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WO2024050722A1 - Film de polyester composite, son procédé de préparation et son utilisation - Google Patents

Film de polyester composite, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2024050722A1
WO2024050722A1 PCT/CN2022/117593 CN2022117593W WO2024050722A1 WO 2024050722 A1 WO2024050722 A1 WO 2024050722A1 CN 2022117593 W CN2022117593 W CN 2022117593W WO 2024050722 A1 WO2024050722 A1 WO 2024050722A1
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WO
WIPO (PCT)
Prior art keywords
polyester
parts
composite
oxygen
polyester film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2022/117593
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English (en)
Chinese (zh)
Inventor
朱中亚
王帅
夏建中
李学法
张国平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou Nanopore New Materials Technology Co Ltd
Original Assignee
Yangzhou Nanopore New Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou Nanopore New Materials Technology Co Ltd filed Critical Yangzhou Nanopore New Materials Technology Co Ltd
Priority to PCT/CN2022/117593 priority Critical patent/WO2024050722A1/fr
Priority to PCT/CN2023/117459 priority patent/WO2024051776A1/fr
Publication of WO2024050722A1 publication Critical patent/WO2024050722A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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 technical field of polymer materials, and in particular to a composite polyester film and its preparation method and application.
  • the polymer film As the base film layer of the composite current collector, the polymer film has the characteristics of high tensile strength, soft texture, low thermal expansion coefficient, and shrinkage when exposed to heat, which can reduce short circuits inside the battery when the composite current collector is used in batteries. Risk, reduce the risk of battery heating, burning or explosion, and improve battery safety.
  • the traditional process of preparing composite current collectors using polyester film as the base film (1) The bonding force between the polyester film and the conductive layer is weak, and the conductive layer is easy to fall off during the current collector preparation process. This results in a low yield rate of composite current collectors; (2) poor mechanical properties and prone to membrane rupture during the preparation process.
  • the composite polyester film has good surface adhesion, can improve the bonding force between the polyester film and the conductive layer, and reduces the cost of current collector preparation.
  • the probability of the conductive layer falling off during the process; the composite polyester film also has good mechanical properties, which can reduce the probability of membrane rupture during the preparation process of the current collector, thereby improving the yield rate of the composite current collector.
  • this application provides a composite polyester film, including: an intermediate layer and a first outer layer and a second outer layer respectively located on two opposite surfaces of the intermediate layer;
  • the middle layer includes the following components by mass:
  • the first outer layer includes the following mass parts of each component:
  • the second outer layer includes the following mass parts of each component:
  • the oxygen-containing functional group modified polyester includes pentaerythritol-modified polyester, glycerol-modified polyester, polytetrahydrofuran ether-modified polyester, pyromellitic dianhydride-modified One or more of polyester, 2,5-furandicarboxylic acid modified polyester, hydroxyl-terminated hyperbranched polyester, and cetyl-terminated hyperbranched polyester.
  • the characteristic viscosity of the oxygen-containing functional group modified polyester is 0.600-0.750 dL/g.
  • the molecular weight distribution of the oxygen-containing functional group modified polyester is 1.7-2.5.
  • the molar proportion of modified units in the oxygen-containing functional group modified polyester is 5% to 15%.
  • the polyester includes polyethylene terephthalate and its derivatives, polyethylene 2,6-naphthalate and its derivatives, polybutylene terephthalate Ester and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate-1,4-cyclohexanedimethanol, poly2, Trimethylene 6-naphthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene 2,6-naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate One or more of alcohol esters and their derivatives, polybutylene adipate terephthalate and its derivatives, and polyarylate and its derivatives.
  • the polyester has an intrinsic viscosity of 0.600 to 0.800 dL/g.
  • the polyester has a molecular weight distribution of 1.7 to 2.5.
  • the middle layer further includes additives with a mass fraction of 0.1 to 1 part.
  • the first outer layer further includes additives in a mass fraction of 0.1 to 1 part.
  • the second outer layer further includes additives with a mass fraction of 0.1 to 1 part.
  • the additives include one or more of slip agents, antioxidants, antistatic agents, and nucleating agents.
  • the average particle size of the additive is less than or equal to 30% of the thickness of the layer in which the additive is located.
  • the thickness ratio of the middle layer, the first outer layer and the second outer layer is (70 ⁇ 90): (5 ⁇ 15): (5 ⁇ 15).
  • this application provides a method for preparing a composite polyester film, including:
  • the film is stretched.
  • the stretching includes transverse stretching and longitudinal stretching.
  • the transverse stretching ratio is (3-4):1.
  • the longitudinal stretching ratio is (3-5):1.
  • the stretching further includes: heat treating the film.
  • the present application provides a composite current collector, including: a composite polyester film as described in any one of the above and a conductive layer located on at least one surface of the composite polyester film.
  • the present application also provides a battery, including the composite current collector as described in any one of the above.
  • this application also provides an electronic product, including the above-mentioned battery.
  • the components of the above-mentioned composite polyester film include polyester and oxygen-containing functional group modified polyester, and its structure is a three-layer structure of a first outer layer-a middle layer-a second outer layer.
  • An appropriate amount of oxygen-containing functional group-modified polyester is blended into the outer polyester raw material.
  • Oxygen-containing functional group modification can give the polyester a branched structure and increase the content of oxygen-containing functional groups in the polyester molecular chain, thereby inhibiting the crystallization of the surface polyester. , to increase the free volume of the surface polyester.
  • the increase in the free volume and surface tension of the surface polyester can promote the adhesion performance of the polyester film surface.
  • the oxygen-containing functional group-modified polyester can improve the crystallinity and plasticity of the middle layer of the polyester film and improve the mechanical properties of the polyester film.
  • the above-mentioned preparation method of the composite polyester film adopts co-extrusion and stretching methods, and blends the functional material oxygen-containing functional group-modified polyester into the main material polyester of each layer.
  • the crystallinity of the main material is achieved by regulating the amount of functional materials.
  • plasticity control combined with the corresponding film-forming process, can prepare a polyester film with improved surface adhesion and mechanical properties, reducing the probability of the conductive layer falling off during the current collector preparation process, thereby improving the yield rate of the composite current collector. .
  • the composite current collector prepared with the above-mentioned composite polyester film as the supporting layer has an improved bonding force between the supporting layer and the conductive layer, which can reduce the risk of the conductive layer falling off during the preparation process and improve the yield.
  • Figure 1 is a schematic structural diagram of a composite polyester film provided by an embodiment of the present application.
  • Figure 2 is a flow chart of a preparation method of a composite polyester film provided by an embodiment of the present application
  • Figure 3 is a schematic diagram of a composite current collector provided by an embodiment of the present application.
  • First outer layer 2. Middle layer; 3. Second outer layer; 4. First protective layer; 5. First conductive layer; 6. Composite polyester film; 7. Second conductive layer; 8. Second protective 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.
  • an embodiment of the present application provides a composite polyester film, including: an intermediate layer 2 and a first outer layer 1 and a second outer layer 3 respectively located on two opposite surfaces of the intermediate layer;
  • the middle layer includes the following components by mass:
  • the first outer layer includes the following mass parts of each component:
  • the second outer layer includes the following mass parts of each component:
  • the components of the composite polyester film include polyester and oxygen-containing functional group modified polyester, and its structure is a three-layer structure of a first outer layer-a middle layer-a second outer layer. Blend an appropriate amount of oxygen-containing functional group-modified polyester and additives into the polyester raw material of the outer layer.
  • the oxygen-containing functional group modification can endow the polyester with branches. structure and increase the content of oxygen-containing functional groups in the molecular chain of polyester. The branched structure with higher content makes it more difficult for polyester polymers to be arranged regularly.
  • the intermolecular force increases, which also causes high It becomes more difficult to arrange the molecules in a regular manner, thereby inhibiting the crystallization of the surface polyester and increasing the free volume of the surface polyester; the increase in the free volume and surface tension of the surface polyester can make the surface of the polyester film have better adhesion.
  • a smaller amount of oxygen-containing functional group-modified polyester is blended in the middle layer.
  • the oxygen-containing functional group-modified polyester can improve the middle layer of the polyester film.
  • the crystallinity and plasticity of the layer can also improve the mechanical properties of the composite polyester film.
  • the selection of polyester and oxygen-containing functional group-modified polyester in each layer may be the same or different.
  • the oxygen-containing functional group-modified polyester includes pentaerythritol-modified polyester, glycerol-modified polyester, polytetrahydrofuran ether-modified polyester, pyromellitic dianhydride-modified polyester.
  • pentaerythritol-modified polyester glycerol-modified polyester
  • polytetrahydrofuran ether-modified polyester pyromellitic dianhydride-modified polyester.
  • ester, 2,5-furandicarboxylic acid modified polyester, hydroxyl-terminated hyperbranched polyester, and cetyl-terminated hyperbranched polyester is one or more of ester, 2,5-furandicarboxylic acid modified polyester, hydroxyl-terminated hyperbranched polyester, and cetyl-terminated hyperbranched polyester.
  • the polyester includes polyethylene terephthalate and its derivatives, polyethylene 2,6-naphthalate and its derivatives, polybutylene terephthalate and its derivatives, poly1,4-cyclohexanedimethanol terephthalate and its derivatives, polyethylene terephthalate-1,4-cyclohexanedimethanol, poly2,6 -Trimethylene naphthalate and its derivatives, polytrimethylene terephthalate and its derivatives, polybutylene 2,6-naphthalate and its derivatives, polybutylene 2,5-furandicarboxylate One or more of esters and their derivatives, polybutylene adipate terephthalate and its derivatives, and polyarylate and its derivatives.
  • the oxygen-containing functional group modified polyester has a characteristic viscosity of 0.600-0.750 dL/g.
  • the characteristic viscosity of the oxygen-containing functional group-modified polyester is 0.650 to 0.750 dL/g.
  • the oxygen functional group modified polyester has a characteristic viscosity of 0.650dL/g, 0.670dL/g, 0.690dL/g, 0.710dL/g, 0.730 or 0.750dL/g.
  • the oxygen-containing functional group modified polyester has a molecular weight distribution of 1.7 to 2.5.
  • the molecular weight distribution of the oxygen-containing functional group-modified polyester is 1.8 to 2.2.
  • the molecular weight distribution of the oxygen-containing functional group modified polyester is 1.8, 1.9, 2.0, 2.1 or 2.2.
  • the molar proportion of modified units in the oxygen-containing functional group-modified polyester is 5% to 15%.
  • the molar proportion of modified units in the oxygen-containing functional group-modified polyester is 8% to 12%.
  • the molar proportion of modified units in the oxygen-containing functional group modified polyester is 8%, 9%, 10%, 11% or 12%.
  • the polyester has an intrinsic viscosity of 0.600 to 0.800 dL/g.
  • the intrinsic viscosity of polyester is too low, the average molecular weight of the polyester film is low, and the mechanical properties of the prepared polyester film are poor; when the intrinsic viscosity of polyester is too high, the average molecular weight of the polyester film is high, which will lead to film formation. The properties deteriorate and membrane breakage is prone to occur.
  • the prepared polyester film can have both good mechanical properties and good film-forming properties.
  • the intrinsic viscosity of the polyester is 0.650-0.750dL/g.
  • the polyester has an intrinsic viscosity of 0.650dL/g, 0.670dL/g, 0.690dL/g, 0.710dL/g, 0.730dL/g or 0.750dL/g.
  • the polyester has a molecular weight distribution of 1.7 to 2.5.
  • the molecular weight distribution of polyester is too low, the film-forming performance will deteriorate; when the molecular weight distribution of polyester is too high, the stability of the prepared polyester film will deteriorate. Within the molecular weight distribution range of the polyester, better film-forming properties and stability of the prepared polyester film can be achieved simultaneously.
  • the polyester has a molecular weight distribution of 1.9 to 2.3. Further optionally, the polyester has a molecular weight distribution of 1.9, 2.0, 2.1, 2.2 or 2.3.
  • the middle layer further includes additives in a mass fraction of 0.1 to 1 part.
  • the first outer layer further includes additives in a mass fraction of 0.1 to 1 part.
  • the second outer layer further includes additives in a mass fraction of 0.1 to 1 part.
  • the middle layer further includes an additive in a mass fraction of 0.1 to 1 part; the first outer layer further includes an additive in a mass fraction of 0.1 to 1 part; and the second outer layer further includes an additive in a mass fraction of 0.1 to 1 part. It is 0.1 part to 1 part additive.
  • the middle layer includes the following mass percentages of each component:
  • the first outer layer includes the following mass percentages of each component:
  • the second outer layer includes the following mass percentages of each component:
  • the raw materials of the middle layer are the following mass percentages of each component:
  • the raw materials of the first outer layer are each component in the following mass percentage:
  • the raw materials of the second outer layer are each component in the following mass percentage:
  • the additives include one or more of slip agents, antioxidants, antistatic agents, and nucleating agents.
  • the slip agent includes one or more of titanium dioxide, silica, calcium carbonate, talc, kaolin, diatomaceous earth, siloxane, and acrylate;
  • Antioxidants include one or more of phosphonate and bisphenol A phosphite
  • Antistatic agents include one or more of glycerol, polyglycerol, polyethylene glycol, polyether ester, carbon black, graphite, and conductive fibers;
  • the nucleating agent includes one or more of zinc oxide, aluminum oxide, magnesium oxide, copper oxide, barium sulfate, sodium carbonate, triphenyl phosphate, benzophenone, polycaprolactone, magnesium stearate, and sodium benzoate. kind.
  • the average particle size of the additive is 0.01-1.5 microns.
  • the polyester film can have good properties.
  • the additive has an average particle size of 0.01 micron, 0.05 micron, 0.1 micron, 0.3 micron, 0.5 micron, 0.7 micron, 1.0 micron or 1.5 micron.
  • the average particle size of the additive is less than or equal to 30% of the thickness of the layer in which the additive is located.
  • the average particle size of the additive is less than or equal to 30% of the thickness of the layer where the additive is located, which can reduce film defects caused by the mismatch between the thickness of the layer and the particle size of the additive.
  • the thickness ratio of the middle layer, the first outer layer and the second outer layer is (70 ⁇ 90): (5 ⁇ 15): (5 ⁇ 15).
  • the thickness of the composite polyester film is 2-20 microns.
  • the thickness of the composite polyester film is 2 microns, 5 microns, 7 microns, 10 microns, 15 microns or 20 microns.
  • an embodiment of the present application also provides a method for preparing a composite polyester film, which includes the following steps:
  • the preparation method of the composite polyester film includes the following steps:
  • the preparation method of the composite polyester film includes the following steps:
  • stretching includes transverse stretching and longitudinal stretching.
  • stretching includes transverse stretching and longitudinal stretching in sequence, or stretching includes longitudinal stretching and transverse stretching in sequence.
  • the transverse stretching ratio is (3-4):1.
  • the longitudinal stretching ratio is (3-5):1.
  • longitudinal stretching includes the following steps:
  • Preheating Preheat the formed film before stretching.
  • the preheating temperature is 70 ⁇ 100°C;
  • Heat setting The film obtained after being stretched longitudinally is subjected to heat setting treatment.
  • the heat setting treatment temperature is 165 ⁇ 180°C;
  • transverse stretching includes the following steps:
  • Preheating Preheat the film before transverse stretching.
  • the preheating temperature is 80 to 120°C;
  • Heat setting The diaphragm obtained after being stretched laterally is subjected to heat setting treatment.
  • the heat setting treatment temperature is 150 ⁇ 250°C;
  • the method before the middle layer slice, the first outer layer slice and the second outer layer slice are melted and co-extruded, the method further includes: separately crystallizing the middle layer slice, the first outer layer slice and the second outer layer slice. . Crystallizing the slices can increase the crystallinity of the polyester and reduce the mutual adhesion between the slices during the drying process.
  • the crystallization treatment temperature is 130-185°C, and the treatment time is 20-130 minutes.
  • the treatment temperature of the crystallization treatment is 130°C, 140°C, 150°C, 160°C, 170°C or 185°C; the treatment time of the crystallization treatment is 20min, 30min, 40min, 50min, 70min, 90min, 110min or 130min.
  • the method before the middle layer slice, the first outer layer slice and the second outer layer slice are melted and co-extruded, the method further includes: drying the middle layer slice, the first outer layer slice and the second outer layer slice respectively. . Drying the slices can remove moisture from the raw material and reduce oxidation of the polyester during the subsequent melt extrusion process.
  • the drying treatment temperature is 130-175°C, and the treatment time is 110-300 minutes.
  • the drying processing temperature is 130°C, 140°C, 150°C, 160°C or 175°C; the drying processing time is 110min, 130min, 150min, 170min, 200min, 220min, 250min or 300min.
  • the method further includes: heat treating the film.
  • the heat treatment includes a first heat treatment, a second heat treatment and a third heat treatment performed in sequence.
  • the treatment temperature of the first heat treatment is 130-160°C, and the treatment time is 0.5-2 min; the treatment temperature of the second heat treatment is 160-220°C, and the treatment time is 0.5-5 min; the treatment of the third heat treatment The temperature is 70 ⁇ 100°C, and the processing time is 0.5 ⁇ 2min.
  • Heat treatment can reduce the residual stress of the diaphragm and moderately increase the crystallinity of the diaphragm, thereby reducing the thermal shrinkage rate of the diaphragm and increasing the tensile strength of the diaphragm.
  • the treatment temperature of the first heat treatment is 130°C, 140°C, 150°C or 160°C; the treatment time is 0.5min, 0.7min, 1min, 1.2min, 1.5min, 1.7min or 2min; the temperature of the second heat treatment It is 160°C, 170°C, 180°C, 190°C, 200°C, 210°C or 220°C; the processing time is, 0.5min, 0.7min, 1min, 1.5min, 2min, 2.5min, 3min, 4min or 5min; third The heat treatment temperature is 70°C, 80°C, 90°C or 100°C; the treatment time is 0.5min, 0.7min, 1min, 1.2min, 1.5min, 1.7min or 2min.
  • An embodiment of the present application also provides a composite current collector, including: a composite polyester film as described above and a conductive layer located on at least one surface of the composite polyester film.
  • a protective layer is further included, and the protective layer is located on a surface of the conductive layer away from the flexible polyester film.
  • the thickness of the conductive layer is 500-2000 nm.
  • the thickness of the conductive layer is 700-1200nm.
  • the thickness of the conductive layer is 700nm, 800nm, 900nm, 1000nm, 1100nm or 1200nm.
  • the thickness of the protective layer is 10-150 nm.
  • the thickness of the protective layer is 10nm, 30nm, 50nm, 70nm, 100nm, 120nm or 150nm.
  • the thickness of the protective layer is less than or equal to 10% of the thickness of the conductive layer.
  • the thickness of the protective layer is 1%, 3%, 5%, 7% or 10% of the thickness of the conductive layer.
  • the composite current collector includes: a composite polyester film 6, a first conductive layer 5 and a second conductive layer 7 respectively located on two opposite surfaces of the composite polyester film, and a first conductive layer located far away from the first conductive layer.
  • the material of the conductive layer is selected from one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium, and silver.
  • the conductive layer is prepared by one or more of physical vapor deposition, electroplating, and chemical plating.
  • physical vapor deposition includes: resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, and magnetron sputtering.
  • the material of the protective layer is selected from nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen One or more of black, carbon nanoquantum dots, carbon nanotubes, carbon nanofibers, and graphene.
  • the protective layer is prepared by one or more of physical vapor deposition, chemical vapor deposition, in-situ molding, and coating.
  • physical vapor deposition is selected from vacuum evaporation or magnetron sputtering
  • chemical vapor deposition is selected from atmospheric pressure chemical vapor deposition or plasma enhanced chemical vapor deposition
  • in-situ forming is selected from in-situ formation of metal oxide on the surface of the conductive layer
  • the method of physical passivation layer; the coating method is selected from die coating, blade coating, and extrusion coating.
  • An embodiment of the present application provides a battery, including: any of the above composite current collectors.
  • An embodiment of the present application also provides an electronic product, including: the above-mentioned battery.
  • the selected polyester is polyethylene terephthalate (PET), with an intrinsic viscosity of 0.675dL/g and a molecular weight distribution of 2.2;
  • the oxygen-containing functional group modified polyester is pentaerythritol modified Polyethylene terephthalate (PENTA-PET), the molar ratio of modified units is 10%, and the intrinsic viscosity is 0.645dL/g;
  • the additives are antioxidant 300 and alumina with an average particle size of 0.2 microns. .
  • the preparation method of composite polyester film is:
  • the middle layer slices, the first outer layer slices and the second outer layer slices are prepared from PET, PENTA-PET and additives by heating, melting, mixing, extrusion, and shaping into slices.
  • the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the first outer slice are: 94%, 5.0%, 0.5%, 0.5%; in the second outer slice, the mass percentages of PET, PENTA-PET, antioxidant 300, and The mass percentages of oxidant 300 and alumina are: 94%, 5.0%, 0.5%, 0.5%; the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the middle layer slice are: 98.5%, 0.5% , 0.5%, 0.5%.
  • the molten material extruded from the die is cast onto a cast roller, and is formed by the cast roller and water-cooling cooling treatment to cast a cast sheet with a thickness of 54 microns.
  • step (4) The cast sheet obtained in step (4) is sequentially preheated at 90°C, longitudinally stretched at 110°C, with a stretching ratio of 3:1, heat set at 170°C, and then stretched at 40°C. Cooling and forming is carried out below.
  • step (6) Preheat the longitudinally stretched film in step (5) at 90°C, transversely stretch at 120°C with a stretching ratio of 3:1, and heat set at 170°C. , cooling and forming at 110°C.
  • Heat treatment is performed on the biaxially stretched film.
  • the specific process is the first heat treatment in sequence: the treatment temperature is 140°C, the treatment time is 0.5min; the second heat treatment: the treatment temperature is 170°C, the treatment time is 0.5min. min; third heat treatment: the treatment temperature is 80°C, and the treatment time is 0.5 min.
  • the heat-treated diaphragm is cooled in the platform area, and then enters the winding system through the traction system to wind the diaphragm to prepare a 6-micron-thick composite polyester film.
  • Preparation of the conductive layer Place the composite polyester film prepared above and whose surface has been cleaned in a vacuum evaporation chamber, and use high-purity aluminum wire (purity greater than 99.99) in the metal evaporation chamber at a high temperature of 1300 to 2000°C. %) melts and evaporates. In this example, the temperature is 1500°C.
  • the evaporated metal atoms pass through the cooling system in the vacuum coating chamber and are deposited on the two opposite surfaces of the composite polyester film to form an aluminum conductive layer with a thickness of 1 micron.
  • Embodiment 2 is basically the same as Embodiment 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the first outer layer slice and the second outer layer slice are: 89.0%, 10.0%, 0.5 %, 0.5%.
  • Embodiment 3 is basically the same as Embodiment 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the first outer layer slice and the second outer layer slice are: 84.0%, 15.0%, and 0.5 %, 0.5%.
  • Embodiment 4 is basically the same as Embodiment 3, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the first outer slice and the second outer slice are: 79.0%, 20.0%, 0.5 %, 0.5%.
  • Example 5 is basically the same as Example 3, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the middle layer slices are: 98.0%, 1.0%, 0.5%, and 0.5%.
  • Example 6 is basically the same as Example 3, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the middle layer slices are: 97.0%, 2.0%, 0.5%, and 0.5%.
  • Example 7 is basically the same as Example 3, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the middle layer slices are: 96.0%, 3.0%, 0.5%, and 0.5%.
  • Example 8 is basically the same as Example 5, except that the longitudinal stretch ratio is 4:1.
  • Example 9 is basically the same as Example 5, except that the longitudinal stretch ratio is 5:1.
  • Example 10 is basically the same as Example 8, except that the transverse stretching ratio is 3.5:1.
  • Example 11 is basically the same as Example 8, except that the transverse stretching ratio is 4:1.
  • Example 12 is basically the same as Example 10, except that PENTA-PET is replaced by polytetrahydrofuran ether (PTMG)-modified PET.
  • PTMG polytetrahydrofuran ether
  • Example 13 is basically the same as Example 10, except that PENTA-PET is replaced by 2,5-furandicarboxylic acid (FDCA)-modified PET.
  • FDCA 2,5-furandicarboxylic acid
  • Example 14 is basically the same as Example 10, except that PENTA-PET is replaced by hydroxyl-terminated hyperbranched polyester (HBP-OH).
  • HBP-OH hydroxyl-terminated hyperbranched polyester
  • Comparative Example 1 is basically the same as Example 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the middle layer slices are: 99.0%, 0%, 0.5%, and 0.5%; the first outer layer The mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the first layer slice and the second outer layer slice are in order: 99.0%, 0%, 0.5%, and 0.5%.
  • Comparative Example 2 is basically the same as Example 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the first and second outer slices are: 76.0%, 23%, and 0.5 respectively. %, 0.5%.
  • Comparative Example 3 is basically the same as Example 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the first outer layer slice and the second outer layer slice are: 96.0%, 3%, and 0.5 %, 0.5%.
  • Comparative Example 4 is basically the same as Example 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and alumina in the middle layer slices are: 98.7%, 0.3%, 0.5%, and 0.5%.
  • Comparative Example 5 is basically the same as Example 1, except that the mass percentages of PET, PENTA-PET, antioxidant 300, and aluminum oxide in the middle layer slices are: 94.0%, 5%, 0.5%, and 0.5%.
  • Comparative Example 6 is basically the same as Example 1, except that the longitudinal stretch ratio is 2:1.
  • Comparative Example 7 is basically the same as Example 1, except that the transverse stretching ratio is 2:1.
  • the factors affecting the surface adhesion performance of the polyester film in the composite polyester films prepared in Examples 1 to 14 and Comparative Examples 1 to 7 are: the free volume of the outer layer, the tensile strength that characterizes the mechanical properties of the polyester film and the composite current collector. The tensile strength, elongation at break, and the bonding force between the polyester film and the conductive layer in the composite current collector were tested and characterized.
  • the specific test methods are as follows:
  • the free volume of the outer layer of the composite polyester film is mainly affected by the content of oxygen-containing functional group-modified polyester in the outer layer. As the content of oxygen-containing functional group-modified polyester increases, the free volume of the outer layer first increases and then decreases. This is Mainly because increasing the content of oxygen-containing functional group-modified polyester can inhibit the crystallization of the polyester film, thereby increasing the free volume.
  • the mass percentage of oxygen-containing functional group-modified polyester in the outer layer is 15%.
  • the tensile strength and elongation at break of the composite polyester film are mainly affected by the content and draw ratio of the oxygen-containing functional group-modified polyester in the middle layer.
  • the content of oxygen-containing functional group-modified polyester in the middle layer can improve the crystallization ability of polyester, the force between polyester polymers and the plasticity, thereby improving the tensile strength of the polyester film.
  • the middle layer The mass percentage of oxygen-containing functional group modified polyester is 1%. Due to the addition of oxygen-containing functional group-modified polyester, the plasticity of polyester polymer materials can be improved, thereby increasing the draw ratio during processing.
  • the ratio is reduced, taking into account the tensile strength and elongation at break.
  • the preferred stretch ratio is 4:1 in the longitudinal direction and 3.5:1 in the transverse direction.
  • the membrane rupture rate, tensile strength and elongation at break during the preparation process of the composite current collector are mainly affected by the mechanical properties of the polyester film. Improving the mechanical properties of the polyester film can improve the mechanical properties of the composite current collector. , reduce the membrane rupture rate.
  • the bonding force between the polyester film and the conductive layer of the composite current collector is mainly affected by the free volume of the surface layer of the polyester film. Increasing the free volume of the surface layer of the polyester film further enhances the bonding force with the conductive layer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente demande concerne un film de polyester composite, son procédé de préparation et son utilisation. Le film de polyester composite comprend : une couche intermédiaire (2), et une première couche externe (1) et une seconde couche externe (3) qui sont respectivement situées sur deux surfaces opposées de la couche intermédiaire (2), la couche intermédiaire (2) comprenant les composants suivants en parties en masse : 96,0 à 99,4 parties d'un polyester et 0,5 à 3 parties d'un polyester modifié avec un groupe fonctionnel contenant de l'oxygène ; la première couche externe (1) comprenant les composants suivants en parties en masse : 79,0 à 94,9 parties d'un polyester et 5 à 20 parties d'un polyester modifié avec un groupe fonctionnel contenant de l'oxygène ; et la seconde couche externe (3) comprenant les composants suivants en parties en masse : 79,0 à 94,9 parties d'un polyester et 5 à 20 parties d'un polyester modifié par un groupe fonctionnel contenant de l'oxygène.
PCT/CN2022/117593 2022-09-07 2022-09-07 Film de polyester composite, son procédé de préparation et son utilisation Ceased WO2024050722A1 (fr)

Priority Applications (2)

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PCT/CN2022/117593 WO2024050722A1 (fr) 2022-09-07 2022-09-07 Film de polyester composite, son procédé de préparation et son utilisation
PCT/CN2023/117459 WO2024051776A1 (fr) 2022-09-07 2023-09-07 Film de polyester composite, son procédé de préparation et son utilisation

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PCT/CN2022/117593 WO2024050722A1 (fr) 2022-09-07 2022-09-07 Film de polyester composite, son procédé de préparation et son utilisation

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101652247A (zh) * 2007-03-30 2010-02-17 富士胶片株式会社 导电性物质吸附性树脂薄膜、导电性物质吸附性树脂薄膜的制造方法、使用其的带金属层的树脂薄膜及带金属层的树脂薄膜的制造方法
CN106459239A (zh) * 2014-05-30 2017-02-22 理研科技株式会社 活性能量线固化性树脂组合物，使用了该树脂组合物的硬涂层层合膜及透明树脂层合体
CN109648966A (zh) * 2018-12-27 2019-04-19 合肥乐凯科技产业有限公司 一种高阻隔聚酯薄膜
US20200216661A1 (en) * 2019-01-03 2020-07-09 Nan Ya Plastics Corporation White polyester film with properties of lightweight and low-shrinkage
CN115583088A (zh) * 2022-09-07 2023-01-10 扬州纳力新材料科技有限公司 复合聚酯膜及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101652247A (zh) * 2007-03-30 2010-02-17 富士胶片株式会社 导电性物质吸附性树脂薄膜、导电性物质吸附性树脂薄膜的制造方法、使用其的带金属层的树脂薄膜及带金属层的树脂薄膜的制造方法
CN106459239A (zh) * 2014-05-30 2017-02-22 理研科技株式会社 活性能量线固化性树脂组合物，使用了该树脂组合物的硬涂层层合膜及透明树脂层合体
CN109648966A (zh) * 2018-12-27 2019-04-19 合肥乐凯科技产业有限公司 一种高阻隔聚酯薄膜
US20200216661A1 (en) * 2019-01-03 2020-07-09 Nan Ya Plastics Corporation White polyester film with properties of lightweight and low-shrinkage
CN115583088A (zh) * 2022-09-07 2023-01-10 扬州纳力新材料科技有限公司 复合聚酯膜及其制备方法和应用

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