WO2024050696A1 - Manufacturing method for composite membrane, and composite membrane and use thereof - Google Patents

Manufacturing method for composite membrane, and composite membrane and use thereof Download PDF

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Publication number
WO2024050696A1
WO2024050696A1 PCT/CN2022/117305 CN2022117305W WO2024050696A1 WO 2024050696 A1 WO2024050696 A1 WO 2024050696A1 CN 2022117305 W CN2022117305 W CN 2022117305W WO 2024050696 A1 WO2024050696 A1 WO 2024050696A1
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WO
WIPO (PCT)
Prior art keywords
film
composite
polymer
membrane
porous polymer
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PCT/CN2022/117305
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French (fr)
Chinese (zh)
Inventor
朱中亚
王帅
夏建中
李学法
张国平
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扬州纳力新材料科技有限公司
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Priority to PCT/CN2022/117305 priority Critical patent/WO2024050696A1/en
Publication of WO2024050696A1 publication Critical patent/WO2024050696A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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

Definitions

  • the present application relates to the field of battery technology, and in particular to a manufacturing method of a composite film, a composite film and its application.
  • Metalized polymer film products include composite current collectors, thin film electrodes, packaging aluminized films, printed films, etc.
  • Metalized polymer films are widely used in electronics, packaging, printing and other fields due to their excellent conductivity, barrier, flexibility and light weight properties.
  • Traditional technology usually uses physical vapor deposition technology to directly deposit a metal conductive layer on the surface of polymer films such as polypropylene, polyethylene, polyester, etc. to manufacture metallized polymer films. Due to the large difference in surface tension between polymer films such as polypropylene, polyethylene, and polyester and the metal conductive layer, the affinity between the two is poor, which affects the firmness between the polymer film and the metal conductive layer.
  • a manufacturing method of a composite film, a composite film and its application are provided.
  • the present application provides a composite film, which includes a polymer base film, an adhesive layer and a porous polymer film;
  • the adhesive layer and the porous polymer film are provided on at least one surface of the polymer base film, and the adhesive layer is located between the polymer base film and the porous polymer film for attaching The two are bonded, and the hydrophilic polymer is attached to the surface and/or pores of the porous polymer membrane.
  • the hydrophilic polymer includes polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazine, polyglutamine One or more of amino acids and polyethylene glycol.
  • the material of the bonding layer includes one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber;
  • the thickness of the adhesive layer is 20 to 500 nm.
  • the thickness of the adhesive layer ranges from 50 to 200 nm.
  • the material of the porous polymer membrane includes polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, poly One or more of ethersulfone, polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives;
  • the thickness of the porous polymer membrane is 1 ⁇ m or more.
  • the porous polymer membrane has a thickness of 2 to 20 ⁇ m.
  • the material of the polymer-based film includes polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate ( PBT), polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), poly One or more of phenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and their derivatives;
  • the thickness of the polymer base film is 1 ⁇ m or more.
  • the polymer base film has a thickness of 2 to 50 ⁇ m.
  • the average pore diameter of the porous polymer membrane is 20-500 nm; the porosity of the porous polymer membrane is 10%-80%.
  • the average pore diameter of the porous polymer membrane is 50-200 nm; the porosity of the porous polymer membrane is 20%-60%.
  • This application also provides a manufacturing method for the above composite membrane, which manufacturing method includes the following steps:
  • step S1 the coating amount of the adhesive is 0.1 to 2 ⁇ m.
  • the binder in step S1, includes a volatile solvent and a binding substance, wherein the mass percentage of the binding substance is 40% to 70%;
  • the volatile solvent includes but is not limited to one or more of acetone, ethyl acetate, methyl ethyl ketone, cyclohexanone, toluene and dioxane;
  • the bonding substance includes, but is not limited to, one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber.
  • the hot pressing process includes a hot pressing temperature of 50 to 90°C, a hot pressing pressure of 0.2 to 1.2 MPa, and a hot pressing time of 5 to 90 seconds.
  • step S3 the concentration of the solution containing hydrophilic polymer is 0.01 to 0.2 wt%.
  • step S3 the concentration of the solution containing hydrophilic polymer is 0.02 to 0.15 wt%.
  • the present application also provides a metallized composite film, which includes a composite film and a metal conductive layer.
  • the composite film is the above-mentioned composite film or a composite film produced by the above-mentioned manufacturing method.
  • the metal conductive layer is provided on the surface of the composite film. The surface of the porous polymer membrane;
  • the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
  • the thickness of the metal conductive layer is 300-2000 nm.
  • the thickness of the metal conductive layer ranges from 500 to 1000 nm.
  • this application also provides a composite current collector, which includes the above-mentioned metallized composite film.
  • the composite current collector further includes a protective layer located on the surface of the metal conductive layer;
  • the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, One or more of carbon nanoquantum dots, carbon nanotubes, carbon nanofibers and graphene;
  • the thickness of the protective layer is 10-200 nm.
  • the thickness of the protective layer is 50-100 nm.
  • the present application also provides an electrode, which includes the above composite current collector.
  • this application also provides a battery, which includes the above-mentioned electrode.
  • this application also provides an electrical device, which includes the above-mentioned battery.
  • the above numerical interval is considered to be continuous and includes the minimum value and maximum value of the range, as well as every value between such minimum value and maximum value. Further, when a range refers to an integer, every integer between the minimum value and the maximum value of the range is included. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
  • One embodiment of the present application provides a composite film, which includes a polymer base film, an adhesive layer and a porous polymer film;
  • An adhesive layer and a porous polymer film are provided on at least one surface of the polymer base film.
  • the adhesive layer is located between the polymer base film and the porous polymer film for bonding the two.
  • Metalized polymer films usually use polymer films such as polypropylene, polyethylene or polyester as the base material.
  • the polarity of the base material is weak, resulting in low surface tension.
  • Polymer base materials with low surface tension are associated with high surface tension.
  • the affinity between the metal conductive layers is poor; in addition, the surface of the polymer substrate is relatively flat and does not have precise physical bonding sites. Therefore, the polymer substrate and the surface metal conductive layer are not firmly bonded.
  • this application constructs a porous polymer membrane on the surface of the polymer base membrane to provide physical riveting sites.
  • the hydrophilic polymer attached to the surface and/or pores of the porous polymer membrane can be attached to its surface and /Or build a polar surface within the pores, thereby obtaining a composite membrane with a higher surface polarity.
  • Using the composite film as a base material to produce a metallized composite film can make the composite film very firmly bonded to the surface metal conductive layer.
  • the hydrophilic polymer includes polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazine, polyglutamic acid and one or more of polyethylene glycol.
  • the hydrophilic polymer can be polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazynic acid, polyglutamic acid and Any one of polyethylene glycol, the hydrophilic polymer can also be polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethylcellulose, nanocellulose, polyurethane A mixture of acid, polyglutamic acid and polyethylene glycol mixed in any proportion.
  • the material of the bonding layer includes one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber;
  • the thickness of the adhesive layer is 20 to 500 nm.
  • the thickness of the adhesive layer ranges from 50 to 200 nm.
  • the material of the adhesive layer can be any one of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber.
  • the material of the adhesive layer It may also be a mixture of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber in any proportion.
  • the thickness of the adhesive layer can be any value between 20 and 500 ⁇ m or 50 and 200 nm, such as: 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 70 ⁇ m, 90 ⁇ m, 120 ⁇ m, 150 ⁇ m, 200 ⁇ m, 220 ⁇ m, 250 ⁇ m, 270 ⁇ m, 300 ⁇ m, 320 ⁇ m, 360 ⁇ m, 390 ⁇ m, 410 ⁇ m, 450 ⁇ m, 470 ⁇ m, 500 ⁇ m, etc.
  • the thickness of the adhesive layer is too low, the bonding effect will be poor. If the thickness of the adhesive layer exceeds a certain range, continuing to increase its thickness will not significantly promote the improvement of the bonding effect.
  • the material of the porous polymer membrane includes polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone , one or more of polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives;
  • the thickness of the porous polymer membrane is 1 ⁇ m or more.
  • the thickness of the porous polymer membrane ranges from 2 to 20 ⁇ m.
  • the material of the porous polymer membrane can be polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone, Any one of polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives.
  • the material of the porous polymer membrane can also be polyethylene or polypropylene.
  • polyvinylidene fluoride polytetrafluoroethylene
  • polyvinyl chloride polyacrylonitrile
  • polyurethane cellulose acetate
  • polysulfone polyethersulfone
  • polyamide polyimide
  • polystyrene polyoxyethylene
  • the thickness of the porous polymer membrane can be 2 to 20 ⁇ m. It can be understood that the thickness of the porous polymer membrane can also be any value between 1 and 20 ⁇ m, such as: 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m , 14 ⁇ m, 15 ⁇ m, 16 ⁇ m, 17 ⁇ m, 18 ⁇ m, 19 ⁇ m, 20 ⁇ m, etc.
  • the porous polymer membrane is produced by biaxial stretching, electrospinning or phase inversion.
  • the material of the polymer-based film includes polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide One or more of ether (PPS), polyphenylene ether (PPO), polystyrene (PS) and their derivatives.
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • PVC polyvinyl chloride
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PPS polyphenylene sulfide
  • the material of the polymer-based film can be polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and any of their derivatives.
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN Polyethylene naphthalate
  • PI polyimide
  • PVC polyvinyl chloride
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PPS polyphenylene sulfide
  • PPO polyphenylene
  • the material of the polymer base film can also be polypropylene (PP), polyethylene (PE), poly Ethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polychloride Ethylene (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and many of their derivatives A mixture obtained by mixing in any proportion;
  • the thickness of the polymer base film is 1 ⁇ m or more.
  • the polymer base film has a thickness of 2 to 50 ⁇ m.
  • the thickness of the polymer base film can be any value between 1 to 50 ⁇ m or 2 to 50 ⁇ m, such as: 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 13 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 23 ⁇ m, 25 ⁇ m, 28 ⁇ m , 30 ⁇ m, 32 ⁇ m, 35 ⁇ m, 37 ⁇ m, 40 ⁇ m, 42 ⁇ m, 45 ⁇ m, 47 ⁇ m, 50 ⁇ m, etc.
  • the material of the polymer-based membrane may be the same as the material of the porous polymer membrane, or may be different.
  • the manufacturing method of the polymer-based film includes, but is not limited to, one of biaxial stretching, uniaxial stretching, casting, calendering and blown film.
  • the average pore diameter of the porous polymer membrane is 20-500 nm; the porosity of the porous polymer membrane is 10%-80%.
  • the average pore diameter of the porous polymer membrane is 50-200 nm; the porosity of the porous polymer membrane is 20%-60%.
  • the average pore size of the porous polymer membrane is too large or too small, it is not conducive to controlling the porosity of the porous polymer membrane, nor is it conducive to the close combination of the polymer base membrane and the metal conductive layer; if the porosity of the porous polymer membrane is too low, it is not conducive to controlling the porosity of the porous polymer membrane. If the polymer base film and the metal conductive layer are tightly combined and the porosity is too high, the mechanical properties of the polymer base film will decrease.
  • This application also provides a manufacturing method for the above composite membrane, which includes the following steps:
  • a porous polymer film is constructed on the surface of the above-mentioned polymer-based film to provide physical riveting sites.
  • polar surfaces are constructed on the surface and pores of the porous polymer, which can effectively increase its surface tension and thereby improve the conductivity of the composite film and metal. layer affinity.
  • the surface tension of the above-mentioned composite film is high and stable for a long time, and can be firmly combined with the metal conductive layer.
  • step S1 the coating amount of the adhesive is 0.1 to 2 ⁇ m.
  • the coating amount of the adhesive can be any value between 0.1 and 2 ⁇ m, such as: 0.1 ⁇ m, 0.3 ⁇ m, 0.5 ⁇ m, 0.8 ⁇ m, 1.0 ⁇ m, 1.3 ⁇ m, 1.5 ⁇ m, 1.7 ⁇ m or 2.0 ⁇ m. wait.
  • the binder in step S1, includes a volatile solvent and a binding substance, wherein the mass percentage of the binding substance is 40% to 70%;
  • volatile solvents include, but are not limited to, one or more of acetone, ethyl acetate, methyl ethyl ketone, cyclohexanone, toluene and dioxane;
  • the bonding substance includes, but is not limited to, one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber.
  • the drying in step S1 is divided into three stages of drying, the temperatures are set to 50-60°C, 60-70°C, and 70-80°C in sequence, and the drying times of the three stages are 0.1-5 minutes respectively.
  • the drying in step S1 is used to remove part of the solvent in the adhesive and achieve partial solidification of the adhesive.
  • the hot pressing process includes a hot pressing temperature of 50 to 90°C, a hot pressing pressure of 0.2 to 1.2 MPa, and a hot pressing time of 5 to 90 seconds.
  • the hot pressing temperature can be any value between 50°C and 90°C, such as: 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, etc.; heat
  • the pressing force can be any value between 0.2 and 1.2MPa, such as: 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa or 1.2MPa, etc.
  • the hot pressing time can be any value between 5 and 90s, such as: 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s or 90s etc.
  • the curing temperature in step S2 is 50-60°C, and the curing time is 0.5-48 hours.
  • the curing temperature can be any value between 50 and 60°C, such as: 50°C, 52°C, 54°C, 56°C, 58°C or 60°C, etc.;
  • the aging time can be any value between 0.5 and 48h. Values, such as: 0.5h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, etc.
  • the dip coating process of step S3 includes the following steps:
  • step S3 the concentration of the solution containing the hydrophilic polymer is 0.01 to 0.2 wt%.
  • step S3 the concentration of the solution containing the hydrophilic polymer is 0.02 to 0.15 wt%.
  • the concentration of the solution containing the hydrophilic polymer is low. Therefore, the hydrophilic polymer only coats the porous skeleton on the surface of the porous polymer and does not affect the porosity and pore size of the porous polymer. It can be understood that the concentration of the solution containing the hydrophilic polymer can be any value between 0.01 to 0.2wt% or 0.02 to 0.15wt%, such as: 0.01wt%, 0.02wt%, 0.04wt%, 0.06wt%, 0.08wt%, 0.10wt%, 0.12wt%, 0.15wt% or 0.2wt%, etc.
  • the present application also provides a metallized composite film, which includes a composite film and a metal conductive layer.
  • the composite film is the above-mentioned composite film or a composite film produced by the above-mentioned manufacturing method.
  • the metal conductive layer is provided on the porous polymer film of the composite film. surface;
  • the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
  • the thickness of the metal conductive layer is 300-2000nm.
  • the thickness of the metal conductive layer ranges from 500 to 1000 nm.
  • the material of the metal conductive layer can be any one of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver, or can be copper, copper alloy, aluminum, aluminum alloy, nickel, A mixture of nickel alloy, titanium and silver in any proportion.
  • the thickness of the metal conductive layer can be any value between 300 ⁇ 2000nm or 500 ⁇ 1000nm, such as: 300nm, 330nm, 360nm, 400nm, 430nm, 460nm, 500nm, 525nm, 575nm, 600nm, 635nm, 680nm, 700nm, 710nm, 770nm, 800nm, 870nm, 900nm, 950nm, 1000nm, 1070nm, 1100nm, 1150nm, 1200nm, 1250nm, 1300nm, 1350nm, 1400nm, 1600nm, 1800nm or 2000nm, etc.
  • the manufacturing method of the metal conductive layer includes but is not limited to at least one of physical vapor deposition, chemical plating and electroplating; wherein the physical vapor deposition method includes but is not limited to magnetron sputtering, resistance heating vacuum. At least one of an evaporation method, a laser heating vacuum evaporation method, and an electron beam heating vacuum evaporation method.
  • this application also provides a composite current collector, including the above-mentioned metallized composite film.
  • the material of the metal conductive layer in the composite cathode current collector can be aluminum or aluminum alloy; the aluminum content in the aluminum alloy can be greater than or equal to 80wt%, and further, the aluminum content in the aluminum alloy can be greater than 90wt%.
  • the material of the metal conductive layer in the composite negative electrode current collector can be copper or copper alloy; the copper content in the copper alloy can be greater than or equal to 80wt%, and further, the copper content in the copper alloy can be greater than 90wt%.
  • the composite current collector further includes a protective layer located on the surface of the metal conductive layer;
  • the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, carbon nanoparticles One or more of quantum dots, carbon nanotubes, carbon nanofibers and graphene.
  • the protective layer is provided to prevent the metal conductive layer from being chemically corroded or physically damaged;
  • the thickness of the protective layer is 10-200 nm.
  • the thickness of the protective layer ranges from 50 to 100 nm.
  • the thickness of the protective layer can be any value between 10 to 200nm or 50 to 100nm, such as: 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 24nm, 28nm, 30nm, 35nm, 45nm, 50nm, 55nm , 65nm, 75nm, 85nm, 95nm, 100nm, 105nm, 115nm, 125nm, 135nm, 145nm, 155nm, 160nm, 180nm or 200nm, etc.
  • the protective layer is composed of two layers.
  • the materials of the two protective layers may be the same or different, and the thickness of the two protective layers may be equal or unequal.
  • the manufacturing method of the protective layer includes but is not limited to at least one of coating method, in-situ molding method and physical vapor deposition method; wherein, the coating method can be die coating method, blade coating method and Extrusion coating method; in-situ forming method can be a method of forming a metal oxide passivation layer in situ on the surface of the metal conductive layer; physical vapor deposition method can be vacuum evaporation method and magnetron sputtering method.
  • the performance of the composite membrane can be effectively improved.
  • Surface tension and adhesion between the composite film and the metal conductive layer are adjusting the average pore size and porosity of the porous polymer membrane, the coating amount of the binder, the hot pressing process and the concentration of the hydrophilic polymer solution.
  • This application also provides an electrode, including the above composite current collector.
  • the above-mentioned electrode can be a positive electrode or a negative electrode, for example, it can be a positive electrode sheet or a negative electrode sheet.
  • the above-mentioned positive electrode sheet can be formed by mixing a positive electrode material, a conductive agent, a binder and a solvent and then coating it on the above-mentioned composite current collector.
  • the above-mentioned negative electrode sheet can be formed by mixing a negative electrode material, a conductive agent, a binder and a solvent and then coating the mixture on the above-mentioned composite current collector.
  • this application also provides a battery including the above electrode.
  • the manufacturing process of the battery is well known to those skilled in the art and can include but is not limited to the following steps: stacking the positive electrode sheet, separator and negative electrode sheet in order and then rolling or folding to obtain Electrode assembly, put the electrode assembly into the packaging bag, inject the electrolyte and seal it to obtain a battery, in which the positive electrode sheet used in the battery adopts the positive electrode sheet manufactured by this application, or the negative electrode sheet used in the battery adopts the positive electrode manufactured by this application.
  • the positive and negative electrode sheets, or the positive and negative electrode sheets used in the battery are the positive and negative electrode sheets manufactured by this application.
  • this application also provides an electrical device including the above-mentioned battery.
  • the above-mentioned battery can be used as a power source or energy storage unit in electrical devices, including but not limited to electric vehicles, mobile phones, tablets, computers, electric toys, wearable devices, drones, energy storage devices, etc.
  • Adhesion test between polymer base film and porous polymer film Cut the manufactured composite film into small strips of 150 mm ⁇ 15 mm, and fix the small strips of porous polymer film to the upper clamp of the tensile machine for polymerization. The material-based film is fixed to the lower clamp of the tensile machine, and the two are peeled off at an angle of 180° and at a speed of 100mm/min. The peeling force, that is, the bonding force between the two, is used to evaluate the bond between the two. Adhesion stability.
  • the small strip of ethylene acrylic acid copolymer film of the sample is fixed on the upper clamp of the tensile machine, and the remaining part is fixed on the lower clamp. After being fixed, the two are peeled off at an angle of 180° and a speed of 100mm/min to test the peeling force, that is Adhesion between composite film and metal conductive layer.
  • the polymer base film in this embodiment is a biaxially stretched polypropylene film with a thickness of 4.5 ⁇ m.
  • the binder consists of component A and component B with a mass ratio of 5:3.
  • Component A is an acetone solution of 50wt% polyurethane prepolymer
  • component B is 60wt% trimethylolpropane and toluene.
  • the porous polymer membrane is a porous polyethylene membrane with a thickness of 2 ⁇ m, an average pore diameter of 50 nm, and a porosity of 25%;
  • the solution containing the hydrophilic polymer is a 0.05wt% polyvinyl alcohol solution.
  • the manufacturing method of composite membrane includes the following steps:
  • the manufacturing method of composite cathode current collector includes the following steps:
  • the surface of the above composite film is cleaned, and then placed in a vacuum evaporation chamber.
  • the high-purity aluminum wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at 1300 to 2000°C.
  • the evaporated metal atoms After the cooling system in the vacuum coating chamber, it is deposited on both surfaces of the composite film to form an aluminum metal conductive layer with a thickness of 1 ⁇ m;
  • NMP nitrogen methylpyrrolidone
  • the manufacturing method of composite negative electrode current collector includes the following steps:
  • the surface of the above composite film is cleaned, and then placed in a vacuum evaporation chamber.
  • the high-purity copper wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at 1400 to 2000°C.
  • the evaporated metal atoms After the cooling system in the vacuum coating chamber, it is deposited on both surfaces of the composite film to form a copper metal conductive layer with a thickness of 1 ⁇ m;
  • step S2 It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 60°C.
  • step S2 It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 70°C.
  • step S2 It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 90°C.
  • the hot pressing pressure in step S2 is 0.5 MPa.
  • step S2 It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.7MPa.
  • step S2 It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.9MPa.
  • step S2 it is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 1.2MPa.
  • the hot pressing time in step S2 is 5 s.
  • the hot pressing time in step S2 is 30 s.
  • the hot pressing time in step S2 is 50 s.
  • the hot pressing time in step S2 is 90 s.
  • the coating amount of the two-component polyurethane in step S1 is 0.5 ⁇ m.
  • the coating amount of the two-component polyurethane in step S1 is 1.0 ⁇ m.
  • the coating amount of the two-component polyurethane in step S1 is 2.0 ⁇ m.
  • Example 13 It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 70 nm and the porosity is 30%.
  • Example 13 It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 100 nm and the porosity is 40%.
  • Example 13 It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 150 nm and the porosity is 50%.
  • Example 20 It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 20 nm and the porosity is 10%.
  • Example 20 It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 200 nm and the porosity is 60%.
  • Example 20 It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 500 nm and the porosity is 80%.
  • Example 17 It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.01 wt%.
  • Example 17 It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.1 wt%.
  • Example 17 It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.2 wt%.
  • the porous polymer membrane is a porous polypropylene membrane with a thickness of 2 ⁇ m, an average pore diameter of 100 nm, and a porosity of 40%.
  • the porous polymer membrane is a porous polyvinylidene fluoride membrane with a thickness of 2 ⁇ m, an average pore diameter of 100 nm, and a porosity of 40%.
  • Example 23 It is basically the same as Example 23, except that the composite film is replaced with a 4.5 ⁇ m thick polypropylene film.
  • step S3 is not performed when manufacturing the composite film.
  • step S2 It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 45°C.
  • step S2 It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 95°C.
  • Example 23 It is basically the same as Example 23, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.1 MPa.
  • Example 23 It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing pressure in step S2 is 1.3MPa.
  • Example 23 It is basically the same as Example 23, except that the concentration of the polyvinyl alcohol solution is 0.005wt%.
  • Example 23 It is basically the same as Example 23, except that the concentration of the polyvinyl alcohol solution is 0.25wt%.
  • Example 23 It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 18 nm and the porosity is 10%.
  • Example 23 It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 505 nm and the porosity is 80%.
  • Example 23 It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 20 nm and the porosity is 8%.
  • Example 23 It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 500 nm and the porosity is 82%.
  • step S2 It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing time in step S2 is 3 seconds.
  • the hot pressing time in step S2 is 92 s.
  • the bonding force of the composite film in Table 1 refers to the bonding force between the polymer base film and the porous polymer film.
  • the bonding force of the composite cathode current collector refers to the bonding force between the composite film and the aluminum metal conductive layer.
  • Bonding force, the bonding force of the composite negative electrode current collector refers to the bonding force between the composite film and the copper metal conductive layer.
  • Steps S1 and S2 have a greater impact on the bonding performance between the polymer base film and the porous polymer film, while the structure of the porous polymer film (average pore size, porosity) and the dip coating process in step S3 have a greater impact on the bonding performance between the polymer base film and the porous polymer film.
  • the bonding force between the composite film and the aluminum metal conductive layer, and the composite film and the copper metal conductive layer has a greater influence.

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Abstract

A manufacturing method for a composite membrane, and a composite membrane and the use thereof. The composite membrane comprises a polymer base membrane, a bonding layer and a porous polymer membrane, wherein at least one surface of the polymer base membrane is provided with the bonding layer and the porous polymer membrane, the bonding layer is located between the polymer base membrane and the porous polymer membrane for bonding the two, and a hydrophilic polymer is attached to the surface or in pores of the porous polymer membrane.

Description

复合膜的制造方法、复合膜及其应用Manufacturing method of composite membrane, composite membrane and its application 技术领域Technical field
本申请涉及电池技术领域，特别是涉及一种复合膜的制造方法、复合膜及其应用。The present application relates to the field of battery technology, and in particular to a manufacturing method of a composite film, a composite film and its application.
背景技术Background technique
金属化聚合物膜产品包括复合集流体、薄膜电极、包装镀铝膜、印刷薄膜等。金属化聚合物膜由于其优良的导电、阻隔、柔韧及质量轻等性能而被广泛运用于电子、包装、印刷等领域。传统技术通常采用物理气相沉积技术直接在聚丙烯、聚乙烯、聚酯类等聚合物膜表面沉积金属导电层以制造金属化聚合物膜。由于聚丙烯、聚乙烯、聚酯类等聚合物膜与金属导电层的表面张力相差较大，导致两者之间亲和力较差，影响了聚合物膜与金属导电层之间的牢固强度。Metalized polymer film products include composite current collectors, thin film electrodes, packaging aluminized films, printed films, etc. Metalized polymer films are widely used in electronics, packaging, printing and other fields due to their excellent conductivity, barrier, flexibility and light weight properties. Traditional technology usually uses physical vapor deposition technology to directly deposit a metal conductive layer on the surface of polymer films such as polypropylene, polyethylene, polyester, etc. to manufacture metallized polymer films. Due to the large difference in surface tension between polymer films such as polypropylene, polyethylene, and polyester and the metal conductive layer, the affinity between the two is poor, which affects the firmness between the polymer film and the metal conductive layer.
发明内容Contents of the invention
根据本申请的各种实施例，提供一种复合膜的制造方法、复合膜及其应用。According to various embodiments of the present application, a manufacturing method of a composite film, a composite film and its application are provided.
以下是本申请的技术方案：The following is the technical solution for this application:
本申请提供了一种复合膜，所述复合膜包括聚合物基膜、粘结层和多孔聚合物膜；The present application provides a composite film, which includes a polymer base film, an adhesive layer and a porous polymer film;
所述聚合物基膜的至少一个表面上设置有所述粘结层和所述多孔聚合物膜，所述粘结层位于所述聚合物基膜与所述多孔聚合物膜之间用于将两者粘合，所述多孔聚合物膜的表面和/或孔隙内附着有亲水聚合物。The adhesive layer and the porous polymer film are provided on at least one surface of the polymer base film, and the adhesive layer is located between the polymer base film and the porous polymer film for attaching The two are bonded, and the hydrophilic polymer is attached to the surface and/or pores of the porous polymer membrane.
在一些实施方式中，所述亲水聚合物包括聚乙烯醇、聚丙烯酸、聚乙烯亚胺、壳聚糖、海藻酸钠、羧甲基纤维素、纳米纤维素、聚懒氨酸、聚谷氨酸和聚乙二醇中的一种或多种。In some embodiments, the hydrophilic polymer includes polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazine, polyglutamine One or more of amino acids and polyethylene glycol.
在一些实施方式中，所述粘结层的材料包括聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的一种或多种；In some embodiments, the material of the bonding layer includes one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber;
可选地，所述粘结层的厚度为20～500nm。Optionally, the thickness of the adhesive layer is 20 to 500 nm.
在一些实施方式中，所述粘结层的厚度为50～200nm。In some embodiments, the thickness of the adhesive layer ranges from 50 to 200 nm.
在一些实施方式中，所述多孔聚合物膜的材料包括聚乙烯、聚丙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚氨酯、醋酸纤维素、聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚苯乙烯、聚氧乙烯、聚对苯二甲酸乙二醇酯以及它们的衍生物中的一种或多种；In some embodiments, the material of the porous polymer membrane includes polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, poly One or more of ethersulfone, polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives;
可选地，所述多孔聚合物膜的厚度为1μm以上。Optionally, the thickness of the porous polymer membrane is 1 μm or more.
在一些实施方式中，所述多孔聚合物膜的厚度为2～20μm。In some embodiments, the porous polymer membrane has a thickness of 2 to 20 μm.
在一些实施方式中，所述聚合物基膜的材料包括聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚丙乙烯、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚苯醚(PPO)、聚苯乙烯(PS)以及它们的衍生物中的一种或多种；In some embodiments, the material of the polymer-based film includes polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate ( PBT), polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), poly One or more of phenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and their derivatives;
可选地，所述聚合物基膜的厚度为1μm以上。Optionally, the thickness of the polymer base film is 1 μm or more.
在一些实施方式中，所述聚合物基膜的厚度为2～50μm。In some embodiments, the polymer base film has a thickness of 2 to 50 μm.
在一些实施方式中，所述多孔聚合物膜的平均孔径为20～500nm；所述多孔聚合物膜的孔隙率为10％～80％。In some embodiments, the average pore diameter of the porous polymer membrane is 20-500 nm; the porosity of the porous polymer membrane is 10%-80%.
在一些实施方式中，所述多孔聚合物膜的平均孔径为50～200nm；所述多孔聚合物膜的孔隙率为20％～60％。In some embodiments, the average pore diameter of the porous polymer membrane is 50-200 nm; the porosity of the porous polymer membrane is 20%-60%.
本申请还提供了上述复合膜的制造方法，所述制造方法包括以下步骤：This application also provides a manufacturing method for the above composite membrane, which manufacturing method includes the following steps:
S1.在聚合物基膜的至少一个表面涂覆粘结剂，干燥后形成粘结层；S1. Coat adhesive on at least one surface of the polymer base film, and form an adhesive layer after drying;
S2.将多孔聚合物膜与所述粘结层贴合，经热压和熟化得到半成品；S2. Laminate the porous polymer film to the adhesive layer, and obtain a semi-finished product through hot pressing and aging;
S3.利用含有亲水聚合物的溶液对所述半成品进行浸涂处理，干燥后使所述多孔聚合物膜的表面和/或孔隙内附着有所述亲水聚合物。S3. Use a solution containing a hydrophilic polymer to dip-coat the semi-finished product, and after drying, the hydrophilic polymer is attached to the surface and/or pores of the porous polymer film.
在一些实施方式中，步骤S1中，所述粘结剂的涂覆量为0.1～2μm。In some embodiments, in step S1, the coating amount of the adhesive is 0.1 to 2 μm.
在一些实施方式中，步骤S1中，所述粘结剂包括挥发性溶剂和粘结物质，其中，所述粘结物质的质量百分比为40％～70％；In some embodiments, in step S1, the binder includes a volatile solvent and a binding substance, wherein the mass percentage of the binding substance is 40% to 70%;
可选地，所述挥发性溶剂包括但不限于丙酮、乙酸乙酯、甲乙酮、环己酮、甲苯二甲苯和二氧六环中的一种或多种；Optionally, the volatile solvent includes but is not limited to one or more of acetone, ethyl acetate, methyl ethyl ketone, cyclohexanone, toluene and dioxane;
可选地，所述粘结物质包括但不限于聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的一种或多种。Optionally, the bonding substance includes, but is not limited to, one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber.
在一些实施方式中，步骤S2中，所述热压的工艺包括热压温度50～90℃，热压压力0.2～1.2MPa，热压时间5～90s。In some embodiments, in step S2, the hot pressing process includes a hot pressing temperature of 50 to 90°C, a hot pressing pressure of 0.2 to 1.2 MPa, and a hot pressing time of 5 to 90 seconds.
在一些实施方式中，步骤S3中，所述含有亲水聚合物的溶液的浓度为0.01～0.2wt％。In some embodiments, in step S3, the concentration of the solution containing hydrophilic polymer is 0.01 to 0.2 wt%.
在一些实施方式中，步骤S3中，所述含有亲水聚合物的溶液的浓度为0.02～0.15wt％。In some embodiments, in step S3, the concentration of the solution containing hydrophilic polymer is 0.02 to 0.15 wt%.
本申请还提供了一种金属化复合膜，包括复合膜和金属导电层，所述复合膜为上述复合膜或上述制造方法制得的复合膜，所述金属导电层设置在所述复合膜的多孔聚合物膜的表面；The present application also provides a metallized composite film, which includes a composite film and a metal conductive layer. The composite film is the above-mentioned composite film or a composite film produced by the above-mentioned manufacturing method. The metal conductive layer is provided on the surface of the composite film. The surface of the porous polymer membrane;
可选地，所述金属导电层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的一种或多种；Optionally, the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
可选地，所述金属导电层的厚度为300～2000nm。Optionally, the thickness of the metal conductive layer is 300-2000 nm.
在一些实施方式中，金属导电层的厚度为500～1000nm。In some embodiments, the thickness of the metal conductive layer ranges from 500 to 1000 nm.
进一步地，本申请还提供了一种复合集流体，所述复合集流体包括上述金属化复合膜。Furthermore, this application also provides a composite current collector, which includes the above-mentioned metallized composite film.
在一些实施方式中，所述复合集流体还包括保护层，所述保护层位于所述金属导电层的表面上；In some embodiments, the composite current collector further includes a protective layer located on the surface of the metal conductive layer;
可选地，所述保护层的材料包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种；Optionally, the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, One or more of carbon nanoquantum dots, carbon nanotubes, carbon nanofibers and graphene;
可选地，所述保护层的厚度为10～200nm。Optionally, the thickness of the protective layer is 10-200 nm.
在一些实施方式中，所述保护层的厚度为50～100nm。In some embodiments, the thickness of the protective layer is 50-100 nm.
本申请还提供了一种电极，所述电极包括上述复合集流体。The present application also provides an electrode, which includes the above composite current collector.
进一步地，本申请还提供了一种电池，所述电池包括上述电极。Furthermore, this application also provides a battery, which includes the above-mentioned electrode.
更进一步地，本申请还提供了一种用电装置，所述用电装置包括上述电池。Furthermore, this application also provides an electrical device, which includes the above-mentioned battery.
本申请的一个或多个实施例的细节在下面的描述中提出。本申请的其它特征、目的和优点将从说明书以及权利要求书变得明显。The details of one or more embodiments of the application are set forth in the description below. Other features, objects and advantages of the application will become apparent from the description and claims.
具体实施方式Detailed ways
下面将结合具体的实施例，对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solution of the present application will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。本文所使用的术语“一种或多种”包括一个或多个相关的所列项目的任意的和所有的组合。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing specific embodiments only and is not intended to limit the application. As used herein, the term "one or more" includes any and all combinations of one or more of the associated listed items.
本申请中，涉及到数值区间，如无特别说明，上述数值区间内视为连续，且包括该范围的最小值及最大值，以及这种最小值与最大值之间的每一个值。进一步地，当范围是指整数时，包括该范围的最小值与最大值之间的每一个整数。此外，当提供多个范围描述特征或特性时，可以合并该范围。换言之，除非另有指明，否则本文中所公开之所有范围应理解为包括其中所归入的任何及所有的子范围。In this application, when it comes to numerical intervals, unless otherwise specified, the above numerical interval is considered to be continuous and includes the minimum value and maximum value of the range, as well as every value between such minimum value and maximum value. Further, when a range refers to an integer, every integer between the minimum value and the maximum value of the range is included. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
本申请一实施方式提供了一种复合膜，该复合膜包括聚合物基膜、粘结层和多孔聚合 物膜；One embodiment of the present application provides a composite film, which includes a polymer base film, an adhesive layer and a porous polymer film;
聚合物基膜的至少一个表面上设置有粘结层和多孔聚合物膜，粘结层位于聚合物基膜与多孔聚合物膜之间用于将两者粘合，多孔聚合物膜的表面和/或孔隙内附着有亲水聚合物。An adhesive layer and a porous polymer film are provided on at least one surface of the polymer base film. The adhesive layer is located between the polymer base film and the porous polymer film for bonding the two. The surface of the porous polymer film and / Or there is a hydrophilic polymer attached to the pores.
在金属化聚合物膜实际制造过程中存在聚合物基材与表面金属导电层结合不牢固的问题。传统技术采用电晕法提升聚合物基材的表面张力，进而提升其与表面金属导电层的结合力，但是电晕法提升聚合物基材的表面张力幅度有限且存储过程中聚合物基材的表面张力存在衰减问题。In the actual manufacturing process of metallized polymer films, there is a problem that the polymer substrate and the surface metal conductive layer are not firmly bonded. Traditional technology uses the corona method to increase the surface tension of the polymer substrate, thereby improving its bonding force with the surface metal conductive layer. However, the corona method to increase the surface tension of the polymer substrate is limited and the polymer substrate changes during storage. There is a decay problem with surface tension.
从界面粘结学的角度看，影响聚合物基材与表面金属导电层结合牢固性的两个关键因素为聚合物基材表面的结构和性质。金属化聚合物膜通常以聚丙烯、聚乙烯或聚酯等聚合物膜为基材，该基材的极性较弱，导致表面张力较低，低表面张力的聚合物基材与高表面张力的金属导电层之间的亲合力较差；另外，聚合物基材的表面比较平整，不具备物理精密结合的位点，因此，聚合物基材与表面金属导电层结合不牢固。为了解决上述技术问题，本申请在聚合物基膜的表面构建多孔聚合物膜，提供物理铆合位点，多孔聚合物膜的表面和/或孔隙内附着的亲水聚合物能够在其表面和/或孔隙内构建极性表面，从而得到一种表面极性较高的复合膜。以该复合膜为基材制造金属化复合膜，能够使该复合膜与表面金属导电层的结合非常牢固。From the perspective of interface bonding, the two key factors that affect the bonding strength between the polymer substrate and the surface metal conductive layer are the structure and properties of the polymer substrate surface. Metalized polymer films usually use polymer films such as polypropylene, polyethylene or polyester as the base material. The polarity of the base material is weak, resulting in low surface tension. Polymer base materials with low surface tension are associated with high surface tension. The affinity between the metal conductive layers is poor; in addition, the surface of the polymer substrate is relatively flat and does not have precise physical bonding sites. Therefore, the polymer substrate and the surface metal conductive layer are not firmly bonded. In order to solve the above technical problems, this application constructs a porous polymer membrane on the surface of the polymer base membrane to provide physical riveting sites. The hydrophilic polymer attached to the surface and/or pores of the porous polymer membrane can be attached to its surface and /Or build a polar surface within the pores, thereby obtaining a composite membrane with a higher surface polarity. Using the composite film as a base material to produce a metallized composite film can make the composite film very firmly bonded to the surface metal conductive layer.
在一些实施方式中，亲水聚合物包括聚乙烯醇、聚丙烯酸、聚乙烯亚胺、壳聚糖、海藻酸钠、羧甲基纤维素、纳米纤维素、聚懒氨酸、聚谷氨酸和聚乙二醇中的一种或多种。In some embodiments, the hydrophilic polymer includes polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazine, polyglutamic acid and one or more of polyethylene glycol.
可以理解地，亲水聚合物可以为聚乙烯醇、聚丙烯酸、聚乙烯亚胺、壳聚糖、海藻酸钠、羧甲基纤维素、纳米纤维素、聚懒氨酸、聚谷氨酸和聚乙二醇中的任意一种，亲水聚合物也可以为聚乙烯醇、聚丙烯酸、聚乙烯亚胺、壳聚糖、海藻酸钠、羧甲基纤维素、纳米纤维素、聚懒氨酸、聚谷氨酸和聚乙二醇中的多种按照任意比例混合得到的混合物。It can be understood that the hydrophilic polymer can be polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, nanocellulose, polylazynic acid, polyglutamic acid and Any one of polyethylene glycol, the hydrophilic polymer can also be polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethylcellulose, nanocellulose, polyurethane A mixture of acid, polyglutamic acid and polyethylene glycol mixed in any proportion.
在一些实施方式中，粘结层的材料包括聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的一种或多种；In some embodiments, the material of the bonding layer includes one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber;
可选地，粘结层的厚度为20～500nm。Optionally, the thickness of the adhesive layer is 20 to 500 nm.
在一些实施方式中，粘结层的厚度为50～200nm。In some embodiments, the thickness of the adhesive layer ranges from 50 to 200 nm.
可以理解地，粘结层的材料可以为聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的任意一种，粘结层的材料也可以为聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的多种按照任意比例混合得到的混合物。It can be understood that the material of the adhesive layer can be any one of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber. The material of the adhesive layer It may also be a mixture of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber in any proportion.
可以理解地，粘结层的厚度可以为20～500μm或50～200nm之间的任意值，例如：20μm、30μm、40μm、50μm、70μm、90μm、120μm、150μm、200μm、220μm、250μm、270μm、300μm、320μm、360μm、390μm、410μm、450μm、470μm、500μm等。其中，若粘结层的厚度过低，粘结的效果则会较差，若粘结层的厚度超过一定范围，继续增加其厚度，对粘结效果的提升没有明显的促进作用。It can be understood that the thickness of the adhesive layer can be any value between 20 and 500 μm or 50 and 200 nm, such as: 20 μm, 30 μm, 40 μm, 50 μm, 70 μm, 90 μm, 120 μm, 150 μm, 200 μm, 220 μm, 250 μm, 270 μm, 300μm, 320μm, 360μm, 390μm, 410μm, 450μm, 470μm, 500μm, etc. Among them, if the thickness of the adhesive layer is too low, the bonding effect will be poor. If the thickness of the adhesive layer exceeds a certain range, continuing to increase its thickness will not significantly promote the improvement of the bonding effect.
在一些实施方式中，多孔聚合物膜的材料包括聚乙烯、聚丙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚氨酯、醋酸纤维素、聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚苯乙烯、聚氧乙烯、聚对苯二甲酸乙二醇酯以及它们的衍生物中的一种或多种；In some embodiments, the material of the porous polymer membrane includes polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone , one or more of polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives;
可选地，多孔聚合物膜的厚度为1μm以上。Optionally, the thickness of the porous polymer membrane is 1 μm or more.
在一些实施方式中，多孔聚合物膜的厚度为2～20μm。In some embodiments, the thickness of the porous polymer membrane ranges from 2 to 20 μm.
可以理解地，多孔聚合物膜的材料可以为聚乙烯、聚丙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚氨酯、醋酸纤维素、聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚苯乙烯、聚氧乙烯、聚对苯二甲酸乙二醇酯以及它们的衍生物中的任意一种，多孔聚合物膜的材料也可以为聚乙烯、聚丙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚氨酯、醋酸纤维素、聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚苯乙烯、聚氧乙烯、聚对苯二甲酸乙二醇酯以及它们的衍生物中的多种按照任意比例混合得到的混合物。It can be understood that the material of the porous polymer membrane can be polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone, Any one of polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and their derivatives. The material of the porous polymer membrane can also be polyethylene or polypropylene. , polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone, polyamide, polyimide, polystyrene, polyoxyethylene, poly A mixture obtained by mixing multiple types of ethylene terephthalate and their derivatives in any proportion.
考虑到用途、生产成本及稳定性，多孔聚合物膜的厚度可以为2～20μm。可以理解地，多孔聚合物膜的厚度可以还可以为1～20μm之间的任意值，例如：1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、12μm、13μm、14μm、15μm、16μm、17μm、18μm、19μm、20μm等。Considering the use, production cost and stability, the thickness of the porous polymer membrane can be 2 to 20 μm. It can be understood that the thickness of the porous polymer membrane can also be any value between 1 and 20 μm, such as: 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm , 14μm, 15μm, 16μm, 17μm, 18μm, 19μm, 20μm, etc.
可选地，多孔聚合物膜通过双向拉伸法、静电纺丝法或相转化法制造。Alternatively, the porous polymer membrane is produced by biaxial stretching, electrospinning or phase inversion.
在一些实施方式中，聚合物基膜的材料包括聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚丙乙烯、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚苯醚(PPO)、聚苯乙烯(PS)以及它们的衍生物中的一种或多种。In some embodiments, the material of the polymer-based film includes polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) , polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide One or more of ether (PPS), polyphenylene ether (PPO), polystyrene (PS) and their derivatives.
可以理解地，聚合物基膜的材料可以为聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚丙乙烯、聚氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚苯醚(PPO)、聚苯乙烯(PS)以及它们的衍生物中的任意一种，聚合物基膜的材料也可以为聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)、聚丙乙烯、聚 氯乙烯(PVC)、聚偏氟乙烯(PVDF)、聚四氟乙烯(PTFE)、聚苯硫醚(PPS)、聚苯醚(PPO)、聚苯乙烯(PS)以及它们的衍生物中的多种按照任意比例混合得到的混合物；It can be understood that the material of the polymer-based film can be polypropylene (PP), polyethylene (PE), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and any of their derivatives. The material of the polymer base film can also be polypropylene (PP), polyethylene (PE), poly Ethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyimide (PI), polypropylene, polychloride Ethylene (PVC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyphenylene sulfide (PPS), polyphenylene ether (PPO), polystyrene (PS) and many of their derivatives A mixture obtained by mixing in any proportion;
可选地，聚合物基膜的厚度为1μm以上。Optionally, the thickness of the polymer base film is 1 μm or more.
在一些实施方式中，聚合物基膜的厚度为2～50μm。In some embodiments, the polymer base film has a thickness of 2 to 50 μm.
可以理解地，聚合物基膜的厚度可以为1～50μm或2～50μm之间的任意值，例如：1μm、2μm、5μm、8μm、10μm、13μm、15μm、18μm、20μm、23μm、25μm、28μm、30μm、32μm、35μm、37μm、40μm、42μm、45μm、47μm、50μm等。It can be understood that the thickness of the polymer base film can be any value between 1 to 50 μm or 2 to 50 μm, such as: 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm, 20 μm, 23 μm, 25 μm, 28 μm , 30μm, 32μm, 35μm, 37μm, 40μm, 42μm, 45μm, 47μm, 50μm, etc.
可选地，聚合物基膜的材料可以与多孔聚合物膜的材料相同，也可以不同。Alternatively, the material of the polymer-based membrane may be the same as the material of the porous polymer membrane, or may be different.
可选地，聚合物基膜的制造方法包括但不限于双向拉伸法、单向拉伸法、流延法、压延法和吹膜法中的一种。Optionally, the manufacturing method of the polymer-based film includes, but is not limited to, one of biaxial stretching, uniaxial stretching, casting, calendering and blown film.
在一些实施方式中，多孔聚合物膜的平均孔径为20～500nm；多孔聚合物膜的孔隙率为10％～80％。In some embodiments, the average pore diameter of the porous polymer membrane is 20-500 nm; the porosity of the porous polymer membrane is 10%-80%.
在一些实施方式中，多孔聚合物膜的平均孔径为50～200nm；多孔聚合物膜的孔隙率为20％～60％。In some embodiments, the average pore diameter of the porous polymer membrane is 50-200 nm; the porosity of the porous polymer membrane is 20%-60%.
多孔聚合物膜的平均孔径太大或太小均不利于控制多孔聚合物膜的孔隙率，也不利于聚合物基膜与金属导电层的紧密结合；多孔聚合物膜的孔隙率太低不利于聚合物基膜与金属导电层的紧密结合，孔隙率太高，则聚合物基膜的机械性能下降。If the average pore size of the porous polymer membrane is too large or too small, it is not conducive to controlling the porosity of the porous polymer membrane, nor is it conducive to the close combination of the polymer base membrane and the metal conductive layer; if the porosity of the porous polymer membrane is too low, it is not conducive to controlling the porosity of the porous polymer membrane. If the polymer base film and the metal conductive layer are tightly combined and the porosity is too high, the mechanical properties of the polymer base film will decrease.
本申请还提供了上述复合膜的制造方法，包括以下步骤：This application also provides a manufacturing method for the above composite membrane, which includes the following steps:
S1.在聚合物基膜的至少一个表面涂覆粘结剂，干燥后形成粘结层；S1. Coat adhesive on at least one surface of the polymer base film, and form an adhesive layer after drying;
S2.将多孔聚合物膜与粘结层贴合，经热压和熟化得到半成品；S2. Laminate the porous polymer film and the adhesive layer, and obtain the semi-finished product through hot pressing and aging;
S3.利用含有亲水聚合物的溶液对半成品进行浸涂处理，干燥后使多孔聚合物膜的表面和/或孔隙内附着有亲水聚合物。S3. Use a solution containing a hydrophilic polymer to dip-coat the semi-finished product. After drying, the hydrophilic polymer is attached to the surface and/or pores of the porous polymer film.
上述聚合物基膜的表面构建有多孔聚合物膜，以提供物理铆合位点，同时在多孔聚合物表面及孔内构建极性表面，能够有效提升其表面张力，进而提高复合膜与金属导电层的亲和力。上述复合膜的表面张力较高且长期稳定，能够与金属导电层牢固结合。A porous polymer film is constructed on the surface of the above-mentioned polymer-based film to provide physical riveting sites. At the same time, polar surfaces are constructed on the surface and pores of the porous polymer, which can effectively increase its surface tension and thereby improve the conductivity of the composite film and metal. layer affinity. The surface tension of the above-mentioned composite film is high and stable for a long time, and can be firmly combined with the metal conductive layer.
在一些实施方式中，步骤S1中，粘结剂的涂覆量为0.1～2μm。In some embodiments, in step S1, the coating amount of the adhesive is 0.1 to 2 μm.
可以理解地，粘结剂的涂覆量可以为0.1～2μm之间的任意值，例如：0.1μm、0.3μm、0.5μm、0.8μm、1.0μm、1.3μm、1.5μm、1.7μm或2.0μm等。It can be understood that the coating amount of the adhesive can be any value between 0.1 and 2 μm, such as: 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm, 1.0 μm, 1.3 μm, 1.5 μm, 1.7 μm or 2.0 μm. wait.
在一些实施方式中，步骤S1中，粘结剂包括挥发性溶剂和粘结物质，其中，粘结物质的质量百分比为40％～70％；In some embodiments, in step S1, the binder includes a volatile solvent and a binding substance, wherein the mass percentage of the binding substance is 40% to 70%;
可选地，挥发性溶剂包括但不限于丙酮、乙酸乙酯、甲乙酮、环己酮、甲苯二甲苯和 二氧六环中的一种或多种；Alternatively, volatile solvents include, but are not limited to, one or more of acetone, ethyl acetate, methyl ethyl ketone, cyclohexanone, toluene and dioxane;
可选地，粘结物质包括但不限于聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的一种或多种。Optionally, the bonding substance includes, but is not limited to, one or more of polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin and chlorinated rubber.
在一些实施方式中，步骤S1的干燥分为三段烘干，温度依次设置为50～60℃、60～70℃、70～80℃，三段的烘干时间分别为0.1～5min。In some embodiments, the drying in step S1 is divided into three stages of drying, the temperatures are set to 50-60°C, 60-70°C, and 70-80°C in sequence, and the drying times of the three stages are 0.1-5 minutes respectively.
步骤S1的干燥用于除去粘结剂中的部分溶剂，实现粘结剂的部分固化。The drying in step S1 is used to remove part of the solvent in the adhesive and achieve partial solidification of the adhesive.
在一些实施方式中，步骤S2中，热压的工艺包括热压温度50～90℃，热压压力0.2～1.2MPa，热压时间5～90s。In some embodiments, in step S2, the hot pressing process includes a hot pressing temperature of 50 to 90°C, a hot pressing pressure of 0.2 to 1.2 MPa, and a hot pressing time of 5 to 90 seconds.
可以理解地，热压温度可以为50～90℃之间的任意值，例如：50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃或90℃等；热压压力可以为0.2～1.2MPa之间的任意值，例如：0.2MPa、0.3MPa、0.4MPa、0.5MPa、0.6MPa、0.7MPa、0.8MPa、0.9MPa、1.0MPa、1.1MPa或1.2MPa等；热压时间可以为5～90s之间的任意值，例如：5s、10s、15s、20s、25s、30s、35s、40s、45s、50s、55s、60s、65s、70s、75s、80s、85s或90s等。It can be understood that the hot pressing temperature can be any value between 50°C and 90°C, such as: 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or 90°C, etc.; heat The pressing force can be any value between 0.2 and 1.2MPa, such as: 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa or 1.2MPa, etc.; The hot pressing time can be any value between 5 and 90s, such as: 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s or 90s etc.
在一些实施方式中，步骤S2的熟化温度为50～60℃，熟化时间为0.5～48h。In some embodiments, the curing temperature in step S2 is 50-60°C, and the curing time is 0.5-48 hours.
可以理解地，熟化温度可以为50～60℃之间的任意值，例如：50℃、52℃、54℃、56℃、58℃或60℃等；熟化时间可以为0.5～48h之间的任意值，例如：0.5h、5h、10h、15h、20h、25h、30h、35h、40h、45h或48h等。Understandably, the curing temperature can be any value between 50 and 60°C, such as: 50°C, 52°C, 54°C, 56°C, 58°C or 60°C, etc.; the aging time can be any value between 0.5 and 48h. Values, such as: 0.5h, 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 48h, etc.
在一些实施方式中，步骤S3的浸涂处理包括以下步骤：In some embodiments, the dip coating process of step S3 includes the following steps:
将半成品浸入醇类溶液中5～60s，取出后浸入纯水中5～60s，之后浸入含有亲水聚合物的溶液中10～90s；Immerse the semi-finished product in the alcohol solution for 5 to 60 seconds, take it out and immerse it in pure water for 5 to 60 seconds, and then immerse it in a solution containing hydrophilic polymer for 10 to 90 seconds;
除去半成品表面残留的亲水聚合物溶液，在60～90℃下干燥0.5～5min，得到复合膜。Remove the remaining hydrophilic polymer solution on the surface of the semi-finished product and dry it at 60-90°C for 0.5-5 minutes to obtain a composite film.
在一些实施方式中，步骤S3中，含有亲水聚合物的溶液的浓度为0.01～0.2wt％。In some embodiments, in step S3, the concentration of the solution containing the hydrophilic polymer is 0.01 to 0.2 wt%.
在一些实施方式中，步骤S3中，含有亲水聚合物的溶液的浓度为0.02～0.15wt％。In some embodiments, in step S3, the concentration of the solution containing the hydrophilic polymer is 0.02 to 0.15 wt%.
需要解释的是，含有亲水聚合物的溶液的浓度较低，因此，亲水聚合物仅对多孔聚合物表面的多孔骨架进行涂覆包裹，不影响多孔聚合物的孔隙率及孔径。可以理解地，含有亲水聚合物的溶液的浓度可以为0.01～0.2wt％或0.02～0.15wt％之间的任意值，例如：0.01wt％、0.02wt％、0.04wt％、0.06wt％、0.08wt％、0.10wt％、0.12wt％、0.15wt％或0.2wt％等。It should be explained that the concentration of the solution containing the hydrophilic polymer is low. Therefore, the hydrophilic polymer only coats the porous skeleton on the surface of the porous polymer and does not affect the porosity and pore size of the porous polymer. It can be understood that the concentration of the solution containing the hydrophilic polymer can be any value between 0.01 to 0.2wt% or 0.02 to 0.15wt%, such as: 0.01wt%, 0.02wt%, 0.04wt%, 0.06wt%, 0.08wt%, 0.10wt%, 0.12wt%, 0.15wt% or 0.2wt%, etc.
本申请还提供了一种金属化复合膜，包括复合膜和金属导电层，该复合膜为上述复合膜或上述制造方法制得的复合膜，金属导电层设置在复合膜的多孔聚合物膜的表面；The present application also provides a metallized composite film, which includes a composite film and a metal conductive layer. The composite film is the above-mentioned composite film or a composite film produced by the above-mentioned manufacturing method. The metal conductive layer is provided on the porous polymer film of the composite film. surface;
可选地，金属导电层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的 一种或多种；Optionally, the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
可选地，金属导电层的厚度为300～2000nm。Optionally, the thickness of the metal conductive layer is 300-2000nm.
在一些实施方式中，金属导电层的厚度为500～1000nm。In some embodiments, the thickness of the metal conductive layer ranges from 500 to 1000 nm.
可以理解地，金属导电层的材料可以为铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的任意一种，也可以为铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的多种按照任意比例混合得到的混合物。金属导电层的厚度可以为300～2000nm或500～1000nm之间的任意值，例如：300nm、330nm、360nm、400nm、430nm、460nm、500nm、525nm、575nm、600nm、635nm、680nm、700nm、710nm、770nm、800nm、870nm、900nm、950nm、1000nm、1070nm、1100nm、1150nm、1200nm、1250nm、1300nm、1350nm、1400nm、1600nm、1800nm或2000nm等。It can be understood that the material of the metal conductive layer can be any one of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver, or can be copper, copper alloy, aluminum, aluminum alloy, nickel, A mixture of nickel alloy, titanium and silver in any proportion. The thickness of the metal conductive layer can be any value between 300~2000nm or 500~1000nm, such as: 300nm, 330nm, 360nm, 400nm, 430nm, 460nm, 500nm, 525nm, 575nm, 600nm, 635nm, 680nm, 700nm, 710nm, 770nm, 800nm, 870nm, 900nm, 950nm, 1000nm, 1070nm, 1100nm, 1150nm, 1200nm, 1250nm, 1300nm, 1350nm, 1400nm, 1600nm, 1800nm or 2000nm, etc.
可选地，金属导电层的制造方法包括但不仅限于物理气相沉积法、化学镀法和电镀法中的至少一种；其中，物理气相沉积法包括但不仅限于磁控溅射法、电阻加热真空蒸镀法、激光加热真空蒸镀法和电子束加热真空蒸镀法中的至少一种。Optionally, the manufacturing method of the metal conductive layer includes but is not limited to at least one of physical vapor deposition, chemical plating and electroplating; wherein the physical vapor deposition method includes but is not limited to magnetron sputtering, resistance heating vacuum. At least one of an evaporation method, a laser heating vacuum evaporation method, and an electron beam heating vacuum evaporation method.
进一步地，本申请还提供了一种复合集流体，包括上述金属化复合膜。Furthermore, this application also provides a composite current collector, including the above-mentioned metallized composite film.
复合正极集流体中金属导电层的材料可以为铝或铝合金；铝合金中铝的含量大于等于80wt％，进一步地，铝合金中铝的含量可以大于90wt％。The material of the metal conductive layer in the composite cathode current collector can be aluminum or aluminum alloy; the aluminum content in the aluminum alloy can be greater than or equal to 80wt%, and further, the aluminum content in the aluminum alloy can be greater than 90wt%.
复合负极集流体中金属导电层的材料可以为铜或铜合金；铜合金中铜的含量大于等于80wt％，进一步地，铜合金中铜的含量可以大于90wt％。The material of the metal conductive layer in the composite negative electrode current collector can be copper or copper alloy; the copper content in the copper alloy can be greater than or equal to 80wt%, and further, the copper content in the copper alloy can be greater than 90wt%.
在一些实施方式中，复合集流体还包括保护层，该保护层位于金属导电层的表面上；In some embodiments, the composite current collector further includes a protective layer located on the surface of the metal conductive layer;
可选地，保护层的材料包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种。设置的保护层用于防止金属导电层被化学腐蚀或物理破坏；Optionally, the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, carbon nanoparticles One or more of quantum dots, carbon nanotubes, carbon nanofibers and graphene. The protective layer is provided to prevent the metal conductive layer from being chemically corroded or physically damaged;
可选地，保护层的厚度为10～200nm。Optionally, the thickness of the protective layer is 10-200 nm.
在一些实施方式中，保护层的厚度为50～100nm。In some embodiments, the thickness of the protective layer ranges from 50 to 100 nm.
可以理解地，保护层的厚度可以为10～200nm或50～100nm之间的任意值，例如：10nm、12nm、14nm、16nm、18nm、20nm、24nm、28nm、30nm、35nm、45nm、50nm、55nm、65nm、75nm、85nm、95nm、100nm、105nm、115nm、125nm、135nm、145nm、155nm、160nm、180nm或200nm等。Understandably, the thickness of the protective layer can be any value between 10 to 200nm or 50 to 100nm, such as: 10nm, 12nm, 14nm, 16nm, 18nm, 20nm, 24nm, 28nm, 30nm, 35nm, 45nm, 50nm, 55nm , 65nm, 75nm, 85nm, 95nm, 100nm, 105nm, 115nm, 125nm, 135nm, 145nm, 155nm, 160nm, 180nm or 200nm, etc.
在一些实施方式中，保护层为两层，两层保护层的材料可以相同也可以不同，两层保护层的厚度可以相等也可以不相等。In some embodiments, the protective layer is composed of two layers. The materials of the two protective layers may be the same or different, and the thickness of the two protective layers may be equal or unequal.
可选地，保护层的制造方法包括但不仅限于涂布法、原位成型法和物理气相沉积法中 的至少一种；其中，涂布法可以是模头涂布法、刮刀涂布法和挤压涂布法；原位成型法可以是在金属导电层表面原位形成金属氧化物钝化层的方法；物理气相沉积法可以是真空蒸镀法和磁控溅射法。Optionally, the manufacturing method of the protective layer includes but is not limited to at least one of coating method, in-situ molding method and physical vapor deposition method; wherein, the coating method can be die coating method, blade coating method and Extrusion coating method; in-situ forming method can be a method of forming a metal oxide passivation layer in situ on the surface of the metal conductive layer; physical vapor deposition method can be vacuum evaporation method and magnetron sputtering method.
本申请的复合膜的制造方法中，通过调整多孔聚合物膜的平均孔径和孔隙率、粘结剂的涂覆量、热压的工艺和亲水聚合物溶液的浓度，能够有效提高复合膜的表面张力以及复合膜与金属导电层之间的粘结力。In the manufacturing method of the composite membrane of the present application, by adjusting the average pore size and porosity of the porous polymer membrane, the coating amount of the binder, the hot pressing process and the concentration of the hydrophilic polymer solution, the performance of the composite membrane can be effectively improved. Surface tension and adhesion between the composite film and the metal conductive layer.
本申请还提供了一种电极，包括上述复合集流体。This application also provides an electrode, including the above composite current collector.
需要说明的是，上述电极可以是正极或者负极，例如可以是正极片或者负极片，上述正极片可以由正极材料、导电剂、粘结剂和溶剂混合后涂覆在上述复合集流体上形成，上述负极片可以由负极材料、导电剂、粘结剂和溶剂混合后涂覆在上述复合集流体上形成。It should be noted that the above-mentioned electrode can be a positive electrode or a negative electrode, for example, it can be a positive electrode sheet or a negative electrode sheet. The above-mentioned positive electrode sheet can be formed by mixing a positive electrode material, a conductive agent, a binder and a solvent and then coating it on the above-mentioned composite current collector. The above-mentioned negative electrode sheet can be formed by mixing a negative electrode material, a conductive agent, a binder and a solvent and then coating the mixture on the above-mentioned composite current collector.
进一步地，本申请还提供了一种电池，包括上述电极。Furthermore, this application also provides a battery including the above electrode.
本申请对电池没有特别的限制，电池的制造过程为本领域技术人员所熟知的，可以包括但不限于以下步骤：将正极片、隔膜和负极片按顺序堆叠后进行卷绕或者折叠等操作得到电极组件，将电极组件放入包装袋内，注入电解液并封口，得到电池，其中，电池中使用的正极片采用本申请制造的正极片，或者电池中使用的负极片采用本申请制造的正极片，再或者电池中使用的正极片和负极片均为本申请制造的正极片和负极片。This application has no special restrictions on the battery. The manufacturing process of the battery is well known to those skilled in the art and can include but is not limited to the following steps: stacking the positive electrode sheet, separator and negative electrode sheet in order and then rolling or folding to obtain Electrode assembly, put the electrode assembly into the packaging bag, inject the electrolyte and seal it to obtain a battery, in which the positive electrode sheet used in the battery adopts the positive electrode sheet manufactured by this application, or the negative electrode sheet used in the battery adopts the positive electrode manufactured by this application. The positive and negative electrode sheets, or the positive and negative electrode sheets used in the battery, are the positive and negative electrode sheets manufactured by this application.
更进一步地，本申请还提供了一种用电装置，包括上述电池。Furthermore, this application also provides an electrical device including the above-mentioned battery.
上述电池可以作为电源或者能量储存单元用于用电装置中，上述用电装置包括但不仅限于电动车辆、手机、平板、电脑、电动玩具、可穿戴设备、无人机、储能装置等。The above-mentioned battery can be used as a power source or energy storage unit in electrical devices, including but not limited to electric vehicles, mobile phones, tablets, computers, electric toys, wearable devices, drones, energy storage devices, etc.
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。表面张力和粘结力测试按照如下方法进行。Hereinafter, embodiments of the present application will be described in more detail with reference to Examples and Comparative Examples. Surface tension and adhesion tests were performed as follows.
(1)表面张力测试：参照GB/T 14216-2008，对复合膜进行表面张力测试，初始表面张力为刚制造完成的复合膜的表面张力，并将制造完成的复合膜放置三个月，对其表面张力进行测试。(1) Surface tension test: Refer to GB/T 14216-2008, conduct a surface tension test on the composite film. The initial surface tension is the surface tension of the newly manufactured composite film, and place the manufactured composite film for three months. Its surface tension is tested.
(2)聚合物基膜与多孔聚合物膜之间的粘结力测试：将制造的复合膜裁成150mm×15mm的小条，小条的多孔聚合物膜与拉力机的上夹具固定，聚合物基膜与拉力机的下夹具固定，将二者以180°的角度、100mm/min的速度进行剥离，测试剥离力，即二者之间的粘结力，用于评估二者之间的粘合稳定性。(2) Adhesion test between polymer base film and porous polymer film: Cut the manufactured composite film into small strips of 150 mm × 15 mm, and fix the small strips of porous polymer film to the upper clamp of the tensile machine for polymerization. The material-based film is fixed to the lower clamp of the tensile machine, and the two are peeled off at an angle of 180° and at a speed of 100mm/min. The peeling force, that is, the bonding force between the two, is used to evaluate the bond between the two. Adhesion stability.
(3)复合膜与铝金属导电层/铜金属导电层之间的粘结力测试：在1mm厚的铝箔上粘接一层Permacel P-94双面胶，在双面胶的上方粘接复合正极集流体/复合负极集流体，在复合正极集流体/复合负极集流体上方覆盖一层乙烯丙烯酸共聚物薄膜(杜邦Nurcel0903， 厚度为50μm)，然后在1.3×10 5N/m 2、120℃下热压10s，冷却至室温，裁成150mm×15mm的小条。最后将样品小条的乙烯丙烯酸共聚物薄膜固定于拉力机的上夹具，其余部分固定在下夹具，固定好后将二者以180°的角度、100mm/min的速度进行剥离，测试剥离力，即复合膜与金属导电层的粘结力。 (3) Adhesion test between the composite film and the aluminum metal conductive layer/copper metal conductive layer: bond a layer of Permacel P-94 double-sided tape on a 1mm thick aluminum foil, and bond the composite film on top of the double-sided tape The positive electrode current collector/composite negative electrode current collector is covered with a layer of ethylene acrylic acid copolymer film (DuPont Nurcel0903, thickness 50μm) on the composite positive electrode current collector/composite negative electrode current collector, and then heated at 1.3×10 5 N/m 2 and 120℃ Heat and press for 10 seconds, cool to room temperature, and cut into small strips of 150mm×15mm. Finally, the small strip of ethylene acrylic acid copolymer film of the sample is fixed on the upper clamp of the tensile machine, and the remaining part is fixed on the lower clamp. After being fixed, the two are peeled off at an angle of 180° and a speed of 100mm/min to test the peeling force, that is Adhesion between composite film and metal conductive layer.
实施例1Example 1
本实施例的聚合物基膜采用双向拉伸聚丙烯膜，其厚度为4.5μm。粘结剂由质量比为5：3的A组分和B组分组成，A组分为50wt％的聚氨酯预聚体的丙酮溶液，B组分为60wt％的三羟甲基丙烷与甲苯二异氰酸酯加成物的乙酸乙酯溶液，其中，三羟甲基丙烷与甲苯二异氰酸酯的摩尔比为1：3；粘结剂中的有机溶剂挥发后固化形成粘结层。多孔聚合物膜采用多孔聚乙烯膜，其厚度为2μm，平均孔径为50nm，孔隙率为25％；含有亲水聚合物的溶液为0.05wt％的聚乙烯醇溶液。The polymer base film in this embodiment is a biaxially stretched polypropylene film with a thickness of 4.5 μm. The binder consists of component A and component B with a mass ratio of 5:3. Component A is an acetone solution of 50wt% polyurethane prepolymer, and component B is 60wt% trimethylolpropane and toluene. An ethyl acetate solution of isocyanate adduct, in which the molar ratio of trimethylolpropane to toluene diisocyanate is 1:3; the organic solvent in the adhesive volatilizes and solidifies to form an adhesive layer. The porous polymer membrane is a porous polyethylene membrane with a thickness of 2 μm, an average pore diameter of 50 nm, and a porosity of 25%; the solution containing the hydrophilic polymer is a 0.05wt% polyvinyl alcohol solution.
复合膜的制造方法，包括如下步骤：The manufacturing method of composite membrane includes the following steps:
S1.通过挤压涂布法在双向拉伸聚丙烯膜的双面分别涂覆粘结剂，涂覆量为0.1μm，涂覆完成后进入热风烘箱内进行干燥，干燥完成后双向拉伸聚丙烯膜的双面形成粘结层；其中，热风烘箱为三段烘箱，其温度依次设置为50℃、60℃、70℃，处理时间依次为1min、1min、1min；S1. Coat the adhesive on both sides of the biaxially oriented polypropylene film by the extrusion coating method. The coating amount is 0.1μm. After the coating is completed, it is dried in a hot air oven. After drying, the biaxially oriented polypropylene film is dried. An adhesive layer is formed on both sides of the propylene film; among them, the hot air oven is a three-stage oven, the temperature is set to 50°C, 60°C, and 70°C, and the processing time is 1min, 1min, and 1min;
S2.将双向拉伸聚丙烯膜的双面粘结层分别与多孔聚乙烯膜对齐贴合，经热压辊热压处理后，在50℃烘箱内熟化12h，得到半成品，其中，热压温度为50℃，热压压力为0.2MPa，热压时间为10s；S2. Align and fit the double-sided adhesive layer of the biaxially stretched polypropylene film with the porous polyethylene film. After hot pressing with a hot pressing roller, mature it in a 50°C oven for 12 hours to obtain a semi-finished product. The hot pressing temperature The temperature is 50℃, the hot pressing pressure is 0.2MPa, and the hot pressing time is 10s;
S3.将半成品浸入体积浓度为50％的异丙醇溶液中，浸泡20s，然后将其浸入纯水清洗槽，清洗30s，再将其置于0.05wt％聚乙烯醇溶液中浸涂60s，浸涂完成后经风刀(风机频率30Hz)除液20s，进入70℃热风箱中干燥2min，得到复合膜。S3. Immerse the semi-finished product in an isopropyl alcohol solution with a volume concentration of 50% for 20s, then immerse it in a pure water cleaning tank, clean it for 30s, and then dip it into a 0.05wt% polyvinyl alcohol solution for 60s. After the coating is completed, the liquid is removed by an air knife (fan frequency 30Hz) for 20 seconds, and then dried in a hot air box at 70°C for 2 minutes to obtain a composite film.
复合正极集流体的制造方法，包括以下步骤：The manufacturing method of composite cathode current collector includes the following steps:
(1)制造铝金属导电层(1) Manufacturing aluminum metal conductive layer
对上述复合膜的表面进行清洁，之后将其置于真空蒸镀的舱体内，金属蒸发室内的高纯铝丝(纯度大于99.99％)在1300～2000℃条件下熔化蒸发，蒸发后的金属原子经过真空镀膜室内的冷却系统，沉积在复合膜的两个表面，形成铝金属导电层，其厚度为1μm；The surface of the above composite film is cleaned, and then placed in a vacuum evaporation chamber. The high-purity aluminum wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at 1300 to 2000°C. The evaporated metal atoms After the cooling system in the vacuum coating chamber, it is deposited on both surfaces of the composite film to form an aluminum metal conductive layer with a thickness of 1 μm;
(2)制造保护层(2) Create protective layer
将1g碳纳米管分散到999g氮甲基吡咯烷酮(NMP)溶液中，通过超声分散使两者充分混合，得到固含量为0.1wt％的涂布液，然后通过模头涂布法将涂布液均匀涂覆到铝金属导电层的表面，其中涂覆量控制在90μm，在100℃下干燥，得到复合正极集流体。Disperse 1g of carbon nanotubes into 999g of nitrogen methylpyrrolidone (NMP) solution, mix the two thoroughly through ultrasonic dispersion, and obtain a coating liquid with a solid content of 0.1wt%. The coating liquid is then used for die coating. Coat evenly onto the surface of the aluminum metal conductive layer, with the coating amount controlled at 90 μm, and dry at 100°C to obtain a composite positive electrode current collector.
复合负极集流体的制造方法，包括以下步骤：The manufacturing method of composite negative electrode current collector includes the following steps:
(1)制造铜金属导电层(1) Manufacturing copper metal conductive layer
对上述复合膜的表面进行清洁，之后将其置于真空蒸镀的舱体内，金属蒸发室内的高纯铜丝(纯度大于99.99％)在1400～2000℃条件下熔化蒸发，蒸发后的金属原子经过真空镀膜室内的冷却系统，沉积在复合膜的两个表面，形成铜金属导电层，其厚度为1μm；The surface of the above composite film is cleaned, and then placed in a vacuum evaporation chamber. The high-purity copper wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at 1400 to 2000°C. The evaporated metal atoms After the cooling system in the vacuum coating chamber, it is deposited on both surfaces of the composite film to form a copper metal conductive layer with a thickness of 1 μm;
(2)制造保护层(2) Create protective layer
将1g石墨烯均匀分散到999g氮甲基吡咯烷酮(NMP)溶液中，通过超声分散使两者充分混合，得到固含量为0.1wt％的涂布液，然后通过模头涂布法将涂布液均匀涂覆到铜金属导电层的表面，其中涂覆量控制在80μm，在100℃下干燥，得到复合负极集流体。1g of graphene was evenly dispersed into 999g of nitrogen methylpyrrolidone (NMP) solution, and the two were thoroughly mixed by ultrasonic dispersion to obtain a coating liquid with a solid content of 0.1wt%. The coating liquid was then dispersed by die coating. Coat evenly onto the surface of the copper metal conductive layer, with the coating amount controlled at 80 μm, and dry at 100°C to obtain a composite negative electrode current collector.
实施例2Example 2
与实施例1基本相同，区别在于：制造复合膜时，步骤S2中热压温度为60℃。It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 60°C.
实施例3Example 3
与实施例1基本相同，区别在于：制造复合膜时，步骤S2中热压温度为70℃。It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 70°C.
实施例4Example 4
与实施例1基本相同，区别在于：制造复合膜时，步骤S2中热压温度为90℃。It is basically the same as Example 1, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 90°C.
实施例5Example 5
与实施例3基本相同，区别在于：制造复合膜时，步骤S2中热压压力为0.5MPa。It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.5 MPa.
实施例6Example 6
与实施例3基本相同，区别在于：制造复合膜时，步骤S2中热压压力为0.7MPa。It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.7MPa.
实施例7Example 7
与实施例3基本相同，区别在于：制造复合膜时，步骤S2中热压压力为0.9MPa。It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.9MPa.
实施例8Example 8
与实施例3基本相同，区别在于：制造复合膜时，步骤S2中热压压力为1.2MPa。It is basically the same as Example 3, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 1.2MPa.
实施例9Example 9
与实施例6基本相同，区别在于：制造复合膜时，步骤S2中热压时间为5s。It is basically the same as Example 6, except that when manufacturing the composite film, the hot pressing time in step S2 is 5 s.
实施例10Example 10
与实施例6基本相同，区别在于：制造复合膜时，步骤S2中热压时间为30s。It is basically the same as Example 6, except that when manufacturing the composite film, the hot pressing time in step S2 is 30 s.
实施例11Example 11
与实施例6基本相同，区别在于：制造复合膜时，步骤S2中热压时间为50s。It is basically the same as Example 6, except that when manufacturing the composite film, the hot pressing time in step S2 is 50 s.
实施例12Example 12
与实施例6基本相同，区别在于：制造复合膜时，步骤S2中热压时间为90s。It is basically the same as Example 6, except that when manufacturing the composite film, the hot pressing time in step S2 is 90 s.
实施例13Example 13
与实施例10基本相同，区别在于：制造复合膜时，步骤S1中双组分聚氨酯的涂覆量为0.5μm。It is basically the same as Example 10, except that when manufacturing the composite film, the coating amount of the two-component polyurethane in step S1 is 0.5 μm.
实施例14Example 14
与实施例10基本相同，区别在于：制造复合膜时，步骤S1中双组分聚氨酯的涂覆量为1.0μm。It is basically the same as Example 10, except that when manufacturing the composite film, the coating amount of the two-component polyurethane in step S1 is 1.0 μm.
实施例15Example 15
与实施例10基本相同，区别在于：制造复合膜时，步骤S1中双组分聚氨酯的涂覆量为2.0μm。It is basically the same as Example 10, except that when manufacturing the composite film, the coating amount of the two-component polyurethane in step S1 is 2.0 μm.
实施例16Example 16
与实施例13基本相同，区别在于：多孔聚乙烯膜的平均孔径为70nm，孔隙率为30％。It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 70 nm and the porosity is 30%.
实施例17Example 17
与实施例13基本相同，区别在于：多孔聚乙烯膜的平均孔径为100nm，孔隙率为40％。It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 100 nm and the porosity is 40%.
实施例18Example 18
与实施例13基本相同，区别在于：多孔聚乙烯膜的平均孔径为150nm，孔隙率为50％。It is basically the same as Example 13, except that the average pore diameter of the porous polyethylene membrane is 150 nm and the porosity is 50%.
实施例19Example 19
与实施例20基本相同，区别在于：多孔聚乙烯膜的平均孔径为20nm，孔隙率为10％。It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 20 nm and the porosity is 10%.
实施例20Example 20
与实施例20基本相同，区别在于：多孔聚乙烯膜的平均孔径为200nm，孔隙率为60％。It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 200 nm and the porosity is 60%.
实施例21Example 21
与实施例20基本相同，区别在于：多孔聚乙烯膜的平均孔径为500nm，孔隙率为80％。It is basically the same as Example 20, except that the average pore diameter of the porous polyethylene membrane is 500 nm and the porosity is 80%.
实施例22Example 22
与实施例17基本相同，区别在于：聚乙烯醇溶液的浓度为0.01wt％。It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.01 wt%.
实施例23Example 23
与实施例17基本相同，区别在于：聚乙烯醇溶液的浓度为0.1wt％。It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.1 wt%.
实施例24Example 24
与实施例17基本相同，区别在于：聚乙烯醇溶液的浓度为0.2wt％。It is basically the same as Example 17, except that the concentration of the polyvinyl alcohol solution is 0.2 wt%.
实施例25Example 25
与实施例23基本相同，区别在于：多孔聚合物膜采用多孔聚丙烯膜，其厚度为2μm，平均孔径为100nm，孔隙率为40％。It is basically the same as Example 23, except that the porous polymer membrane is a porous polypropylene membrane with a thickness of 2 μm, an average pore diameter of 100 nm, and a porosity of 40%.
实施例26Example 26
与实施例23基本相同，区别在于：多孔聚合物膜采用多孔聚偏二氟乙烯膜，其厚度为2μm，平均孔径为100nm，孔隙率为40％。It is basically the same as Example 23, except that the porous polymer membrane is a porous polyvinylidene fluoride membrane with a thickness of 2 μm, an average pore diameter of 100 nm, and a porosity of 40%.
对比例1Comparative example 1
与实施例23基本相同，区别在于：将复合膜替换成4.5μm厚的聚丙烯膜。It is basically the same as Example 23, except that the composite film is replaced with a 4.5 μm thick polypropylene film.
对比例2Comparative example 2
与实施例23基本相同，区别在于：制造复合膜时，不进行步骤S3处理。It is basically the same as Example 23, except that step S3 is not performed when manufacturing the composite film.
对比例3Comparative example 3
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压温度为45℃。It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 45°C.
对比例4Comparative example 4
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压温度为95℃。It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing temperature in step S2 is 95°C.
对比例5Comparative example 5
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压压力为0.1MPa。It is basically the same as Example 23, except that when manufacturing the composite membrane, the hot pressing pressure in step S2 is 0.1 MPa.
对比例6Comparative example 6
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压压力为1.3MPa。It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing pressure in step S2 is 1.3MPa.
对比例7Comparative example 7
与实施例23基本相同，区别在于：聚乙烯醇溶液的浓度为0.005wt％。It is basically the same as Example 23, except that the concentration of the polyvinyl alcohol solution is 0.005wt%.
对比例8Comparative example 8
与实施例23基本相同，区别在于：聚乙烯醇溶液的浓度为0.25wt％。It is basically the same as Example 23, except that the concentration of the polyvinyl alcohol solution is 0.25wt%.
对比例9Comparative example 9
与实施例23基本相同，区别在于：多孔聚乙烯膜的平均孔径为18nm，孔隙率为10％。It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 18 nm and the porosity is 10%.
对比例10Comparative example 10
与实施例23基本相同，区别在于：多孔聚乙烯膜的平均孔径为505nm，孔隙率为80％。It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 505 nm and the porosity is 80%.
对比例11Comparative example 11
与实施例23基本相同，区别在于：多孔聚乙烯膜的平均孔径为20nm，孔隙率为8％。It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 20 nm and the porosity is 8%.
对比例12Comparative example 12
与实施例23基本相同，区别在于：多孔聚乙烯膜的平均孔径为500nm，孔隙率为82％。It is basically the same as Example 23, except that the average pore diameter of the porous polyethylene membrane is 500 nm and the porosity is 82%.
对比例13Comparative example 13
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压时间为3s。It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing time in step S2 is 3 seconds.
对比例14Comparative example 14
与实施例23基本相同，区别在于：制造复合膜时，步骤S2中热压时间为92s。It is basically the same as Example 23, except that when manufacturing the composite film, the hot pressing time in step S2 is 92 s.
表1表面张力和粘结力测试结果Table 1 Surface tension and adhesion test results
Figure PCTCN2022117305-appb-000001
Figure PCTCN2022117305-appb-000001
注：表1中复合膜的粘结力指的是聚合物基膜与多孔聚合物膜之间的粘结力，复合正 极集流体的粘结力指的是复合膜与铝金属导电层的粘结力，复合负极集流体的粘结力指的是复合膜与铜金属导电层的粘结力。Note: The bonding force of the composite film in Table 1 refers to the bonding force between the polymer base film and the porous polymer film. The bonding force of the composite cathode current collector refers to the bonding force between the composite film and the aluminum metal conductive layer. Bonding force, the bonding force of the composite negative electrode current collector refers to the bonding force between the composite film and the copper metal conductive layer.
从表1可以看出：It can be seen from Table 1:
(1)本申请实施例1～26的聚合物基膜与多孔聚合物膜之间的粘结力较好，保证了后续应用的稳定性；(1) The adhesion between the polymer base film and the porous polymer film in Examples 1 to 26 of the present application is good, ensuring the stability of subsequent applications;
(2)观察实施例23和对比例1～3发现，与传统的聚合物膜基材相比，本申请制造的复合膜与铝金属导电层或铜金属导电层之间的粘结力显著提升；(2) Observing Example 23 and Comparative Examples 1 to 3, it was found that compared with traditional polymer film substrates, the bonding force between the composite film produced by the present application and the aluminum metal conductive layer or copper metal conductive layer was significantly improved. ;
(3)步骤S1和步骤S2对聚合物基膜与多孔聚合物膜之间的粘结性能影响较大，而多孔聚合物膜的结构(平均孔径、孔隙率)以及步骤S3的浸涂工艺对复合膜与铝金属导电层、复合膜与铜金属导电层之间的粘结力影响较大。(3) Steps S1 and S2 have a greater impact on the bonding performance between the polymer base film and the porous polymer film, while the structure of the porous polymer film (average pore size, porosity) and the dip coating process in step S3 have a greater impact on the bonding performance between the polymer base film and the porous polymer film. The bonding force between the composite film and the aluminum metal conductive layer, and the composite film and the copper metal conductive layer has a greater influence.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, All should be considered to be within the scope of this manual.
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。The above-described embodiments only express several implementation modes of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all fall within the protection scope of the present application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims (16)

  1. 一种复合膜，其特征在于，所述复合膜包括聚合物基膜、粘结层和多孔聚合物膜；A composite film, characterized in that the composite film includes a polymer base film, an adhesive layer and a porous polymer film;
    所述聚合物基膜的至少一个表面上设置有所述粘结层和所述多孔聚合物膜，所述粘结层位于所述聚合物基膜与所述多孔聚合物膜之间用于将两者粘合，所述多孔聚合物膜的表面和/或孔隙内附着有亲水聚合物。The adhesive layer and the porous polymer film are provided on at least one surface of the polymer base film, and the adhesive layer is located between the polymer base film and the porous polymer film for attaching The two are bonded, and the hydrophilic polymer is attached to the surface and/or pores of the porous polymer membrane.
  2. 根据权利要求1所述的复合膜，其特征在于，所述亲水聚合物包括聚乙烯醇、聚丙烯酸、聚乙烯亚胺、壳聚糖、海藻酸钠、羧甲基纤维素、纳米纤维素、聚懒氨酸、聚谷氨酸和聚乙二醇中的一种或多种。The composite film according to claim 1, wherein the hydrophilic polymer includes polyvinyl alcohol, polyacrylic acid, polyethylenimine, chitosan, sodium alginate, carboxymethyl cellulose, and nanocellulose. , one or more of polylanine, polyglutamic acid and polyethylene glycol.
  3. 根据权利要求1～2任一项所述的复合膜，其特征在于，所述粘结层的材料包括聚氨酯、环氧树脂、乙烯丙烯酸树脂、聚丙烯酸树脂、有机硅树脂、醋酸乙烯树脂、丙烯酸树脂和氯化橡胶中的一种或多种；The composite film according to any one of claims 1 to 2, characterized in that the material of the adhesive layer includes polyurethane, epoxy resin, ethylene acrylic resin, polyacrylic resin, silicone resin, vinyl acetate resin, acrylic resin One or more of resin and chlorinated rubber;
    可选地，所述粘结层的厚度为20～500nm。Optionally, the thickness of the adhesive layer is 20 to 500 nm.
  4. 根据权利要求1～3任一项所述的复合膜，其特征在于，所述多孔聚合物膜的材料包括聚乙烯、聚丙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯乙烯、聚丙烯腈、聚氨酯、醋酸纤维素、聚砜、聚醚砜、聚酰胺、聚酰亚胺、聚苯乙烯、聚氧乙烯、聚对苯二甲酸乙二醇酯以及它们的衍生物中的一种或多种；The composite membrane according to any one of claims 1 to 3, characterized in that the material of the porous polymer membrane includes polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride, polyvinyl chloride, Acrylonitrile, polyurethane, cellulose acetate, polysulfone, polyethersulfone, polyamide, polyimide, polystyrene, polyoxyethylene, polyethylene terephthalate and one of their derivatives or more;
    可选地，所述多孔聚合物膜的厚度为1μm以上。Optionally, the thickness of the porous polymer membrane is 1 μm or more.
  5. 根据权利要求1～4任一项所述的复合膜，其特征在于，所述聚合物基膜的材料包括聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚丙乙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚苯硫醚、聚苯醚、聚苯乙烯以及它们的衍生物中的一种或多种；The composite film according to any one of claims 1 to 4, characterized in that the material of the polymer base film includes polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate. Glycol ester, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene ether, polystyrene and their one or more derivatives;
    可选地，所述聚合物基膜的厚度为1μm以上。Optionally, the thickness of the polymer base film is 1 μm or more.
  6. 根据权利要求1～5任一项所述的复合膜，其特征在于，所述多孔聚合物膜的平均孔径为20～500nm；所述多孔聚合物膜的孔隙率为10％～80％。The composite membrane according to any one of claims 1 to 5, characterized in that the average pore diameter of the porous polymer membrane is 20 to 500 nm; the porosity of the porous polymer membrane is 10% to 80%.
  7. 如权利要求1～6任一项所述的复合膜的制造方法，其特征在于，所述制造方法包括以下步骤：The manufacturing method of a composite membrane according to any one of claims 1 to 6, characterized in that the manufacturing method includes the following steps:
    S1.在聚合物基膜的至少一个表面涂覆粘结剂，干燥后形成粘结层；S1. Coat adhesive on at least one surface of the polymer base film, and form an adhesive layer after drying;
    S2.将多孔聚合物膜与所述粘结层贴合，经热压和熟化得到半成品；S2. Laminate the porous polymer film to the adhesive layer, and obtain a semi-finished product through hot pressing and aging;
    S3.利用含有亲水聚合物的溶液对所述半成品进行浸涂处理，干燥后使所述多孔聚合物膜的表面和/或孔隙内附着有所述亲水聚合物。S3. Use a solution containing a hydrophilic polymer to dip-coat the semi-finished product, and after drying, the hydrophilic polymer is attached to the surface and/or pores of the porous polymer film.
  8. 根据权利要求7所述的制造方法，其特征在于，步骤S1中，所述粘结剂的涂覆量为0.1～2μm。The manufacturing method according to claim 7, characterized in that in step S1, the coating amount of the adhesive is 0.1-2 μm.
  9. 根据权利要求7～8任一项所述的制造方法，其特征在于，步骤S2中，所述热压的工艺包括热压温度50～90℃，热压压力0.2～1.2MPa，热压时间5～90s。The manufacturing method according to any one of claims 7 to 8, characterized in that in step S2, the hot pressing process includes a hot pressing temperature of 50-90°C, a hot pressing pressure of 0.2-1.2MPa, and a hot pressing time of 5 ~90s.
  10. 根据权利要求7～9任一项所述的制造方法，其特征在于，步骤S3中，所述含有亲水聚合物的溶液的浓度为0.01～0.2wt％。The manufacturing method according to any one of claims 7 to 9, wherein in step S3, the concentration of the solution containing hydrophilic polymer is 0.01 to 0.2 wt%.
  11. 一种金属化复合膜，其特征在于，包括复合膜和金属导电层，所述复合膜为权利要求1～6任一项所述的复合膜或权利要求7～10任一项所述的制造方法制得的复合膜，所述金属导电层设置在所述复合膜的多孔聚合物膜的表面；A metallized composite film, characterized in that it includes a composite film and a metal conductive layer. The composite film is the composite film according to any one of claims 1 to 6 or the manufacturing process according to any one of claims 7 to 10. In the composite membrane prepared by the method, the metal conductive layer is provided on the surface of the porous polymer film of the composite membrane;
    可选地，所述金属导电层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的一种或多种；Optionally, the material of the metal conductive layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
    可选地，所述金属导电层的厚度为300～2000nm。Optionally, the thickness of the metal conductive layer is 300-2000 nm.
  12. 一种复合集流体，其特征在于，包括权利要求11所述的金属化复合膜。A composite current collector, characterized by comprising the metallized composite film according to claim 11.
  13. 根据权利要求12所述的复合集流体，其特征在于，还包括保护层，所述保护层位于所述金属导电层的表面上；The composite current collector according to claim 12, further comprising a protective layer located on the surface of the metal conductive layer;
    可选地，所述保护层的材料包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种；Optionally, the material of the protective layer includes nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, One or more of carbon nanoquantum dots, carbon nanotubes, carbon nanofibers and graphene;
    可选地，所述保护层的厚度为10～200nm。Optionally, the thickness of the protective layer is 10-200 nm.
  14. 一种电极，其特征在于，包括权利要求12～13任一项所述的复合集流体。An electrode, characterized in that it includes the composite current collector according to any one of claims 12 to 13.
  15. 一种电池，其特征在于，包括权利要求14所述的电极。A battery characterized by comprising the electrode according to claim 14.
  16. 一种用电装置，其特征在于，包括权利要求15所述的电池。An electrical device, characterized by comprising the battery according to claim 15.
PCT/CN2022/117305 2022-09-06 2022-09-06 Manufacturing method for composite membrane, and composite membrane and use thereof WO2024050696A1 (en)

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