WO2024000803A1 - Preparation method for composite current collector, and composite current collector - Google Patents

Preparation method for composite current collector, and composite current collector Download PDF

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Publication number
WO2024000803A1
WO2024000803A1 PCT/CN2022/116777 CN2022116777W WO2024000803A1 WO 2024000803 A1 WO2024000803 A1 WO 2024000803A1 CN 2022116777 W CN2022116777 W CN 2022116777W WO 2024000803 A1 WO2024000803 A1 WO 2024000803A1
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Prior art keywords
current collector
layer
composite current
metal
base material
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PCT/CN2022/116777
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French (fr)
Chinese (zh)
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王成豪
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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Publication of WO2024000803A1 publication Critical patent/WO2024000803A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of lithium ion batteries, and in particular to a preparation method of a composite current collector and a composite current collector.
  • the current composite current collectors are mainly copper current collectors and aluminum current collectors.
  • the copper current collectors or aluminum current collectors are composed of two parts, including a thin film substrate layer in the middle and a thin film substrate layer arranged opposite to each other. Metal coating on both surfaces.
  • the thickness requirement of the metal coating is generally about 0.5 ⁇ m-1.5 ⁇ m.
  • the way to prepare the composite current collector is through evaporation process.
  • the binding force between the metal coating and the negatively charged polar groups on the film substrate layer is relatively poor. , resulting in poor peeling force between the metal coating and the film substrate layer, causing the composite current collector to easily delaminate during the cutting process, resulting in defective products, and also causing the battery pole pieces to fall off during the production process.
  • a preparation method of composite current collector including the following steps:
  • the nickel ions are bombarded at high speed on two opposite surfaces of the thin film base material layer, so as to form metallic nickel layers on the two opposite surfaces of the thin film base material layer;
  • a metal plating layer is evaporated on the surface of the metallic nickel layer.
  • the purity of the metal plating layer and the metal nickel layer is both ⁇ 99.8%.
  • the metal plating layer is a metal aluminum layer or a metal copper layer.
  • the thickness of the film base material layer ranges from 1 ⁇ m to 25 ⁇ m, and the thickness of the metal plating layer ranges from 0.5 ⁇ m to 1.5 ⁇ m.
  • the thickness of the metallic nickel layer ranges from 0.5 ⁇ m to 1 ⁇ m.
  • the puncture strength of the film base material layer is ⁇ 100gf
  • the MD tensile strength is ⁇ 200MPa
  • the TD tensile strength is ⁇ 200MPa
  • the MD elongation is ⁇ 30%
  • the TD elongation is ⁇ 30%.
  • the film base material layer includes at least one of an insulating polymer material, an insulating polymer composite material, a conductive polymer material, and a conductive polymer composite material.
  • the insulating polymer material includes polyamide (PA), polyterephthalate, polyimide (PI), polyethylene (PE), polypropylene (PP), polystyrene Ethylene (PPE), polyvinyl chloride (PVC), aramid, acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PET), polyterephthalamide Phenylenediamine (PPTA), polypropylene (PPE), polyoxymethylene (POM), epoxy resin, phenolic resin, polytetrafluoroethylene (PTEE), polyvinylidene fluoride (PVDF), silicone rubber, polycarbonate (PC) ), at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), cellulose, starch, protein, their derivatives, their cross-linked products and their copolymers.
  • PA polyamide
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • starch protein
  • protein poly
  • the insulating polymer composite material is a composite material formed of the insulating polymer material and an inorganic material.
  • This application also provides a composite current collector, including:
  • the metal nickel layer and the metal plating layer are respectively provided on two surfaces of the film base material layer that are opposite to each other.
  • metallic nickel is ionized to generate nickel ions, and under the action of a magnetic field, the nickel ions are bombarded at high speed on two opposite surfaces of the film substrate layer, so that the positively charged nickel ions can interact with the film substrate.
  • the negatively charged polar groups on the surface of the material layer are combined to form more chemical bonds on the surface of the film base material layer to improve the bonding force and peeling force between the film base material layer and the metal nickel layer; through the metal plating layer Setting a metal nickel layer between the metal plating layer and the film base material layer can improve the bonding force and peeling force between the metal plating layer and the film base material layer, making the metal plating layer and the film base material layer less likely to fall off, thereby ensuring the electrical performance and safety of the battery. It can also solve the problem of delamination that easily occurs during the cutting process, resulting in defective products and material falling off during the filmmaking process, causing serious product defects, and ensures product quality.
  • Figure 1 is a schematic structural diagram of a composite current collector shown in an embodiment of the present invention
  • Figure 2 is a schematic flow chart of the steps of a method for preparing a composite current collector according to an embodiment of the present invention
  • FIG. 3 is a schematic flowchart of the steps of a preparation method of a composite current collector shown in a pair of proportions of the present invention.
  • Composite current collector 100. Thin film substrate layer; 200. Metal nickel layer; 300. Metal plating layer.
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include at least one of these features.
  • “plurality” means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
  • connection In the present invention, unless otherwise clearly stated and limited, the terms “installation”, “connection”, “connection”, “fixing” and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated into one; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interactive relationship between two elements, unless otherwise specified restrictions. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
  • a first feature being “on” or “below” a second feature may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. touch.
  • the terms “above”, “above” and “above” the first feature is above the second feature may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is higher in level than the second feature.
  • "Below”, “below” and “beneath” the first feature to the second feature may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature has a smaller horizontal height than the second feature.
  • an embodiment of the present application also provides a method for preparing a composite current collector 10, which includes the following steps:
  • Step 1 Ionize metallic nickel to generate nickel ions.
  • Step 2 Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. It should be understood that when nickel ions bombard the two opposite surfaces of the film base material layer 100 at high speed, the positively charged nickel ions can combine with the negatively charged polar groups on the surface of the film base material layer 100 to form More chemical bonds are formed on the surface of the film base material layer 100 to improve the bonding force and peeling force between the film base material layer 100 and the metal nickel layer 200 .
  • the speed at which nickel ions bombard the two opposite surfaces of the thin film substrate layer 100 is not limited in this application and can be set according to the usage requirements.
  • the speed at which nickel ions bombard two surfaces of the thin film substrate layer 100 located opposite to each other is 150 m/s.
  • Step 3 evaporate the metal plating layer 300 on the surface of the metal nickel layer 200. After the preparation of the composite current collector 10 is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
  • the purity of the metal plating layer 300 is ⁇ 99.8%. That is to say, the metal plating layer 300 in this application uses high-purity metal. Specifically, the metal plating layer 300 is a metal aluminum layer or a metal copper layer. The purity of the metallic nickel layer 200 is ⁇ 99.8%. That is to say, the metallic nickel layer 200 in this application uses high-purity metallic nickel. High-purity metallic nickel has excellent corrosion resistance, high electric vacuum performance and electromagnetic control performance.
  • the metal coating 300 adopts a metal aluminum layer, and the purity of the metal aluminum layer is ⁇ 99.8%.
  • the high-purity metallic aluminum layer has low deformation resistance, high electrical conductivity and good plasticity.
  • the metal plating layer 300 adopts a metallic copper layer, and the purity of the metallic copper layer is ⁇ 99.8%.
  • the high-purity metallic copper layer has good ductility, heat transfer and electrical conductivity.
  • the peeling force between the metal coating 300 and the polymer film layer is ⁇ 8N/m.
  • the peeling force between the metal plating layer 300 and the film base material layer 100 is 10 N/m.
  • the peeling force between the metal plating layer 300 and the film base material layer 100 is relatively high, which can prevent the metal plating layer 300 from falling off from the film base material layer 100, thus ensuring the electrical performance and safety of the battery.
  • the thickness of the film base material layer 100 ranges from 1 ⁇ m to 25 ⁇ m, and the thickness of the metal plating layer 300 ranges from 0.5 ⁇ m to 1.5 ⁇ m.
  • the thickness of the metallic nickel layer 200 ranges from 0.5 ⁇ m to 1 ⁇ m. It should be understood that the thickness of the composite current collector 10 of the present application ranges from 3 ⁇ m to 30 ⁇ m.
  • the thickness of the film base material layer 100 is 20 ⁇ m
  • the thickness of the metal plating layer 300 is 1.2 ⁇ m.
  • the thickness of the metallic nickel layer 200 is 1 ⁇ m.
  • the puncture strength of the film base material layer 100 is ⁇ 100gf
  • the MD tensile strength is ⁇ 200MPa
  • the TD tensile strength is ⁇ 200MPa
  • the MD elongation is ⁇ 30%, TD. Elongation ⁇ 30%.
  • the puncture strength of the film base material layer 100 is ⁇ 300f
  • the MD tensile strength is ⁇ 400MPa
  • the TD tensile strength is ⁇ 400MPa
  • the MD elongation is ⁇ 50%
  • the TD elongation is ⁇ 50%.
  • MD (Machine Direction, machine direction) refers to the longitudinal direction
  • TD (Transverse Direction, perpendicular to the machine direction) refers to the transverse direction.
  • the upper limit of the puncture strength, MD tensile strength, TD tensile strength, MD elongation, and TD elongation of the film base material layer 100 is not limited in this application and can be set according to the needs of use.
  • the lower limit of the puncture strength of the film base material layer 100 shall not be less than 100gf, the lower limit of the MD tensile strength shall not be less than 200MPa, the lower limit of the TD tensile strength shall not be less than 200MPa, the lower limit of the MD elongation shall not be less than 30%, TD The lower limit of the elongation shall not be less than 30%, otherwise the mechanical properties of the film base material layer 100 will be affected, and ultimately the puncture strength, MD tensile strength, TD tensile strength, MD elongation, and TD elongation of the composite current collector 10 will be affected.
  • the film base material layer 100 includes at least one of an insulating polymer material, an insulating polymer composite material, a conductive polymer material, and a conductive polymer composite material.
  • insulating polymer materials include polyamide (PA), polyterephthalate, polyimide (PI), polyethylene (PE), polypropylene (PP), polystyrene (PPE), polyethylene Vinyl chloride (PVC), aramid, acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PET), polyphenylene terephthalamide (PPTA) , polypropylene (PPE), polyoxymethylene (POM), epoxy resin, phenolic resin, polytetrafluoroethylene (PTEE), polyvinylidene fluoride (PVDF), silicone rubber (Silicone rubber), polycarbonate (PC), At least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), cellulose, starch, protein, their derivatives, their cross-linked products and their copolymers.
  • PA polyamide
  • PEG polyethylene glycol
  • PEG polyethylene glycol
  • starch protein
  • protein their derivatives,
  • the above-mentioned insulating polymer composite material is a composite material formed of an insulating polymer material and an inorganic material.
  • the inorganic material may be at least one of ceramic materials, glass materials, and ceramic composite materials.
  • the above-mentioned conductive polymer material may be at least one of doped polysulfide nitride and doped polyacetylene.
  • the above-mentioned conductive polymer composite material may be a composite material formed of an insulating polymer material and a conductive material.
  • the conductive material may be at least one of conductive carbon materials, metal materials, and composite conductive materials. More specifically, the conductive carbon material is selected from at least one of carbon black, carbon nanotubes, graphite, acetylene black, and graphene.
  • the metal material is selected from at least one of metal nickel, metal iron, metal copper, metal aluminum or alloys of the above metals.
  • the composite conductive material is selected from at least one of metal nickel-coated graphite powder and metal nickel-coated carbon fiber.
  • An embodiment of the present application also provides a composite current collector 10, which includes a film base material layer 100. Two surfaces of the film base material layer 100 arranged opposite to each other are respectively provided with a metal nickel layer 200 and a metal nickel layer 200. Metal plating 300.
  • the bonding force and peeling force between the film base material layer 100 and the metal plating layer 300 can be improved, making the metal plating layer 300 and the film base material layer 100 less likely to fall off. , thereby ensuring the electrical performance and safety of the battery and improving the quality of the product.
  • the puncture strength of the composite current collector 10 is ⁇ 50gf, the MD tensile strength is ⁇ 150MPa, the TD tensile strength is ⁇ 150MPa, the MD elongation is ⁇ 10%, and the TD elongation is ⁇ 10%.
  • the composite current collector 10 has a puncture strength of 130 gf, an MD tensile strength of 300 MPa, and a TD tensile strength of 300 MPa.
  • the MD elongation is 60% and the TD elongation is 60%.
  • Step 1 Select a 6 ⁇ m film substrate layer 100, a 99.9% purity metal aluminum layer, and a 99.9% purity metal nickel layer.
  • the film base material layer 100 is made of polybutylene terephthalate (PET).
  • Step 2 Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
  • Step 3 Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 0.5 ⁇ m.
  • Step 4 evaporate the metal plating layer 300 on the surface of the metal nickel layer 200.
  • the thickness of the metal plating layer 300 is 0.5 ⁇ m
  • the metal nickel layer 200 is a metal aluminum layer.
  • Step 1 Select a 25 ⁇ m film substrate layer 100, a 99.9% purity metal copper layer, and a 99.9% purity metal nickel layer.
  • the film base material layer 100 is made of polybutylene terephthalate (PET).
  • Step 2 Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
  • Step 3 Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 1 ⁇ m.
  • Step 4 evaporate the metal plating layer 300 on the surface of the metal nickel layer 200.
  • the thickness of the metal plating layer 300 is 1.5 ⁇ m
  • the metal nickel layer 200 is a metal copper layer.
  • a 30 ⁇ m composite current collector 10 is produced. After the preparation is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
  • Step 1 Select a 1 ⁇ m thin film substrate layer 100, a 99.9% purity metal aluminum layer, and a 99.8% purity metal nickel layer.
  • the film base material layer 100 is made of polybutylene terephthalate (PET).
  • Step 2 Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
  • Step 3 Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 0.5 ⁇ m.
  • Step 4 evaporate the metal plating layer 300 on the surface of the metal nickel layer 200.
  • the thickness of the metal plating layer 300 is 0.5 ⁇ m
  • the metal nickel layer 200 is a metal copper layer.
  • the preparation method of the composite current collector 10 provided in this comparative example includes the following steps:
  • Step 1 Select a 6 ⁇ m film substrate layer 100 and a 99.9% purity metal aluminum layer.
  • the film base material layer 100 is made of polybutylene terephthalate (PET).
  • Step 2 Put the 6 ⁇ m thin film base material layer 100 and the 99.9% purity metal aluminum layer into the vacuum coating equipment respectively, and evaporate the metal aluminum layers on the two opposite surfaces of the thin film base material layer 100 to obtain the result.
  • the thickness of the metallic aluminum layer is 1 ⁇ m.
  • the preparation method of the composite current collector 10 provided in this comparative example includes the following steps:
  • Step 1 Select a 25 ⁇ m film substrate layer 100 and a 99.9% purity metal aluminum layer.
  • the film base material layer 100 is made of polybutylene terephthalate (PET).
  • Step 2 Put the 25 ⁇ m thin film base material layer 100 and the 99.9% purity metal aluminum layer into the vacuum coating equipment respectively, and evaporate the metal aluminum layers on the two opposite surfaces of the thin film base material layer 100 to obtain the result.
  • the thickness of the metallic aluminum layer is 2.5 ⁇ m.
  • the peeling force of the composite current collector 10 of Examples 1-3 and Comparative Examples 1-2 was tested, and the effect data as shown in Table 1 was obtained. It should be understood that the peeling force of the composite current collector 10 refers to the peeling force between the metal plating layer 300 and the film base material layer 100 .
  • Table 1 shows the peeling force test data of composite current collector 10.
  • the peeling force of the composite current collector 10 of the present invention is greater than the peeling force of the composite current collector 10 of the comparative example, and the peeling force of the composite current collector 10 is closely related to the thickness of the film base material layer 100 and the thickness of the metal plating layer 300 It has nothing to do with the material of the metal plating layer 300 and is related to the purity of the metal nickel layer 200 . The higher the purity of the metal nickel layer 200 , the greater the peeling force of the composite current collector 10 .

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Abstract

The present invention relates to a preparation method for a composite current collector, and a composite current collector. The preparation method for a composite current collector comprises the following steps: ionizing metal nickel to generate nickel ions; and under the action of a magnetic field, bombarding the two oppositely disposed surfaces of a thin film substrate layer with the nickel ions at a high speed, so as to form metal nickel layers on the two oppositely disposed surfaces of the thin film substrate layer. In the present invention, the nickel ions are used for bombarding the surfaces of the thin film substrate layer at a high speed, such that the nickel ions can be bonded to negatively charged polar groups on the surfaces of the thin film substrate layer to generate chemical bonds; and by arranging the metal nickel layers between a metal coating and the thin film substrate layer, the binding force and the stripping force between the metal coating and the thin film substrate layer can be improved, such that the metal coating and the thin film substrate layer are not prone to falling off, thereby ensuring the electrical properties and safety of a battery, and moreover the problems of defective products due to liability to layering during a slitting process and serious product defects caused by the phenomena of material falling during a sheet preparation process can be solved.

Description

复合集流体的制备方法及复合集流体Preparation method of composite current collector and composite current collector 技术领域Technical field
本发明涉及锂离子电池技术领域，特别是涉及一种复合集流体的制备方法及复合集流体。The present invention relates to the technical field of lithium ion batteries, and in particular to a preparation method of a composite current collector and a composite current collector.
背景技术Background technique
目前的复合集流体主要为铜集流体和铝集流体两种，其中铜集流体或者铝集流体均由两部分构成，包含设置于中间的薄膜基材层和设置于薄膜基材层相背设置的两个表面的金属镀层。金属镀层的厚度要求一般为0.5μm-1.5μm左右，制备复合集流体的方式是通过蒸镀工艺完成，但是由于金属镀层与薄膜基材层上的负电荷的极性基团的结合力比较差，导致金属镀层与薄膜基材层之间的剥离力差，导致复合集流体在分切的过程中容易发生分层，造成产品不良，也会导致电池极片在制片的过程中发生掉料现象，造成严重的产品缺陷；同时也会导致电池在使用过程中，电池内部进行呼吸式的膨胀与收缩，引起金属镀层与薄膜基材层发生脱落现象，进而影响电池内部的正负极界面，导致电池的电性能变差，同时也影响电池的安全性。The current composite current collectors are mainly copper current collectors and aluminum current collectors. The copper current collectors or aluminum current collectors are composed of two parts, including a thin film substrate layer in the middle and a thin film substrate layer arranged opposite to each other. Metal coating on both surfaces. The thickness requirement of the metal coating is generally about 0.5μm-1.5μm. The way to prepare the composite current collector is through evaporation process. However, the binding force between the metal coating and the negatively charged polar groups on the film substrate layer is relatively poor. , resulting in poor peeling force between the metal coating and the film substrate layer, causing the composite current collector to easily delaminate during the cutting process, resulting in defective products, and also causing the battery pole pieces to fall off during the production process. Phenomenon, causing serious product defects; at the same time, it will also cause the internal breathing expansion and contraction of the battery during use, causing the metal coating and the film substrate layer to fall off, thereby affecting the positive and negative electrode interfaces inside the battery. This causes the battery's electrical performance to deteriorate and also affects the battery's safety.
发明内容Contents of the invention
基于此，有必要提供一种能够提高金属镀层与薄膜基材层的结合力及剥离力，使得金属镀层与薄膜基材层不易发生脱落，从而保证电池的电性能及安全性，且能够解决在分切的过程中容易发生分层，造成产品不良及在制片的过程中发生掉料现象，造成严重的产品缺陷的问题的复合集流体的制备方法及复合 集流体。Based on this, it is necessary to provide a method that can improve the bonding force and peeling force of the metal coating and the film substrate layer, so that the metal coating and the film substrate layer are not easy to fall off, thereby ensuring the electrical performance and safety of the battery, and can solve the problem of Delamination is likely to occur during the cutting process, resulting in product defects and material falling out during the filmmaking process, resulting in a composite current collector preparation method and composite current collector causing serious product defects.
一种复合集流体的制备方法，包括以下步骤：A preparation method of composite current collector, including the following steps:
将金属镍进行电离，以生成镍离子；Ionizing metallic nickel to generate nickel ions;
在磁场作用下，使所述镍离子高速轰击薄膜基材层相背设置的两个表面，以在所述薄膜基材层相背设置的两个表面分别形成金属镍层；Under the action of a magnetic field, the nickel ions are bombarded at high speed on two opposite surfaces of the thin film base material layer, so as to form metallic nickel layers on the two opposite surfaces of the thin film base material layer;
在所述金属镍层的表面蒸镀金属镀层。A metal plating layer is evaporated on the surface of the metallic nickel layer.
在其中一个实施例中，所述金属镀层及所述金属镍层的纯度均≥99.8％。In one embodiment, the purity of the metal plating layer and the metal nickel layer is both ≥99.8%.
在其中一个实施例中，所述金属镀层为金属铝层或金属铜层。In one embodiment, the metal plating layer is a metal aluminum layer or a metal copper layer.
在其中一个实施例中，所述薄膜基材层的厚度范围为1μm-25μm，所述金属镀层的厚度范围为0.5μm-1.5μm。In one embodiment, the thickness of the film base material layer ranges from 1 μm to 25 μm, and the thickness of the metal plating layer ranges from 0.5 μm to 1.5 μm.
在其中一个实施例中，所述金属镍层的厚度范围为0.5μm-1μm。In one embodiment, the thickness of the metallic nickel layer ranges from 0.5 μm to 1 μm.
在其中一个实施例中，所述薄膜基材层的穿刺强度≥100gf，MD拉伸强度≥200MPa,TD拉伸强度≥200MPa，MD延伸率≥30％,TD延伸率≥30％。In one embodiment, the puncture strength of the film base material layer is ≥100gf, the MD tensile strength is ≥200MPa, the TD tensile strength is ≥200MPa, the MD elongation is ≥30%, and the TD elongation is ≥30%.
在其中一个实施例中，所述薄膜基材层包括绝缘高分子材料、绝缘高分子复合材料、导电高分子材料、导电高分子复合材料中的至少一种。In one embodiment, the film base material layer includes at least one of an insulating polymer material, an insulating polymer composite material, a conductive polymer material, and a conductive polymer composite material.
在其中一个实施例中，所述绝缘高分子材料包括聚酰胺(PA)、聚对苯二甲酸酯、聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PPE)、聚氯乙烯(PVC)、芳纶、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚对苯二甲酸丁二醇酯(PET)、聚对苯二甲酰对苯二胺(PPTA)、聚丙乙烯(PPE)、聚甲醛(POM)、环氧树脂、酚醛树脂、聚四氟乙烯(PTEE)、聚偏氟乙烯(PVDF)、硅橡胶、聚碳酸酯(PC)、聚乙烯醇(PVA)、聚乙二醇(PEG)、纤维素、淀粉、蛋白质、它们的衍生物、它们的交联物及它们的共聚物中的至少一种。In one embodiment, the insulating polymer material includes polyamide (PA), polyterephthalate, polyimide (PI), polyethylene (PE), polypropylene (PP), polystyrene Ethylene (PPE), polyvinyl chloride (PVC), aramid, acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PET), polyterephthalamide Phenylenediamine (PPTA), polypropylene (PPE), polyoxymethylene (POM), epoxy resin, phenolic resin, polytetrafluoroethylene (PTEE), polyvinylidene fluoride (PVDF), silicone rubber, polycarbonate (PC) ), at least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), cellulose, starch, protein, their derivatives, their cross-linked products and their copolymers.
在其中一个实施例中，所述绝缘高分子复合材料为所述绝缘高分子材料与 无机材料形成的复合材料。In one embodiment, the insulating polymer composite material is a composite material formed of the insulating polymer material and an inorganic material.
本申请还提供了一种复合集流体，包括：This application also provides a composite current collector, including:
所述薄膜基材层，所述薄膜基材层相背设置的两个表面上分别依次设有所述金属镍层和所述金属镀层。As for the film base material layer, the metal nickel layer and the metal plating layer are respectively provided on two surfaces of the film base material layer that are opposite to each other.
上述方案中，通过将金属镍进行电离，以生成镍离子，并在磁场作用下，使镍离子高速轰击薄膜基材层相背设置的两个表面，使带正电的镍离子能够与薄膜基材层表面的负电荷的极性基团进行结合，以在薄膜基材层的表面上形成更多的化学键，以提高薄膜基材层与金属镍层的结合力及剥离力；通过在金属镀层与薄膜基材层之间设置金属镍层，能够提高金属镀层与薄膜基材层的结合力及剥离力，使得金属镀层与薄膜基材层不易发生脱落，从而保证电池的电性能及安全性，且能够解决在分切的过程中容易发生分层，造成产品不良及在制片的过程中发生掉料现象，造成严重的产品缺陷的问题，确保产品质量。In the above scheme, metallic nickel is ionized to generate nickel ions, and under the action of a magnetic field, the nickel ions are bombarded at high speed on two opposite surfaces of the film substrate layer, so that the positively charged nickel ions can interact with the film substrate. The negatively charged polar groups on the surface of the material layer are combined to form more chemical bonds on the surface of the film base material layer to improve the bonding force and peeling force between the film base material layer and the metal nickel layer; through the metal plating layer Setting a metal nickel layer between the metal plating layer and the film base material layer can improve the bonding force and peeling force between the metal plating layer and the film base material layer, making the metal plating layer and the film base material layer less likely to fall off, thereby ensuring the electrical performance and safety of the battery. It can also solve the problem of delamination that easily occurs during the cutting process, resulting in defective products and material falling off during the filmmaking process, causing serious product defects, and ensures product quality.
附图说明Description of drawings
构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。The drawings forming a part of this application are used to provide a further understanding of the present invention. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without exerting creative efforts.
图1为本发明一实施例所示的复合集流体的结构示意图；Figure 1 is a schematic structural diagram of a composite current collector shown in an embodiment of the present invention;
图2为本发明一实施例所示的复合集流体的制备方法的步骤流程示意图；Figure 2 is a schematic flow chart of the steps of a method for preparing a composite current collector according to an embodiment of the present invention;
图3为本发明一对比例所示的复合集流体的制备方法的步骤流程示意图。FIG. 3 is a schematic flowchart of the steps of a preparation method of a composite current collector shown in a pair of proportions of the present invention.
附图标记说明Explanation of reference signs
10、复合集流体；100、薄膜基材层；200、金属镍层；300、金属镀层。10. Composite current collector; 100. Thin film substrate layer; 200. Metal nickel layer; 300. Metal plating layer.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施例的限制。In order to make the above objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, the present invention can be implemented in many other ways different from those described here. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
在本发明的描述中，需要理解的是，术语“中心”、“纵向”、“横向”、“长度”、“宽度”、“厚度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”、“顺时针”、“逆时针”、“轴向”、“径向”、“周向”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", " "Back", "Left", "Right", "Vertical", "Horizontal", "Top", "Bottom", "Inside", "Outside", "Clockwise", "Counterclockwise", "Axis" The orientations or positional relationships indicated by "radial direction", "circumferential direction", etc. are based on the orientations or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply the device or device referred to. Elements must have a specific orientation, be constructed and operate in a specific orientation and therefore are not to be construed as limitations of the invention.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。在本发明的描述中，“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include at least one of these features. In the description of the present invention, "plurality" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.
在本发明中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”、“固定”等术语应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或成一体；可以是机械连接，也可以是电连接；可以是直接相连，也 可以通过中间媒介间接相连，可以是两个元件内部的连通或两个元件的相互作用关系，除非另有明确的限定。对于本领域的普通技术人员而言，可以根据具体情况理解上述术语在本发明中的具体含义。In the present invention, unless otherwise clearly stated and limited, the terms "installation", "connection", "connection", "fixing" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a detachable connection. , or integrated into one; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interactive relationship between two elements, unless otherwise specified restrictions. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
在本发明中，除非另有明确的规定和限定，第一特征在第二特征“上”或“下”可以是第一和第二特征直接接触，或第一和第二特征通过中间媒介间接接触。而且，第一特征在第二特征“之上”、“上方”和“上面”可是第一特征在第二特征正上方或斜上方，或仅仅表示第一特征水平高度高于第二特征。第一特征在第二特征“之下”、“下方”和“下面”可以是第一特征在第二特征正下方或斜下方，或仅仅表示第一特征水平高度小于第二特征。In the present invention, unless otherwise expressly stated and limited, a first feature being "on" or "below" a second feature may mean that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. touch. Furthermore, the terms "above", "above" and "above" the first feature is above the second feature may mean that the first feature is directly above or diagonally above the second feature, or simply means that the first feature is higher in level than the second feature. "Below", "below" and "beneath" the first feature to the second feature may mean that the first feature is directly below or diagonally below the second feature, or simply means that the first feature has a smaller horizontal height than the second feature.
需要说明的是，当元件被称为“固定于”或“设置于”另一个元件，它可以直接在另一个元件上或者也可以存在居中的元件。当一个元件被认为是“连接”另一个元件，它可以是直接连接到另一个元件或者可能同时存在居中元件。本文所使用的术语“垂直的”、“水平的”、“上”、“下”、“左”、“右”以及类似的表述只是为了说明的目的，并不表示是唯一的实施方式。It should be noted that when an element is referred to as being "mounted" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is said to be "connected" to another element, it can be directly connected to the other element or there may also be intervening elements present. The terms "vertical", "horizontal", "upper", "lower", "left", "right" and similar expressions used herein are for illustrative purposes only and do not represent the only implementation manner.
请参阅图1及图2，本申请的一实施例还提供了一种复合集流体10的制备方法，包括以下步骤：Referring to Figures 1 and 2, an embodiment of the present application also provides a method for preparing a composite current collector 10, which includes the following steps:
步骤1：将金属镍进行电离，以生成镍离子。Step 1: Ionize metallic nickel to generate nickel ions.
步骤2：在磁场作用下，使镍离子高速轰击薄膜基材层100相背设置的两个表面，以在薄膜基材层100相背设置的两个表面分别形成金属镍层200。需要理解的是：在镍离子高速轰击薄膜基材层100相背设置的两个表面时，带正电的镍离子能够与薄膜基材层100表面的负电荷的极性基团进行结合，以在薄膜基材层100的表面上形成更多的化学键，以提高薄膜基材层100与金属镍层200的结合力及剥离力。Step 2: Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. It should be understood that when nickel ions bombard the two opposite surfaces of the film base material layer 100 at high speed, the positively charged nickel ions can combine with the negatively charged polar groups on the surface of the film base material layer 100 to form More chemical bonds are formed on the surface of the film base material layer 100 to improve the bonding force and peeling force between the film base material layer 100 and the metal nickel layer 200 .
镍离子轰击薄膜基材层100相背设置的两个表面的速度，本申请不做限制，可根据使用需求自行设定。示例性地，镍离子轰击薄膜基材层100相背设置的两个表面的速度为150m/s。The speed at which nickel ions bombard the two opposite surfaces of the thin film substrate layer 100 is not limited in this application and can be set according to the usage requirements. For example, the speed at which nickel ions bombard two surfaces of the thin film substrate layer 100 located opposite to each other is 150 m/s.
更需要理解的是：在金属镍进行电离，以生成镍离子及在薄膜基材层100相背设置的两个表面形成金属镍层200的过程均在真空环境下进行，以减少金属镍层200内的杂质。What needs to be more understood is that the processes of ionizing the metal nickel to generate nickel ions and forming the metal nickel layer 200 on the two opposite surfaces of the film base material layer 100 are all carried out in a vacuum environment to reduce the metal nickel layer 200 impurities inside.
步骤3：在金属镍层200的表面蒸镀金属镀层300。在复合集流体10制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Step 3: evaporate the metal plating layer 300 on the surface of the metal nickel layer 200. After the preparation of the composite current collector 10 is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
请参阅图1，根据本申请的一些实施例，可选地，金属镀层300的纯度≥99.8％。也就是说，本申请中的金属镀层300采用的是高纯度的金属。具体地，金属镀层300为金属铝层或金属铜层。金属镍层200的纯度均≥99.8％。也就是说，本申请中的金属镍层200采用的是高纯度的金属镍。高纯度的金属镍具有优良的耐蚀性，较高的电真空性能和电磁控制性能。Referring to Figure 1, according to some embodiments of the present application, optionally, the purity of the metal plating layer 300 is ≥99.8%. That is to say, the metal plating layer 300 in this application uses high-purity metal. Specifically, the metal plating layer 300 is a metal aluminum layer or a metal copper layer. The purity of the metallic nickel layer 200 is ≥99.8%. That is to say, the metallic nickel layer 200 in this application uses high-purity metallic nickel. High-purity metallic nickel has excellent corrosion resistance, high electric vacuum performance and electromagnetic control performance.
在一个实施例中，金属镀层300采用金属铝层，金属铝层的纯度≥99.8％。高纯度的金属铝层具有低的变形抗力、高的电导率及良好的塑性等性能。在另一个实施例中，金属镀层300采用金属铜层，金属铜层的纯度≥99.8％。高纯度的金属铜层具有良好的延展性、传热性及导电性。In one embodiment, the metal coating 300 adopts a metal aluminum layer, and the purity of the metal aluminum layer is ≥99.8%. The high-purity metallic aluminum layer has low deformation resistance, high electrical conductivity and good plasticity. In another embodiment, the metal plating layer 300 adopts a metallic copper layer, and the purity of the metallic copper layer is ≥99.8%. The high-purity metallic copper layer has good ductility, heat transfer and electrical conductivity.
金属镀层300与高分子薄膜层之间的剥离力≥8N/m。示例性地，金属镀层300与薄膜基材层100之间的剥离力为10N/m。金属镀层300与薄膜基材层100之间的剥离力较高，能够使得金属镀层300与薄膜基材层100之间不易发生脱落的现象，从而保证电池的电性能及安全性。The peeling force between the metal coating 300 and the polymer film layer is ≥8N/m. For example, the peeling force between the metal plating layer 300 and the film base material layer 100 is 10 N/m. The peeling force between the metal plating layer 300 and the film base material layer 100 is relatively high, which can prevent the metal plating layer 300 from falling off from the film base material layer 100, thus ensuring the electrical performance and safety of the battery.
请参阅图1，根据本申请的一些实施例，可选地，薄膜基材层100的厚度范围为1μm-25μm，金属镀层300的厚度范围为0.5μm-1.5μm。金属镍层200 的厚度范围为0.5μm-1μm。需要理解的是：本申请的复合集流体10的厚度范围为3μm-30μm。示例性地，薄膜基材层100的厚度为20μm，金属镀层300的厚度为1.2μm。金属镍层200的厚度为1μm。Referring to Figure 1, according to some embodiments of the present application, optionally, the thickness of the film base material layer 100 ranges from 1 μm to 25 μm, and the thickness of the metal plating layer 300 ranges from 0.5 μm to 1.5 μm. The thickness of the metallic nickel layer 200 ranges from 0.5 μm to 1 μm. It should be understood that the thickness of the composite current collector 10 of the present application ranges from 3 μm to 30 μm. For example, the thickness of the film base material layer 100 is 20 μm, and the thickness of the metal plating layer 300 is 1.2 μm. The thickness of the metallic nickel layer 200 is 1 μm.
请参阅图1，根据本申请的一些实施例，可选地，薄膜基材层100的穿刺强度≥100gf，MD拉伸强度≥200MPa,TD拉伸强度≥200MPa，MD延伸率≥30％,TD延伸率≥30％。示例性地，薄膜基材层100的穿刺强度≥300f，MD拉伸强度≥400MPa,TD拉伸强度≥400MPa，MD延伸率≥50％,TD延伸率≥50％。需要说明的是：MD(Machine Direction，机械方向)是指纵向，TD(Transverse Direction，垂直于机械方向)是指横向。Please refer to Figure 1. According to some embodiments of the present application, optionally, the puncture strength of the film base material layer 100 is ≥100gf, the MD tensile strength is ≥200MPa, the TD tensile strength is ≥200MPa, and the MD elongation is ≥30%, TD. Elongation ≥30%. For example, the puncture strength of the film base material layer 100 is ≥300f, the MD tensile strength is ≥400MPa, the TD tensile strength is ≥400MPa, the MD elongation is ≥50%, and the TD elongation is ≥50%. It should be noted that: MD (Machine Direction, machine direction) refers to the longitudinal direction, and TD (Transverse Direction, perpendicular to the machine direction) refers to the transverse direction.
需要说明的是：对于薄膜基材层100的穿刺强度、MD拉伸强度、TD拉伸强度、MD延伸率、TD延伸率的上限本申请不做限制，可根据使用需要自行设定。对于薄膜基材层100的穿刺强度的下限不得低于100gf，MD拉伸强度的下限不得低于200MPa，TD拉伸强度的下限不得低于200MPa，MD延伸率的下限不得低于30％，TD延伸率的下限不得低于30％，否则会影响薄膜基材层100的力学性能，最终影响复合集流体10的穿刺强度、MD拉伸强度、TD拉伸强度、MD延伸率、TD延伸率。It should be noted that the upper limit of the puncture strength, MD tensile strength, TD tensile strength, MD elongation, and TD elongation of the film base material layer 100 is not limited in this application and can be set according to the needs of use. The lower limit of the puncture strength of the film base material layer 100 shall not be less than 100gf, the lower limit of the MD tensile strength shall not be less than 200MPa, the lower limit of the TD tensile strength shall not be less than 200MPa, the lower limit of the MD elongation shall not be less than 30%, TD The lower limit of the elongation shall not be less than 30%, otherwise the mechanical properties of the film base material layer 100 will be affected, and ultimately the puncture strength, MD tensile strength, TD tensile strength, MD elongation, and TD elongation of the composite current collector 10 will be affected.
请参阅图1，根据本申请的一些实施例，可选地，薄膜基材层100包括绝缘高分子材料、绝缘高分子复合材料、导电高分子材料、导电高分子复合材料中的至少一种。Referring to Figure 1, according to some embodiments of the present application, optionally, the film base material layer 100 includes at least one of an insulating polymer material, an insulating polymer composite material, a conductive polymer material, and a conductive polymer composite material.
具体地，绝缘高分子材料包括聚酰胺(PA)、聚对苯二甲酸酯、聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PPE)、聚氯乙烯(PVC)、芳纶、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚对苯二甲酸丁二醇酯(PET)、聚对苯二甲酰对苯二胺(PPTA)、聚丙乙烯(PPE)、聚甲醛(POM)、环氧树脂、酚醛树脂、聚四氟乙 烯(PTEE)、聚偏氟乙烯(PVDF)、硅橡胶(Silicone rubber)、聚碳酸酯(PC)、聚乙烯醇(PVA)、聚乙二醇(PEG)、纤维素、淀粉、蛋白质、它们的衍生物、它们的交联物及它们的共聚物中的至少一种。Specifically, insulating polymer materials include polyamide (PA), polyterephthalate, polyimide (PI), polyethylene (PE), polypropylene (PP), polystyrene (PPE), polyethylene Vinyl chloride (PVC), aramid, acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PET), polyphenylene terephthalamide (PPTA) , polypropylene (PPE), polyoxymethylene (POM), epoxy resin, phenolic resin, polytetrafluoroethylene (PTEE), polyvinylidene fluoride (PVDF), silicone rubber (Silicone rubber), polycarbonate (PC), At least one of polyvinyl alcohol (PVA), polyethylene glycol (PEG), cellulose, starch, protein, their derivatives, their cross-linked products and their copolymers.
上述的绝缘高分子复合材料为绝缘高分子材料与无机材料形成的复合材料。其中，无机材料可以是陶瓷材料、玻璃材料、陶瓷复合材料中的至少一种。The above-mentioned insulating polymer composite material is a composite material formed of an insulating polymer material and an inorganic material. The inorganic material may be at least one of ceramic materials, glass materials, and ceramic composite materials.
上述的导电高分子材料可以是经掺杂的聚氮化硫、经掺杂的聚乙炔中的至少一种。The above-mentioned conductive polymer material may be at least one of doped polysulfide nitride and doped polyacetylene.
上述的导电高分子复合材料，可以是绝缘高分子材料与导电材料形成的复合材料。具体地，导电材料可以是导电碳材料、金属材料、复合导电材料中的至少一种。更具体地，导电碳材料选自碳黑、碳纳米管、石墨、乙炔黑、石墨烯中的至少一种。金属材料选自金属镍、金属铁、金属铜、金属铝或上述金属的合金中的至少一种。复合导电材料选自金属镍包覆的石墨粉、金属镍包覆的碳纤维中的至少一种。The above-mentioned conductive polymer composite material may be a composite material formed of an insulating polymer material and a conductive material. Specifically, the conductive material may be at least one of conductive carbon materials, metal materials, and composite conductive materials. More specifically, the conductive carbon material is selected from at least one of carbon black, carbon nanotubes, graphite, acetylene black, and graphene. The metal material is selected from at least one of metal nickel, metal iron, metal copper, metal aluminum or alloys of the above metals. The composite conductive material is selected from at least one of metal nickel-coated graphite powder and metal nickel-coated carbon fiber.
请参阅图1，本申请的一实施例还提供了一种复合集流体10，包括薄膜基材层100，薄膜基材层100相背设置的两个表面上分别依次设有金属镍层200和金属镀层300。Please refer to Figure 1. An embodiment of the present application also provides a composite current collector 10, which includes a film base material layer 100. Two surfaces of the film base material layer 100 arranged opposite to each other are respectively provided with a metal nickel layer 200 and a metal nickel layer 200. Metal plating 300.
通过在薄膜基材层100与金属镀层300设置金属镍层200，能够提高薄膜基材层100与金属镀层300的结合力及剥离力，使得金属镀层300与薄膜基材层100不易发生脱落的现象，从而保证电池的电性能及安全性，提高了产品的品质。By disposing the metal nickel layer 200 on the film base material layer 100 and the metal plating layer 300, the bonding force and peeling force between the film base material layer 100 and the metal plating layer 300 can be improved, making the metal plating layer 300 and the film base material layer 100 less likely to fall off. , thereby ensuring the electrical performance and safety of the battery and improving the quality of the product.
复合集流体10的穿刺强度≥50gf，MD拉伸强度≥150MPa,TD拉伸强度≥150MPa，MD延伸率≥10％,TD延伸率≥10％。示例性地，复合集流体10的穿刺强度为130gf，MD拉伸强度为300MPa，TD拉伸强度为300MPa。MD延伸率为60％，TD延伸率为60％。The puncture strength of the composite current collector 10 is ≥50gf, the MD tensile strength is ≥150MPa, the TD tensile strength is ≥150MPa, the MD elongation is ≥10%, and the TD elongation is ≥10%. For example, the composite current collector 10 has a puncture strength of 130 gf, an MD tensile strength of 300 MPa, and a TD tensile strength of 300 MPa. The MD elongation is 60% and the TD elongation is 60%.
实施例：Example:
下述实施例更具体地描述了本发明公开的内容，这些实施例仅仅用于阐述性说明，因为在本发明公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。The present disclosure is more particularly described in the following examples, which are intended to be illustrative only, as it will be apparent to those skilled in the art that various modifications and changes can be made within the scope of the present disclosure. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods, and can be directly were used without further processing and the equipment used in the examples is commercially available.
复合集流体10的制备方法Preparation method of composite current collector 10
实施例1：Example 1:
步骤1：选取6μm的薄膜基材层100、99.9％纯度的金属铝层及99.9％纯度的金属镍。其中，薄膜基材层100采用聚对苯二甲酸丁二醇酯(PET)。Step 1: Select a 6 μm film substrate layer 100, a 99.9% purity metal aluminum layer, and a 99.9% purity metal nickel layer. Among them, the film base material layer 100 is made of polybutylene terephthalate (PET).
步骤2：将金属镍进行电离，以生成镍离子。具体地，镍离子为+2价。Step 2: Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
步骤3：在磁场作用下，使镍离子高速轰击薄膜基材层100相背设置的两个表面，以在薄膜基材层100相背设置的两个表面分别形成金属镍层200。具体地，在磁场作用下，镍离子以150m/s的速度轰击薄膜基材层100相背设置的两个表面。其中，金属镍层200的厚度为0.5μm。Step 3: Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 0.5 μm.
步骤4：在金属镍层200的表面蒸镀金属镀层300。其中，金属镀层300的厚度为0.5μm，金属镍层200为金属铝层。Step 4: evaporate the metal plating layer 300 on the surface of the metal nickel layer 200. Among them, the thickness of the metal plating layer 300 is 0.5 μm, and the metal nickel layer 200 is a metal aluminum layer.
最终制得8μm的复合集流体10，在制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Finally, an 8 μm composite current collector 10 is produced. After the preparation is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
实施例2：Example 2:
步骤1：选取25μm的薄膜基材层100、99.9％纯度的金属铜层及99.9％纯度的金属镍。其中，薄膜基材层100采用聚对苯二甲酸丁二醇酯(PET)。Step 1: Select a 25 μm film substrate layer 100, a 99.9% purity metal copper layer, and a 99.9% purity metal nickel layer. Among them, the film base material layer 100 is made of polybutylene terephthalate (PET).
步骤2：将金属镍进行电离，以生成镍离子。具体地，镍离子为+2价。Step 2: Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
步骤3：在磁场作用下，使镍离子高速轰击薄膜基材层100相背设置的两个表面，以在薄膜基材层100相背设置的两个表面分别形成金属镍层200。具体地，在磁场作用下，镍离子以150m/s的速度轰击薄膜基材层100相背设置的两个表面。其中，金属镍层200的厚度为1μm。Step 3: Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 1 μm.
步骤4：在金属镍层200的表面蒸镀金属镀层300。其中，金属镀层300的厚度为1.5μm，金属镍层200为金属铜层。Step 4: evaporate the metal plating layer 300 on the surface of the metal nickel layer 200. Among them, the thickness of the metal plating layer 300 is 1.5 μm, and the metal nickel layer 200 is a metal copper layer.
最终制得30μm的复合集流体10，在制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Finally, a 30 μm composite current collector 10 is produced. After the preparation is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
实施例3Example 3
步骤1：选取1μm的薄膜基材层100、99.9％纯度的金属铝层及99.8％纯度的金属镍。其中，薄膜基材层100采用聚对苯二甲酸丁二醇酯(PET)。Step 1: Select a 1 μm thin film substrate layer 100, a 99.9% purity metal aluminum layer, and a 99.8% purity metal nickel layer. Among them, the film base material layer 100 is made of polybutylene terephthalate (PET).
步骤2：将金属镍进行电离，以生成镍离子。具体地，镍离子为+2价。Step 2: Ionize metallic nickel to generate nickel ions. Specifically, nickel ions have a valence of +2.
步骤3：在磁场作用下，使镍离子高速轰击薄膜基材层100相背设置的两个表面，以在薄膜基材层100相背设置的两个表面分别形成金属镍层200。具体地，在磁场作用下，镍离子以150m/s的速度轰击薄膜基材层100相背设置的两个表面。其中，金属镍层200的厚度为0.5μm。Step 3: Under the action of a magnetic field, nickel ions are bombarded with high speed on two opposite surfaces of the thin film base material layer 100 to form metallic nickel layers 200 on the two opposite surfaces of the thin film base material layer 100 respectively. Specifically, under the action of a magnetic field, nickel ions bombard two opposite surfaces of the film base material layer 100 at a speed of 150 m/s. The thickness of the metallic nickel layer 200 is 0.5 μm.
步骤4：在金属镍层200的表面蒸镀金属镀层300。其中，金属镀层300的厚度为0.5μm，金属镍层200为金属铜层。Step 4: evaporate the metal plating layer 300 on the surface of the metal nickel layer 200. Among them, the thickness of the metal plating layer 300 is 0.5 μm, and the metal nickel layer 200 is a metal copper layer.
最终制得3μm的复合集流体10，在制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Finally, a 3 μm composite current collector 10 is produced. After the preparation is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
对比例1：Comparative example 1:
请参阅图3，本对比例提供的复合集流体10的制备方法，包括以下步骤：Please refer to Figure 3. The preparation method of the composite current collector 10 provided in this comparative example includes the following steps:
步骤1：选取6μm的薄膜基材层100及99.9％纯度的金属铝层。其中，薄膜基材层100采用聚对苯二甲酸丁二醇酯(PET)。Step 1: Select a 6 μm film substrate layer 100 and a 99.9% purity metal aluminum layer. Among them, the film base material layer 100 is made of polybutylene terephthalate (PET).
步骤2：将6μm的薄膜基材层100及99.9％纯度的金属铝层分别投入真空镀膜设备内，并在薄膜基材层100相背设置的两个表面蒸镀金属铝层，即可得到所需的复合集流体10。其中，本实施例中，金属铝层的厚度为1μm。Step 2: Put the 6 μm thin film base material layer 100 and the 99.9% purity metal aluminum layer into the vacuum coating equipment respectively, and evaporate the metal aluminum layers on the two opposite surfaces of the thin film base material layer 100 to obtain the result. The required composite current collector 10. In this embodiment, the thickness of the metallic aluminum layer is 1 μm.
最终制得8μm的复合集流体10。在复合集流体10制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Finally, an 8 μm composite current collector 10 was produced. After the preparation of the composite current collector 10 is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
对比例2：Comparative example 2:
本对比例提供的复合集流体10的制备方法，包括以下步骤：The preparation method of the composite current collector 10 provided in this comparative example includes the following steps:
步骤1：选取25μm的薄膜基材层100及99.9％纯度的金属铝层。其中，薄膜基材层100采用聚对苯二甲酸丁二醇酯(PET)。Step 1: Select a 25 μm film substrate layer 100 and a 99.9% purity metal aluminum layer. Among them, the film base material layer 100 is made of polybutylene terephthalate (PET).
步骤2：将25μm的薄膜基材层100及99.9％纯度的金属铝层分别投入真空镀膜设备内，并在薄膜基材层100相背设置的两个表面蒸镀金属铝层，即可得到所需的复合集流体10。其中，本实施例中，金属铝层的厚度为2.5μm。Step 2: Put the 25 μm thin film base material layer 100 and the 99.9% purity metal aluminum layer into the vacuum coating equipment respectively, and evaporate the metal aluminum layers on the two opposite surfaces of the thin film base material layer 100 to obtain the result. The required composite current collector 10. In this embodiment, the thickness of the metallic aluminum layer is 2.5 μm.
最终制得30μm的复合集流体10。在复合集流体10制备完成后，对复合集流体10进行分切收卷以及真空包装作业。Finally, a 30 μm composite current collector 10 was produced. After the preparation of the composite current collector 10 is completed, the composite current collector 10 is cut, rolled, and vacuum packed.
对实施例1-3、对比例1-2的复合集流体10的剥离力进行测试，得到如表1所述的效果数据。需要理解的是：复合集流体10的剥离力是指金属镀层300与薄膜基材层100之间的剥离力。The peeling force of the composite current collector 10 of Examples 1-3 and Comparative Examples 1-2 was tested, and the effect data as shown in Table 1 was obtained. It should be understood that the peeling force of the composite current collector 10 refers to the peeling force between the metal plating layer 300 and the film base material layer 100 .
表1为复合集流体10的剥离力测试数据。Table 1 shows the peeling force test data of composite current collector 10.
方案plan 剥离力(N/M)Peeling force(N/M)
实施例1Example 1 1010
实施例2Example 2 1010
实施例3Example 3 9.69.6
对比例1Comparative example 1 33
对比例2Comparative example 2 33
表1Table 1
从上表可以看出本发明的复合集流体10的剥离力大于对比例的复合集流体10的剥离力，且复合集流体10的剥离力与薄膜基材层100的厚度、金属镀层300的厚度及金属镀层300的材料无关，与金属镍层200的纯度有关，金属镍层200的纯度越高，复合集流体10的剥离力越大。It can be seen from the above table that the peeling force of the composite current collector 10 of the present invention is greater than the peeling force of the composite current collector 10 of the comparative example, and the peeling force of the composite current collector 10 is closely related to the thickness of the film base material layer 100 and the thickness of the metal plating layer 300 It has nothing to do with the material of the metal plating layer 300 and is related to the purity of the metal nickel layer 200 . The higher the purity of the metal nickel layer 200 , the greater the peeling force of the composite current collector 10 .
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发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the invention. 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 invention, and these all belong to the protection scope of the present invention. Therefore, the scope of protection of the patent of the present invention should be determined by the appended claims.

Claims (10)

  1. 一种复合集流体的制备方法，其特征在于，包括以下步骤：A method for preparing a composite current collector, characterized in that it includes the following steps:
    将金属镍进行电离，以生成镍离子；Ionizing metallic nickel to generate nickel ions;
    在磁场作用下，使所述镍离子高速轰击薄膜基材层相背设置的两个表面，以在所述薄膜基材层相背设置的两个表面分别形成金属镍层；Under the action of a magnetic field, the nickel ions are bombarded at high speed on two opposite surfaces of the thin film base material layer, so as to form metallic nickel layers on the two opposite surfaces of the thin film base material layer;
    在所述金属镍层的表面蒸镀金属镀层。A metal plating layer is evaporated on the surface of the metallic nickel layer.
  2. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述金属镀层及所述金属镍层的纯度均≥99.8％。The method for preparing a composite current collector according to claim 1, wherein the purity of the metal plating layer and the metal nickel layer is both ≥99.8%.
  3. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述金属镀层为金属铝层或金属铜层。The method for preparing a composite current collector according to claim 1, wherein the metal plating layer is a metal aluminum layer or a metal copper layer.
  4. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述薄膜基材层的厚度范围为1μm-25μm，所述金属镀层的厚度范围为0.5μm-1.5μm。The method for preparing a composite current collector according to claim 1, wherein the thickness of the film base material layer ranges from 1 μm to 25 μm, and the thickness of the metal plating layer ranges from 0.5 μm to 1.5 μm.
  5. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述金属镍层的厚度范围为0.5μm-1μm。The method for preparing a composite current collector according to claim 1, wherein the thickness of the metallic nickel layer ranges from 0.5 μm to 1 μm.
  6. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述薄膜基材层的穿刺强度≥100gf，MD拉伸强度≥200MPa,TD拉伸强度≥200MPa，MD延伸率≥30％,TD延伸率≥30％。The preparation method of composite current collector according to claim 1, characterized in that the puncture strength of the film base material layer is ≥ 100gf, the MD tensile strength is ≥ 200 MPa, the TD tensile strength is ≥ 200 MPa, and the MD elongation is ≥ 30%. , TD elongation ≥ 30%.
  7. 根据权利要求1所述的复合集流体的制备方法，其特征在于，所述薄膜基材层包括绝缘高分子材料、绝缘高分子复合材料、导电高分子材料、导电高分子复合材料中的至少一种。The method for preparing a composite current collector according to claim 1, wherein the film base material layer includes at least one of an insulating polymer material, an insulating polymer composite material, a conductive polymer material, and a conductive polymer composite material. kind.
  8. 根据权利要求7所述的复合集流体的制备方法，其特征在于，所述绝缘高分子材料包括聚酰胺(PA)、聚对苯二甲酸酯、聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PPE)、聚氯乙烯(PVC)、芳纶、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、聚对苯二甲酸丁二醇酯(PET)、聚对苯二甲酰对苯二胺(PPTA)、 聚丙乙烯(PPE)、聚甲醛(POM)、环氧树脂、酚醛树脂、聚四氟乙烯(PTEE)、聚偏氟乙烯(PVDF)、硅橡胶、聚碳酸酯(PC)、聚乙烯醇(PVA)、聚乙二醇(PEG)、纤维素、淀粉、蛋白质、它们的衍生物、它们的交联物及它们的共聚物中的至少一种。The method for preparing a composite current collector according to claim 7, wherein the insulating polymer material includes polyamide (PA), polyterephthalate, polyimide (PI), polyethylene ( PE), polypropylene (PP), polystyrene (PPE), polyvinyl chloride (PVC), aramid, acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PET), polyphenylene terephthalamide (PPTA), polypropylene (PPE), polyoxymethylene (POM), epoxy resin, phenolic resin, polytetrafluoroethylene (PTEE), polyvinylidene fluoride ( PVDF), silicone rubber, polycarbonate (PC), polyvinyl alcohol (PVA), polyethylene glycol (PEG), cellulose, starch, protein, their derivatives, their cross-linked products and their copolymers at least one of them.
  9. 根据权利要求7所述的复合集流体的制备方法，其特征在于，所述绝缘高分子复合材料为所述绝缘高分子材料与无机材料形成的复合材料。The method for preparing a composite current collector according to claim 7, wherein the insulating polymer composite material is a composite material formed of the insulating polymer material and an inorganic material.
  10. 一种采用如权利要求1-9任一所述的复合集流体的制备方法制备的复合集流体，其特征在于，包括：A composite current collector prepared by the preparation method of a composite current collector according to any one of claims 1 to 9, characterized in that it includes:
    所述薄膜基材层，所述薄膜基材层相背设置的两个表面上分别依次设有所述金属镍层和所述金属镀层。As for the film base material layer, the metal nickel layer and the metal plating layer are respectively provided on two surfaces of the film base material layer that are opposite to each other.
PCT/CN2022/116777 2022-06-29 2022-09-02 Preparation method for composite current collector, and composite current collector WO2024000803A1 (en)

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CN111748764A (en) * 2020-07-10 2020-10-09 北京市辐射中心 Preparation method and device of negative current collector
CN113745525A (en) * 2021-06-16 2021-12-03 浙江柔震科技有限公司 Flexible composite plastic film and preparation and test method thereof
CN114015994A (en) * 2021-11-03 2022-02-08 合肥国轩高科动力能源有限公司 Preparation method of ultrathin composite current collector

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010218971A (en) * 2009-03-18 2010-09-30 Toyota Motor Corp Manufacturing method of current collector for nonaqueous electrolyte secondary battery, and current collector
CN106981665A (en) * 2017-04-14 2017-07-25 深圳鑫智美科技有限公司 A kind of negative current collector, its preparation method and its application
CN111748764A (en) * 2020-07-10 2020-10-09 北京市辐射中心 Preparation method and device of negative current collector
CN113745525A (en) * 2021-06-16 2021-12-03 浙江柔震科技有限公司 Flexible composite plastic film and preparation and test method thereof
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