WO2024104393A1 - Matériau de polypropylène composite multicouche, procédé de préparation s'y rapportant et utilisation associée - Google Patents

Matériau de polypropylène composite multicouche, procédé de préparation s'y rapportant et utilisation associée Download PDF

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Publication number
WO2024104393A1
WO2024104393A1 PCT/CN2023/131848 CN2023131848W WO2024104393A1 WO 2024104393 A1 WO2024104393 A1 WO 2024104393A1 CN 2023131848 W CN2023131848 W CN 2023131848W WO 2024104393 A1 WO2024104393 A1 WO 2024104393A1
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polypropylene
modified
layer
composite
polypropylene material
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PCT/CN2023/131848
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English (en)
Chinese (zh)
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朱中亚
王帅
夏建中
李学法
张国平
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扬州纳力新材料科技有限公司
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Publication of WO2024104393A1 publication Critical patent/WO2024104393A1/fr

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    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to the technical field of composite materials, in particular to a multi-layer composite polypropylene material and a preparation method and application thereof.
  • composite current collectors based on polymer films have received widespread attention and application in the new energy industry.
  • the preparation process of the composite current collector is usually: a layer of metal (aluminum, copper, etc.) material is deposited on a polymer film (such as polypropylene, polyethylene, polyester, etc.) by physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the prepared surface metallized film with a certain conductivity is the composite current collector.
  • composite current collectors based on polymer films have the advantages of low cost, light weight and good internal insulation. These advantages enable the composite current collector to reduce the cost of the battery and improve the energy density and safety of the battery when used in the battery.
  • composite current collectors based on polypropylene films are more common.
  • the process of preparing composite current collectors with traditional polypropylene films as base films due to the weak polarity of the polypropylene film itself, its surface tension is low, and the affinity between the polypropylene film with low surface tension and the metal layer with high surface tension is poor, which leads to low adhesion between the interface of the two and weak bonding, that is, there is a problem of poor surface adhesion performance.
  • the method of corona treatment on the surface of polypropylene film is usually adopted to increase the surface tension of the film, thereby improving the bonding firmness between the polypropylene film and the metal material, but this method has the following shortcomings: the surface tension of the polymer film after corona treatment is unstable. After being stored for a period of time, the surface tension decreases and finally approaches the surface tension of the polymer film before treatment, that is, there is a problem of unstable storage.
  • a multilayer composite polypropylene material which has high surface tension and good storage stability, strong affinity with metals, and can be firmly combined with metals. It can be used to prepare a composite current collector and further used in pole pieces or batteries.
  • a multi-layer composite polypropylene material the structure of which comprises a first modified layer, a core layer and a second modified layer which are stacked;
  • the first modified layer includes a first modified polypropylene
  • the core layer comprises polypropylene
  • the second modified layer includes a second modified polypropylene
  • the first modified polypropylene and the second modified polypropylene are independently selected from one or more of small molecule graft-modified polypropylene and oligomer graft-modified polypropylene.
  • the polypropylene in the core layer is unmodified polypropylene.
  • the polypropylene in the core layer does not comprise modified polypropylene.
  • the small molecule grafted modified polypropylene includes: maleic anhydride grafted modified polypropylene, acrylic acid-maleic anhydride grafted modified polypropylene, diethylenetriamine-methacrylate glycidyl grafted modified polypropylene, acrylamide grafted modified polypropylene, acrylamide-acrylic acid grafted modified polypropylene, succinic anhydride grafted polypropylene, succinylfluorescein-succinic anhydride grafted polypropylene and one or more of modified polypropylenes in which hydrogen in the polar modified molecules is replaced by methyl, ethyl or halogen atoms.
  • the oligomer grafted modified polypropylene includes: polypropylene grafted with maleic anhydride oligomer, polypropylene grafted with (acrylic acid-maleic anhydride) oligomer, polypropylene grafted with di(ethylenetriamine-glycidyl methacrylate) oligomer, polypropylene grafted with acrylamide oligomer, polypropylene grafted with (acrylamide-acrylic acid) oligomer, polypropylene grafted with succinic anhydride oligomer, and polypropylene grafted with (succinyl) anhydride oligomer.
  • the polymerization degree of the oligomer is 2-20, preferably 5-10. Too high polymerization degree of the oligomer is easy to form defects in the modified layer.
  • the combination of small molecule grafted modified polypropylene and oligomer grafted modified polypropylene is preferred.
  • the grafting ratio g of the first modified polypropylene and the second modified polypropylene satisfies: 0.1% ⁇ g ⁇ 2%.
  • the first modified polypropylene has a melt index of about (3.1-4.1) g/10 min/(230° C./2.16 kg) and a molecular weight distribution index of about 4.5-5.6.
  • the melt index of the second modified polypropylene is about (3.2-4.0) g/10 min/(230° C./2.16 kg), and the molecular weight distribution index is about 4.5-5.6.
  • the polypropylene in the core layer is unmodified polypropylene, and the melt index of the polypropylene is about (3.0-3.9) g/10 min/(230° C./2.16 kg), the molecular weight distribution index is about 4.5-5.2, and the isotacticity is about ⁇ 97%.
  • the mass percentage of the first modified polypropylene is about ⁇ 20%.
  • the first modified layer further includes a first polypropylene and a first antioxidant
  • the first modified layer includes about 0%-79.8% of the first polypropylene, about 20%-99.9% of the first modified polypropylene and about 0.1%-0.6% of the first antioxidant.
  • the first polypropylene has a melt index of about (3.0-3.9) g/10 min/(230° C./2.16 kg), a molecular weight distribution index of about 4.5-5.2, and an isotacticity of about 89%-97%.
  • the first antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, and p-tert-butylcatechol.
  • the mass percentage of the second modified polypropylene is The content is approximately ⁇ 20%.
  • the second modified layer further includes a second polypropylene and a second antioxidant
  • the second modified layer includes about 0%-79.8% of the second polypropylene, about 20%-99.9% of the second modified polypropylene and about 0.1%-0.6% of the second antioxidant.
  • the second polypropylene has a melt index of about (3.0-3.9) g/10 min/(230° C./2.16 kg), a molecular weight distribution index of about 4.5-5.2, and an isotacticity of about 89%-97%.
  • the difference between the isotacticity of the first polypropylene and the isotacticity of the polypropylene in the core layer is about 1%-8%, preferably 2%-8%.
  • the second antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol and p-tert-butylcatechol.
  • the core layer further comprises a third antioxidant
  • the core layer includes about 99.5%-99.8% of the polypropylene and about 0.2%-0.5% of the third antioxidant.
  • the core layer is composed of unmodified polypropylene and a third antioxidant
  • the core layer includes about 99.5%-99.8% of the polypropylene and about 0.2%-0.5% of the third antioxidant.
  • the third antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, and p-tert-butylcatechol.
  • the thickness of the multi-layer composite polypropylene material is about ⁇ 1 ⁇ m, wherein the thickness of the first modified layer and the second modified layer account for about 5%-15% respectively, and the thickness of the core layer accounts for about 70%-90%.
  • the present application also provides a method for preparing the multi-layer composite polypropylene material as described above.
  • the technical solution is as follows:
  • a method for preparing the multilayer composite polypropylene material as described above comprises the following steps:
  • the first modified layer intermediate, the core layer intermediate and the second modified layer intermediate are composite-molded by a sheet-making process at about 15-60° C. to prepare a multi-layer composite polypropylene material intermediate;
  • the multi-layer composite polypropylene material intermediate is subjected to synchronous stretching treatment to prepare the multi-layer composite polypropylene material, and the total longitudinal stretching ratio is about 5-9 times and the total transverse stretching ratio is about 4-8 times.
  • the synchronous stretching comprises the following steps:
  • the raw material comprising the second modified polypropylene is melted at about 200-260° C., Extrusion at 230-260° C. to prepare a second modified layer intermediate;
  • the first modified layer intermediate, the core layer intermediate and the second modified layer intermediate are composite-molded by a sheet-making process at about 15-60° C. to prepare a multi-layer composite polypropylene material intermediate;
  • the multi-layer composite polypropylene material intermediate is subjected to asynchronous stretching treatment to prepare the multi-layer composite polypropylene material, and the total longitudinal stretching ratio is about 5-9 times and the total transverse stretching ratio is about 4-8 times.
  • the asynchronous stretching comprises the following steps:
  • thermoforming treatment on the multi-layer composite polypropylene material III at a temperature of about 165-170° C. to prepare a multi-layer composite polypropylene material IV;
  • the multi-layer composite polypropylene material IV is heat-treated at about 120-135° C. to prepare the multi-layer composite polypropylene material.
  • the present application also provides a composite current collector, the structure of which includes a first protective layer, a first metal layer, a support layer, a second metal layer and a second protective layer arranged in layers;
  • the support layer comprises a composite polypropylene material according to above.
  • the first protective layer and the second protective layer independently include: one or more of an inactive metal and its alloy, a metal oxide and a carbon material;
  • the first metal layer and the second metal layer independently include metals and alloys thereof with a resistivity of about ⁇ 8 ⁇ 10-8 ⁇ m.
  • the inactive metal is selected from nickel and/or chromium.
  • the inactive metal alloy is selected from one or more of a nickel-based alloy, a chromium-based alloy, and a nickel-chromium-copper alloy.
  • the metal oxide is selected from copper oxide.
  • the carbon material is selected from one or more of aluminum oxide, nickel oxide, chromium oxide, cobalt oxide and copper chromium oxide.
  • the carbon material is selected from one or more of graphite, carbon black, acetylene black, Ketjen black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers and graphene.
  • the metal with a resistivity of about ⁇ 8 ⁇ 10-8 ⁇ m is selected from one or more of copper, aluminum, silver, gold, zinc, molybdenum, cobalt, and nickel, and the alloy that meets the requirements is selected from one or more of copper alloys, aluminum alloys, and nickel alloys.
  • the present application also provides a pole piece, comprising the composite current collector as described above.
  • the present application also provides a battery, comprising the pole piece as described above.
  • FIG1 is a schematic diagram of the structure of a multilayer composite polypropylene material provided according to one or more embodiments
  • FIG2 is a flow chart of a method for preparing a multilayer composite polypropylene material according to one or more embodiments
  • FIG3 is a flow chart of a method for preparing a multilayer composite polypropylene material according to one or more embodiments
  • FIG4 is a schematic diagram of the structure of a composite current collector according to one or more embodiments.
  • FIG5 is a schematic diagram showing the result of measuring energy density varying with cycle number when the composite current collector sample provided according to one or more embodiments is an electrode current collector of a battery.
  • the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.
  • any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and any upper limit can be combined with any other upper limit to form an unspecified range.
  • each separately disclosed point or single value can itself be combined as a lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unspecified range.
  • the temperature parameters in the present invention allow both constant temperature treatment and treatment within a certain temperature range.
  • the constant temperature treatment allows the temperature to be within the precision range controlled by the instrument. fluctuation.
  • the unit of the data range when it comes to the unit of the data range, if there is a unit only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same.
  • 150-160°C means that the units of the left endpoint "150” and the right endpoint "160” are both °C (degrees Celsius).
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as “first” and “second” may explicitly or implicitly include at least one of the features.
  • the meaning of “multiple” is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.
  • severeal is at least one, such as one, two, etc., unless otherwise clearly and specifically defined.
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or may include steps (a), (c) and (b), or may include steps (c), (a) and (b), etc.
  • the grafting ratio refers to the ratio of the mass of the polar monomer grafted onto the polypropylene to the mass of the grafted polypropylene.
  • the isotacticity is obtained by testing according to GB/T 2412-2008 standard.
  • the transverse stretch ratio refers to the elongation multiple of the stretched material in the transverse direction (or width) relative to the unstretched material
  • the longitudinal stretch ratio refers to the elongation multiple of the stretched material in the longitudinal direction (or length) relative to the unstretched material
  • the composite current collector based on polypropylene film has the characteristics of low cost, light weight, and good internal insulation, the material polarity of the polypropylene film itself is weak, resulting in low surface tension.
  • the affinity between the low surface tension polypropylene film and the high surface tension metal layer is poor, which causes adhesion between the two interfaces.
  • the force is low and the bonding is not strong, that is, there is a problem of poor surface adhesion and unstable surface tension.
  • the present invention provides a multi-layer composite polypropylene material which has high surface tension, good storage stability, strong affinity with metals, and can be firmly bonded together.
  • a multi-layer composite polypropylene material the structure of which comprises a first modified layer, a core layer and a second modified layer which are stacked;
  • the first modified layer includes a first modified polypropylene
  • the core layer comprises polypropylene
  • the second modified layer includes a second modified polypropylene
  • the first modified polypropylene and the second modified polypropylene are independently selected from:
  • Small molecule grafted modified polypropylene one or more of maleic anhydride grafted modified polypropylene, acrylic acid-maleic anhydride grafted modified polypropylene, diethylenetriamine-glycidyl methacrylate grafted modified polypropylene, acrylamide grafted modified polypropylene, acrylamide-acrylic acid grafted modified polypropylene, succinic anhydride grafted polypropylene, succinylfluorescein-succinic anhydride grafted polypropylene and modified polypropylene in which hydrogen in the polar modified molecule is replaced by methyl, ethyl or halogen atoms;
  • Oligomer grafted polypropylene polypropylene grafted with maleic anhydride oligomers, polypropylene grafted with (acrylic acid-maleic anhydride) oligomers, polypropylene grafted with glycidyl methacrylate oligomers, polypropylene grafted with di(ethylenetriamine-glycidyl methacrylate) oligomers, polypropylene grafted with acrylamide oligomers, (acrylamide-acrylic acid) oligomers, succinic anhydride grafted polypropylene, (succinylfluorescein-succinic anhydride) oligomers, and one or more of modified polypropylenes in which hydrogen in the polar modified molecule is replaced by methyl, ethyl or halogen atoms.
  • the degree of polymerization of the oligomer is 2-20, preferably 5-10. Too high a polymerization degree of the oligomer is easy to cause polymerization in the modified
  • the composition of small molecule graft-modified polypropylene and oligomer graft-modified polypropylene is preferred.
  • polypropylene modified by polar molecules Compared with unmodified polypropylene, polypropylene modified by polar molecules has greater polarity and surface tension.
  • the present invention effectively improves the surface polarity of the composite polypropylene material and thus improves its surface tension by adding polypropylene modified by polar molecules to the surface layer of the multilayer composite polypropylene material, while ensuring that the tensile strength of the multilayer composite polypropylene material meets the performance requirements of the current collector.
  • the polypropylene modified by polar molecules is not easy to crystallize, and can inhibit the crystallization of polypropylene and increase the free volume.
  • the surface adhesion performance of the composite polypropylene material is jointly promoted by the increase of the surface tension and free volume of the modified layer (surface layer), and the metal bonding force is strong, and it can be firmly combined with the metal.
  • the polar molecules and polypropylene in the modified polypropylene are connected by covalent bonds, the structure is stable, so that the surface tension of the surface layer is stable, and the surface tension will not decay during the storage process, showing excellent storage stability. Therefore, if the composite polypropylene material prepared in this application is used as the substrate of the composite current collector, it can be firmly bonded to the metal layer to improve the battery performance.
  • FIG1 is a schematic diagram of the structure of a composite polypropylene material prepared according to one embodiment of the present invention, wherein 101 represents a first modified layer, 102 represents a core layer, and 103 represents a second modified layer.
  • first modified layer and the second modified layer have the same function, but the material types and contents in the first modified layer and the second modified layer can be the same or different.
  • the core layer does not contain modified polypropylene.
  • the inventors of the present invention have found that the core layer does not contain modified polypropylene, which can ensure that the multi-layer composite polypropylene material meets the mechanical property requirements of the composite current collector, such as tensile strength.
  • the first modified polypropylene and the second modified polypropylene modified by polar molecules are independently selected from: polypropylene grafted with maleic anhydride, polypropylene grafted with acrylic acid and maleic anhydride, polypropylene grafted with diethylenetriamine and glycidyl methacrylate, polypropylene grafted with acrylamide, One or more of modified polypropylene, acrylamide-acrylic acid grafted modified polypropylene, succinic anhydride grafted polypropylene, succinylfluorescein-succinic anhydride grafted polypropylene, and modified polypropylene in which hydrogen in polar modified molecules is replaced by methyl, ethyl or halogen atoms, maleic anhydride oligomer grafted modified polypropylene, (acrylic acid-maleic anhydride) oligomer grafted modified polypropylene, methacrylate glycidyl oligomer grafted modified poly
  • modified polypropylene can better improve the polarity of polypropylene, improve surface tension and storage stability. It can be understood that, in the present invention, the types of the first modified polypropylene and the second modified polypropylene can be the same or different.
  • the inventors of the present invention have found that the increase in the content of polar molecules in the polypropylene molecules can cause the surface tension of the first modified layer and the second modified layer to show an increasing trend; polar molecules in the polypropylene molecules play a role in disrupting the regularity of molecular arrangement on the one hand, and on the other hand, they play a role in crystallization nucleation, and the two restrict each other and affect the free volume.
  • the grafting rate will also affect the film forming properties and surface defects of the material, and thus affect the yield rate. It can be understood that the grafting rates of the first modified polypropylene and the second modified polypropylene can be the same or different.
  • the grafting rates of the first modified polypropylene and the second modified polypropylene are both approximately ⁇ 0.1%, including but not limited to: 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% or 1.6%.
  • the grafting rates of the first modified polypropylene and the second modified polypropylene are respectively about 0.2%-1.5%, which can synergistically improve the surface tension and free volume of the composite polypropylene, thereby improving its bonding strength with the metal.
  • the crystal area is reduced, thus affecting its physical properties such as hardness, strength and rigidity, resulting in defects in the modified layer. If the grafting rate is too low, the polarity, surface tension and free volume of the first modified layer or the second modified layer will be limited.
  • the inventors of the present invention have found that changing the melt index of the modified polypropylene in the first modified layer and/or the second modified layer can adjust the surface tension and free volume, film forming properties and mechanical properties of the modified layer. It is understandable that the melt index of the first modified polypropylene and the second modified polypropylene can be the same or different.
  • the melt index of the first modified polypropylene is about (3.1-4.1) g/10min/(230°C/2.16kg), including but not limited to 3.1 g/10min, 3.2 g/10min, 3.3 g/10min, 3.4 g/10min, 3.5 g/10min, 3.6 g/10min, 3.7 g/10min, 3.8 g/10min, 3.9 g/10min, 4.0 g/10min and 4.1 g/10min.
  • the melt index of the first modified polypropylene is about (3.2-4.0) g/10 min/(230°C/2.16 kg), which can synergistically improve the surface tension and free volume of the composite polypropylene, thereby improving its bonding strength with the metal, and ensuring the film forming property, yield rate and mechanical properties of the material.
  • the melt index of the second modified polypropylene is about (3.1-4.1) g/10min/(230°C/2.16kg), including but not limited to 3.1 g/10min, 3.2 g/10min, 3.3 g/10min, 3.4 g/10min, 3.5 g/10min, 3.6 g/10min, 3.7 g/10min, 3.8 g/10min, 3.9 g/10min, 4.0 g/10min and 4.1 g/10min.
  • the melt index of the second modified polypropylene is about (3.2-4.0) g/10 min/(230°C/2.16 kg), which can synergistically improve the surface tension and free volume of the composite polypropylene, thereby improving its bonding strength with the metal, and ensuring the film forming property, yield rate and mechanical properties of the material.
  • the inventors of the present invention have found that by changing the molecular weight distribution index of the modified polypropylene in the first modified layer and/or the second modified layer, the surface tension and free volume, as well as the film forming property, yield rate and mechanical properties of the modified layer can also be regulated. It can be understood that the molecular weight of the first modified polypropylene and the second modified polypropylene is The distribution indices can be the same or different.
  • the molecular weight distribution index of the first modified polypropylene is about 4.5-5.6, including but not limited to 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5 and 5.6.
  • the molecular weight distribution index of the first modified polypropylene is about 4.6-5.5, which can synergistically improve the surface tension and free volume of the composite polypropylene, thereby improving its bonding strength with the metal, and ensuring the film forming property, yield rate and mechanical properties of the material.
  • the molecular weight distribution index of the second modified polypropylene is about 4.5-5.6, including but not limited to 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5 and 5.6.
  • the molecular weight distribution index of the second modified polypropylene is about 4.6-5.5, which can synergistically improve the surface tension and free volume of the composite polypropylene, thereby improving its bonding strength with the metal, and ensuring the film forming property, yield rate and mechanical properties of the material.
  • adding modified polypropylene grafted with polar molecules to the modified layer can increase the polarity of the modified layer.
  • the inventors of the present invention have found that changing the content of modified polypropylene in the first modified layer and the second modified layer can adjust the surface tension and free volume of the modified layer, as well as the film forming property, yield rate and mechanical properties of the material.
  • the mass percentage of the first modified polypropylene is about ⁇ 20%, including but not limited to 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 48%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 85%, 88%, 90%, 92%, 95%, 96%, 98%, 99.8%, 99% and 100%.
  • the first modified layer further includes a first polypropylene and a first antioxidant.
  • the film forming property, yield rate and mechanical properties of the composite polypropylene material are improved through the action of the polypropylene and the antioxidant.
  • the melt index of the first polypropylene is about (3.0-3.9) g/10 min/(230°C/2.16 kg), including but not limited to 3.0 g/10 min, 3.1 g/10 min, 3.2 g/10 min, 3.3 g/10 min, 3.4 g/10 min, 3.5 g/10 min, 3.6 g/10 min, 3.7 g/10 min, 3.8 g/10 min and 3.9 g/10 min.
  • the molecular weight distribution index of the first polypropylene is about 4.5-5.2, including but not limited to 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1 and 5.2.
  • the inventors of the present invention have found that the isotacticity of polypropylene affects the regularity of the arrangement of the polymer in the modified layer, further affecting the free volume, binding force and adhesion performance, and also affects the mechanical properties and film-forming properties of the composite polypropylene material.
  • the isotacticity of the first polypropylene is about 89%-97%, including but not limited to 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96% and 97%.
  • the isotacticity of the first polypropylene is about 90%-96%, which can synergize the surface tension, free volume, mechanical properties, yield and film-forming properties of the composite polypropylene material.
  • the difference between the isotacticity of the first polypropylene described in the present invention and the isotacticity of the polypropylene is about 1%-8%, preferably 2%-8%, so that the first modified layer and the core layer can be gradually transitioned, which can not only avoid stress concentration problems and improve the overall strength and toughness of the multilayer structure, but also avoid the risk of interlayer delamination or cracking caused by interface stress caused by performance mismatch between adjacent layers.
  • the first antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, and p-tert-butylcatechol.
  • the first modified layer includes about 0%-79.8% of the first polypropylene, about 20%-99.9% of the first modified polypropylene, and about 1%-20% of the first antioxidant, based on mass percentage. 0.1%-0.6%.
  • the content of the first polypropylene includes but is not limited to 0%, 2%, 5%, 10%, 15%, 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 49.8%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75% and 79.8%.
  • the first modified layer includes about 20%-50% of the first polypropylene.
  • the content of the first modified polypropylene includes but is not limited to 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 48%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 85%, 88%, 90%, 92%, 95%, 96%, 99.8% and 99.9%.
  • the first modified layer includes about 20%-99.8% of the first modified polypropylene.
  • the content of the first antioxidant includes, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.6%.
  • the first modified layer includes about 0.2%-0.5% of the first antioxidant in terms of mass percentage.
  • the first modified layer and the second modified layer have the same function, and the description of the second modified layer can refer to the first modified layer, as follows:
  • the mass percentage of the second modified polypropylene is about ⁇ 20%, including but not limited to 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 48%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 85%, 88%, 90%, 92%, 95%, 96%, 98%, 99.8%, 99% and 100%.
  • the mass percentage of the first modified polypropylene is about ⁇ 20%; and in the second modified layer, the mass percentage of the second modified polypropylene is about ⁇ 20%. This can better coordinate the surface tension, free volume, mechanical properties, yield and film-forming properties of the composite polypropylene material.
  • the second modified layer further includes a second polypropylene and a second antioxidant.
  • a second polypropylene and a second antioxidant Through the action of the polypropylene and the antioxidant, the film forming property, the yield rate and the mechanical properties of the composite polypropylene material are improved.
  • the melt index of the second polypropylene is about (3.0-3.9) g/10 min/(230°C/2.16 kg), including but not limited to 3.0 g/10 min, 3.1 g/10 min, 3.2 g/10 min, 3.3 g/10 min, 3.4 g/10 min, 3.5 g/10 min, 3.6 g/10 min, 3.7 g/10 min, 3.8 g/10 min and 3.9 g/10 min.
  • the molecular weight distribution index of the second polypropylene is about 4.5-5.2, including but not limited to 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1 and 5.2.
  • the isotacticity of the second polypropylene is about 89%-97%, including but not limited to 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96% and 97%.
  • the isotacticity of the second polypropylene is about 90%-96%, which can synergize the surface tension, free volume, mechanical properties, yield and film-forming properties of the composite polypropylene material.
  • the difference between the isotacticity of the first polypropylene and the isotacticity of the polypropylene of the present invention is about 1%-8%, preferably 2%-8%, so that the second modified layer and the core layer can be gradually transitioned, which can not only avoid the problem of stress concentration, but also improve the overall strength and toughness of the multilayer structure. It can also avoid the risk of interlayer delamination or cracking caused by interface stress caused by performance mismatch between adjacent layers.
  • the second antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol and p-tert-butylcatechol.
  • the second modified layer includes about 0%-79.8% of the second polypropylene, about 20%-99.9% of the second modified polypropylene, and about 0.1%-0.6% of the second antioxidant.
  • the content of the second polypropylene includes but is not limited to 0%, 2%, 5%, 10%, 15%, 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 49.8%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75% and 79.8%.
  • the second modified layer includes about 20%-50% of the second polypropylene by weight.
  • the content of the second modified polypropylene includes but is not limited to 20%, 22%, 23%, 24%, 25%, 26%, 28%, 30%, 32%, 33%, 34%, 36%, 38%, 40%, 41%, 42%, 44%, 45%, 46%, 48%, 50%, 51%, 52%, 55%, 58%, 60%, 62%, 65%, 70%, 72%, 75%, 80%, 85%, 88%, 90%, 92%, 95%, 96%, 99.8% and 99.9%.
  • the second modified layer includes about 20%-99.8% of the second modified polypropylene in terms of mass percentage.
  • the content of the second antioxidant includes, but is not limited to, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and 0.6%.
  • the second modified layer includes the second anti- The oxidant is about 0.2%-0.5%.
  • the melt index of the polypropylene of the core layer is about (3.0-3.9) g/10min/(230°C/2.16kg), including but not limited to 3.0 g/10min, 3.1 g/10min, 3.2 g/10min, 3.3 g/10min, 3.4 g/10min, 3.5 g/10min, 3.6 g/10min, 3.7 g/10min, 3.8 g/10min and 3.9 g/10min.
  • the molecular weight distribution index of the polypropylene of the core layer is about 4.5-5.2, including but not limited to 4.5, 4.6, 4.7, 4.8, 4.8, 4.9, 5.0, 5.1 and 5.2.
  • the isotacticity of the polypropylene of the core layer is about ⁇ 97%, including but not limited to 97%, 98%, 99% and 100%.
  • the core layer further includes a third antioxidant.
  • the third antioxidant is selected from one or more of triphenyl phosphite, butylated hydroxyanisole, 2,6-di-tert-butyl-4-methylphenol, and p-tert-butylcatechol.
  • the core layer comprises about 99.5%-99.8% of the polypropylene and about 0.2%-0.5% of the third antioxidant, based on mass percentage.
  • the thickness of the multi-layer composite polypropylene material is about ⁇ 1 ⁇ m, so the thinner the polypropylene film is, the more it can promote the improvement of the energy density of the composite current collector, while taking into account the difficulty of production (the thinner the film, the greater the difficulty of production, and the lower the yield rate). In some embodiments, the thickness of the multi-layer composite polypropylene material is about 2 ⁇ m-20 ⁇ m. Among them, in the composite polypropylene material, the thickness proportions of the first modified layer and the second modified layer are independently about 5%-15%, and the thickness proportion of the core layer is about 70%-90%.
  • the present invention greatly improves the stability of the surface tension while ensuring the mechanical properties of the multi-layer composite polypropylene material by controlling the thickness and thickness proportion of the first modified layer, the second modified layer and the core layer, and by controlling the isotacticity of the polypropylene in the first modified layer, the second modified layer and the core layer, thereby solving the current problems of modified polypropylene film.
  • the problem is that high surface tension and excellent mechanical properties cannot be achieved at the same time.
  • the free volume fraction of the multi-layer composite polypropylene material is 0.018-0.04, which can enhance the bonding force between the metal layer and the multi-layer composite polypropylene material.
  • the present invention also provides a method for preparing the multi-layer composite polypropylene material as described above.
  • the technical scheme is as follows:
  • a method for preparing the multilayer composite polypropylene material as described above comprises the following steps:
  • the first modified layer intermediate, the core layer intermediate and the second modified layer intermediate are composite-molded by a sheet-making process at about 15-60° C. to prepare a multi-layer composite polypropylene material intermediate;
  • the multi-layer composite polypropylene material intermediate is subjected to synchronous stretching treatment to prepare the multi-layer composite polypropylene material, and the total longitudinal stretching ratio is about 5-9 times and the total transverse stretching ratio is about 4-8 times.
  • the synchronous stretching comprises the following steps:
  • the inventors of the present invention have found that the first stretching treatment, the second stretching treatment and the third stretching treatment can promote the orderly arrangement of polymer chains and the formation of lattice structures, better control the orientation and arrangement of polymer chains, and reduce the internal stress of polymer films during the stretching process, thereby improving the crystallization performance, mechanical properties and dimensional stability of multi-layer composite polypropylene materials.
  • the multi-step stretching treatment is combined with the multi-step heat setting treatment, the internal stress in the material can be effectively released, the deformation and thermal deformation tendency of the material can be reduced, and the dimensional stability of the material can be improved; the microstructure of the polymer material can also be regulated, thereby improving its mechanical properties and reducing surface defects.
  • the synchronous stretching includes two stages of preheating, three stages of stretching and two stages of heat setting;
  • the two-stage preheating includes a first preheating and a second preheating, and the temperature is gradually increased, the first preheating temperature is about 130-145°C, and the second preheating temperature is about 145-155°C;
  • the three-stage stretching includes a first stretching, a second stretching and a third stretching, and the temperature is gradually increased, the first stretching temperature is about 152-157° C., the second stretching temperature is about 156-160° C., and the third stretching temperature is about 159-162° C.; after the three-stage stretching, the total longitudinal stretching ratio is about 5-9 times (such as 5, 6, 7, 8, 9, in one embodiment, the total longitudinal stretching ratio is about 6-8 times), and the total transverse stretching ratio is about 4-8 times (such as 4, 5, 6, 7, 8, in one embodiment, the total transverse stretching ratio is about 5-7 times);
  • the two heat setting processes include a first heat setting process and a second heat setting process, and the temperature is gradually increased.
  • the first heat setting temperature is about 162-165° C.
  • the second heat setting temperature is about 162-169° C.
  • Another method for preparing the multilayer composite polypropylene material as described above comprises the following steps:
  • the raw material containing the polypropylene is melted at about 200-260°C, and the raw material containing the polypropylene is melted at about 230-260°C. Extrusion to prepare a core layer intermediate;
  • the first modified layer intermediate, the core layer intermediate and the second modified layer intermediate are composite-molded by a sheet-making process at about 15-60° C. to prepare a multi-layer composite polypropylene material intermediate;
  • the multi-layer composite polypropylene material intermediate is subjected to asynchronous stretching treatment to prepare the multi-layer composite polypropylene material, and the total longitudinal stretching ratio is about 5-9 times and the total transverse stretching ratio is about 4-8 times.
  • the asynchronous stretching comprises the following steps:
  • thermoforming treatment on the multi-layer composite polypropylene material III at a temperature of about 165-170° C. to prepare a multi-layer composite polypropylene material IV;
  • the multi-layer composite polypropylene material IV is heat-treated at about 120-135° C. to prepare the multi-layer composite polypropylene material.
  • the longitudinal stretching comprises the following steps:
  • the transverse stretching comprises the following steps:
  • Preheating at about 120-140°C, stretching at about 150-160°C, thermoforming at about 165-170°C, and the total transverse stretching ratio is about 4-8 times (such as 4, 5, 6, 7, 8, in which one of the actual In the embodiment, the total transverse stretching ratio is about 5-7 times);
  • the heat treatment comprises the following steps:
  • the heat treatment is carried out at about 120-135°C to eliminate the internal stress of the membrane and improve the thermal stability of the membrane.
  • the method for preparing the multi-layer composite polypropylene material comprises the following steps:
  • the raw materials used for the first modified layer, core layer and second modified layer are respectively added into the corresponding twin-screw extruder, melted at about 200-260°C, and then filtered through a filter (10 micron filter screen), and the melt is extruded through a die head.
  • the die head temperature is about 230-260°C, and the extrusion amount of the three layers is controlled at about (5%-15%): (70%-90%): (5%-15%).
  • the molten polyester material extruded from the die head is cast onto the casting roll and is formed by the casting roll and water cooling treatment.
  • the cooling temperature is about 15-60°C.
  • Biaxial stretching can be achieved in two ways, namely synchronous stretching and asynchronous stretching.
  • preheating area preheating area
  • stretching area stretch area
  • heat setting area preheating area
  • Preheating zone divided into two sections, the temperature increases successively, i.e. about 130-145°C and about 145-155°C;
  • Stretching zone divided into three sections, the temperature increases successively, namely about 152-157°C, about 156-160°C, about 159-162°C; after three-stage stretching, the stretching ratio: the total longitudinal stretching ratio is about 5-9 times, and the total transverse stretching ratio is about 4-8 times.
  • Heat setting area divided into two sections, the temperature increases successively, i.e. about 162-165°C and about 162-169°C.
  • preheating temperature is about 110-135°C
  • stretching temperature is about 140-150°C
  • total longitudinal stretching ratio is about 5-9 times, and then cooled to room temperature.
  • Transverse stretching preheating temperature is about 120-140°C; stretching temperature is about 150-160°C; heat setting temperature is about 165-170°C; total transverse stretching ratio is about 4-8 times.
  • the heat treatment temperature is about 120-135°C, the purpose is to eliminate the internal stress of the membrane and improve the thermal stability of the membrane.
  • the film After heat treatment, the film is air-cooled in the platform area and then enters the winding system through the traction system for film winding.
  • the winding tension is about 20-30N/m.
  • the present invention also provides a composite current collector, the structure of which includes a first protective layer, a first metal layer, a support layer, a second metal layer and a second protective layer arranged in layers;
  • the support layer comprises a composite polypropylene material according to above.
  • the composite polypropylene material provided by the present invention has high and stable surface tension, excellent surface adhesion performance, strong metal bonding, and can be firmly bonded to metal.
  • the composite polypropylene material prepared by the present invention is used as a support layer of a composite current collector (a carrier of a composite current collector), which can firmly bond to a metal layer and improve battery performance.
  • the thickness of the support layer is about 1 ⁇ m-20 ⁇ m, which better meets the application requirements of the composite current collector while taking into account the difficulty and cost of the preparation process.
  • the two metal layers are located on both sides of the support layer and function as a conductor. It is understandable that the materials of the two metal layers may be consistent or inconsistent, and the thicknesses may be consistent or inconsistent.
  • the first metal layer and the second metal layer independently include: a metal and an alloy thereof with a resistivity of about ⁇ 8 ⁇ 10-8 ⁇ m.
  • the metal with a resistivity of about ⁇ 8 ⁇ 10-8 ⁇ m is one or more of copper, aluminum, silver, gold, zinc, molybdenum, cobalt and nickel, and the alloy that meets the requirements is selected from one or more of copper alloy, aluminum alloy and nickel alloy.
  • the thickness of the first metal layer and the second metal layer are independently about 500 nm-2000 nm.
  • the thickness of the first metal layer and the second metal layer are independently about 700 nm-1200 nm, which can have better conductivity.
  • the first metal layer and the second metal layer are independently prepared by one or more methods such as physical vapor deposition (such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.), electroplating, and chemical plating.
  • physical vapor deposition such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.
  • electroplating such as electroplating, and chemical plating.
  • the first protective layer and the second protective layer are arranged on the side of the metal layer away from the support layer to prevent the metal conductive layer from being chemically corroded or physically damaged. It can be understood that the materials of the two protective layers can be consistent or inconsistent, and the thickness can be consistent or inconsistent.
  • the first protective layer and the second protective layer independently include: one or more of inactive metals and alloys thereof, metal oxides and carbon materials.
  • the inactive metal is selected from nickel and/or chromium.
  • the inactive metal alloy is selected from one or more of nickel-based alloys, chromium-based alloys, and nickel-chromium-copper alloys.
  • the metal oxide is selected from one or more of copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, and copper-chromium oxide.
  • the carbon material is selected from one or more of graphite, carbon black, acetylene black, Ketjen black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers, and graphene.
  • the thickness of the first protective layer and the second protective layer are independently about 10 nm-150 nm.
  • the thickness of the first protective layer and the second protective layer are respectively about 20nm-100nm, and the thickness of the protective layer shall not exceed one tenth of the thickness of the metal layer.
  • the preparation methods of the first protective layer and the second protective layer are independently one or more of physical vapor deposition, chemical vapor deposition, in-situ forming, coating, etc.
  • the vapor deposition method is vacuum evaporation or magnetron sputtering;
  • the chemical vapor deposition is atmospheric pressure chemical vapor deposition or plasma enhanced chemical vapor deposition;
  • the in-situ forming is a method of in-situ forming a metal oxide passivation layer on the surface of the metal layer;
  • the coating method is die coating, blade coating or extrusion coating.
  • FIG. 4 is a schematic diagram of the structure of a composite current collector in an embodiment of the present invention, wherein 401 is a first protective layer, 402 is a first metal layer, 403 is a support layer, 404 is a second metal layer, and 405 is a second protective layer.
  • the present invention also provides a pole piece, comprising the composite current collector as described above.
  • the present invention also provides a battery, comprising the pole piece as described above.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • This embodiment provides a multi-layer composite polypropylene film and a preparation method thereof, a composite current collector and a preparation method thereof.
  • the first modified layer is composed as follows: First Polypropylene 79.8%; First modified polypropylene 20%; First antioxidant 0.2%;
  • the melt index of the first polypropylene is 3.0g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.2, and the isotacticity is 96%.
  • the first modified polypropylene is polypropylene grafted with maleic anhydride, and its melt index is 3.2g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.5, and the grafting rate is 0.2%.
  • the first antioxidant is triphenyl phosphite.
  • the core layer composition is as follows: Polypropylene 99.8%; tertiary antioxidant 0.2%;
  • the melt index of polypropylene is 3.0 g/10 min/(230° C./2.16 kg), the molecular weight distribution index is 5.2, the isotacticity is 97%, and the third antioxidant is triphenyl phosphite.
  • the second modified layer is composed as follows: second polypropylene 79.8%; Second modified polypropylene 20%; Second antioxidant 0.2%;
  • the melt index of the second polypropylene is 3.0g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.2, and the isotacticity is 96%.
  • the second modified polypropylene is polypropylene grafted with maleic anhydride, and its melt index is 3.2g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.5, and the grafting rate is 0.2%.
  • the second antioxidant is triphenyl phosphite.
  • the raw materials of the first modified layer, the core layer and the second modified layer are respectively added into the corresponding twin-screw extruder, melted at 250°C, filtered through a filter (10 micron filter screen), and then extruded through a die head with a die head temperature of 260°C.
  • the extrusion ratio of the three layers is controlled at 10%:80%:10%.
  • the molten polyester material extruded from the die head is cast onto the casting roll, and is formed by the casting roll and water cooling treatment, and the cooling temperature is 30°C.
  • the synchronous stretching process is as follows: it is divided into three areas: preheating area, stretching area, and heat setting area. Specifically:
  • Preheating zone divided into two sections, the temperature increases successively, i.e. 135°C and 150°C;
  • Stretching zone divided into three sections, the temperature increases successively, namely 153°C, 157°C, 160°C; stretching ratio: the total longitudinal stretching ratio is 6 times, and the total transverse stretching ratio is 5 times;
  • Heat setting area divided into two sections, the temperature increases successively, namely 163°C and 166°C.
  • the heat-treated film After the heat-treated film is air-cooled in the platform area, it enters the winding system through the traction system for film winding, and the winding tension is 30N/m.
  • a multi-layer composite polypropylene film with a total thickness of 4.5 microns is prepared, the thickness of the first modified layer and the second modified layer are both 0.45 microns, and the thickness of the core layer is 3.6 microns.
  • metal conductive layer Preparation of metal conductive layer: The multi-layer composite polypropylene film prepared as above and cleaned on the surface is placed in a vacuum evaporation chamber, and the high-purity aluminum wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at a high temperature of 1300-2000°C. The evaporated metal atoms pass through the cooling system in the vacuum coating chamber and are deposited on the two surfaces of the polymer base film to form an aluminum metal conductive layer with a thickness of 1 micron.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the method is basically the same as Example 1, except that the content of each raw material in the modified layer is changed, specifically:
  • polypropylene, maleic anhydride grafted modified polypropylene, and triphenyl phosphite in the first modified layer are 49.8%, 50.0%, and 0.2%, respectively;
  • polypropylene, polypropylene grafted with maleic anhydride and triphenyl phosphite in the second modified layer are 49.8%, 50.0% and 0.2% respectively.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the method is basically the same as Example 1, except that the content of each raw material in the modified layer is changed, specifically:
  • polypropylene, maleic anhydride grafted modified polypropylene, and triphenyl phosphite in the first modified layer are 0%, 99.8%, and 0.2%, respectively;
  • polypropylene, polypropylene grafted with maleic anhydride, and triphenyl phosphite in the second modified layer are 0%, 99.8%, and 0.2%, respectively.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the method is basically the same as Example 1, except that the content of each raw material in the modified layer is changed, specifically:
  • polypropylene, polypropylene grafted with maleic anhydride, and triphenyl phosphite in the first modified layer are 79.5%, 20.0%, and 0.5%, respectively;
  • polypropylene, polypropylene grafted with maleic anhydride and triphenyl phosphite in the second modified layer are 79.5%, 20.0% and 0.5% respectively.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the method is basically the same as Example 1, except that the content of each raw material in the modified layer is changed, specifically:
  • the first modified layer contains polypropylene, maleic anhydride grafted modified polypropylene, and triphenyl phosphite. The contents are 80.8%, 19.0%, and 0.2% respectively;
  • polypropylene, polypropylene grafted with maleic anhydride, and triphenyl phosphite in the second modified layer are 80.8%, 19.0%, and 0.2%, respectively.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the method is basically the same as Example 1, except that the content of each raw material in the modified layer is changed, specifically:
  • polypropylene, maleic anhydride grafted modified polypropylene, and triphenyl phosphite in the first modified layer are 0%, 99.9%, and 0.1%, respectively;
  • polypropylene, polypropylene grafted with maleic anhydride and triphenyl phosphite in the second modified layer are 0%, 99.9% and 0.1% respectively.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the method is basically the same as Example 2, except that the grafting rate of the modified polypropylene in the modified layer is changed, specifically:
  • the grafting rate of polypropylene modified by maleic anhydride grafting in the first modified layer is 0.9%;
  • the grafting rate of the polypropylene modified by grafting with maleic anhydride in the second modified layer was 0.9%.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the method is basically the same as Example 2, except that the grafting rate of the modified polypropylene in the modified layer is changed, specifically:
  • the grafting rate of polypropylene modified by maleic anhydride grafting in the first modified layer is 1.5%;
  • the grafting rate of the polypropylene modified by grafting with maleic anhydride in the second modified layer was 1.5%.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • the method is basically the same as Example 2, except that the grafting rate of the modified polypropylene in the modified layer is changed, specifically:
  • the grafting rate of polypropylene modified by maleic anhydride grafting in the first modified layer is 0.1%
  • the grafting rate of the polypropylene modified by grafting with maleic anhydride in the second modified layer was 0.1%.
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • the method is basically the same as Example 2, except that the grafting rate of the modified polypropylene in the modified layer is changed, specifically:
  • the grafting rate of maleic anhydride grafted polypropylene in the first modified layer is 1.6%;
  • the grafting rate of the polypropylene modified by grafting with maleic anhydride in the second modified layer was 1.6%.
  • Embodiment 11 is a diagrammatic representation of Embodiment 11:
  • the method is substantially the same as Example 7, except that the melt index of the modified polypropylene in the modified layer is changed, specifically:
  • the melt index of the maleic anhydride grafted modified layer in the first modified layer is 3.6 g/10 min/(230°C/2.16 kg);
  • the melt index of the maleic anhydride grafted modified layer in the second modified layer was 3.6 g/10 min/(230° C./2.16 kg).
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • the method is substantially the same as Example 7, except that the melt index of the modified polypropylene in the modified layer is changed, specifically:
  • the melt index of the maleic anhydride grafted modified layer in the first modified layer is 4.0 g/10 min/(230°C/2.16 kg);
  • the melt index of the maleic anhydride grafted modified layer in the second modified layer was 4.0 g/10 min/(230° C./2.16 kg).
  • Embodiment 13 is a diagrammatic representation of Embodiment 13:
  • the method is substantially the same as Example 7, except that the melt index of the modified polypropylene in the modified layer is changed, specifically:
  • the melt index of the maleic anhydride grafted modified layer in the first modified layer is 3.1 g/10 min/(230°C/2.16 kg);
  • the melt index of the maleic anhydride grafted modified layer in the second modified layer was 3.1 g/10 min/(230° C./2.16 kg).
  • Embodiment 14 is a diagrammatic representation of Embodiment 14:
  • the method is substantially the same as Example 7, except that the melt index of the modified polypropylene in the modified layer is changed, specifically:
  • the melt index of the maleic anhydride grafted modified layer in the first modified layer is 4.1 g/10 min/(230°C/2.16 kg);
  • the melt index of the maleic anhydride grafted modified layer in the second modified layer was 4.1 g/10 min/(230° C./2.16 kg).
  • Embodiment 15 is a diagrammatic representation of Embodiment 15:
  • the molecular weight distribution index of the maleic anhydride graft modification in the first modified layer is 5.0;
  • the molecular weight distribution index of the maleic anhydride graft modification in the second modified layer was 5.0.
  • Embodiment 16 is a diagrammatic representation of Embodiment 16:
  • the method is basically the same as Example 11, except that the molecular weight distribution index of the modified polypropylene in the modified layer is changed, specifically:
  • the molecular weight distribution index of maleic anhydride graft modification in the first modified layer is 4.6;
  • the molecular weight distribution index of the maleic anhydride graft modification in the second modified layer was 4.6.
  • Embodiment 17 is a diagrammatic representation of Embodiment 17:
  • the method is basically the same as Example 11, except that the molecular weight distribution index of the modified polypropylene in the modified layer is changed, specifically:
  • the molecular weight distribution index of maleic anhydride graft modification in the first modified layer is 5.6;
  • the molecular weight distribution index of the maleic anhydride graft modification in the second modified layer was 5.6.
  • Embodiment 18 is a diagrammatic representation of Embodiment 18:
  • the method is basically the same as Example 15, except that the molecular weight distribution index of the modified polypropylene in the modified layer is changed, specifically:
  • the molecular weight distribution index of the maleic anhydride grafted modification in the first modified layer is 4.5;
  • the molecular weight distribution index of the maleic anhydride graft modification in the second modified layer was 4.5.
  • Embodiment 19 is a diagrammatic representation of Embodiment 19:
  • Example 15 It is basically the same as Example 15, except that the longitudinal stretching ratio in the synchronous stretching is changed, and the total longitudinal stretching ratio after three-stage stretching treatment is 7:1.
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • Example 15 It is basically the same as Example 15, except that the longitudinal stretching ratio in the synchronous stretching is changed, and the total longitudinal stretching ratio after three-stage stretching treatment is 8:1.
  • Embodiment 21 is a diagrammatic representation of Embodiment 21.
  • Example 15 It is basically the same as Example 15, except that the longitudinal stretching ratio in the synchronous stretching is changed, and the total longitudinal stretching ratio after three-stage stretching treatment is 5:1.
  • Example 15 It is basically the same as Example 15, except that the longitudinal stretching ratio in the synchronous stretching is changed, and the total longitudinal stretching ratio after three-stage stretching treatment is 9:1.
  • Embodiment 23 is a diagrammatic representation of Embodiment 23.
  • the method is basically the same as Example 1, except that the content of each raw material of the core layer is changed, specifically:
  • polypropylene and triphenyl phosphite are 99.5% and 0.5% respectively.
  • Embodiment 24 is a diagrammatic representation of Embodiment 24.
  • Example 19 It is basically the same as Example 19, except that the polypropylene modified by grafting maleic anhydride in the first modified layer and the second modified layer is replaced by polypropylene modified by grafting glycidyl acrylate.
  • Embodiment 25 is a diagrammatic representation of Embodiment 25.
  • Example 19 It is basically the same as Example 19, except that the type of modified polypropylene is changed, specifically, the polypropylene grafted modified with maleic anhydride in the first modified layer and the second modified layer is replaced with polypropylene grafted modified with diethylenetriamine-glycidyl methacrylate.
  • Embodiment 26 is a diagrammatic representation of Embodiment 26.
  • Example 2 It is basically the same as Example 1, except that: the isotacticity of the polypropylene in the first modified layer and the second modified layer is changed, specifically: the isotacticity of the polypropylene in the first modified layer and the second modified layer is 93%.
  • Embodiment 27 is a diagrammatic representation of Embodiment 27.
  • Example 2 It is basically the same as Example 1, except that: the isotacticity of the polypropylene in the first modified layer and the second modified layer is changed, specifically: the isotacticity of the polypropylene in the first modified layer and the second modified layer is 90%.
  • Embodiment 28 is a diagrammatic representation of Embodiment 28:
  • Example 2 It is basically the same as Example 1, except that: the isotacticity of the polypropylene in the first modified layer and the second modified layer is changed, specifically: the isotacticity of the polypropylene in the first modified layer and the second modified layer is 89%.
  • Embodiment 29 is a diagrammatic representation of Embodiment 29.
  • Example 2 It is basically the same as Example 1, except that: the isotacticity of the polypropylene in the first modified layer and the second modified layer is changed, specifically: the isotacticity of the polypropylene in the first modified layer and the second modified layer is 97%.
  • Embodiment 30 is a diagrammatic representation of Embodiment 30.
  • Example 2 It is basically the same as Example 1, except that the isotacticity of the polypropylene used in the core layer is 99%.
  • Embodiment 31 is a diagrammatic representation of Embodiment 31.
  • Example 2 It is basically the same as Example 1, except that the isotacticity of the polypropylene used in the core layer is 96%.
  • Embodiment 32 is a diagrammatic representation of Embodiment 32.
  • Example 2 It is basically the same as Example 1, except that the concentration of the antioxidant triphenyl phosphite used in the first modified layer, the core layer and the second modified layer is 0.1%.
  • the contents of polypropylene, maleic anhydride grafted polypropylene, and triphenyl phosphite in the first modified layer are 79.9%, 20%, and 0.1%, respectively;
  • the contents of polypropylene and triphenyl phosphite in the core layer are 99.9% and 0.1% respectively;
  • polypropylene, polypropylene grafted with maleic anhydride and triphenyl phosphite in the second modified layer are 79.9%, 20% and 0.1% respectively.
  • Embodiment 33 is a diagrammatic representation of Embodiment 33.
  • Example 2 It is basically the same as Example 1, except that the concentration of the antioxidant triphenyl phosphite used in the first modified layer, the core layer and the second modified layer is 0.6%.
  • the contents of polypropylene, maleic anhydride grafted polypropylene, and triphenyl phosphite in the first modified layer are 79.4%, 20%, and 0.6%, respectively;
  • the contents of polypropylene and triphenyl phosphite in the core layer are 99.4% and 0.6% respectively;
  • polypropylene, polypropylene grafted with maleic anhydride and triphenyl phosphite in the second modified layer are 79.4%, 20% and 0.6% respectively.
  • Embodiment 34 is a diagrammatic representation of Embodiment 34.
  • the method is basically the same as Example 1, except that the content of the polypropylene grafted with maleic anhydride in the second modified layer is changed, specifically:
  • the first modified layer is composed as follows: First Polypropylene 79.8%; First modified polypropylene 20%; First antioxidant 0.2%;
  • the melt index of the first polypropylene is 3.0g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.2, and the isotacticity is 96%.
  • the first modified polypropylene is polypropylene grafted with maleic anhydride, and its melt index is 3.2g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.5, and the grafting rate is 0.2%.
  • the first antioxidant is triphenyl phosphite.
  • the core layer composition is as follows: Polypropylene 99.8%; tertiary antioxidant 0.2%;
  • the melt index of polypropylene is 3.0 g/10 min/(230° C./2.16 kg), the molecular weight distribution index is 5.2, the isotacticity is 97%, and the third antioxidant is triphenyl phosphite.
  • the second modified layer is composed as follows: second polypropylene 69.8%; Second modified polypropylene 30%; Second antioxidant 0.2%;
  • the second polypropylene has a melt index of 3.0 g/10 min/(230° C./2.16 kg), a molecular weight distribution index of 5.2, and an isotacticity of 96%.
  • the second modified polypropylene is a polypropylene grafted with maleic anhydride. Its melt index is 3.2 g/10 min/(230° C./2.16 kg), its molecular weight distribution index is 5.5, its grafting rate is 0.2%, and its second antioxidant is triphenyl phosphite.
  • Embodiment 35 is a diagrammatic representation of Embodiment 35.
  • the method is basically the same as Example 1, except that the type of modified polypropylene in the second modified layer is changed, specifically:
  • the first modified layer is composed as follows: First Polypropylene 79.8%; First modified polypropylene 20%; First antioxidant 0.2%;
  • the melt index of the first polypropylene is 3.0g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.2, and the isotacticity is 96%.
  • the first modified polypropylene is polypropylene grafted with maleic anhydride, and its melt index is 3.2g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.5, and the grafting rate is 0.2%.
  • the first antioxidant is triphenyl phosphite.
  • the core layer composition is as follows: Polypropylene 99.8%; tertiary antioxidant 0.2%;
  • the melt index of polypropylene is 3.0 g/10 min/(230° C./2.16 kg), the molecular weight distribution index is 5.2, the isotacticity is 97%, and the third antioxidant is triphenyl phosphite.
  • the second modified layer is composed as follows: second polypropylene 79.8%; Second modified polypropylene 20%; Second antioxidant 0.2%;
  • the melt index of the second polypropylene is 3.0g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.2, and the isotacticity is 96%.
  • the second modified polypropylene is diethylenetriamine-methacrylate grafted modified polypropylene, and its melt index is 3.2g/10min/(230°C/2.16kg), the molecular weight distribution index is 5.5, and the grafting rate is 0.2%.
  • the second antioxidant is triphenyl phosphite.
  • Embodiment 36 is a diagrammatic representation of Embodiment 36.
  • Example 19 It is basically the same as Example 19, except that the modified polypropylene in the first and second modified layers is polypropylene graft-modified with maleic anhydride oligomer (degree of polymerization is 10).
  • Embodiment 37 is a diagrammatic representation of Embodiment 37.
  • Example 19 It is basically the same as Example 19, except that the modified polypropylene in the first and second modified layers is polypropylene grafted with succinylfluorescein-succinic anhydride.
  • Embodiment 38 is a diagrammatic representation of Embodiment 38.
  • the modified polypropylene in the first and second modified layers is a mixture of polypropylene grafted with maleic anhydride oligomer (degree of polymerization is 10) and polypropylene grafted with succinylfluorescein-succinic anhydride, and the mass ratio of the two is 1:1.
  • the method is basically the same as Example 1, except that no polypropylene modified by grafting maleic anhydride is added to the first modified layer and the second modified layer.
  • Example 2 The same as Example 1, except that the first modified layer does not contain maleic anhydride grafted modified Polypropylene.
  • Example 2 It is basically the same as Example 1, except that: all three layers are modified layers: that is, the contents of polypropylene, maleic anhydride grafted modified polypropylene, and triphenyl phosphite in the first modified layer, the second modified layer, and the core layer are 79.8%, 20%, and 0.2%, respectively.
  • the method is basically the same as Example 1, except that: the synchronous stretching is set to 1 stage, the stretching is in place in one step, the temperature is 160°C; the stretching ratio: the total longitudinal stretching ratio is 6 times, and the total transverse stretching ratio is 5 times;
  • the method is basically the same as Example 2, except that the grafting rate of the modified polypropylene in the modified layer is changed, specifically:
  • the grafting rate of polypropylene modified by maleic anhydride grafting in the first modified layer is 2.2%;
  • the grafting rate of the polypropylene modified by grafting with maleic anhydride in the second modified layer was 2.2%.
  • the purpose of preparing the multilayer composite polypropylene film is to improve the surface adhesion performance of the film and Mechanical properties, thereby improving the performance of the composite current collector prepared with this polypropylene film as the substrate.
  • the factors affecting the surface adhesion performance of the polypropylene film namely the surface tension and surface free volume, the adhesion between the multi-layer composite polypropylene film and the surface metal layer in the composite current collector, and other indicators are tested and characterized.
  • the tensile strength of the prepared multi-layer composite polypropylene film and the defective rate caused by surface defects are also tested.
  • the specific test methods are as follows:
  • the bonding strength between the multi-layer composite polypropylene film and the metal layer in the composite current collector a layer of Permacel P-94 double-sided tape is bonded on a 1mm thick aluminum foil, the composite current collector is bonded on the double-sided tape, and a layer of ethylene acrylic acid copolymer film (DuPont Nurcel0903, thickness of 50 ⁇ m) is covered on the composite current collector, and then hot-pressed at 1.3 ⁇ 105N/m2 and 120°C for 10s, cooled to room temperature, and cut into 150mm ⁇ 15mm strips. Finally, the ethylene acrylic acid copolymer film of the sample strip is fixed to the upper fixture of the tensile machine, and the rest is fixed to the lower fixture. After fixing, the two are peeled at an angle of 180o and a speed of 100mm/min to test the peeling force, that is, the bonding strength between the multi-layer composite polypropylene film and the metal layer.
  • Adhesion 1 and Adhesion 2 in the table represent the adhesion between the first modified layer, the second modified layer and the metal layer of the multi-layer composite polypropylene film, respectively.
  • the tensile strength of the prepared multi-layer composite polypropylene film basically shows a trend of first increasing and then remaining basically unchanged when the content of the antioxidant in the modified layer and the core layer is increased. This is because the increase in the content of the antioxidant can reduce the degradation rate of polypropylene during the melting process, thereby reducing the decrease in the average molecular weight of polypropylene. However, the increase in the content of the antioxidant in the modified layer and the core layer has little effect on the surface tension and free volume of the modified layer.
  • Example 1 It can be seen from Example 1 and Comparative Example 5 that, compared with one-step stretching, multiple stretching treatments can make the prepared multi-layer composite polypropylene film have better tensile strength and lower defective rate.
  • the composite current collector samples prepared in Examples 1, 2, 3 and Comparative Example 1 are used as the electrode current collectors of the battery, and lithium iron phosphate is used as the positive electrode material, graphite is used as the negative electrode material, and carbonate is used as the electrolyte to prepare soft-pack batteries.
  • the prepared batteries are subjected to cycle experiments at a charge and discharge rate of 0.5C, and the changes in energy density (unit mass of active electrode material) with the number of cycles are shown in Figure 5.

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Abstract

Matériau de polypropylène composite multicouche, procédé de préparation s'y rapportant et utilisation associée. Le matériau de polypropylène composite multicouche comprend une première couche modifiée (101), une couche centrale (102) et une seconde couche modifiée (103) qui sont agencées de manière empilée, la première couche modifiée (101) comprenant un premier polypropylène modifié ; la couche centrale (102) comprenant du polypropylène ; la seconde couche modifiée (103) comprenant un second polypropylène modifié ; et les premier et second polypropylènes modifiés étant chacun indépendamment choisis parmi : un ou plusieurs éléments parmi le polypropylène modifié par greffage d'anhydride maléique, le polypropylène modifié par greffage d'acide acrylique-anhydride maléique, le polypropylène modifié par greffage de diéthylènetriamine-méthacrylate de glycidyle, le polypropylène modifié par greffage d'acrylamide, le polypropylène modifié par greffage d'acide acrylique-acrylamide, le polypropylène greffé par anhydride succinique, le polypropylène greffé par anhydride succinique-fluorescéine succinyle, ainsi que des polypropylènes modifiés dans lesquels de l'hydrogène dans des molécules modifiées polaires est substitué par un atome de méthyle, d'éthyle ou d'halogène ; et un ou plusieurs éléments parmi le polypropylène modifié par greffage d'oligomère d'anhydride maléique, le polypropylène modifié par greffage d'oligomère (acide acrylique-anhydride maléique), le polypropylène modifié par greffage d'oligomère de méthacrylate de glycidyle, le polypropylène modifié par greffage d'oligomère de di(éthylène triamine-méthacrylate de glycidyle), le polypropylène modifié par greffage d'oligomère d'acrylamide, le polypropylène greffé d'oligomère (acrylamide-acide acrylique), le polypropylène greffé d'oligomère d'anhydride succinique, le polypropylène greffé d'oligomère (fluorescéine succinyle-anhydride succinique), ainsi que des polypropylènes modifiés dans lesquels de l'hydrogène dans des molécules modifiées polaires est substitué par un atome de méthyle, d'éthyle ou d'halogène.
PCT/CN2023/131848 2022-11-15 2023-11-15 Matériau de polypropylène composite multicouche, procédé de préparation s'y rapportant et utilisation associée WO2024104393A1 (fr)

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