WO2024050696A1 - Procédé de fabrication d'une membrane composite, membrane composite et son utilisation - Google Patents

Procédé de fabrication d'une membrane composite, membrane composite et son utilisation 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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WIPO (PCT)
Prior art keywords
film
composite
polymer
membrane
porous polymer
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PCT/CN2022/117305
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English (en)
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/fr
Publication of WO2024050696A1 publication Critical patent/WO2024050696A1/fr

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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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une membrane composite, et une membrane composite et son utilisation. La membrane composite comprend une membrane de base polymère, une couche de liaison et une membrane polymère poreuse, au moins une surface de la membrane de base polymère étant pourvue de la couche de liaison et de la membrane polymère poreuse, la couche de liaison étant située entre la membrane de base polymère et la membrane polymère poreuse pour lier les deux, et un polymère hydrophile étant fixé à la surface ou dans des pores de la membrane polymère poreuse.
PCT/CN2022/117305 2022-09-06 2022-09-06 Procédé de fabrication d'une membrane composite, membrane composite et son utilisation WO2024050696A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160046104A1 (en) * 2014-08-14 2016-02-18 Mitsubishi Polyester Film, Inc. Laminate Containing Coated Polyester Film
CN109311267A (zh) * 2016-06-06 2019-02-05 巴斯夫涂料有限公司 制备复合材料的新方法
CN110416467A (zh) * 2018-04-28 2019-11-05 比亚迪股份有限公司 聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法
CN110997312A (zh) * 2017-08-24 2020-04-10 巴斯夫涂料有限公司 由膜、固体粘合剂聚合物和聚氨酯层制得的复合材料的制备
CN112543786A (zh) * 2018-07-31 2021-03-23 W.L.戈尔及同仁股份有限公司 聚乙烯膜
CN113795954A (zh) * 2021-01-23 2021-12-14 宁德新能源科技有限公司 复合集流体、应用所述复合集流体的电池和电子装置
CN114479146A (zh) * 2022-02-17 2022-05-13 江阴纳力新材料科技有限公司 聚多酚改性的聚合物膜及其制备方法、金属化聚合物膜
CN114678536A (zh) * 2022-04-29 2022-06-28 扬州纳力新材料科技有限公司 集流体及其制备方法和应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160046104A1 (en) * 2014-08-14 2016-02-18 Mitsubishi Polyester Film, Inc. Laminate Containing Coated Polyester Film
CN109311267A (zh) * 2016-06-06 2019-02-05 巴斯夫涂料有限公司 制备复合材料的新方法
CN110997312A (zh) * 2017-08-24 2020-04-10 巴斯夫涂料有限公司 由膜、固体粘合剂聚合物和聚氨酯层制得的复合材料的制备
CN110416467A (zh) * 2018-04-28 2019-11-05 比亚迪股份有限公司 聚合物隔膜及其制备方法和应用以及锂离子电池及其制备方法
CN112543786A (zh) * 2018-07-31 2021-03-23 W.L.戈尔及同仁股份有限公司 聚乙烯膜
CN113795954A (zh) * 2021-01-23 2021-12-14 宁德新能源科技有限公司 复合集流体、应用所述复合集流体的电池和电子装置
CN114479146A (zh) * 2022-02-17 2022-05-13 江阴纳力新材料科技有限公司 聚多酚改性的聚合物膜及其制备方法、金属化聚合物膜
CN114678536A (zh) * 2022-04-29 2022-06-28 扬州纳力新材料科技有限公司 集流体及其制备方法和应用

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