000 rpm, a temperature of 15 to 30° C., and a time of 20 to 60 min.
  • the particle size treatment in the above step (4) can be achieved by a grinder or a homogenizer.
  • a homogenizer is used to achieve the particle size treatment in this application, but it is not limited to the homogenizer equipment in the embodiments of this application.
  • the dispersed mixed solution in the above step (4) has a D50 of ⁇ 1.2 ⁇ m and a D90 of ⁇ 5 ⁇ m.
  • the mixed slurry is stirred in a double planetary mixer at a reverse stirring speed of 10 ⁇ 2 rpm, a vacuum degree of ⁇ -0.07 KPa, a temperature of 15 to 30° C., and a time of 30 to 60 min.
  • the modified conductive slurry is coated in a coating machine, and the foil is first subjected to corona treatment or a preheating oven or both to remove the oil on the foil surface and increase the dyne value of the foil, wherein the corona power is not less than 6KW and the preheating oven temperature is 85-120°C.
  • the modified conductive paste is coated in a coating machine at a coating speed of 60 to 120 m/min and a drying temperature of 80 to 120°C.
  • an embodiment of the present application provides an application of the carbon-coated current collector as described in the first aspect in a lithium-ion battery or a sodium-ion battery.
  • the carbon-coated current collector provided in the embodiment of the present application is synthesized by reacting isobornyl methacrylate, methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate with silicone oil to synthesize a modified acrylic resin.
  • silicone oil contains an alkoxy hydrolysis substituent, which makes it have a certain water resistance; fluorosilane is introduced, and the fluorosilane contains a fluorinated hydrocarbon, which can induce hydrophobicity and also contains an alkoxy hydrolysis substituent.
  • the modified conductive carbon material and the binder can form silanol through the hydrolysis reaction of their respective alkoxy groups, and then form a new hydrogen bond with the OH group, and at the same time form a covalent bond on the surface of the carbon material, forming a highly cross-linked network structure, further enhancing water resistance, and the water-resistant wiping can reach more than 200 times, up to 218-232 times.
  • Carbon material SPLi brand name SUPER P LI, manufacturer IMERYS
  • Vinyl silicone oil triisopropoxyvinylsilane, brand JS2891, manufacturer Hubei Jusheng;
  • Methyl silicone oil polydimethylsiloxane, brand name YX168, manufacturer Yixin Chemical;
  • the present embodiment provides a carbon-coated current collector and a preparation method thereof, wherein the carbon-coated current collector comprises a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating comprises a combination of a modified conductive carbon material and a binder;
  • the raw materials for preparing the binder include, by weight: 50 g methyl isobutyl ketone, 28 g toluene solution, 24 g isobornyl methacrylate, 24 g methyl methacrylate, 24 g n-butyl acrylate, 24 g hydroxyethyl acrylate, 20 g silicone oil (triisopropoxyvinyl silane), and 52.5 g azobisisobutyronitrile.
  • the modified conductive carbon material is a fluorosilane-modified carbon material SPLi, and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to the carbon material SPLi is 2:10.
  • the raw materials for preparing the conductive coating include, by weight, 5g of modified conductive carbon material, 7g of binder, 15g of wetting agent (isopropyl alcohol), and 73g of solvent water;
  • the preparation method of the adhesive is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 80°C, isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinylsilane) are added in sequence, and 18% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 2 hours, and then 9% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 3 hours, and after cooling, an adhesive is obtained with a solid content of 44 ⁇ 2%.
  • the preparation method of the modified conductive carbon material comprises: adjusting the pH value of water to 4-5 with acetic acid, then adding an anhydrous ethanol solution containing 2% fluorosilane, stirring for 10 minutes, adding the carbon material SPLi, and heating at 50°C. The mixture was stirred at high speed for 5 h, then centrifuged, washed twice with 1:1 ethanol-water solution, and finally washed once with anhydrous ethanol, and dried in a vacuum oven at 55 °C for 24 h to obtain a modified conductive carbon material.
  • the preparation method of the carbon-coated current collector is as follows:
  • step (2) adding the modified conductive carbon material to the binder aqueous solution in step (1) in two equal portions, with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and each time being 15 min, to obtain a conductive carbon aqueous solution;
  • step (3) slowly adding the wetting agent isopropanol into the conductive carbon aqueous solution in step (2), with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and the time being 30 min, to obtain a mixed solution;
  • step (3) (4) homogenizing or sand-milling the mixed solution in step (3) to obtain a dispersed mixed solution with a D50 of 0.886 ⁇ m and a D90 of 4.34 ⁇ m;
  • step (4) The mixed slurry in step (4) is subjected to vacuum treatment, the reverse stirring speed of the double planetary mixer is 10 rpm, the vacuum degree is ⁇ -0.07 KPa, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a modified conductive slurry.
  • the modified conductive slurry in step (5) is coated on a double-sided smooth aluminum foil by a coating machine.
  • the aluminum foil is pretreated by a corona machine.
  • the coating speed is 60 m/min
  • the oven temperature is 80° C.
  • the time is 40 min, and after drying, it is rolled up to obtain a carbon-coated current collector.
  • the present embodiment provides a carbon-coated current collector and a preparation method thereof, wherein the carbon-coated current collector comprises a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating comprises a combination of a modified conductive carbon material and a binder;
  • the raw materials for preparing the binder include, by weight: 50 g methyl isobutyl ketone, 24 g methyl Benzene solution, 24g of isobornyl methacrylate, 24g of methyl methacrylate, 24g of n-butyl acrylate, 24g of hydroxyethyl acrylate, 20g of silicone oil (triisopropoxyvinylsilane), and 52.5g of azobisisobutyronitrile.
  • the modified conductive carbon material is a fluorosilane-modified carbon material (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to the carbon material is 2:10.
  • the raw materials for preparing the conductive coating include, by weight, 8g of modified conductive carbon material, 7g of binder, 15g of wetting agent (isopropyl alcohol), and 70g of solvent water;
  • the preparation method of the adhesive is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 80°C, isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinylsilane) are added in sequence, and 18% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 2 hours, and then 9% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 3 hours, and after cooling, an adhesive is obtained with a solid content of 44 ⁇ 2%.
  • the preparation method of the modified conductive carbon material is as follows: adjust the pH value of water to 4-5 with acetic acid, then add an anhydrous ethanol solution containing 2% fluorosilane, stir for 10 minutes, add carbon material SPLi, stir at high speed at 50°C for 5 hours, then centrifuge, wash twice with 1:1 ethanol water solution, finally wash once with anhydrous ethanol, put in a vacuum oven at 55°C and dry for 24 hours.
  • the modified conductive carbon material is obtained.
  • the preparation method of the carbon-coated current collector is as follows:
  • step (2) adding the modified conductive carbon material to the binder aqueous solution in step (1) in two equal portions, with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and each time being 15 min, to obtain a conductive carbon aqueous solution;
  • step (3) slowly adding the wetting agent isopropanol into the conductive carbon aqueous solution in step (2), with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and the time being 30 min, to obtain a mixed solution;
  • step (3) (4) homogenizing or sand-milling the mixed solution in step (3) to obtain a dispersed mixed solution with a D50 of 0.912 ⁇ m and a D90 of 4.12 ⁇ m;
  • step (4) The mixed slurry in step (4) is subjected to vacuum treatment, the reverse stirring speed of the double planetary mixer is 10 rpm, the vacuum degree is ⁇ -0.07 KPa, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a modified conductive slurry.
  • the modified conductive slurry in step (5) is coated on a double-sided smooth aluminum foil by a coating machine.
  • the aluminum foil is pretreated by a corona machine.
  • the coating speed is 80 m/min
  • the oven temperature is 100° C.
  • the time is 30 min
  • the carbon-coated current collector is rolled up.
  • the present embodiment provides a carbon-coated current collector and a preparation method thereof, wherein the carbon-coated current collector comprises a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating comprises a combination of a modified conductive carbon material and a binder;
  • the raw materials for preparing the binder include, by weight: 50 g methyl isobutyl ketone, 28 g toluene solution, 24 g isobornyl methacrylate, 24 g methyl methacrylate, 24 g n-butyl acrylate, 24 g hydroxyethyl acrylate, 20 g silicone oil (triisopropoxyvinyl silane), and 52.5 g azobisisobutyronitrile.
  • the modified conductive carbon material is a fluorosilane-modified carbon material (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to the carbon material is 2:10.
  • the raw materials for preparing the conductive coating include, by weight: 6g of modified conductive carbon material, 10g of binder, 10g of wetting agent (isopropanol), and 74g of solvent water;
  • the preparation method of the binder is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask equipped with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 80° C., and isobornyl methacrylate monomer is added to the mixture.
  • the monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinyl silane) are added in sequence, and 18% of the initiator azobisisobutyronitrile solution by mass of the above mixture (the ratio of initiator to solvent is 1:37) is added, and the mixture is kept warm for 2 hours. Then, 9% of the initiator azobisisobutyronitrile solution by mass of the above mixture (the ratio of initiator to solvent is 1:37) is added, and the mixture is kept warm for 3 hours. After cooling, a binder with a solid content of 44 ⁇ 2% is obtained.
  • the preparation method of the modified conductive carbon material is as follows: adjust the pH value of water to 4-5 with acetic acid, then add an anhydrous ethanol solution containing 2% fluorosilane, stir for 10 minutes, add carbon material SPLi and conductive graphite SK6, stir at high speed for 5 hours at 50°C, then centrifuge, wash twice with 1:1 ethanol aqueous solution, finally wash once with anhydrous ethanol, put in a vacuum oven at 55°C and dry for 24 hours.
  • the modified conductive carbon material is obtained.
  • the preparation method of the carbon-coated current collector is as follows:
  • step (2) adding the modified conductive carbon material to the binder aqueous solution in step (1) in two equal portions, with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and each time being 15 min, to obtain a conductive carbon aqueous solution;
  • step (3) slowly adding the wetting agent isopropanol into the conductive carbon aqueous solution in step (2), with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and the time being 30 min, to obtain a mixed solution;
  • step (3) (4) homogenizing or sand-milling the mixed solution in step (3) to obtain a dispersed mixed solution with a D50 of 0.912 ⁇ m and a D90 of 4.12 ⁇ m;
  • step (4) The mixed slurry in step (4) is subjected to vacuum treatment, the reverse stirring speed of the double planetary mixer is 10 rpm, the vacuum degree is ⁇ -0.07 KPa, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a modified conductive slurry.
  • the modified conductive slurry in step (5) is coated on a double-sided smooth aluminum foil by a coating machine.
  • the aluminum foil is pretreated by a corona machine.
  • the coating speed is 100 m/min
  • the oven temperature is 120° C.
  • the time is 30 min, and after drying, it is rolled up to obtain a carbon-coated current collector.
  • the present embodiment provides a carbon-coated current collector and a preparation method thereof, wherein the carbon-coated current collector comprises a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating comprises a combination of a modified conductive carbon material and a binder;
  • the raw materials for preparing the binder include, by weight: 60 g of methyl isobutyl ketone, 30 g of toluene solution, 25 g of isobornyl methacrylate, 25 g of methyl methacrylate, 25 g of n-butyl acrylate, 25 g of hydroxyethyl acrylate, 22 g of silicone oil polydimethylsiloxane, and 55 g of azobisisobutyronitrile.
  • the modified conductive carbon material is a fluorosilane-modified carbon material (the mass ratio of SP-Li and conductive graphite SK6 is 8:2), and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to carbon material is 1:6.
  • the raw materials for preparing the conductive coating include, by weight: 6g of modified conductive carbon material, 10g of binder, 10g of wetting agent (isopropanol), and 74g of solvent water;
  • the preparation method of the adhesive is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 80°C, isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (polydimethylsiloxane) are added in sequence, and 18% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 2 hours, and then 9% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 3 hours, and after cooling, an adhesive is obtained with a solid content of 44 ⁇ 2%.
  • the preparation method of the modified conductive carbon material comprises: adjusting water to a pH value of 4 to 5 with acetic acid, then adding an anhydrous ethanol solution containing 2% fluorosilane, stirring for 10 minutes, adding carbon material SPLi and conductive graphite SK6, stirring at high speed at 50° C. for 5 hours, then centrifuging, washing twice with a 1:1 ethanol aqueous solution, and finally washing with an anhydrous
  • the product was washed once with ethanol and dried in a vacuum oven at 55°C for 24 hours to obtain the modified conductive carbon material.
  • the preparation method of the carbon-coated current collector is as follows:
  • step (2) adding the modified conductive carbon material to the binder aqueous solution in step (1) in two equal portions, with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and each time being 15 min, to obtain a conductive carbon aqueous solution;
  • step (3) slowly adding the wetting agent isopropanol into the conductive carbon aqueous solution in step (2), with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and the time being 30 min, to obtain a mixed solution;
  • step (3) (4) homogenizing or sand-milling the mixed solution in step (3) to obtain a dispersed mixed solution with a D50 of 0.912 ⁇ m and a D90 of 4.12 ⁇ m;
  • step (4) The mixed slurry in step (4) is subjected to vacuum treatment, the reverse stirring speed of the double planetary mixer is 10 rpm, the vacuum degree is ⁇ -0.07 KPa, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a modified conductive slurry.
  • the modified conductive slurry in step (5) is coated on a double-sided smooth aluminum foil by a coating machine.
  • the aluminum foil is pretreated by a corona machine.
  • the coating speed is 100 m/min
  • the oven temperature is 120° C.
  • the time is 30 min, and after drying, it is rolled up to obtain a carbon-coated current collector.
  • the present embodiment provides a carbon-coated current collector and a preparation method thereof, wherein the carbon-coated current collector comprises a foil and a conductive coating disposed on the surface of the foil, wherein the conductive coating comprises a combination of a modified conductive carbon material and a binder;
  • the raw materials for preparing the binder comprise, by weight: 50 g methyl isobutyl ketone, 28 g toluene solution, 24 g isobornyl methacrylate, 24 g methyl methacrylate, 24 g n-butyl acrylate, 24g hydroxyethyl acrylate, 20g silicone oil (polydimethylsiloxane), 52.5g azobisisobutyronitrile.
  • the modified conductive carbon material is a fluorosilane-modified carbon material (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to the carbon material is 2:10.
  • the raw materials for preparing the conductive coating include, by weight: 6g of modified conductive carbon material, 10g of binder, 10g of wetting agent polyethylene glycol, and 74g of solvent water;
  • the preparation method of the adhesive is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 85° C., isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (polydimethylsiloxane) are added in sequence, and 18% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, and the mixture is kept warm for 3 hours, and then 9% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, and the mixture is kept warm for 4 hours. After cooling, an adhesive with a solid content of 44 ⁇ 2% is obtained.
  • the preparation method of the modified conductive carbon material is as follows: adjust the pH value of water to 4-5 with acetic acid, then add an anhydrous ethanol solution containing 2% fluorosilane, stir for 10 minutes, add carbon material SPLi and conductive graphite SK6, stir at high speed at 50°C for 5 hours, then centrifuge, wash twice with 1:1 ethanol aqueous solution, finally wash once with anhydrous ethanol, put in a vacuum oven and dry at 60°C for 30 hours.
  • the modified conductive carbon material is obtained.
  • the preparation method of the carbon-coated current collector is as follows:
  • step (2) adding the modified conductive carbon material to the binder aqueous solution in step (1) in two equal portions, with the stirring speed of the double planetary mixer being 60 rpm, the dispersion speed being 4000 rpm, the temperature being 25 ⁇ 5° C., and each time being 15 min, to obtain a conductive carbon aqueous solution;
  • step (3) Slowly add the wetting agent isopropyl alcohol to the conductive carbon aqueous solution in step (2),
  • the stirring speed of the stirrer is 60 rpm, the dispersion speed is 4000 rpm, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a mixed solution;
  • step (3) (4) homogenizing or sand-milling the mixed solution in step (3) to obtain a dispersed mixed solution with a D50 of 0.912 ⁇ m and a D90 of 4.12 ⁇ m;
  • step (4) The mixed slurry in step (4) is subjected to vacuum treatment, the reverse stirring speed of the double planetary mixer is 10 rpm, the vacuum degree is ⁇ -0.07 KPa, the temperature is 25 ⁇ 5°C, and the time is 30 min to obtain a modified conductive slurry.
  • the modified conductive slurry in step (5) is coated on a double-sided smooth aluminum foil by a coating machine.
  • the aluminum foil is pretreated by a corona machine.
  • the coating speed is 100 m/min
  • the oven temperature is 80° C.
  • the time is 60 min, and after drying, it is rolled up to obtain a carbon-coated current collector.
  • This comparative example provides a carbon-coated current collector and a preparation method thereof.
  • the raw materials for preparing the carbon-coated current collector include, by weight: 5g of conductive material SP-Li, 12.8g of binder acrylic polymer, 0.1g of additive sodium hydroxide, 15g of wetting agent, and 67.1g of solvent;
  • the preparation method of the carbon-coated current collector is as follows:
  • the present comparative example provides a carbon-coated current collector and a preparation method thereof.
  • the raw materials for preparing the carbon-coated current collector include, by weight: 8 g of conductive material SP-Li and conductive graphite SK6 (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), 12.8 g of binder acrylic polymer, 0.1 g of additive sodium hydroxide, 15 g of moistening Agent, 64.1g solvent;
  • the preparation method of the carbon-coated current collector is as follows:
  • This comparative example provides a carbon-coated current collector and a preparation method thereof.
  • the raw materials for preparing the carbon-coated current collector include, by weight: 6 g of conductive material, namely, SP-Li and conductive graphite SK6 (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), 13.5 g of binder acrylic polymer, 0.1 g of additive sodium hydroxide, 20 g of wetting agent, and 60.4 g of solvent;
  • the preparation method of the carbon-coated current collector is as follows:
  • This comparative example provides a carbon-coated current collector and a preparation method thereof.
  • the raw materials for preparing the carbon-coated current collector include, by weight, 5g of modified conductive carbon material, 12.8g of binder acrylic polymer, 0.1g of additive sodium hydroxide, 15g of wetting agent, and 67.1g of solvent water;
  • the modified conductive carbon material is a fluorosilane-modified carbon material SPLi, and the mass ratio of fluorosilane heptadecafluorodecyltrimethoxysilane to the carbon material SPLi is 2:10.
  • the preparation method of the modified conductive carbon material comprises: adjusting the pH value of water to 4-5 with acetic acid, and then adding An anhydrous ethanol solution containing 2% fluorosilane was stirred for 10 minutes, and then the carbon material SPLi was added. The mixture was stirred at high speed at 50°C for 5 hours, and then centrifuged. The mixture was washed twice with a 1:1 ethanol-water solution and finally washed once with anhydrous ethanol. The mixture was placed in a vacuum oven and dried at 55°C for 24 hours to obtain a modified conductive carbon material.
  • the preparation method of the carbon-coated current collector is as follows:
  • This comparative example provides a carbon-coated current collector and a preparation method thereof.
  • the raw materials for preparing the carbon-coated current collector include, by weight: 8g of conductive material, namely, SP-Li and conductive graphite SK6 (the mass ratio of SP-Li to conductive graphite SK6 is 8:2), 7g of binder, 15g of wetting agent, and 70g of solvent water;
  • the preparation method of the adhesive is as follows: methyl isobutyl ketone and toluene solution are added in sequence to a three-necked flask with a stirrer, a condenser and a nitrogen connecting tube, the temperature is raised to 80°C, isobornyl methacrylate monomer, methyl methacrylate monomer, n-butyl acrylate monomer, hydroxyethyl acrylate monomer and silicone oil (triisopropoxyvinylsilane) are added in sequence, and 18% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 2 hours, and then 9% of the mixed mass of the initiator azobisisobutyronitrile solution (the ratio of the initiator to the solvent is 1:37) is added, the mixture is kept warm for 3 hours, and after cooling, an adhesive is obtained with a solid content of 44 ⁇ 2%.
  • the preparation method of the carbon-coated current collector is as follows:
  • the present application uses the above-mentioned embodiments to illustrate a carbon-coated current collector and its preparation method and application, but the present application is not limited to the above-mentioned embodiments, which does not mean that the present application must rely on the above-mentioned embodiments to be implemented.
  • the technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the present application product, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.

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Abstract

一种涂炭集流体，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合，所述粘结剂的制备原料以重量份计包括：40-60份甲基异丁基酮、25-30份溶剂、20-25份甲基丙烯酸异冰片酯、20-25份甲基丙烯酸甲酯、20-25份丙烯酸正丁酯、20-25份丙烯酸羟乙酯、18-22份硅油、50-55份引发剂；所述改性导电碳材料为氟硅烷改性的碳材料；改性后的导电碳材料与粘结剂又能够通过各自烷氧基的水解反应形成硅烷醇，然后与OH基团形成新的氢键，同时在碳材料表面形成共价键，形成了高度交联的网络结构，进一步增强耐水性，耐水擦拭可以达到200次以上。

Description

一种涂炭集流体及其制备方法和应用 技术领域
本申请实施例涉及锂离子电池技术领域，例如一种涂炭集流体及其制备方法和应用。
背景技术
锂离子电池、钠离子电池的制造过程中，为了提高集流体对活性物质电流收集强度和活性物质对极片的粘接性能，先在集流体表面涂一层导电材料，再在制造极片时直接将活性物质涂在带导电材料集流体的表面。
其中，锂离子二次电池在环保要求的趋势下，正极活性物质涂层从原先的油性体系逐渐向水性体系发展；而近年来发展起来的水系二次电池钠离子电池，正负极活性物质涂层均为水性体系，对集流体涂层耐水性的要求更高。
目前锂电用的耐水、疏水性粘结剂是丁苯胶乳SBR。虽然使用SBR作为粘结剂配制集流体涂碳层浆料时，涂层具有一定耐水性，但由于SBR在浆料中不稳定出现飘蓝现象，会导致涂层一致性差，耐水性不强。
CN113140706A提供了一种电池涂炭工艺及一种锂离子电池的制备方法，电池涂炭工艺包括步骤：S1、制作涂炭浆料，所述涂炭浆料包括质量百分比为10％-20％的导电碳黑、70％-80％的去离子水、5％-10％的丁苯橡胶和2％-4％的分散剂；S2、将所述涂炭浆料喷涂到锂离子电池的小尺寸圆柱钢壳或圆柱铝壳的内表面。锂离子电池的制备方法是通过在小的圆柱钢壳或小的圆柱铝壳电池内表面进行涂炭处理，改善了钢壳或铝壳的集流体与活性物质的电子导电性，进而降低锂离子电池的内阻，提升锂离子电池的容量，从而增加了锂离子电池内部的空间利用率。CN110034302A公开了一种超薄涂炭集流体及其制备方法，包括以下步骤：将集流体清洗后再进行带正电处理，得到表面带正电荷的集流 体；将粘结剂溶解后，依次加入阴离子表面活性剂和导电剂，搅拌均匀形成带负电荷的水性导电浆料；将所述带负电荷的水性导电浆料超声雾化成气溶胶后，静电沉积在所述带正电荷的集流体上，然后烘干，得到超薄涂炭集流体，其导电涂层薄且均匀，粘附力强，具有良好的导电性能。
由于相关技术中的涂炭集流体存在耐水性差等问题。因此，开发一种不使用丁苯胶乳液粘结剂，制备耐水性能好的涂炭集流体，是本领域亟待解决的问题。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种涂炭集流体及其制备方法和应用，通过粘结剂和改性导电碳材料，粘结剂中引入硅油，含有烷氧基水解取代基，使其具有一定耐水性，改性导电碳材料中引入氟硅烷，含有氟化烃，能够诱导疏水性，进一步增强耐水性。
第一方面，本申请实施例提供涂炭集流体，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合，所述粘结剂的制备原料以重量份计包括：40-60份甲基异丁基酮、25-30份溶剂、20-25份甲基丙烯酸异冰片酯、20-25份甲基丙烯酸甲酯、20-25份丙烯酸正丁酯、20-25份丙烯酸羟乙酯、18-22份硅油、50-55份引发剂；所述改性导电碳材料为氟硅烷改性的碳材料。
优选地，所述甲基异丁基酮的重量份为40-60份，例如可以为40份、45份、50份、55份、60份，以及上述点值之间的具体点值，限于篇幅及出于简明的考 虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述溶剂的重量份为25-30份，例如可以为25份、27份、29份、30份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述甲基丙烯酸异冰片酯的重量份为20-25份，例如可以为20份、22份、23份、25份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述甲基丙烯酸甲酯的重量份为20-25份，例如可以为20份、22份、23份、25份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述丙烯酸正丁酯的重量份为20-25份，例如可以为20份、22份、23份、25份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述丙烯酸羟乙酯的重量份为20-25份，例如可以为20份、22份、23份、25份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述硅油的重量份为18-22份，例如可以为18份、20份、22份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述引发剂的重量份为50-55份，例如可以为50份、51份、52份、53份、55份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述溶剂包括甲苯。
优选地，所述引发剂包括偶氮二异丁腈。
通过甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)反应合成粘结剂，使用时因为硅油的引入，含有烷氧基水解取代基，使其具有一定耐水性。
优选地，所述硅油包括甲基硅油、乙基硅油、苯基硅油、甲基含氢硅油、甲基苯基硅油、甲基氯苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油、甲基羟基硅油、乙基含氢硅油或羟基含氢硅油中的任意一种或至少两种的组合。
优选地，所述氟硅烷包括十七氟癸基三甲氧基硅烷；
优选地，所述氟硅烷包括碳原子数小于10、氟原子数大于10的有机硅类。
优选地，所述氟硅烷与碳材料的质量比为1：(4-6)，例如可以为1：4、1：4.5、1：5、1：5.5、1：6，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
引入氟硅烷，氟硅烷含有氟化烃，能够诱导疏水性，同时也含有烷氧基水解取代基。改性后的导电碳材料与改性后的丙烯酸树脂又能够通过各自烷氧基的水解反应形成硅烷醇，然后与OH基团形成新的氢键，同时在碳材料表面形成共价键，形成了高度交联的网络结构，进一步增强耐水性。
优选地，所述改性导电涂层材料以重量份计包括：5-10份改性导电碳材料、7-22份粘结剂、3-20份润湿剂。
优选地，所述改性导电碳材料的重量份为5-10份，例如可以为5份、7份、9份、10份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述粘结剂的重量份为7-22份，例如可以为7份、10份、15份、 20份、22份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述润湿剂的重量份为3-20份，例如可以为3份、5份、10份、15份、20份，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述碳材料包括导电炭黑、导电石墨、炭纳米管、炭纳米纤维或石墨烯中的任意一种或在至少两种的组合。
优选地，所述润湿剂包括异丙醇、丙二醇、正辛醇、聚乙二醇或聚氧乙烯醚中的任意一种或至少两种的组合。
优选地，所述箔材包括铝箔、钛箔或复合铝箔中的任意一种或至少两种的组合。
本申请避开SBR耐水性粘结剂的使用，对丙烯酸树脂进行改性制备得到粘结剂，生成的烷氧基保证疏水性；对导电碳材料进行硅烷改性，制备浆料及涂碳集流体，通过改性基团的交联反应，使涂碳集流体具有超强耐水性。
第二方面，本申请实施例提供一种如第一方面所述的涂炭集流体的制备方法，所述制备方法包括：
(1)将甲基异丁基酮、溶剂、甲基丙烯酸异冰片酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸羟乙酯、硅油、引发剂混合，进行反应，得到所述粘结剂；将氟硅烷的醇溶液与碳材料混合并进行改性，得到所述改性导电碳材料；
(2)将步骤(1)得到的粘结剂与改性导电碳材料混合，得到改性导电浆料；
(3)将步骤(2)得到的改性导电浆料涂布在箔材表面，干燥，得到所述涂炭集流体。
优选地，所述制备方法具体包括：
(1)在氮气条件下，将甲基异丁基酮、溶剂、甲基丙烯酸异冰片酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸羟乙酯、硅油、部分引发剂混合，进行第一次保温，加入剩余引发剂混合，进行第二次保温，冷却后得到所述粘结剂；
在酸性条件下，氟硅烷的醇溶液与碳材料混合并进行改性、离心、清洗、真空干燥后，得到所述改性导电碳材料；
(2)将步骤(1)得到的粘结剂与改性导电碳材料混合，得到改性导电浆料；
(3)将步骤(2)得到的改性导电浆料涂布在箔材表面，烘干，得到所述涂炭集流体。
优选地，步骤(1)所述第一次保温的温度为75-85℃，例如可以为75℃、80℃、85℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述第一次保温的时间为1-3h，例如可以为1h、1.5h、2h、3h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述第二次保温的温度为75-85℃，例如可以为75℃、80℃、85℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述第二次保温的时间为2-4h，例如可以为2h、2.5h、3h、4h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述改性的温度为40-60℃，例如可以为40℃、45℃、50℃、 55℃、60℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述改性的时间为4-6h，例如可以为4h、4.5h、5h、6h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述清洗包括乙醇清洗。
优选地，所述真空干燥的温度为50-60℃，例如可以为50℃、55℃、60℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述真空干燥的时间为20-30h，例如可以为20h、22h、25h、30h，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，步骤(2)所述混合在搅拌下进行。
优选地，所述搅拌的速率为10-5000rmp，例如可以为10rmp、50rmp、100rmp、1000rmp、2000rmp、4000rmp、5000rmp，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述混合的温度为15-30℃，例如可以为15℃、20℃、25℃、30℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述混合的时间为95-240min，例如可以为95min、100min、120min、140min、160min、180min、200min、220min、240min，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围 包括的具体点值。
优选地，步骤(2)所述混合的物料还包括润湿剂、溶剂。
优选地，所述涂布包括使用匀浆棒进行分散。
优选地，所述涂布的速率为60-120m/min，例如可以为60m/min、80m/min、100m/min、120m/min，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述干燥的温度为80-120℃，例如可以为80℃、90℃、100℃、120℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
优选地，所述干燥的时间为30-60min，例如可以为30min、35min、40min、50min、55min、60min，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
在一个优选技术方案中，所述涂炭集流体的具体制备方法包括如下步骤：
所述粘结剂的制备方法包括：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至75-85℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂体积比为1：35-40)，75-85℃保温1-3h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂体积比为1：35-40)，75-85℃保温2-4h，冷却后，得到粘结剂。
所述改性导电碳材料的制备方法包括：用乙酸将水调到pH值为4～5，然后加入含1-3％氟硅烷的无水乙醇溶液，搅拌8-12min后，加入碳材料，在40-60℃下高速搅拌4-6h，然后离心，用体积比为1：(1-2)乙醇水溶液清洗1-3次，最 后用无水乙醇清洗1-3次，放入真空烘箱中50-60℃下干燥20-30h，即得改性导电碳材料。
所述涂炭集流体的制备方法包括：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，低速搅拌；
(2)将改性导电碳材料平均分多次依次加入上一步骤中的粘结剂水溶液中，得到导电炭水溶液；
(3)将润湿剂缓慢加入至上一步骤中的导电炭水溶液中，得到混合溶液；
(4)将上一步骤中的混合溶液经过均质或砂磨，得到分散混合溶液；
(5)将上一步骤中的分散混合溶液经过抽真空处理，得到改性导电浆料。
(6)将上一步骤中的改性导电浆料经过涂布机涂敷在上述箔材上，烘干后收卷得到超强耐水性涂炭集流体。
上述步骤(1)粘结剂水溶液在双行星搅拌机的搅拌速度10～30rpm，分散速度为2000～4000rpm，温度为15～30℃，时间15～30min。
上述步骤(2)中改性导电材料在双行星搅拌机的搅拌速度40～80rpm，分散速度为3000～6000rpm，温度为15～30℃，时间30～90min。
上述步骤(3)中润湿剂在双行星搅拌机的搅拌速度40～80rpm，分散速度为3000～6000rpm，温度为15～30℃，时间20～60min。
上述步骤(4)中粒径处理可以通过研磨机、均质机中的一种设备来实现，后面具体实施例中均以均质机来实现本申请中的粒径处理，但不局限于本申请实施例中的均质机设备。
上述步骤(4)中分散混合溶液的D50＜1.2μm，D90＜5μm。
上述步骤(5)中混合浆料在双行星搅拌机的反转搅拌速度10±2rpm，真空度为＜-0.07KPa，温度为15～30℃，时间30～60min。
上述步骤(6)中，改性导电浆料在涂布机中涂布，箔材先经过电晕或预热烘箱或两者均有，预处理除掉箔材表面油和提高箔材达因值，其中电晕功率不小于6KW，预热烘箱温度85～120℃。
上述步骤(6)中，改性导电浆料在涂布机中涂布，涂布速度60～120m/min，烘干温度80～120℃。
第三方面，本申请实施例提供一种如第一方面所述的涂炭集流体在锂离子电池或钠离子电池中的应用。
相对于相关技术，本申请实施例具有以下有益效果：
本申请实施例提供的涂炭集流体，通过甲基丙烯酸异冰片酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸羟乙酯与硅油反应合成改性丙烯酸树脂，作为粘结剂使用时因为硅油的引入，含有烷氧基水解取代基，使其具有一定耐水性；引入氟硅烷，氟硅烷含有氟化烃，能够诱导疏水性，同时也含有烷氧基水解取代基。改性后的导电碳材料与粘结剂又能够通过各自烷氧基的水解反应形成硅烷醇，然后与OH基团形成新的氢键，同时在碳材料表面形成共价键，形成了高度交联的网络结构，进一步增强耐水性，耐水擦拭可以达到200次以上，可达218-232次。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
本申请实施例及对比例中用到的实验材料如下：
(1)碳材料SPLi，牌号SUPER P LI，厂家IMERYS；
(2)导电石墨SK6，牌号TIMREX KS 6，厂家IMERYS；
(3)聚乙二醇，牌号PEG400，厂家南通亨斯特；
(4)乙烯基硅油：三异丙氧基乙烯基硅烷，牌号JS2891，厂家湖北巨胜；
(5)十七氟癸基三甲氧基硅烷，厂家湖北巨胜；
(6)甲基硅油：聚二甲基硅氧烷，牌号YX168，厂家亿信化工；
实施例1
本实施例提供一种涂炭集流体及其制备方法，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合；所述粘结剂的制备原料以重量份计包括：50g甲基异丁基酮、28g甲苯溶液、24g甲基丙烯酸异冰片酯、24g甲基丙烯酸甲酯、24g丙烯酸正丁酯、24g丙烯酸羟乙酯、20g硅油(三异丙氧基乙烯基硅烷)、52.5g偶氮二异丁腈。
所述改性导电碳材料为氟硅烷改性的碳材料SPLi，氟硅烷十七氟癸基三甲氧基硅烷与碳材料SPLi的质量比为2:10。
所述导电涂层的制备原料以重量份计包括5g改性导电碳材料、7g粘结剂、15g润湿剂(异丙醇)、73g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至80℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温2h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，冷却后，得到粘结剂，固含44±2％。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi，在50℃下高 速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水乙醇清洗1次，放入真空烘箱中55℃下干燥24h，即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，双行星搅拌机的搅拌速度15rpm，分散速度为2000rpm，温度为25±5℃，时间15min.
(2)将改性导电碳材料平均分两次依次加入步骤(1)中的粘结剂水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，每次时间15min，得到导电炭水溶液；
(3)将润湿剂异丙醇缓慢加入至步骤(2)中的导电炭水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，时间30min，得到混合溶液；
(4)将步骤(3)中的混合溶液经过均质或砂磨，处理后D50＝0.886μm，D90＝4.34μm，得到分散混合溶液；
(5)将步骤(4)中的混合浆料经过抽真空处理，双行星搅拌机的反转搅拌速度10rpm，真空度为＜-0.07KPa，温度为25±5℃，时间30min，得到改性导电浆料。
(6)将步骤(5)中的改性导电浆料经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机预处理，涂布速度60m/min，烘箱温度80℃，时间为40min，烘干后收卷得到涂炭集流体。
实施例2
本实施例提供一种涂炭集流体及其制备方法，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合；所述粘结剂的制备原料以重量份计包括：50g甲基异丁基酮、24g甲 苯溶液、24g甲基丙烯酸异冰片酯、24g甲基丙烯酸甲酯、24g丙烯酸正丁酯、24g丙烯酸羟乙酯、20g硅油(三异丙氧基乙烯基硅烷)、52.5g偶氮二异丁腈。
所述改性导电碳材料为氟硅烷改性的碳材料(SP-Li和导电石墨SK6质量比为8：2)，氟硅烷十七氟癸基三甲氧基硅烷与碳材料的质量比为2:10。
所述导电涂层的制备原料以重量份计包括8g改性导电碳材料、7g粘结剂、15g润湿剂(异丙醇)、70g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至80℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温2h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，冷却后，得到粘结剂，固含44±2％。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi，在50℃下高速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水乙醇清洗1次，放入真空烘箱中55℃下干燥24h。即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，双行星搅拌机的搅拌速度15rpm，分散速度为2000rpm，温度为25±5℃，时间15min.
(2)将改性导电碳材料平均分两次依次加入步骤(1)中的粘结剂水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，每次时间15min，得到导电炭水溶液；
(3)将润湿剂异丙醇缓慢加入至步骤(2)中的导电炭水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，时间30min，得到混合溶液；
(4)将步骤(3)中的混合溶液经过均质或砂磨，处理后D50＝0.912μm，D90＝4.12μm，得到分散混合溶液；
(5)将步骤(4)中的混合浆料经过抽真空处理，双行星搅拌机的反转搅拌速度10rpm，真空度为＜-0.07KPa，温度为25±5℃，时间30min，得到改性导电浆料。
(6)将步骤(5)中的改性导电浆料经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机预处理，涂布速度80m/min，烘箱温度100℃，时间为30min，烘干后收卷得到涂炭集流体。
实施例3
本实施例提供一种涂炭集流体及其制备方法，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合；所述粘结剂的制备原料以重量份计包括：50g甲基异丁基酮、28g甲苯溶液、24g甲基丙烯酸异冰片酯、24g甲基丙烯酸甲酯、24g丙烯酸正丁酯、24g丙烯酸羟乙酯、20g硅油(三异丙氧基乙烯基硅烷)、52.5g偶氮二异丁腈。
所述改性导电碳材料为氟硅烷改性的碳材料(SP-Li和导电石墨SK6质量比为8：2)，氟硅烷十七氟癸基三甲氧基硅烷与碳材料的质量比为2:10。
所述导电涂层的制备原料以重量份计包括：6g改性导电碳材料、10g粘结剂、10g润湿剂(异丙醇)、74g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至80℃，将甲基丙烯酸异冰片酯单 体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温2h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，冷却后，得到粘结剂，固含44±2％。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi和导电石墨SK6，在50℃下高速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水乙醇清洗1次，放入真空烘箱中55℃下干燥24h。即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，双行星搅拌机的搅拌速度15rpm，分散速度为2000rpm，温度为25±5℃，时间15min.
(2)将改性导电碳材料平均分两次依次加入步骤(1)中的粘结剂水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，每次时间15min，得到导电炭水溶液；
(3)将润湿剂异丙醇缓慢加入至步骤(2)中的导电炭水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，时间30min，得到混合溶液；
(4)将步骤(3)中的混合溶液经过均质或砂磨，处理后D50＝0.912μm，D90＝4.12μm，得到分散混合溶液；
(5)将步骤(4)中的混合浆料经过抽真空处理，双行星搅拌机的反转搅拌速度10rpm，真空度为＜-0.07KPa，温度为25±5℃，时间30min，得到改性导电浆料。
(6)将步骤(5)中的改性导电浆料经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机预处理，涂布速度100m/min，烘箱温度120℃，时间为30min，烘干后收卷得到涂炭集流体。
实施例4
本实施例提供一种涂炭集流体及其制备方法，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合；所述粘结剂的制备原料以重量份计包括：60g甲基异丁基酮、30g甲苯溶液、25g甲基丙烯酸异冰片酯、25g甲基丙烯酸甲酯、25g丙烯酸正丁酯、25g丙烯酸羟乙酯、22g硅油聚二甲基硅氧烷、55g偶氮二异丁腈。
所述改性导电碳材料为氟硅烷改性的碳材料(SP-Li和导电石墨SK6质量比为8：2)，氟硅烷十七氟癸基三甲氧基硅烷与碳材料的质量比为1:6.
所述导电涂层的制备原料以重量份计包括：6g改性导电碳材料、10g粘结剂、10g润湿剂(异丙醇)、74g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至80℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(聚二甲基硅氧烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温2h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，冷却后，得到粘结剂，固含44±2％。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi和导电石墨SK6，在50℃下高速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水 乙醇清洗1次，放入真空烘箱中55℃下干燥24h。即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，双行星搅拌机的搅拌速度15rpm，分散速度为2000rpm，温度为25±5℃，时间15min.
(2)将改性导电碳材料平均分两次依次加入步骤(1)中的粘结剂水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，每次时间15min，得到导电炭水溶液；
(3)将润湿剂异丙醇缓慢加入至步骤(2)中的导电炭水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，时间30min，得到混合溶液；
(4)将步骤(3)中的混合溶液经过均质或砂磨，处理后D50＝0.912μm，D90＝4.12μm，得到分散混合溶液；
(5)将步骤(4)中的混合浆料经过抽真空处理，双行星搅拌机的反转搅拌速度10rpm，真空度为＜-0.07KPa，温度为25±5℃，时间30min，得到改性导电浆料。
(6)将步骤(5)中的改性导电浆料经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机预处理，涂布速度100m/min，烘箱温度120℃，时间为30min，烘干后收卷得到涂炭集流体。
实施例5
本实施例提供一种涂炭集流体及其制备方法，所述涂炭集流体包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合；所述粘结剂的制备原料以重量份计包括：50g甲基异丁基酮、28g甲苯溶液、24g甲基丙烯酸异冰片酯、24g甲基丙烯酸甲酯、24g丙烯酸正丁酯、 24g丙烯酸羟乙酯、20g硅油(聚二甲基硅氧烷)、52.5g偶氮二异丁腈。
所述改性导电碳材料为氟硅烷改性的碳材料(SP-Li和导电石墨SK6质量比为8：2)，氟硅烷十七氟癸基三甲氧基硅烷与碳材料的质量比为2:10。
所述导电涂层的制备原料以重量份计包括：6g改性导电碳材料、10g粘结剂、10g润湿剂聚乙二醇、74g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至85℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(聚二甲基硅氧烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温4h，冷却后，得到粘结剂，固含44±2％。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi和导电石墨SK6，在50℃下高速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水乙醇清洗1次，放入真空烘箱中60℃下干燥30h。即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
(1)按配方配制粘结剂水溶液，将粘结剂加入至余量溶剂水中，双行星搅拌机的搅拌速度15rpm，分散速度为2000rpm，温度为25±5℃，时间15min.
(2)将改性导电碳材料平均分两次依次加入步骤(1)中的粘结剂水溶液中，双行星搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，每次时间15min，得到导电炭水溶液；
(3)将润湿剂异丙醇缓慢加入至步骤(2)中的导电炭水溶液中，双行星 搅拌机的搅拌速度60rpm，分散速度为4000rpm，温度为25±5℃，时间30min，得到混合溶液；
(4)将步骤(3)中的混合溶液经过均质或砂磨，处理后D50＝0.912μm，D90＝4.12μm，得到分散混合溶液；
(5)将步骤(4)中的混合浆料经过抽真空处理，双行星搅拌机的反转搅拌速度10rpm，真空度为＜-0.07KPa，温度为25±5℃，时间30min，得到改性导电浆料。
(6)将步骤(5)中的改性导电浆料经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机预处理，涂布速度100m/min，烘箱温度80℃，时间为60min，烘干后收卷得到涂炭集流体。
对比例1
本对比例提供一种涂炭集流体及其制备方法，所述涂炭集流体的制备原料以重量份计包括：5g导电材料为SP-Li，12.8g粘结剂丙烯酸聚合物，0.1g添加剂氢氧化钠，15g润湿剂，67.1g溶剂；
所述涂炭集流体的制备方法具体如下：
按顺序依次加入，分别进行搅拌分散，均质后D50＝0.899μm，D90＝4.21μm，抽真空处理30min(真空度为＜-0.07KPa)，得到导电浆料(固含量为8.3％，浆料pH为6.2)，经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机6KW预处理，涂布速度60m/min，烘箱温度80℃烘干后收卷得到涂炭集流体。
对比例2
本对比例提供一种涂炭集流体及其制备方法，所述涂炭集流体的制备原料以重量份计包括：8g导电材料为SP-Li和导电石墨SK6(SP-Li和导电石墨SK6质量比为8：2)，12.8g粘结剂丙烯酸聚合物，0.1g添加剂氢氧化钠，15g润湿 剂，64.1g溶剂；
所述涂炭集流体的制备方法具体如下：
按顺序依次加入，分别进行搅拌分散，均质后D50＝0.941μm，D90＝4.78μm，抽真空处理30min(真空度为＜-0.07KPa)，得到导电浆料(固含量为10.9％，浆料pH为6.5)，经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机6KW预处理，涂布速度80m/min，烘箱温度100℃烘干后收卷得到涂炭集流体。
对比例3
本对比例提供一种涂炭集流体及其制备方法，所述涂炭集流体的制备原料以重量份计包括：6g导电材料为SP-Li和导电石墨SK6(SP-Li和导电石墨SK6质量比为8：2)，13.5g粘结剂丙烯酸聚合物，0.1g添加剂氢氧化钠，20g润湿剂，60.4g溶剂；
所述涂炭集流体的制备方法具体如下：
按顺序依次加入，分别进行搅拌分散，均质后D50＝1.193μm，D90＝4.86μm，抽真空处理30min(真空度为＜-0.07KPa)，得到导电浆料(固含量为10.45％，浆料pH为6.9)，经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机6KW预处理，涂布速度100m/min，烘箱温度120℃烘干后收卷得到涂炭集流体。
对比例4
本对比例提供一种涂炭集流体及其制备方法，所述涂炭集流体的制备原料以重量份计包括5g改性导电碳材料、12.8g粘结剂丙烯酸聚合物，0.1g添加剂氢氧化钠，15g润湿剂，67.1g溶剂水；
所述改性导电碳材料为氟硅烷改性的碳材料SPLi，氟硅烷十七氟癸基三甲氧基硅烷与碳材料SPLi的质量比为2:10。
所述改性导电碳材料的制备方法：用乙酸将水调到pH值为4～5，然后加入 含2％氟硅烷的无水乙醇溶液，搅拌10min后，加入碳材料SPLi，在50℃下高速搅拌5h，然后离心，用1：1乙醇水溶液清洗2次，最后用无水乙醇清洗1次，放入真空烘箱中55℃下干燥24h，即得改性导电碳材料。
所述涂炭集流体的制备方法具体如下：
按顺序依次加入，分别进行搅拌分散，均质后D50＝0.899μm，D90＝4.21μm，抽真空处理30min(真空度为＜-0.07KPa)，得到导电浆料(固含量为8.3％，浆料pH为6.2)，经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机6KW预处理，涂布速度60m/min，烘箱温度80℃烘干后收卷得到涂炭集流体。
对比例5
本对比例提供一种涂炭集流体及其制备方法，所述涂炭集流体的制备原料以重量份计包括：8g导电材料为SP-Li和导电石墨SK6(SP-Li和导电石墨SK6质量比为8：2)，7g粘结剂、15g润湿剂、70g溶剂水；
所述粘结剂的制备方法：在带有搅拌器、冷凝管和氮气连接管的三口烧瓶中依次加入甲基异丁基酮和甲苯溶液，升温至80℃，将甲基丙烯酸异冰片酯单体、甲基丙烯酸甲酯单体、丙烯酸正丁酯单体、丙烯酸羟乙酯单体与硅油(三异丙氧基乙烯基硅烷)依次加入，并加入上述混合质量的18％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温2h，再加入上述混合质量的9％引发剂偶氮二异丁腈溶液(引发剂和溶剂比为1：37)，保温3h，冷却后，得到粘结剂，固含44±2％。
所述涂炭集流体的制备方法具体如下：
按顺序依次加入，分别进行搅拌分散，均质后D50＝0.941μm，D90＝4.78μm，抽真空处理30min(真空度为＜-0.07KPa)，得到导电浆料(固含量为10.9％，浆料pH为6.5)，经过涂布机涂敷在双面光铝箔上，铝箔经过电晕机6KW预处 理，涂布速度80m/min，烘箱温度100℃烘干后收卷得到涂炭集流体。
对实施例1-5，对比例1-5得到的涂炭集流体进行性能测试，测试方法如下：
(1)面电阻(将10cm*10cm样品平整放置，用四探针电阻测试仪探针进行测试)；
(2)耐水擦拭(将涂碳箔固定在桌面上，将25g砝码+55g调节杆(共80g)压在浸满纯水的棉签上，施加作用力F来回拉动砝码和调节杆使棉签对涂碳箔涂层面进行擦拭，观察有无涂层变色脱落并记录擦拭次数)；
按照上述性能测试方法测试实施例1-5、对比例1-5得到的涂炭集流体的各项性能，测试结果如表1所示。
表1
从表1的数据可知，实施例具有明显的耐水性，耐水次数可达200次以上； 从对比例4和5可知，单纯使用改性导电碳材料和硅氧烷丙烯酸树脂粘结剂，相较于对比例1-5，有一定耐水性，但相较于实施例，耐水性太差，说明改性导电碳材料和硅氧烷丙烯酸树脂能够通过各自烷氧基的水解反应形成硅烷醇，然后与OH基团形成新的氢键，同时在碳材料表面形成共价键，形成了高度交联的网络结构，进一步增强了耐水性。
申请人声明，本申请通过上述实施例来说明本申请的一种涂炭集流体及其制备方法和应用，但本申请并不局限于上述实施例，即不意味着本申请必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。

Claims (15)

  1. 一种涂炭集流体，其包括箔材和设置于所述箔材表面的导电涂层，所述导电涂层包括改性导电碳材料和粘结剂的组合，所述粘结剂的制备原料以重量份计包括：40-60份甲基异丁基酮、25-30份溶剂、20-25份甲基丙烯酸异冰片酯、20-25份甲基丙烯酸甲酯、20-25份丙烯酸正丁酯、20-25份丙烯酸羟乙酯、18-22份硅油、50-55份引发剂；所述改性导电碳材料为氟硅烷改性的碳材料。
  2. 根据权利要求1所述的涂炭集流体，其中，所述溶剂包括甲苯。
  3. 根据权利要求1或2所述的涂炭集流体，其中，所述引发剂包括偶氮二异丁腈。
  4. 根据权利要求1-3任一项所述的涂炭集流体，其中，所述硅油包括甲基硅油、乙基硅油、苯基硅油、甲基含氢硅油、甲基苯基硅油、甲基乙氧基硅油、甲基三氟丙基硅油、甲基乙烯基硅油、甲基羟基硅油、乙基含氢硅油或羟基含氢硅油中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的涂炭集流体，其中，所述氟硅烷包括十七氟癸基三甲氧基硅烷；
    优选地，所述氟硅烷与碳材料的质量比为1：(4-6)。
  6. 根据权利要求1-5任一项所述的涂炭集流体，其中，所述改性导电涂层材料以重量份计包括：5-10份改性导电碳材料、7-22份粘结剂、3-20份润湿剂；
    优选地，所述碳材料包括导电炭黑、导电石墨、炭纳米管、炭纳米纤维或石墨烯中的任意一种或在至少两种的组合；
    优选地，所述润湿剂包括异丙醇、丙二醇、正辛醇、聚乙二醇或聚氧乙烯醚中的任意一种或至少两种的组合。
  7. 根据权利要求1-6任一项所述涂炭集流体，其中，所述箔材包括铝箔、钛箔或复合铝箔中的任意一种或至少两种的组合。
  8. 一种如权利要求1-7任一项所述的涂炭集流体的制备方法，其包括：
    (1)将甲基异丁基酮、溶剂、甲基丙烯酸异冰片酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸羟乙酯、硅油、引发剂混合，进行反应，得到所述粘结剂；将氟硅烷的醇溶液与碳材料混合并进行改性，得到所述改性导电碳材料；
    (2)将步骤(1)得到的粘结剂与改性导电碳材料混合，得到改性导电浆料；
    (3)将步骤(2)得到的改性导电浆料涂布在箔材表面，干燥，得到所述涂炭集流体。
  9. 根据权利要求8所述的制备方法，其中，所述制备方法具体包括：
    (1)在氮气条件下，将甲基异丁基酮、溶剂、甲基丙烯酸异冰片酯、甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸羟乙酯、硅油、部分引发剂混合，进行第一次保温，加入剩余引发剂混合，进行第二次保温，冷却后得到所述粘结剂；
    在酸性条件下，氟硅烷的醇溶液与碳材料混合并进行改性、离心、清洗、真空干燥后，得到所述改性导电碳材料；
    (2)将步骤(1)得到的粘结剂与改性导电碳材料混合，得到改性导电浆料；
    (3)将步骤(2)得到的改性导电浆料涂布在箔材表面，烘干，得到所述涂炭集流体。
  10. 根据权利要求9所述的制备方法，其中，步骤(1)所述第一次保温的温度为75-85℃；
    优选地，所述第一次保温的时间为1-3h。
  11. 根据权利要求9或10所述的制备方法，其中，所述第二次保温的温度为75-85℃；
    优选地，所述第二次保温的时间为2-4h。
  12. 根据权利要求9-11任一项所述的制备方法，其中，所述改性的温度为40-60℃；
    优选地，所述改性的时间为4-6h；
    优选地，所述清洗包括乙醇清洗；
    优选地，所述真空干燥的温度为50-60℃；
    优选地，所述真空干燥的时间为20-30h。
  13. 根据权利要求9-12任一项所述的制备方法，其中，步骤(2)所述混合在搅拌下进行；
    优选地，所述搅拌的速率为10-5000rmp；
    优选地，所述混合的温度为15-30℃；
    优选地，所述混合的时间为95-240min。
  14. 根据权利要9-13任一项所述的制备方法，其中，步骤(2)所述混合的物料还包括润湿剂、溶剂；
    优选地，所述涂布包括使用匀浆棒进行分散；
    优选地，所述涂布的速率为60-120m/min；
    优选地，所述干燥的温度为80-120℃；
    优选地，所述干燥的时间为30～60min。
  15. 一种如权利要求1-7任一项所述的涂炭集流体在锂离子电池或钠离子电池中的应用。
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