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WO2024244050A1 - Modified polypropylene film, preparation method therefor and use thereof - Google Patents

Modified polypropylene film, preparation method therefor and use thereof Download PDF

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Publication number
WO2024244050A1
WO2024244050A1 PCT/CN2023/099589 CN2023099589W WO2024244050A1 WO 2024244050 A1 WO2024244050 A1 WO 2024244050A1 CN 2023099589 W CN2023099589 W CN 2023099589W WO 2024244050 A1 WO2024244050 A1 WO 2024244050A1
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WIPO (PCT)
Prior art keywords
modified polypropylene
polypropylene film
film
preparation
modified
Prior art date
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Pending
Application number
PCT/CN2023/099589
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French (fr)
Chinese (zh)
Inventor
朱中亚
王帅
夏建中
李学法
张国平
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Jiangyin Nanopore Innovative Materials Technology Ltd
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Jiangyin Nanopore Innovative Materials Technology Ltd
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Priority to KR1020257032885A priority Critical patent/KR20250166169A/en
Publication of WO2024244050A1 publication Critical patent/WO2024244050A1/en
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application belongs to the technical field of high molecular polymer membranes, for example, a modified polypropylene membrane 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 characteristics of low cost, light weight, and good internal insulation. These characteristics 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.
  • modified polypropylene is prepared by selecting a specific modifier, and the modified polypropylene is used as a preparation raw material to prepare a modified polypropylene film with excellent performance, making it suitable for use as a composite current collector base film.
  • an embodiment of the present application provides a modified polypropylene film, wherein the raw material for preparing the modified polypropylene film includes modified polypropylene;
  • the modifier for modifying the polypropylene includes terpene alcohol.
  • the hydroxyl groups in the terpene alcohol molecules are used to increase the surface tension of the prepared modified polypropylene film, and the terpene alcohol molecules have a conjugated structure and can form an electronic conjugated system with metal atoms.
  • the increase in surface tension and the formation of the conjugated structure jointly promote the interaction between the metal atoms and the modified polypropylene film, thereby increasing the adhesion between the base film and the metal layer in the prepared composite current collector; on the other hand, the dielectric constant of the polypropylene modified by terpene alcohol is higher than that of polypropylene.
  • Introducing terpene alcohol-modified polypropylene into the raw materials for preparing the modified polypropylene film can increase the dielectric constant of the modified polypropylene film, thereby solving the problem of holes caused by the breakdown of the polypropylene film during physical vapor deposition.
  • polar functional groups and conjugated structures are introduced into the modified polypropylene film to improve the Improve the dielectric constant of modified polypropylene film.
  • the grafting rate is the ratio of the mass of the terpene alcohol monomer grafted onto the polypropylene to the mass of the grafted polypropylene.
  • the performance of the modified polypropylene film is improved, so that it has a higher dielectric constant and higher mechanical properties. If the grafting rate of terpene alcohol in the modified polypropylene is too low, the performance improvement of the prepared polypropylene film is limited; if the grafting rate of terpene alcohol in the modified polypropylene is too high, the modified polypropylene with too high a grafting rate will affect the orientation and crystallization of the polypropylene polymer during the stretching process, thereby resulting in a decrease in the tensile strength of the prepared modified polypropylene film.
  • the terpene alcohol includes any one of 4-terpene alcohol, ⁇ -terpineol, carveol, lavandulol, nerol, geraniol, or a combination of at least two thereof.
  • the preparation method of the modified polypropylene comprises the following steps:
  • the reactor is fully replaced and dried with nitrogen, and then the uniformly mixed terpene alcohol, polypropylene, organic solvent and catalyst are added into the reactor, and then the temperature is raised to 60-100° C. in a nitrogen atmosphere, and the reaction is carried out for 2-24 hours, and then the temperature is lowered to room temperature, and the mixed liquid is discharged from the reactor with nitrogen, and the modified polypropylene is obtained after filtering, washing and drying;
  • the organic solvent is selected from C6-C20 alkane solvents (for example, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20, etc.), further selected from n-hexane.
  • C6-C20 alkane solvents for example, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20, etc.
  • the catalyst is selected from any one of a Ziegler-Natta catalyst, a DQC catalyst or a HR catalyst.
  • HR catalyst is purchased from Sinopec Catalyst Co., Ltd.
  • the mass of the added terpene alcohol is 0.50-150 g
  • the mass of the polypropylene is 890.0-999.5 g
  • the volume of the organic solvent is 800-2000 mL
  • the mass of the catalyst is 10-50 g.
  • the mass of the added terpene alcohol can be 0.50g, 1.00g, 2.00g, 5.00g, 10.0g, 20.0g, 40.0g, 60.0g, 80.0g, 100g, 120g, 135g or 150g, etc.
  • the mass of the polypropylene may be 890.0 g, 900.0 g, 910.0 g, 920.0 g, 930.0 g, 940.0 g, 950.0 g, 960.0 g, 970.0 g, 980.0 g, 990.0 g or 999.5 g, etc.
  • the volume of the organic solvent can be 800 mL, 900 mL, 1000 mL, 1100 mL, 1200 mL, 1300 mL, 1400 mL, 1500 mL, 1600 mL, 1700 mL, 1800 mL, 1900 mL or 2000 mL, etc.
  • the mass of the catalyst can be 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g or 50g, etc.
  • the reaction temperature for preparing the modified polypropylene can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C, and the reaction time can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc.
  • the melt index of the polypropylene in the modified polypropylene is 3.0-4.0 g/10 min, for example, it can be 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, 3.9 g/10 min. Or 4.0g/10min, etc.
  • the stretching step of preparing the modified polypropylene film is easy to form a film, and the performance of the prepared modified polypropylene film is good. If the melt index of polypropylene is too low and the molecular weight is too large, the film forming property of the modified polypropylene film during the film drawing process is poor; if the melt index of polypropylene is too high and the molecular weight is too low, its film forming property is poor and the mechanical properties of the prepared modified polypropylene film are poor.
  • test conditions for the melt index are 230°C/2.16kg.
  • the molecular weight distribution of the polypropylene in the modified polypropylene is 4.5-5.5, for example, it can be 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4 or 5.5.
  • the prepared modified polypropylene film has good mechanical properties and a high yield rate. If the molecular weight distribution index of polypropylene is too high, the content of small molecular weight polypropylene is more, resulting in poor mechanical properties and poor film-forming properties of the prepared film; if the molecular weight distribution index of polypropylene is too low, the film-forming properties of the modified polypropylene deteriorate during the film drawing process, resulting in a decrease in the product yield rate.
  • the isotacticity of the polypropylene in the modified polypropylene is ⁇ 95%, for example, it may be 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98%, etc.
  • the mechanical properties of the modified polypropylene film can be further improved by controlling the isotacticity of polypropylene to be ⁇ 95%.
  • the improvement of the regularity of polypropylene can improve the orientation and crystallinity of the prepared film, thereby improving the mechanical properties of the modified polypropylene film.
  • the mass percentage of the modified polypropylene is ⁇ 0.5%, for example, it can be 0.5%, 1%, 2%, 5%, 7%, 10%, 13%, 15%, 18%, 20% or 24%, etc.
  • the performance of the modified polypropylene film can be significantly improved by controlling the mass percentage of modified polypropylene in the raw material for preparing the modified polypropylene film to ⁇ 0.5%. If the mass percentage of modified polypropylene is too low, the improvement of the performance of the modified polypropylene film is limited.
  • the raw materials for preparing the modified polypropylene film also include polypropylene.
  • the thickness of the modified polypropylene film is ⁇ 1 ⁇ m (for example, it can be 1 ⁇ m, 2 ⁇ m, 5 ⁇ m, 7 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, 18 ⁇ m, 20 ⁇ m, 24 ⁇ m, 27 ⁇ m or 30 ⁇ m, etc.), preferably 2-20 ⁇ m.
  • the thinner the modified polypropylene film is the more it can promote the improvement of the energy density of the composite current collector, but the production difficulty must be taken into account at the same time. Since the thinner the modified polypropylene film is, the greater the production difficulty and the lower the yield rate, in the embodiment of the present application, the thickness of the modified polypropylene film is controlled to be ⁇ 1 ⁇ m, which can not only prepare a modified polypropylene film with excellent performance, but also take into account the production process of the modified polypropylene film, so that it has a higher yield rate.
  • an embodiment of the present application provides a method for preparing the modified polypropylene film as described in the first aspect, the preparation method comprising the following steps:
  • step (2) Casting the molten material obtained in step (1) onto a casting roll, cooling and forming the molten material, and then biaxially stretching the molten material to obtain the modified polypropylene film.
  • modified polypropylene as the raw material for preparing the modified polypropylene film and selecting the melt extrusion-biaxial stretching preparation process, a modified polypropylene film with a higher dielectric constant and better mechanical properties is prepared, making it suitable for use as a composite current collector base film.
  • the melting temperature is 200-260°C, for example, it can be 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C or 260°C, etc.
  • the filtering method includes filtering through a filter with a filter screen of 10 ⁇ m.
  • the cooling molding method is molding through water cooling treatment.
  • the cooling molding temperature is 15-60°C, for example, it can be 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.
  • melting and extrusion are carried out in a twin-screw extruder.
  • the biaxial stretching includes synchronous stretching and asynchronous stretching.
  • the synchronous stretching process includes preheating, stretching and heat setting.
  • the preheating zone includes a first preheating zone and a second preheating zone.
  • the temperature of the first preheating zone is 130-145°C, for example, it can be 130°C, 132°C, 135°C, 137°C, 140°C, 142°C or 145°C.
  • the temperature of the second preheating zone is 145-155°C, for example, it can be 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C or 155°C, etc.
  • the stretching temperature includes a first stretching temperature and a second stretching temperature.
  • the first stretching temperature is 155-160°C, for example, 155°C, 156°C, 157°C, 158°C, 159°C or 160°C.
  • the second stretching temperature is 160-165°C, for example, 160°C, 161°C, 162°C, 163°C, 164°C or 165°C.
  • the longitudinal stretching ratio of the stretching is 6-8, for example, it can be 6, 6.3, 6.5, 6.8, 7, 7.2, 7.5, 7.7 or 8, etc.
  • the stretched transverse stretching zones are 5-7, for example, 5, 5.2, 5.5, 5.8, 6, 6.3, 6.5, 6.8 or 7, etc.
  • the heat setting temperature is 165-169°C, for example, 165°C, 166°C, 167°C, 168°C or 169°C.
  • the asynchronous stretching process includes longitudinal stretching, transverse stretching and heat treatment.
  • the preheating temperature for longitudinal stretching is 115-140°C, for example, 115°C, 118°C, 120°C, 124°C, 127°C, 130°C, 132°C, 135°C, 138°C or 140°C, etc.
  • the stretching temperature of the longitudinal stretching is 140-150°C, for example, it can be 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C or 150°C, etc.
  • the longitudinal stretching ratio of the longitudinal stretching is 6-8, for example, it can be 6, 6.3, 6.5, 6.8, 7, 7.2, 7.5, 7.7 or 8, etc.
  • the longitudinal stretching further includes a post-processing step.
  • the post-treatment method includes cooling to room temperature.
  • the preheating temperature for transverse stretching is 120-140°C, for example, it may be 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C, 136°C, 138°C or 140°C, etc.
  • the stretching temperature of the transverse stretching is 140-160°C, for example, it can be 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C or 160°C, etc.
  • the heat setting temperature of the transverse stretching is 165-169°C, for example, 165°C, 166°C, 167°C, 168°C or 169°C.
  • the stretching ratio of the transverse stretching is 5-7, for example, it can be 5, 5.2, 5.5, 5.8, 6, 6.3, 6.5, 6.8 or 7.
  • the heat treatment temperature is 110-140°C, for example, 110°C, 112°C, 115°C, 118°C, 120°C, 124°C, 127°C, 130°C, 132°C, 135°C, 138°C or 140°C. wait.
  • the biaxial stretching further includes a post-processing step.
  • the post-processing method includes: after air cooling in the platform area, entering the winding system through the traction system to wind up the film.
  • the winding tension is 20-30 N/m, for example, it can be 20 N/m, 21 N/m, 22 N/m, 23 N/m, 24 N/m, 25 N/m, 26 N/m, 27 N/m, 28 N/m, 29 N/m or 30 N/m, etc.
  • the preparation method of the modified polypropylene film comprises the following steps:
  • step (2) casting the molten material obtained in step (1) onto a casting roll, cooling it with water at 15-60° C. to form it, biaxially stretching it, and then air cooling it in a platform area, and then entering a winding system through a traction system, and winding the film under a winding tension of 20-30 N/m to obtain the modified polypropylene film;
  • the biaxial stretching is synchronous stretching or asynchronous stretching.
  • the biaxial stretching is synchronous stretching, and the synchronous stretching includes the following process:
  • Stretching divided into two stages, the temperature increases successively, i.e. 155-160°C, 160-165°C; stretching ratio: longitudinal stretching ratio is 6-8, transverse stretching ratio is 5-7;
  • the biaxial stretching is asynchronous stretching
  • the asynchronous stretching includes the following process:
  • Transverse stretching preheating temperature: 120-140°C; stretching temperature: 140-160°C; heat setting temperature The temperature is 165-169°C; the transverse stretching ratio is 5-7;
  • the heat treatment temperature is 110-140°C, the purpose is to eliminate the internal stress of the membrane and improve the thermal stability of the membrane.
  • an embodiment of the present application further provides a composite current collector, the composite current collector comprising a metal layer and a polymer film layer;
  • the polymer film layer is the modified polypropylene film as described in the first aspect.
  • the modified polypropylene film provided in the first aspect of the present application is used as a carrier or supporting layer of the composite current collector.
  • the material of the metal layer is selected from metal or metal alloy, and the metal is selected from any one of copper, aluminum, silver, gold, and nickel, or a combination of at least two thereof.
  • the composite current collector includes a first protective layer, a first metal layer, a polymer film layer, a second metal layer and a second protective layer stacked in sequence;
  • the polymer film layer is the modified polypropylene film as described in the first aspect.
  • the materials of the first metal layer and the second metal layer are each independently selected from metals or metal alloys.
  • the metal is selected from any one of copper, aluminum, silver, gold, nickel, or a combination of at least two thereof.
  • the thickness of the first metal layer and the second metal layer are independently selected from 500-2000 nm (for example, 500 nm, 700 nm, 1000 nm, 1200 nm, 1500 nm, 1800 nm or 2000 nm, etc.), and more preferably 700-1500 nm.
  • the first metal layer and the second metal layer are each independently prepared by physical vapor deposition (such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.), electroplating or chemical plating, or a combination of at least two of them.
  • physical vapor deposition such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.
  • electroplating or chemical plating, or a combination of at least two of them.
  • the materials of the first protective layer and the second protective layer are independently selected from Any one of aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper oxide, copper chromium oxide, formic acid-copper complex, nickel-chromium alloy, graphite, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers and graphene, or a combination of at least two thereof.
  • the thickness of the first protective layer and the second protective layer are each independently selected from 10-150nm (for example, it can be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm, etc.), and is further preferably 20-100nm.
  • the sum of the thicknesses of the first protective layer and the second protective layer is less than or equal to one tenth of the sum of the thicknesses of the first metal layer and the second metal layer.
  • the preparation methods of the first protective layer and the second protective layer independently include any one of physical vapor deposition, chemical vapor deposition, in-situ forming, and coating, or a combination of at least two of them.
  • the physical vapor deposition method is preferably vacuum evaporation and magnetron sputtering
  • the chemical vapor deposition is preferably atmospheric pressure chemical vapor deposition and plasma enhanced chemical vapor deposition
  • the in-situ forming is preferably a method of in-situ forming a metal oxide passivation layer on the surface of the metal layer
  • the coating method is preferably die coating, blade coating, and extrusion coating.
  • an embodiment of the present application provides a battery, comprising the composite current collector as described in the third aspect.
  • the present application obtains modified polypropylene by selecting a specific modifier, and uses the modified polypropylene as a raw material.
  • the prepared modified polypropylene film has the characteristics of strong surface adhesion, high dielectric constant, good mechanical properties, etc., and its surface tension is 38-59 mN/m, dielectric constant is 2.6-4.0 mN/m, and tensile strength is 185-225 MPa;
  • FIG1 is a schematic diagram of the structure of a composite current collector provided in Application Example 1;
  • 1 is the first protective layer
  • 2 is the first metal layer
  • 3 is the polymer film layer
  • 4 is the second metal layer
  • 5 is the second protective layer.
  • melt index is 3.0 g/10 min (230°C/2.16 kg), molecular weight distribution index is 4.5, isotacticity is 96%, purchased from Singapore TPC Company, model FS3028;
  • melt index is 3.0 g/10 min (230°C/2.16 kg), molecular weight distribution index is 4.5, isotacticity is 93%, purchased from Singapore TPC Company, model FS3025;
  • HR catalyst purchased from Sinopec Catalyst Co., Ltd.
  • the polypropylene used in the following preparation examples is polypropylene of model FS3028.
  • Preparation Examples 1-5 respectively provide a 4-terpene alcohol modified polypropylene
  • Preparation Examples 6-9 and Preparation Comparative Example 1 respectively provide an ⁇ -terpineol modified polypropylene, lavandulol modified polypropylene, geraniol modified polypropylene, and acryl alcohol modified polypropylene;
  • the preparation method of the above modified polypropylene is as follows:
  • the reactor was fully replaced and dried with nitrogen, and then the uniformly mixed modifier, polypropylene, n-hexane (1500 mL) and HR catalyst were added to the reactor, and then the temperature was raised under a nitrogen atmosphere for modification reaction, and then the temperature was lowered, and the mixed liquid was discharged from the reactor with nitrogen, filtered, washed and dried to obtain modified polypropylene;
  • the dosage of the modifier, polypropylene and HR catalyst is shown in Table 1 below, and the reaction temperature and time are also shown in Table 1 below.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the raw materials for preparing the modified polypropylene film include the following components in percentage by mass: 4-terpene provided in Preparation Example 1 Enol modified polypropylene 0.5% and polypropylene 99.5%;
  • melt index of polypropylene is 3.0g/10min (230°C/2.16kg), the molecular weight distribution index is 4.5, and the isotacticity is 96%;
  • the grafting rate of 4-terpene alcohol in the 4-terpene alcohol-modified polypropylene is 0.05%.
  • the preparation method of the above-mentioned modified polypropylene film is as follows:
  • step (2) casting the molten material obtained in step (1) onto a casting roll, water-cooling the molten material at 20° C. to form the molten material, biaxially stretching the molten material, air-cooling the molten material in the platform area, and then entering the winding system through the traction system.
  • the molten material is wound under a winding tension of 30 N/m to obtain a modified polypropylene film with a thickness of 4.5 ⁇ m;
  • the biaxial stretching is asynchronous stretching, and the asynchronous stretching includes the following process:
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the raw materials for preparing the modified polypropylene film include the following components in weight percentage: 50% of 4-terpene alcohol modified polypropylene and 50% of polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the raw material for preparing the modified polypropylene film is only the 4-terpene alcohol modified polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the raw materials for preparing the modified polypropylene film include the following components in weight percentage: 0.4% of 4-terpene alcohol-modified polypropylene and 99.6% of polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 1.0% provided in Preparation Example 2, and other conditions are the same as in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 5.0% provided in Preparation Example 3, and other conditions are the same as in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4, and other conditions are the same as in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof, which is different from Embodiment 1 only in that: The 4-terpene alcohol-modified polypropylene provided in Preparation Example 1 was replaced with the 4-terpene alcohol-modified polypropylene with a grafting rate of 11.0% provided in Preparation Example 5, and other conditions were the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 0.04% provided in Preparation Example 6, and other conditions are the same as in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the raw material for preparing the modified polypropylene film is only 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4, and other conditions are the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof, which is different from Example 10 only in that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the ⁇ -terpineol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 7, and other conditions are the same as those in Example 10.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by lavender alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 8, and other conditions are the same as Example 10.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the geraniol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 9, and other conditions are the same as those in Example 10.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 1 is that the polypropylene (FS3028) with a melt index of 3.0 g/10 min (230° C./2.16 kg), a molecular weight distribution index of 4.5, and an isotacticity of 96% is replaced by a polypropylene (FS3025) with a melt index of 3.0 g/10 min (230° C./2.16 kg), a molecular weight distribution index of 4.5, and an isotacticity of 93%.
  • the other conditions are the same as those in Example 1.
  • This comparative example provides a polypropylene film and a preparation method thereof, which is different from Example 1 only in that the raw material for preparing the polypropylene film is only polypropylene (FS3028), and other conditions are the same as those in Example 1.
  • This embodiment provides a modified polypropylene film and a preparation method thereof.
  • the only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the propylene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Comparative Example 1, and other conditions are the same as those in Example 10.
  • This application example provides a composite current collector and a preparation method thereof.
  • the structural schematic diagram of the composite current collector is shown in FIG1 , comprising a first protective layer 1, a first metal layer 2, a polymer film layer 3, a second metal layer 4, and a second protective layer 5 which are sequentially stacked;
  • the polymer film layer 3 is the modified polypropylene film provided in Example 1.
  • the preparation method of the composite current collector is as follows:
  • the modified polypropylene film provided in Example 1 is placed in a magnetron sputtering chamber, copper metal with a purity of 99.99% is used as a target material, argon gas is used as a gas source, and a copper metal layer with a thickness of 100 nm is plated on both sides of the modified polypropylene film by a magnetron sputtering method in the magnetron sputtering chamber to obtain a composite film; the prepared composite film is used as a substrate for electroplating to thicken the conductive copper layer and obtain a first protective layer 1 and a second protective layer 5, and the electroplating is divided into the following three processes: 1 Electroplating to thicken the metal layer: the electroplating solution is 120 g/L copper sulfate, 100 g/L sulfuric acid, 50 mg/L chloride ion, 1.2 mg/L sodium 3-mercapto-1-propane sulfonate, 0.5 mg/L 2- 1.
  • Application Examples 2-14 respectively provide a composite current collector and a preparation method thereof.
  • the difference from Application Example 1 is that the modified polypropylene film provided in Example 1 is replaced by the modified polypropylene film provided in Examples 2-14 in sequence, and other conditions are the same as those in Application Example 1.
  • Comparative Application Examples 1-2 respectively provide a composite current collector and a preparation method thereof.
  • the difference from Application Example 1 is that the modified polypropylene film provided in Example 1 is replaced by the polypropylene film provided in Comparative Example 1 and the modified polypropylene film provided in Comparative Example 2, respectively, and other conditions are the same as those in Application Example 1.
  • modified polypropylene film in this application is to improve the surface adhesion performance and dielectric constant of the polymer film, and then improve the performance of the composite current collector prepared with this modified polypropylene film as the substrate.
  • the surface adhesion performance of the polypropylene film mainly depends on its surface tension, which is ultimately reflected in the adhesion between the base film and the metal layer in the composite current collector; and the change in the dielectric constant of the polypropylene film directly affects the number of holes in the composite current collector prepared therefrom. Therefore, this application tests the surface tension and dielectric constant of the prepared modified polypropylene film, the adhesion between the base film and the metal layer in the prepared composite current collector, and the number of hole defects. In addition, the tensile strength of the prepared modified polypropylene film and the square resistance of the prepared composite current collector were also tested. The specific method is as follows:
  • Dielectric constant The dielectric constant of the modified polypropylene film prepared above was tested according to standard SJ/T1147-1993;
  • 3Tensile strength The tensile strength of the modified polypropylene film prepared above was tested in accordance with standard GB/T 1040.3-2006.
  • the bonding strength between the polypropylene film and the metal layer in the composite current collector a layer of Permacel P-94 double-sided tape is bonded to 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, 50 ⁇ m thick) is covered on the composite current collector, and then hot-pressed at 1.3 ⁇ 105N/m 2 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 off at an angle of 180° and a speed of 100mm/min to test the peeling force, that is, the bonding strength between the polypropylene film and the metal layer;
  • a modified polypropylene with excellent performance is prepared.
  • the modified polypropylene is used as a raw material for preparing a modified polypropylene film, and the content of the modified polypropylene in the modified polypropylene film is controlled within a specific range.
  • the prepared modified polypropylene film has a higher surface tension, a higher dielectric constant and a higher tensile strength. The surface tension is 38 to 59 mN/m, the dielectric constant is 2.6 to 4.0 mN/m, and the tensile strength is 185 to 225 MPa.
  • Example 4 Compared with Example 1, if the content of modified polypropylene in the raw material for preparing the modified polypropylene film is too small (Example 4), the performance improvement of the prepared modified polypropylene film is limited compared with the polypropylene film (Comparative Example 1), and its surface tension, dielectric constant and tensile strength are all lower.
  • Example 9 Compared with Example 1, if the grafting rate of the modifier in the modified polypropylene is low (Example 9), the surface tension, dielectric constant and tensile strength of the prepared modified polypropylene film are also poor; if the grafting rate of the modifier in the modified polypropylene is high (Example 8), the mechanical properties of the prepared modified polypropylene film are poor.
  • Example 1 Compared with Example 1, the surface tension, dielectric constant and tensile strength of the polypropylene film prepared with polypropylene (Comparative Example 1) are all lower; if polypropylene modified with other modifiers is used to prepare the polypropylene film (Comparative Example 2), the surface tension, dielectric constant and tensile strength of the prepared modified polypropylene film are also poor.
  • a modified polypropylene with excellent performance is prepared by selecting a polypropylene with a specific melt index, a specific molecular weight distribution index and a specific regularity, and selecting a specific modifier, while controlling the grafting rate of the modifier within a specific range.
  • the modified polypropylene is used as a raw material for preparing a modified polypropylene film, and the content of the modified polypropylene in the modified polypropylene film is controlled within a specific range.
  • the prepared modified polypropylene film has a higher surface tension, a higher dielectric constant and a higher tensile strength.
  • a modified polypropylene film with excellent performance was prepared by designing the raw materials for preparing the modified polypropylene film.
  • the bonding force between the polymer film (modified polypropylene film) and the metal layer is relatively large, which is 0.9 to 2.7 N/cm.
  • the prepared composite current collector has a smaller bonding force, a larger number of pores, and a larger square resistance.
  • the composite current collector prepared with polypropylene film (Comparative Example 1) has smaller adhesion, more pores, and larger square resistance; if polypropylene modified with other modifiers is used to prepare the polypropylene film, the performance of the composite current collector (Comparative Example 2) obtained is also poor.
  • a modified polypropylene film with excellent performance is prepared, and then a composite current collector with large adhesion between the modified polypropylene film and the metal layer, no holes and small square resistance is prepared.

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Abstract

A modified polypropylene film, a preparation method therefor and a use thereof. A preparation raw material of the modified polypropylene film comprises modified polypropylene, and a modifier for the modified polypropylene comprises terpenol. The preparation method comprises the following steps: (1) melting, filtering and extruding the preparation raw material of the modified polypropylene film to obtain a molten material; and (2) casting the molten material obtained in step (1) onto a casting roller, performing cooling for formation, and carrying out two-way stretching to obtain the modified polypropylene film. Modified polypropylene is prepared using a specific modifier, and a modified polypropylene film having excellent performance is prepared by using the modified polypropylene as a preparation raw material, so that the modified polypropylene film is suitable for being used as a composite current collector base film.

Description

一种改性聚丙烯膜及其制备方法和应用A modified polypropylene film and its preparation method and application

本申请要求在2023年5月29日提交中国专利局、申请号为202310614748.X的中国专利的优先权，以上申请的全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application number 202310614748.X filed with the Chinese Patent Office on May 29, 2023. The entire contents of the above application are incorporated by reference into this application.

技术领域Technical Field

本申请属于高分子聚合物膜技术领域，例如一种改性聚丙烯膜及其制备方法和应用。The present application belongs to the technical field of high molecular polymer membranes, for example, a modified polypropylene membrane and a preparation method and application thereof.

背景技术Background Art

目前，基于高分子聚合物膜的复合集流体得到新能源行业的广泛关注和应用。该复合集流体的制备过程通常为：采用物理气相沉积(PVD)的方法在高分子薄膜(如聚丙烯、聚乙烯、聚酯类等)上沉积一层金属(铝、铜等)材料。制备出的具备一定导电能力的表面金属化的薄膜即为复合集流体。相比传统的集流体，基于高分子聚合物膜的复合集流体具备成本低、质量轻、内部绝缘性好等特点。这些特点使得复合集流体在电池中应用时能够降低电池的成本、并提升电池的能量密度及安全性。At present, 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). The prepared surface metallized film with a certain conductivity is the composite current collector. Compared with traditional current collectors, composite current collectors based on polymer films have the characteristics of low cost, light weight, and good internal insulation. These characteristics 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.

在众多基于高分子聚合物膜的复合集流体中，基于聚丙烯膜的复合集流体较为常见。然而，以传统聚丙烯膜为基膜制备复合集流体过程中，存在如下问题：①由于聚丙烯膜自身材料极性较弱，导致其表面张力较低，低表面张力的聚丙烯膜与高表面张力的金属层之间的亲合力较差，从而引发二者界面之间的附着力较低，结合不牢固，即存在聚丙烯膜表面粘附性能差的问题。②聚丙烯膜的介电常数为2.1，介电常数较低，导致以聚丙烯膜为基膜采用物理气相沉积法制备复合集流体的过程中聚丙烯膜易被局部较高的静电电压击穿，从而产生孔洞缺陷。 Among the many composite current collectors based on polymer films, composite current collectors based on polypropylene films are more common. However, in the process of preparing composite current collectors with traditional polypropylene films as base films, there are the following problems: ① 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, resulting in low adhesion between the interface between the two and weak bonding, that is, the problem of poor surface adhesion of the polypropylene film. ② The dielectric constant of the polypropylene film is 2.1, which is low in dielectric constant. As a result, in the process of preparing composite current collectors with polypropylene film as base film by physical vapor deposition method, the polypropylene film is easily broken down by a local high electrostatic voltage, thereby generating hole defects.

因此，针对传统聚丙烯膜存在的上述问题，并为了制备出高性能的复合集流体，有必要开发一种改性的聚丙烯膜。Therefore, in order to solve the above problems of traditional polypropylene membranes and prepare high-performance composite current collectors, it is necessary to develop a modified polypropylene membrane.

发明内容Summary of the invention

以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.

本申请的目的在于提供一种改性聚丙烯膜及其制备方法和应用。本申请中通过选用特定改性剂制备得到了改性聚丙烯，并以此改性聚丙烯为制备原料，制备得到了性能优异的改性聚丙烯膜，使其适用作复合集流体基膜。The purpose of the present application is to provide a modified polypropylene film and its preparation method and application. In the present application, modified polypropylene is prepared by selecting a specific modifier, and the modified polypropylene is used as a preparation raw material to prepare a modified polypropylene film with excellent performance, making it suitable for use as a composite current collector base film.

为达此目的，本申请采用以下技术方案：To achieve this goal, this application adopts the following technical solutions:

第一方面，本申请实施例提供一种改性聚丙烯膜，所述改性聚丙烯膜的制备原料包括改性聚丙烯；In a first aspect, an embodiment of the present application provides a modified polypropylene film, wherein the raw material for preparing the modified polypropylene film includes modified polypropylene;

所述改性聚丙烯的改性剂包括萜烯醇。The modifier for modifying the polypropylene includes terpene alcohol.

本申请实施例中，通过选用特定改性剂的制备得到改性聚丙烯，并以此改性聚丙烯为制备原料，制备得到了性能优异的改性聚丙烯膜，使其适用作复合集流体基膜。In the examples of the present application, modified polypropylene is obtained by selecting a specific modifier, and the modified polypropylene is used as a raw material to prepare a modified polypropylene film with excellent performance, making it suitable for use as a composite current collector base film.

本申请实施例中，一方面利用萜烯醇分子中的羟基，提升制备的改性聚丙烯膜的表面张力，且萜烯醇分子具有共轭结构，可与金属原子形成电子共轭体系，表面张力的提升及共轭结构的形成共同促进金属原子与改性聚丙烯膜之间的作用力，进而提升制备的复合集流体中基膜与金属层的粘结力；另一方面，萜烯醇改性的聚丙烯的介电常数高于聚丙烯，在改性聚丙烯膜的制备原料中引入萜烯醇改性的聚丙烯可提升改性聚丙烯膜的介电常数，进而解决物理气相沉积过程中聚丙烯膜被击穿而产生的孔洞问题。In the embodiments of the present application, on the one hand, the hydroxyl groups in the terpene alcohol molecules are used to increase the surface tension of the prepared modified polypropylene film, and the terpene alcohol molecules have a conjugated structure and can form an electronic conjugated system with metal atoms. The increase in surface tension and the formation of the conjugated structure jointly promote the interaction between the metal atoms and the modified polypropylene film, thereby increasing the adhesion between the base film and the metal layer in the prepared composite current collector; on the other hand, the dielectric constant of the polypropylene modified by terpene alcohol is higher than that of polypropylene. Introducing terpene alcohol-modified polypropylene into the raw materials for preparing the modified polypropylene film can increase the dielectric constant of the modified polypropylene film, thereby solving the problem of holes caused by the breakdown of the polypropylene film during physical vapor deposition.

本申请实施例中，通过在改性聚丙烯膜中引入极性官能团和共轭结构，提 高了改性聚丙烯膜的介电常数。In the embodiment of the present application, polar functional groups and conjugated structures are introduced into the modified polypropylene film to improve the Improve the dielectric constant of modified polypropylene film.

以下作为本申请的可选技术方案，但不作为对本申请提供的技术方案的限制，通过以下优选的技术方案，可以更好的达到和实现本申请的目的和有益效果。The following are optional technical solutions for the present application, but are not intended to limit the technical solutions provided by the present application. Through the following preferred technical solutions, the objectives and beneficial effects of the present application can be better achieved and realized.

作为本申请的可选技术方案，所述改性聚丙烯中萜烯醇的接枝率≥0.05％(例如可以是0.05％、0.1％、0.5％、1％、2％、3％、4％、5％、6％、7％、8％、9％或10％等)，优选为0.05％-10％。As an optional technical solution of the present application, the grafting rate of terpene alcohol in the modified polypropylene is ≥0.05% (for example, it can be 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.), preferably 0.05%-10%.

本申请实施例中，接枝率为接枝到聚丙烯上的萜烯醇单体的质量与接枝后的聚丙烯的质量比。In the embodiments of the present application, the grafting rate is the ratio of the mass of the terpene alcohol monomer grafted onto the polypropylene to the mass of the grafted polypropylene.

本申请实施例中，通过控制改性聚丙烯中萜烯醇的接枝率在特定的范围内，提升了改性聚丙烯膜的性能，使其具有较高的介电常数和较高的力学性能。若改性聚丙烯中萜烯醇的接枝率过低，对于制备的聚丙烯膜的性能提升有限；若改性聚丙烯中萜烯醇的接枝率过高，过高的接枝率的改性聚丙烯会影响拉伸过程中聚丙烯高分子的取向及结晶，从而导致制备的改性聚丙烯膜的拉伸强度降低。In the examples of the present application, by controlling the grafting rate of terpene alcohol in the modified polypropylene within a specific range, the performance of the modified polypropylene film is improved, so that it has a higher dielectric constant and higher mechanical properties. If the grafting rate of terpene alcohol in the modified polypropylene is too low, the performance improvement of the prepared polypropylene film is limited; if the grafting rate of terpene alcohol in the modified polypropylene is too high, the modified polypropylene with too high a grafting rate will affect the orientation and crystallization of the polypropylene polymer during the stretching process, thereby resulting in a decrease in the tensile strength of the prepared modified polypropylene film.

在一个实施例中，所述萜烯醇包括4-萜烯醇、α-萜品醇、香芹醇、薰衣草醇、橙花醇、香叶醇中的任意一种或至少两种的组合。In one embodiment, the terpene alcohol includes any one of 4-terpene alcohol, α-terpineol, carveol, lavandulol, nerol, geraniol, or a combination of at least two thereof.

本申请实施例中，所述改性聚丙烯的制备方法包括如下步骤：In the embodiment of the present application, the preparation method of the modified polypropylene comprises the following steps:

用氮气充分置换并干燥反应釜，然后向反应釜中加入混合均匀的萜烯醇、聚丙烯、有机溶剂及催化剂，然后在氮气氛围下，升温至60-100℃，反应2-24h，然后降温至室温，将混合料液用氮气从反应釜中排出，经过滤、清洗、干燥，得到改性聚丙烯；The reactor is fully replaced and dried with nitrogen, and then the uniformly mixed terpene alcohol, polypropylene, organic solvent and catalyst are added into the reactor, and then the temperature is raised to 60-100° C. in a nitrogen atmosphere, and the reaction is carried out for 2-24 hours, and then the temperature is lowered to room temperature, and the mixed liquid is discharged from the reactor with nitrogen, and the modified polypropylene is obtained after filtering, washing and drying;

在一个实施例中，所述有机溶剂选自C6-C20的烷烃溶剂(例如可以是C6、 C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19或C20等)，进一步选自正己烷。In one embodiment, the organic solvent is selected from C6-C20 alkane solvents (for example, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19 or C20, etc.), further selected from n-hexane.

在一个实施例中，所述催化剂选自Ziegler-Natta催化剂、DQC催化剂或HR催化剂中的任意一种。In one embodiment, the catalyst is selected from any one of a Ziegler-Natta catalyst, a DQC catalyst or a HR catalyst.

需要说明的是，本申请实施例中对于催化剂的购买厂家没有任何特殊的限制，示例性地包括：HR催化剂购自中国石化催化剂有限公司。It should be noted that there is no special restriction on the manufacturer of the catalyst in the examples of the present application, and illustratively includes: HR catalyst is purchased from Sinopec Catalyst Co., Ltd.

其中，加入的萜烯醇的质量为0.50-150g、聚丙烯的质量为890.0-999.5g、有机溶剂的体积为800-2000mL、催化剂的质量为10-50g。The mass of the added terpene alcohol is 0.50-150 g, the mass of the polypropylene is 890.0-999.5 g, the volume of the organic solvent is 800-2000 mL, and the mass of the catalyst is 10-50 g.

本申请实施例中，加入的萜烯醇的质量可以是0.50g、1.00g、2.00g、5.00g、10.0g、20.0g、40.0g、60.0g、80.0g、100g、120g、135g或150g等。In the embodiments of the present application, the mass of the added terpene alcohol can be 0.50g, 1.00g, 2.00g, 5.00g, 10.0g, 20.0g, 40.0g, 60.0g, 80.0g, 100g, 120g, 135g or 150g, etc.

所述聚丙烯的质量可以是890.0g、900.0g、910.0g、920.0g、930.0g、940.0g、950.0g、960.0g、970.0g、980.0g、990.0g或999.5g等。The mass of the polypropylene may be 890.0 g, 900.0 g, 910.0 g, 920.0 g, 930.0 g, 940.0 g, 950.0 g, 960.0 g, 970.0 g, 980.0 g, 990.0 g or 999.5 g, etc.

所述有机溶剂的体积可以是800mL、900mL、1000mL、1100mL、1200mL、1300mL、1400mL、1500mL、1600mL、1700mL、1800mL、1900mL或2000mL等。The volume of the organic solvent can be 800 mL, 900 mL, 1000 mL, 1100 mL, 1200 mL, 1300 mL, 1400 mL, 1500 mL, 1600 mL, 1700 mL, 1800 mL, 1900 mL or 2000 mL, etc.

所述催化剂的质量可以是10g、15g、20g、25g、30g、35g、40g、45g或50g等。The mass of the catalyst can be 10g, 15g, 20g, 25g, 30g, 35g, 40g, 45g or 50g, etc.

上述制备改性聚丙烯的反应温度可以是60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃或100℃等，反应时间可以是2h、4h、6h、8h、10h、12h、14h、16h、18h、20h、22h或24h等。The reaction temperature for preparing the modified polypropylene can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C or 100°C, and the reaction time can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24h, etc.

作为本申请的可选技术方案，所述改性聚丙烯中聚丙烯的熔融指数为3.0-4.0g/10min，例如可以是3.0g/10min、3.1g/10min、3.2g/10min、3.3g/10min、3.4g/10min、3.5g/10min、3.6g/10min、3.7g/10min、3.8g/10min、3.9.g/10min 或4.0g/10min等。As an optional technical solution of the present application, the melt index of the polypropylene in the modified polypropylene is 3.0-4.0 g/10 min, for example, it can be 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, 3.9 g/10 min. Or 4.0g/10min, etc.

本申请实施例中，通过选用具有特定范围熔融指数的聚丙烯，使制备改性聚丙烯膜的拉伸步骤中，易成膜，且制备得到的改性聚丙烯膜的性能较好。若聚丙烯的熔融指数过低，分子量过大，导致拉膜过程中改性聚丙烯膜的成膜性较差；若聚丙烯的熔融指数过高，分子量过低，则其成膜性较差且制备改性聚丙烯膜的力学性能较差。In the embodiment of the present application, by selecting polypropylene with a specific range of melt index, the stretching step of preparing the modified polypropylene film is easy to form a film, and the performance of the prepared modified polypropylene film is good. If the melt index of polypropylene is too low and the molecular weight is too large, the film forming property of the modified polypropylene film during the film drawing process is poor; if the melt index of polypropylene is too high and the molecular weight is too low, its film forming property is poor and the mechanical properties of the prepared modified polypropylene film are poor.

本申请实施例中，熔融指数的测试条件为230℃/2.16kg。In the examples of the present application, the test conditions for the melt index are 230°C/2.16kg.

在一个实施例中，所述改性聚丙烯中聚丙烯的分子量分布为4.5-5.5，例如可以是4.5、4.6、4.7、4.8、4.9、5.0、5.1、5.2、5.3、5.4或5.5等。In one embodiment, the molecular weight distribution of the polypropylene in the modified polypropylene is 4.5-5.5, for example, it can be 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4 or 5.5.

本申请实施例中，通过控制聚丙烯的分子量分布在特定的范围内，制备得到的改性聚丙烯膜具有较好的力学性能和较高的良品率。若聚丙烯的分子量分布指数过高，则小分子量的聚丙烯含量越多，导致制备的膜的力学性能较差，且成膜性较差；若聚丙烯的分子量分布指数过低，拉膜过程中改姓聚丙烯的成膜性变差，导致产品良品率降低。In the examples of the present application, by controlling the molecular weight distribution of polypropylene within a specific range, the prepared modified polypropylene film has good mechanical properties and a high yield rate. If the molecular weight distribution index of polypropylene is too high, the content of small molecular weight polypropylene is more, resulting in poor mechanical properties and poor film-forming properties of the prepared film; if the molecular weight distribution index of polypropylene is too low, the film-forming properties of the modified polypropylene deteriorate during the film drawing process, resulting in a decrease in the product yield rate.

在一个实施例中，所述改性聚丙烯中聚丙烯的等规度≥95％，例如可以是95％、95.5％、96％、96.5％、97％、97.5％或98％等。In one embodiment, the isotacticity of the polypropylene in the modified polypropylene is ≥95%, for example, it may be 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98%, etc.

本申请实施例中，通过控制聚丙烯的等规度≥95％，可进一步提高改性聚丙烯膜的力学性能。聚丙烯的等规度越高，聚丙烯分子的规整度越高，聚丙烯规整度的提高，可提升制备的膜的取向度及结晶度，从而可提高改性聚丙烯膜的力学性能。In the embodiment of the present application, the mechanical properties of the modified polypropylene film can be further improved by controlling the isotacticity of polypropylene to be ≥95%. The higher the isotacticity of polypropylene, the higher the regularity of polypropylene molecules. The improvement of the regularity of polypropylene can improve the orientation and crystallinity of the prepared film, thereby improving the mechanical properties of the modified polypropylene film.

作为本申请的可选技术方案，以所述改性聚丙烯膜的制备原料的质量百分含量为100％计，所述改性聚丙烯的质量百分的含量≥0.5％，例如可以是0.5％、1％、2％、5％、7％、10％、13％、15％、18％、20％或24％等。 As an optional technical solution of the present application, taking the mass percentage of the raw materials for preparing the modified polypropylene film as 100%, the mass percentage of the modified polypropylene is ≥0.5%, for example, it can be 0.5%, 1%, 2%, 5%, 7%, 10%, 13%, 15%, 18%, 20% or 24%, etc.

本申请实施例中通过控制改性聚丙烯膜的制备原料中改性聚丙烯的质量百分的含量≥0.5％，可明显提升改性聚丙烯膜的性能。若改性聚丙烯的质量百分的含量过低，对于改性聚丙烯膜性能的提升有限。In the embodiment of the present application, the performance of the modified polypropylene film can be significantly improved by controlling the mass percentage of modified polypropylene in the raw material for preparing the modified polypropylene film to ≥ 0.5%. If the mass percentage of modified polypropylene is too low, the improvement of the performance of the modified polypropylene film is limited.

在一个实施例中，所述改性聚丙烯膜的制备原料中还包括聚丙烯。In one embodiment, the raw materials for preparing the modified polypropylene film also include polypropylene.

作为本申请的可选技术方案，所述改性聚丙烯膜的厚度≥1μm(例如可以是1μm、2μm、5μm、7μm、10μm、12μm、15μm、18μm、20μm、24μm、27μm或30μm等)，优选为2～20μm。As an optional technical solution of the present application, the thickness of the modified polypropylene film is ≥1μm (for example, it can be 1μm, 2μm, 5μm, 7μm, 10μm, 12μm, 15μm, 18μm, 20μm, 24μm, 27μm or 30μm, etc.), preferably 2-20μm.

改性聚丙烯膜越薄越能促进复合集流体能量密度的提升，但是需要同时兼顾生产难度，由于改性聚丙烯膜越薄、生产难度越大、良品率越低，因此，本申请实施例中，控制改性聚丙烯膜的厚度≥1μm，既可制备得到性能优异的改性聚丙烯膜，又能兼顾改性聚丙烯膜的生产工艺，使其具有较高的良品率。The thinner the modified polypropylene film is, the more it can promote the improvement of the energy density of the composite current collector, but the production difficulty must be taken into account at the same time. Since the thinner the modified polypropylene film is, the greater the production difficulty and the lower the yield rate, in the embodiment of the present application, the thickness of the modified polypropylene film is controlled to be ≥1 μm, which can not only prepare a modified polypropylene film with excellent performance, but also take into account the production process of the modified polypropylene film, so that it has a higher yield rate.

第二方面，本申请实施例提供一种如第一方面所述的改性聚丙烯膜的制备方法，所述制备方法包括如下步骤：In a second aspect, an embodiment of the present application provides a method for preparing the modified polypropylene film as described in the first aspect, the preparation method comprising the following steps:

(1)将改性聚丙烯膜的制备原料熔融、过滤、挤出，得到熔融料；(1) melting, filtering and extruding the raw materials for preparing the modified polypropylene film to obtain a molten material;

(2)将步骤(1)得到的熔融料流延到铸片辊上，冷却成型后，进行双向拉伸，得到所述改性聚丙烯膜。(2) Casting the molten material obtained in step (1) onto a casting roll, cooling and forming the molten material, and then biaxially stretching the molten material to obtain the modified polypropylene film.

本申请实施例中，通过选用改性聚丙烯作为改性聚丙烯膜的制备原料，并选用熔融挤出-双向拉伸的制备工艺，制备得到了具有较高介电常数和较好力学性能的改性聚丙烯膜，使其适用作复合集流体基膜。In the embodiments of the present application, by selecting modified polypropylene as the raw material for preparing the modified polypropylene film and selecting the melt extrusion-biaxial stretching preparation process, a modified polypropylene film with a higher dielectric constant and better mechanical properties is prepared, making it suitable for use as a composite current collector base film.

作为本申请的可选技术方案，所述熔融的温度为200-260℃，例如可以是200℃、205℃、210℃、215℃、220℃、225℃、230℃、235℃、240℃、245℃、250℃、255℃或260℃等。As an optional technical solution of the present application, the melting temperature is 200-260°C, for example, it can be 200°C, 205°C, 210°C, 215°C, 220°C, 225°C, 230°C, 235°C, 240°C, 245°C, 250°C, 255°C or 260°C, etc.

在一个实施例中，所述过滤的方法包括经滤网为10μm的过滤器进行过滤。 In one embodiment, the filtering method includes filtering through a filter with a filter screen of 10 μm.

在一个实施例中，所述冷却成型的方法为经水冷却处理成型。In one embodiment, the cooling molding method is molding through water cooling treatment.

在一个实施例中，所述冷却成型的温度为15-60℃，例如可以是15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃或60℃等。In one embodiment, the cooling molding temperature is 15-60°C, for example, it can be 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C.

需要说明的是，本申请实施例中熔融、挤出在双螺杆挤出机中进行。It should be noted that in the examples of the present application, melting and extrusion are carried out in a twin-screw extruder.

作为本申请的可选技术方案，所述双向拉伸包括同步拉伸和异步拉伸。As an optional technical solution of the present application, the biaxial stretching includes synchronous stretching and asynchronous stretching.

在一个实施例中，所述同步拉伸的过程包括预热、拉伸和热定型。In one embodiment, the synchronous stretching process includes preheating, stretching and heat setting.

在一个实施例中，所述预热的区域包括第一预热区和第二预热区。In one embodiment, the preheating zone includes a first preheating zone and a second preheating zone.

在一个实施例中，所述第一预热区的温度为130-145℃，例如可以是130℃、132℃、135℃、137℃、140℃、142℃或145℃等。In one embodiment, the temperature of the first preheating zone is 130-145°C, for example, it can be 130°C, 132°C, 135°C, 137°C, 140°C, 142°C or 145°C.

在一个实施例中，所述第二预热区的温度为145-155℃，例如可以是145℃、146℃、147℃、148℃、149℃、150℃、151℃、152℃、153℃、154℃或155℃等。In one embodiment, the temperature of the second preheating zone is 145-155°C, for example, it can be 145°C, 146°C, 147°C, 148°C, 149°C, 150°C, 151°C, 152°C, 153°C, 154°C or 155°C, etc.

在一个实施例中，所述拉伸的温度包括第一拉伸温度和第二拉伸温度。In one embodiment, the stretching temperature includes a first stretching temperature and a second stretching temperature.

在一个实施例中，所述第一拉伸温度的温度为155-160℃，例如可以是155℃、156℃、157℃、158℃、159℃或160℃等。In one embodiment, the first stretching temperature is 155-160°C, for example, 155°C, 156°C, 157°C, 158°C, 159°C or 160°C.

在一个实施例中，所述第二拉伸温度的温度为160-165℃，例如可以是160℃、161℃、162℃、163℃、164℃或165℃等。In one embodiment, the second stretching temperature is 160-165°C, for example, 160°C, 161°C, 162°C, 163°C, 164°C or 165°C.

在一个实施例中，所述拉伸的纵向拉伸比为6-8，例如可以是6、6.3、6.5、6.8、7、7.2、7.5、7.7或8等。In one embodiment, the longitudinal stretching ratio of the stretching is 6-8, for example, it can be 6, 6.3, 6.5, 6.8, 7, 7.2, 7.5, 7.7 or 8, etc.

在一个实施例中，所述拉伸的横向拉伸区为5-7，例如可以是5、5.2、5.5、5.8、6、6.3、6.5、6.8或7等。In one embodiment, the stretched transverse stretching zones are 5-7, for example, 5, 5.2, 5.5, 5.8, 6, 6.3, 6.5, 6.8 or 7, etc.

在一个实施例中，所述热定型的温度为165-169℃，例如可以是165℃、166℃、167℃、168℃或169℃等。 In one embodiment, the heat setting temperature is 165-169°C, for example, 165°C, 166°C, 167°C, 168°C or 169°C.

在一个实施例中，所述异步拉伸的拉伸工艺包括纵向拉伸、横向拉伸和热处理。In one embodiment, the asynchronous stretching process includes longitudinal stretching, transverse stretching and heat treatment.

在一个实施例中，所述纵向拉伸的预热温度为115-140℃，例如可以是115℃、118℃、120℃、124℃、127℃、130℃、132℃、135℃、138℃或140℃等。In one embodiment, the preheating temperature for longitudinal stretching is 115-140°C, for example, 115°C, 118°C, 120°C, 124°C, 127°C, 130°C, 132°C, 135°C, 138°C or 140°C, etc.

在一个实施例中，所述纵向拉伸的拉伸温度为140-150℃，例如可以是140℃、141℃、142℃、143℃、144℃、145℃、146℃、147℃、148℃、149℃或150℃等。In one embodiment, the stretching temperature of the longitudinal stretching is 140-150°C, for example, it can be 140°C, 141°C, 142°C, 143°C, 144°C, 145°C, 146°C, 147°C, 148°C, 149°C or 150°C, etc.

在一个实施例中，所述纵向拉伸的纵向拉伸比为6-8，例如可以是6、6.3、6.5、6.8、7、7.2、7.5、7.7或8等。In one embodiment, the longitudinal stretching ratio of the longitudinal stretching is 6-8, for example, it can be 6, 6.3, 6.5, 6.8, 7, 7.2, 7.5, 7.7 or 8, etc.

在一个实施例中，所述纵向拉伸后还包括后处理的步骤。In one embodiment, the longitudinal stretching further includes a post-processing step.

在一个实施例中，所述后处理的方法包括冷却至室温。In one embodiment, the post-treatment method includes cooling to room temperature.

在一个实施例中，所述横向拉伸的预热温度为120-140℃，例如可以是120℃、122℃、124℃、126℃、128℃、130℃、132℃、134℃、136℃、138℃或140℃等。In one embodiment, the preheating temperature for transverse stretching is 120-140°C, for example, it may be 120°C, 122°C, 124°C, 126°C, 128°C, 130°C, 132°C, 134°C, 136°C, 138°C or 140°C, etc.

在一个实施例中，所述横向拉伸的拉伸温度为140-160℃，例如可以是140℃、142℃、144℃、146℃、148℃、150℃、152℃、154℃、156℃、158℃或160℃等。In one embodiment, the stretching temperature of the transverse stretching is 140-160°C, for example, it can be 140°C, 142°C, 144°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C or 160°C, etc.

在一个实施例中，所述横向拉伸的热定型温度为165-169℃，例如可以是165℃、166℃、167℃、168℃或169℃等。In one embodiment, the heat setting temperature of the transverse stretching is 165-169°C, for example, 165°C, 166°C, 167°C, 168°C or 169°C.

在一个实施例中，所述横向拉伸的拉伸倍率为5-7，例如可以是5、5.2、5.5、5.8、6、6.3、6.5、6.8或7等。In one embodiment, the stretching ratio of the transverse stretching is 5-7, for example, it can be 5, 5.2, 5.5, 5.8, 6, 6.3, 6.5, 6.8 or 7.

在一个实施例中，所述热处理的温度为110-140℃，例如可以是110℃、112℃、115℃、118℃、120℃、124℃、127℃、130℃、132℃、135℃、138℃或140℃ 等。In one embodiment, the heat treatment temperature is 110-140°C, for example, 110°C, 112°C, 115°C, 118°C, 120°C, 124°C, 127°C, 130°C, 132°C, 135°C, 138°C or 140°C. wait.

在一个实施例中，所述双向拉伸后还包括后处理的步骤。In one embodiment, the biaxial stretching further includes a post-processing step.

在一个实施例中，所述后处理的方法包括：经平台区空气冷却后，经牵引系统进入收卷系统，进行膜片收卷。In one embodiment, the post-processing method includes: after air cooling in the platform area, entering the winding system through the traction system to wind up the film.

在一个实施例中，所述收卷的收卷张力为20-30N/m，例如可以是20N/m、21N/m、22N/m、23N/m、24N/m、25N/m、26N/m、27N/m、28N/m、29N/m或30N/m等。In one embodiment, the winding tension is 20-30 N/m, for example, it can be 20 N/m, 21 N/m, 22 N/m, 23 N/m, 24 N/m, 25 N/m, 26 N/m, 27 N/m, 28 N/m, 29 N/m or 30 N/m, etc.

本申请中，所述改性聚丙烯膜的制备方法包括如下步骤：In the present application, the preparation method of the modified polypropylene film comprises the following steps:

(1)将改性聚丙烯膜的制备原料置于双螺杆挤出机内，在200-260℃下熔融后，经滤网为10μm的过滤器进行过滤后，经模头挤出，得到熔融料；(1) placing the raw material for preparing the modified polypropylene film in a twin-screw extruder, melting it at 200-260° C., filtering it through a filter with a filter screen of 10 μm, and extruding it through a die head to obtain a molten material;

(2)将步骤(1)得到的熔融料流延到铸片辊上，在15-60℃下经水冷却成型后，进行双向拉伸，然后经平台区空气冷却后，经牵引系统进入收卷系统，在收卷张力20-30N/m的条件下，进行膜片收卷，得到所述改性聚丙烯膜；(2) casting the molten material obtained in step (1) onto a casting roll, cooling it with water at 15-60° C. to form it, biaxially stretching it, and then air cooling it in a platform area, and then entering a winding system through a traction system, and winding the film under a winding tension of 20-30 N/m to obtain the modified polypropylene film;

所述双向拉伸为同步拉伸或异步拉伸。The biaxial stretching is synchronous stretching or asynchronous stretching.

所述双向拉伸为同步拉伸，所述同步拉伸包括如下过程：The biaxial stretching is synchronous stretching, and the synchronous stretching includes the following process:

①预热：分为两段，温度依次升高，即130-145℃、145-155℃；① Preheating: divided into two stages, the temperature increases successively, i.e. 130-145℃, 145-155℃;

②拉伸：分为两段，温度依次升高，即155-160℃、160-165℃；拉伸比：纵向拉伸比为6-8、横向拉伸比为5-7；② Stretching: divided into two stages, the temperature increases successively, i.e. 155-160℃, 160-165℃; stretching ratio: longitudinal stretching ratio is 6-8, transverse stretching ratio is 5-7;

③热定型：温度为165-169℃；③ Heat setting: temperature is 165-169℃;

或者，所述双向拉伸为异步拉伸，所述异步拉伸包括如下过程：Alternatively, the biaxial stretching is asynchronous stretching, and the asynchronous stretching includes the following process:

①纵向拉伸：预热温度：115-140℃；拉伸温度为140-150℃；纵向拉伸比为6-8，然后冷却至室温；① Longitudinal stretching: preheating temperature: 115-140℃; stretching temperature is 140-150℃; longitudinal stretching ratio is 6-8, and then cooled to room temperature;

②横向拉伸：预热温度：120-140℃；拉伸温度为140-160℃；热定型温度 为165-169℃；横向拉伸比为5-7；② Transverse stretching: preheating temperature: 120-140℃; stretching temperature: 140-160℃; heat setting temperature The temperature is 165-169°C; the transverse stretching ratio is 5-7;

③热处理：热处理温度110-140℃，目的是消除膜内部应力，提高膜的热稳定性。③ Heat treatment: The heat treatment temperature is 110-140℃, the purpose is to eliminate the internal stress of the membrane and improve the thermal stability of the membrane.

第三方面，本申请实施例还提供一种复合集流体，所述复合集流体包括金属层和聚合物膜层；In a third aspect, an embodiment of the present application further provides a composite current collector, the composite current collector comprising a metal layer and a polymer film layer;

所述聚合物膜层为如第一方面所述的改性聚丙烯膜。The polymer film layer is the modified polypropylene film as described in the first aspect.

本申请第一方面提供的改性聚丙烯膜作为复合集流体的载体、支撑层。The modified polypropylene film provided in the first aspect of the present application is used as a carrier or supporting layer of the composite current collector.

在一个实施例中，所述金属层的材料选自金属或金属合金，所述金属选自铜、铝、银、金、镍中的任意一种或至少两种的组合。In one embodiment, the material of the metal layer is selected from metal or metal alloy, and the metal is selected from any one of copper, aluminum, silver, gold, and nickel, or a combination of at least two thereof.

在一个实施例中，所述复合集流体包括依次叠加设置的第一保护层、第一金属层、聚合物膜层、第二金属层和第二保护层；In one embodiment, the composite current collector includes a first protective layer, a first metal layer, a polymer film layer, a second metal layer and a second protective layer stacked in sequence;

所述聚合物膜层为如第一方面所述的改性聚丙烯膜。The polymer film layer is the modified polypropylene film as described in the first aspect.

作为本申请的可选技术方案，所述第一金属层和第一金属层的材料各自独立地选自金属或金属合金。As an optional technical solution of the present application, the materials of the first metal layer and the second metal layer are each independently selected from metals or metal alloys.

在一个实施例中，所述金属选自铜、铝、银、金、镍中的任意一种或至少两种的组合。In one embodiment, the metal is selected from any one of copper, aluminum, silver, gold, nickel, or a combination of at least two thereof.

在一个实施例中，所述第一金属层和第一金属层的厚度各自独立地选自500-2000nm(例如可以是500nm、700nm、1000nm、1200nm、1500nm、1800nm或2000nm等)，进一步优选为700-1500nm。In one embodiment, the thickness of the first metal layer and the second metal layer are independently selected from 500-2000 nm (for example, 500 nm, 700 nm, 1000 nm, 1200 nm, 1500 nm, 1800 nm or 2000 nm, etc.), and more preferably 700-1500 nm.

本申请中，所述第一金属层和第一金属层各自独立地通过物理气相沉积(如电阻加热真空蒸镀、电子束加热真空蒸镀、激光加热真空蒸镀、磁控溅射等)、电镀或化学镀中的任意一种或至少两种的组合制备得到。In the present application, the first metal layer and the second metal layer are each independently prepared by physical vapor deposition (such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation, magnetron sputtering, etc.), electroplating or chemical plating, or a combination of at least two of them.

在一个实施例中，所述第一保护层和第二保护层的材料各自独立地选自氧 化铝、氧化镍、氧化铬、氧化钴、氧化铜、铜铬氧化物、甲酸-铜配合物、镍铬合金、石墨、碳纳米量子点、碳纳米管、碳纳米纤维及石墨烯中的任意一种或至少两种的组合。In one embodiment, the materials of the first protective layer and the second protective layer are independently selected from Any one of aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, copper oxide, copper chromium oxide, formic acid-copper complex, nickel-chromium alloy, graphite, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers and graphene, or a combination of at least two thereof.

在一个实施例中，所述第一保护层和第二保护层的厚度各自独立地选自10-150nm(例如可以是10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm、110nm、120nm、130nm、140nm或150nm等)，进一步优选为20-100nm。In one embodiment, the thickness of the first protective layer and the second protective layer are each independently selected from 10-150nm (for example, it can be 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm or 150nm, etc.), and is further preferably 20-100nm.

在一个实施例中，所述第一保护层和第二保护层的厚度之和≤所述第一金属层和第二金属层厚度之和的十分之一。In one embodiment, the sum of the thicknesses of the first protective layer and the second protective layer is less than or equal to one tenth of the sum of the thicknesses of the first metal layer and the second metal layer.

本申请实施例中，所述第一保护层和第二保护层的制备方法各自独立地包括物理气相沉积法、化学气相沉积法、原位成型法、涂布中任意一种或至少两种的组合。其中物理气相沉积法优选真空蒸镀及磁控溅射；化学气相沉积优选常压化学气相沉积及等离子体增强化学气相沉积；原位成型优选在金属层表面原位形成金属氧化物钝化层的方法；涂布法优选模头涂布、刮刀涂布、挤压涂布。In the embodiment of the present application, the preparation methods of the first protective layer and the second protective layer independently include any one of physical vapor deposition, chemical vapor deposition, in-situ forming, and coating, or a combination of at least two of them. Among them, the physical vapor deposition method is preferably vacuum evaporation and magnetron sputtering; the chemical vapor deposition is preferably atmospheric pressure chemical vapor deposition and plasma enhanced chemical vapor deposition; the in-situ forming is preferably a method of in-situ forming a metal oxide passivation layer on the surface of the metal layer; the coating method is preferably die coating, blade coating, and extrusion coating.

第四方面，本申请实施例提供一种电池，所述电池包括如第三方面所述的复合集流体。In a fourth aspect, an embodiment of the present application provides a battery, comprising the composite current collector as described in the third aspect.

本申请具有以下有益效果：This application has the following beneficial effects:

(1)本申请通过选用特定改性剂的制备得到了改性聚丙烯，并以此改性聚丙烯为制备原料，制备得到的改性聚丙烯膜具有表面粘附性能强、介电常数高、力学性能好等特点，其表面张力为38～59mN/m，介电常数为2.6～4.0mN/m，拉伸强度为185～225MPa；(1) The present application obtains modified polypropylene by selecting a specific modifier, and uses the modified polypropylene as a raw material. The prepared modified polypropylene film has the characteristics of strong surface adhesion, high dielectric constant, good mechanical properties, etc., and its surface tension is 38-59 mN/m, dielectric constant is 2.6-4.0 mN/m, and tensile strength is 185-225 MPa;

(2)以本申请提供的改性聚丙烯膜为基膜制备复合集流体，可以解决复合 集流体中基膜与金属层粘结力弱以及制备的复合集流体孔洞缺陷多的问题，从而制备出结构稳定且低缺陷的复合集流体，复合集流体中聚合物膜(改性聚丙烯膜)与金属层之间的粘结力较大，为0.9～2.7N/cm，且制备得到的复合集流体上没有孔洞，且复合集流体的方阻较小，为17～18mΩ，促进复合集流体在电池中的推广及应用。(2) Using the modified polypropylene film provided in this application as the base film to prepare the composite current collector can solve the problem of composite The problems of weak adhesion between the base film and the metal layer in the current collector and many holes in the prepared composite current collector are solved, so as to prepare a composite current collector with stable structure and low defects. The adhesion between the polymer film (modified polypropylene film) and the metal layer in the composite current collector is relatively large, which is 0.9-2.7N/cm, and there are no holes on the prepared composite current collector. The square resistance of the composite current collector is relatively small, which is 17-18mΩ, which promotes the promotion and application of composite current collectors in batteries.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。The accompanying drawings are used to provide further understanding of the technical solution of this article and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solution of this article and do not constitute a limitation on the technical solution of this article.

图1是应用例1提供的复合集流体的结构示意图；FIG1 is a schematic diagram of the structure of a composite current collector provided in Application Example 1;

其中，1-第一保护层，2-第一金属层，3-聚合物膜层，4-第二金属层，5-第二保护层。Among them, 1 is the first protective layer, 2 is the first metal layer, 3 is the polymer film layer, 4 is the second metal layer, and 5 is the second protective layer.

具体实施方式DETAILED DESCRIPTION

下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。The technical solution of the present application is further described below in conjunction with the accompanying drawings and through specific implementation methods. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

下述实施例和对比例中部分组分来源如下所述：The sources of some components in the following examples and comparative examples are as follows:

聚丙烯：熔融指数为3.0g/10min(230℃/2.16kg)、分子量分布指数为4.5、等规度为96％，购自新加坡TPC公司，型号为FS3028；Polypropylene: melt index is 3.0 g/10 min (230°C/2.16 kg), molecular weight distribution index is 4.5, isotacticity is 96%, purchased from Singapore TPC Company, model FS3028;

聚丙烯：熔融指数为3.0g/10min(230℃/2.16kg)、分子量分布指数为4.5、等规度为93％，购自新加坡TPC公司，型号为FS3025；Polypropylene: melt index is 3.0 g/10 min (230°C/2.16 kg), molecular weight distribution index is 4.5, isotacticity is 93%, purchased from Singapore TPC Company, model FS3025;

催化剂：HR催化剂，购自中国石化催化剂有限公司。Catalyst: HR catalyst, purchased from Sinopec Catalyst Co., Ltd.

下述制备例中使用的聚丙烯均为型号为FS3028的聚丙烯。 The polypropylene used in the following preparation examples is polypropylene of model FS3028.

制备例1-9以及制备对比例1Preparation Examples 1-9 and Comparative Example 1

制备例1-5分别提供一种4-萜烯醇改性聚丙烯、制备例6-9和制备对比例1依次提供一种α-萜品醇改性聚丙烯、薰衣草醇改性聚丙烯、香叶醇改性聚丙烯、丙烯醇改性聚丙烯；Preparation Examples 1-5 respectively provide a 4-terpene alcohol modified polypropylene, Preparation Examples 6-9 and Preparation Comparative Example 1 respectively provide an α-terpineol modified polypropylene, lavandulol modified polypropylene, geraniol modified polypropylene, and acryl alcohol modified polypropylene;

上述改性聚丙烯的制备方法如下：The preparation method of the above modified polypropylene is as follows:

用氮气充分置换并干燥反应釜，然后向反应釜中加入混合均匀的改性剂、聚丙烯、正己烷(1500mL)及HR催化剂，然后在氮气氛围下，升温进行改性反应，然后降温，将混合料液用氮气从反应釜中排出，经过滤、清洗、干燥，得到改性聚丙烯；The reactor was fully replaced and dried with nitrogen, and then the uniformly mixed modifier, polypropylene, n-hexane (1500 mL) and HR catalyst were added to the reactor, and then the temperature was raised under a nitrogen atmosphere for modification reaction, and then the temperature was lowered, and the mixed liquid was discharged from the reactor with nitrogen, filtered, washed and dried to obtain modified polypropylene;

其中，改性剂、聚丙烯和HR催化剂的用量详见下表1，反应的温度和时间也详见下表1。The dosage of the modifier, polypropylene and HR catalyst is shown in Table 1 below, and the reaction temperature and time are also shown in Table 1 below.

表1
Table 1

实施例1Example 1

本实施例提供一种改性聚丙烯膜及其制备方法，按质量百分含量计，所述改性聚丙烯膜的制备原料包括如下质量百分含量的组分：制备例1提供的4-萜 烯醇改性聚丙烯0.5％和聚丙烯99.5％；This embodiment provides a modified polypropylene film and a preparation method thereof. The raw materials for preparing the modified polypropylene film include the following components in percentage by mass: 4-terpene provided in Preparation Example 1 Enol modified polypropylene 0.5% and polypropylene 99.5%;

其中，聚丙烯的熔融指数为3.0g/10min(230℃/2.16kg)、分子量分布指数为4.5、等规度为96％；Among them, the melt index of polypropylene is 3.0g/10min (230℃/2.16kg), the molecular weight distribution index is 4.5, and the isotacticity is 96%;

4-萜烯醇改性聚丙烯中4-萜烯醇的接枝率为0.05％。The grafting rate of 4-terpene alcohol in the 4-terpene alcohol-modified polypropylene is 0.05%.

上述改性聚丙烯膜的制备方法如下：The preparation method of the above-mentioned modified polypropylene film is as follows:

(1)将改性聚丙烯膜的制备原料置于双螺杆挤出机内，在240℃下熔融后，经滤网为10μm的过滤器进行过滤后，经模头挤出，得到熔融料，模头的温度为250℃；(1) placing the raw material for preparing the modified polypropylene film in a twin-screw extruder, melting it at 240° C., filtering it through a filter with a filter screen of 10 μm, and extruding it through a die head to obtain a molten material, wherein the temperature of the die head is 250° C.;

(2)将步骤(1)得到的熔融料流延到铸片辊上，在20℃下经水冷却成型后，进行双向拉伸，然后经平台区空气冷却后，经牵引系统进入收卷系统，在收卷张力30N/m的条件下，进行膜片收卷，得到厚度为4.5μm的改性聚丙烯膜；(2) casting the molten material obtained in step (1) onto a casting roll, water-cooling the molten material at 20° C. to form the molten material, biaxially stretching the molten material, air-cooling the molten material in the platform area, and then entering the winding system through the traction system. The molten material is wound under a winding tension of 30 N/m to obtain a modified polypropylene film with a thickness of 4.5 μm;

所述双向拉伸为异步拉伸，所述异步拉伸包括如下过程：The biaxial stretching is asynchronous stretching, and the asynchronous stretching includes the following process:

①纵向拉伸：预热温度：138℃；拉伸温度为145℃；纵向拉伸比为7，纵向拉伸结束后，冷却至室温；① Longitudinal stretching: preheating temperature: 138℃; stretching temperature: 145℃; longitudinal stretching ratio: 7. After longitudinal stretching, cool to room temperature;

②横向拉伸：预热温度：130℃；拉伸温度为152℃；热定型温度为165℃；横向拉伸比为6；② Transverse stretching: preheating temperature: 130℃; stretching temperature: 152℃; heat setting temperature: 165℃; transverse stretching ratio: 6;

③热处理：热处理温度130℃。③Heat treatment: Heat treatment temperature 130℃.

实施例2Example 2

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，按质量百分含量计，所述改性聚丙烯膜的制备原料包括如下质量百分含量的组分：制备例1提供的4-萜烯醇改性聚丙烯50％和聚丙烯50％，其他条件与实施例1相同。 This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that, calculated by weight percentage, the raw materials for preparing the modified polypropylene film include the following components in weight percentage: 50% of 4-terpene alcohol modified polypropylene and 50% of polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.

实施例3Example 3

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，所述改性聚丙烯膜的制备原料仅为制备例1提供的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the raw material for preparing the modified polypropylene film is only the 4-terpene alcohol modified polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.

实施例4Example 4

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，按质量百分含量计，所述改性聚丙烯膜的制备原料包括如下质量百分含量的组分：制备例1提供的4-萜烯醇改性聚丙烯0.4％和聚丙烯99.6％，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that, calculated by weight percentage, the raw materials for preparing the modified polypropylene film include the following components in weight percentage: 0.4% of 4-terpene alcohol-modified polypropylene and 99.6% of polypropylene provided in Preparation Example 1, and other conditions are the same as those in Example 1.

实施例5Example 5

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，将制备例1提供的4-萜烯醇改性聚丙烯替换为制备例2提供的接枝率为1.0％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 1.0% provided in Preparation Example 2, and other conditions are the same as in Example 1.

实施例6Example 6

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，将制备例1提供的4-萜烯醇改性聚丙烯替换为制备例3提供的接枝率为5.0％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 5.0% provided in Preparation Example 3, and other conditions are the same as in Example 1.

实施例7Example 7

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，将制备例1提供的4-萜烯醇改性聚丙烯替换为制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4, and other conditions are the same as in Example 1.

实施例8Example 8

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于， 将制备例1提供的4-萜烯醇改性聚丙烯替换为制备例5提供的接枝率为11.0％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof, which is different from Embodiment 1 only in that: The 4-terpene alcohol-modified polypropylene provided in Preparation Example 1 was replaced with the 4-terpene alcohol-modified polypropylene with a grafting rate of 11.0% provided in Preparation Example 5, and other conditions were the same as those in Example 1.

实施例9Example 9

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，将制备例1提供的4-萜烯醇改性聚丙烯替换为制备例6提供的接枝率为0.04％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the 4-terpene alcohol modified polypropylene provided in Preparation Example 1 is replaced by the 4-terpene alcohol modified polypropylene with a grafting rate of 0.04% provided in Preparation Example 6, and other conditions are the same as in Example 1.

实施例10Example 10

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，所述改性聚丙烯膜的制备原料仅为制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the raw material for preparing the modified polypropylene film is only 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4, and other conditions are the same as those in Example 1.

实施例11Embodiment 11

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例10的区别仅在于，将制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯替换为制备例7提供的接枝率为10.0％的α-萜品醇改性聚丙烯，其他条件与实施例10相同。This embodiment provides a modified polypropylene film and a preparation method thereof, which is different from Example 10 only in that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the α-terpineol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 7, and other conditions are the same as those in Example 10.

实施例12Example 12

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例10的区别仅在于，将制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯替换为制备例8提供的接枝率为10.0％的薰衣草醇改性聚丙烯，其他条件与实施例10相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by lavender alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 8, and other conditions are the same as Example 10.

实施例13Example 13

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例10的区别仅在于，将制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯替换为制备例9提供的接枝率为10.0％的香叶醇改性聚丙烯，其他条件与实施例10相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the geraniol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 9, and other conditions are the same as those in Example 10.

实施例14 Embodiment 14

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例1的区别仅在于，将熔融指数为3.0g/10min(230℃/2.16kg)、分子量分布指数为4.5、等规度为96％的聚丙烯(FS3028)替换为熔融指数为3.0g/10min(230℃/2.16kg)、分子量分布指数为4.5、等规度为93％的聚丙烯(FS3025)，其他条件与实施例1相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 1 is that the polypropylene (FS3028) with a melt index of 3.0 g/10 min (230° C./2.16 kg), a molecular weight distribution index of 4.5, and an isotacticity of 96% is replaced by a polypropylene (FS3025) with a melt index of 3.0 g/10 min (230° C./2.16 kg), a molecular weight distribution index of 4.5, and an isotacticity of 93%. The other conditions are the same as those in Example 1.

对比例1Comparative Example 1

本对比例提供一种聚丙烯膜及其制备方法，与实施例1的区别仅在于，所述聚丙烯膜的制备原料仅为聚丙烯(FS3028)，其他条件与实施例1相同。This comparative example provides a polypropylene film and a preparation method thereof, which is different from Example 1 only in that the raw material for preparing the polypropylene film is only polypropylene (FS3028), and other conditions are the same as those in Example 1.

对比例2Comparative Example 2

本实施例提供一种改性聚丙烯膜及其制备方法，与实施例10的区别仅在于，将制备例4提供的接枝率为10.0％的4-萜烯醇改性聚丙烯替换为制备对比例1提供的接枝率为10.0％的丙烯醇改性聚丙烯，其他条件与实施例10相同。This embodiment provides a modified polypropylene film and a preparation method thereof. The only difference from Example 10 is that the 4-terpene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Example 4 is replaced by the propylene alcohol modified polypropylene with a grafting rate of 10.0% provided in Preparation Comparative Example 1, and other conditions are the same as those in Example 10.

应用例1Application Example 1

本应用例提供一种复合集流体及其制备方法，所述复合集流体的结构示意图如图1所示，包括依次叠加设置的第一保护层1、第一金属层2、聚合物膜层3、第二金属层4和第二保护层5；This application example provides a composite current collector and a preparation method thereof. The structural schematic diagram of the composite current collector is shown in FIG1 , comprising a first protective layer 1, a first metal layer 2, a polymer film layer 3, a second metal layer 4, and a second protective layer 5 which are sequentially stacked;

所述聚合物膜层3为实施例1提供的改性聚丙烯膜。The polymer film layer 3 is the modified polypropylene film provided in Example 1.

所述复合集流体的制备方法如下：The preparation method of the composite current collector is as follows:

将实施例1提供的改性聚丙烯膜置于磁控溅射的舱体内，以纯度为99.99％的铜金属为靶材，以氩气为气源，在磁控溅射舱体内通过磁控溅射的方法在改性聚丙烯膜两侧分别镀一层厚度为100nm的铜金属层，得到复合薄膜；以此制备的复合薄膜为基材进行电镀，以增厚导电铜层，并获得第一保护层1和第二保护层5，电镀分为如下三个过程：①电镀增厚金属层：电镀液为120g/L硫酸铜、100g/L硫酸、50mg/L氯离子、1.2mg/L 3-巯基-1-丙烷磺酸钠、0.5mg/L 2- 巯基吡啶、180mg/L聚乙二醇10000，电镀液温度为25℃，平均阴极电流密度为2A/dm2，电镀处理5min；②制备第一保护层1和第二保护层5：电镀结束后，将镀好的薄膜在清水槽中进行清洗，然后在盛有5g/L重铬酸钾水溶液的保护层制备槽内制备表面保护层，处理温度为25℃，处理25s，最后再通过清水槽进行清洗；③干燥：在烘箱温度为65℃的条件下对清洗后的薄膜进行干燥，最终得到总厚度为1.2μm的复合集流体(其中，金属层的厚度为1170nm，保护层的厚度为30nm)。The modified polypropylene film provided in Example 1 is placed in a magnetron sputtering chamber, copper metal with a purity of 99.99% is used as a target material, argon gas is used as a gas source, and a copper metal layer with a thickness of 100 nm is plated on both sides of the modified polypropylene film by a magnetron sputtering method in the magnetron sputtering chamber to obtain a composite film; the prepared composite film is used as a substrate for electroplating to thicken the conductive copper layer and obtain a first protective layer 1 and a second protective layer 5, and the electroplating is divided into the following three processes: ① Electroplating to thicken the metal layer: the electroplating solution is 120 g/L copper sulfate, 100 g/L sulfuric acid, 50 mg/L chloride ion, 1.2 mg/L sodium 3-mercapto-1-propane sulfonate, 0.5 mg/L 2- 1. Thiopyridine, 180 mg/L polyethylene glycol 10000, the plating solution temperature is 25°C, the average cathode current density is 2A/dm2, and the electroplating treatment is 5 minutes; 2. Preparation of the first protective layer 1 and the second protective layer 5: After the electroplating is completed, the plated film is washed in a clean water tank, and then the surface protective layer is prepared in a protective layer preparation tank filled with a 5g/L potassium dichromate aqueous solution. The treatment temperature is 25°C, the treatment is 25s, and finally it is washed through a clean water tank; 3. Drying: The cleaned film is dried at an oven temperature of 65°C to finally obtain a composite current collector with a total thickness of 1.2μm (wherein the thickness of the metal layer is 1170nm and the thickness of the protective layer is 30nm).

应用例2-14Application Example 2-14

应用例2-14分别提供一种复合集流体及其制备方法，与应用例1的区别在于，将实施例1提供的改性聚丙烯膜依次替换为实施例2-14提供的改性聚丙烯膜，其他条件与应用例1相同。Application Examples 2-14 respectively provide a composite current collector and a preparation method thereof. The difference from Application Example 1 is that the modified polypropylene film provided in Example 1 is replaced by the modified polypropylene film provided in Examples 2-14 in sequence, and other conditions are the same as those in Application Example 1.

对比应用例1-2Comparative Application Example 1-2

对比应用例1-2分别提供一种复合集流体及其制备方法，与应用例1的区别在于，将实施例1提供的改性聚丙烯膜依次替换为对比例1提供的聚丙烯膜、对比例2提供的改性聚丙烯膜，其他条件与应用例1相同。Comparative Application Examples 1-2 respectively provide a composite current collector and a preparation method thereof. The difference from Application Example 1 is that the modified polypropylene film provided in Example 1 is replaced by the polypropylene film provided in Comparative Example 1 and the modified polypropylene film provided in Comparative Example 2, respectively, and other conditions are the same as those in Application Example 1.

本申请制备改性聚丙烯膜的目的在于提升聚合物膜的表面粘附性能及介电常数，进而提升以此改性聚丙烯膜为基材制备的复合集流体的性能。聚丙烯膜的表面粘附性能主要取决于其表面张力，最终表现在复合集流体中基膜与金属层的粘结力上；而聚丙烯膜介电常数的改变直接影响到其制备的复合集流体的孔洞数量，因此，本申请对制备的改性聚丙烯膜的表面张力及介电常数、制备的复合集流体中基膜与金属层的粘结力及孔洞缺陷数量进行了测试。此外，还对制备的改性聚丙烯膜的拉伸强度及制备的复合集流体的方阻进行了测试。具体方法如下： The purpose of preparing modified polypropylene film in this application is to improve the surface adhesion performance and dielectric constant of the polymer film, and then improve the performance of the composite current collector prepared with this modified polypropylene film as the substrate. The surface adhesion performance of the polypropylene film mainly depends on its surface tension, which is ultimately reflected in the adhesion between the base film and the metal layer in the composite current collector; and the change in the dielectric constant of the polypropylene film directly affects the number of holes in the composite current collector prepared therefrom. Therefore, this application tests the surface tension and dielectric constant of the prepared modified polypropylene film, the adhesion between the base film and the metal layer in the prepared composite current collector, and the number of hole defects. In addition, the tensile strength of the prepared modified polypropylene film and the square resistance of the prepared composite current collector were also tested. The specific method is as follows:

①表面张力：按照标准GB/T 14216-2008对上述制备的改性聚丙烯膜的表面张力进行测试；① Surface tension: The surface tension of the modified polypropylene film prepared above was tested according to standard GB/T 14216-2008;

②介电常数：按照标准SJ/T1147-1993对上述制备的改性聚丙烯膜的介电常数进行测试；② Dielectric constant: The dielectric constant of the modified polypropylene film prepared above was tested according to standard SJ/T1147-1993;

③拉伸强度：按照标准GB/T 1040.3-2006对上述制备的改性聚丙烯膜的拉伸强度进行测试。③Tensile strength: The tensile strength of the modified polypropylene film prepared above was tested in accordance with standard GB/T 1040.3-2006.

④复合集流体中聚丙烯膜与金属层的粘结力：在一个1mm厚的铝箔上粘接一层Permacel P-94双面胶，在双面胶的上方粘接复合集流体，在复合集流体上方覆盖一层乙烯丙烯酸共聚物薄膜(杜邦Nurcel0903，厚度为50μm)，然后在1.3×105N/m2、120℃下热压10s，冷却至室温，裁成150mm×15mm的小条。最后将样品小条的乙烯丙烯酸共聚物薄膜固定于拉力机的上夹具，其余部分固定在下夹具，固定好后二者以180°的角度、100mm/min的速度进行剥离，测试剥离力，即聚丙烯膜与金属层的粘结力；④ The bonding strength between the polypropylene film and the metal layer in the composite current collector: a layer of Permacel P-94 double-sided tape is bonded to 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, 50μm thick) is covered on the composite current collector, and then hot-pressed at 1.3×105N/m 2 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 off at an angle of 180° and a speed of 100mm/min to test the peeling force, that is, the bonding strength between the polypropylene film and the metal layer;

⑤单位面积复合集流体的孔洞缺陷数量：将制备的复合集流体样品置于表面质量检测系统(微觉视电荷耦合器件CCD)中，对其表面进行扫描，然后将光信号转换为电信号输送到计算机上，对单位面积复合集流体孔径小于100μm的孔洞缺陷数量进行统计(一般要求成品不能有超过100μm的孔洞)；⑤ Number of hole defects per unit area of composite current collector: Place the prepared composite current collector sample in a surface quality detection system (micro-vision charge coupled device CCD), scan its surface, and then convert the optical signal into an electrical signal and transmit it to a computer to count the number of hole defects per unit area of composite current collector with a pore size of less than 100 μm (generally, the finished product is required not to have holes larger than 100 μm);

⑥方阻：将制备的复合集流体样品置于样品台上，利用四探针方阻仪对样品的方阻进行测试。⑥ Square resistance: Place the prepared composite current collector sample on the sample stage and use a four-probe square resistance meter to test the square resistance of the sample.

对上述实施例和对比例提供的改性聚丙烯膜或聚丙烯膜的性能测试结果如下表2所示：The performance test results of the modified polypropylene film or polypropylene film provided in the above embodiments and comparative examples are shown in Table 2 below:

表2
Table 2

由上表的数据可知，本申请中通过选用具有特定熔融指数、特定分子量分布指数和特定规整度的聚丙烯、并选用特定的改性剂，同时控制改性剂的接枝率在在特定的范围内，制备得到了性能优异的改性聚丙烯，以此改性聚丙烯作为改性聚丙烯膜的制备原料，并控制改性聚丙烯膜中改姓聚丙烯的含量在特定的范围内，制备得到的改性聚丙烯膜具有较高的表面张力、较高的介电常数和较高的拉伸强度，其表面张力为38～59mN/m，介电常数为2.6～4.0mN/m，拉伸强度为185～225MPa。It can be seen from the data in the above table that in the present application, by selecting polypropylene with a specific melt index, a specific molecular weight distribution index and a specific regularity, and selecting a specific modifier, and controlling the grafting rate of the modifier within a specific range, a modified polypropylene with excellent performance is prepared. The modified polypropylene is used as a raw material for preparing a modified polypropylene film, and the content of the modified polypropylene in the modified polypropylene film is controlled within a specific range. The prepared modified polypropylene film has a higher surface tension, a higher dielectric constant and a higher tensile strength. The surface tension is 38 to 59 mN/m, the dielectric constant is 2.6 to 4.0 mN/m, and the tensile strength is 185 to 225 MPa.

与实施例1相比，若改性聚丙烯膜的制备原料中改性聚丙烯的含量过少(实施例4)，制备得到的改性聚丙烯膜相较于聚丙烯膜(对比例1)的性能提升有限，其表面张力、介电常数和拉伸强度均较低。 Compared with Example 1, if the content of modified polypropylene in the raw material for preparing the modified polypropylene film is too small (Example 4), the performance improvement of the prepared modified polypropylene film is limited compared with the polypropylene film (Comparative Example 1), and its surface tension, dielectric constant and tensile strength are all lower.

与实施例1相比，若改性聚丙烯中改性剂的接枝率较低(实施例9)，制备得到的改性聚丙烯膜的表面张力、介电常数和拉伸强度也较差；若改性聚丙烯中改性剂的接枝率较高(实施例8)，制备得到的改性聚丙烯膜的力学性能较差。Compared with Example 1, if the grafting rate of the modifier in the modified polypropylene is low (Example 9), the surface tension, dielectric constant and tensile strength of the prepared modified polypropylene film are also poor; if the grafting rate of the modifier in the modified polypropylene is high (Example 8), the mechanical properties of the prepared modified polypropylene film are poor.

与实施例1相比，用聚丙烯制备得到的聚丙烯膜(对比例1)的表面张力、介电常数和拉伸强度均较低；若选用其他改性剂改性的聚丙烯制备聚丙烯膜(对比例2)，制备得到的改性聚丙烯膜的表面张力、介电常数和拉伸强度也较差。Compared with Example 1, the surface tension, dielectric constant and tensile strength of the polypropylene film prepared with polypropylene (Comparative Example 1) are all lower; if polypropylene modified with other modifiers is used to prepare the polypropylene film (Comparative Example 2), the surface tension, dielectric constant and tensile strength of the prepared modified polypropylene film are also poor.

综上所述，本申请中通过选用具有特定熔融指数、特定分子量分布指数和特定规整度的聚丙烯、并选用特定的改性剂，同时控制改性剂的接枝率在在特定的范围内，制备得到了性能优异的改性聚丙烯，以此改性聚丙烯作为改性聚丙烯膜的制备原料，并控制改性聚丙烯膜中改姓聚丙烯的含量在特定的范围内，制备得到的改性聚丙烯膜具有较高的表面张力、较高的介电常数和较高的拉伸强度。In summary, in the present application, a modified polypropylene with excellent performance is prepared by selecting a polypropylene with a specific melt index, a specific molecular weight distribution index and a specific regularity, and selecting a specific modifier, while controlling the grafting rate of the modifier within a specific range. The modified polypropylene is used as a raw material for preparing a modified polypropylene film, and the content of the modified polypropylene in the modified polypropylene film is controlled within a specific range. The prepared modified polypropylene film has a higher surface tension, a higher dielectric constant and a higher tensile strength.

对上述应用例和对比应用例提供的复合集流体的性能测试结果如下表3所示：The performance test results of the composite current collectors provided in the above application examples and comparative application examples are shown in Table 3 below:

表3
Table 3

由上表的内容可知，本申请中，通过对改姓聚丙烯膜制备原料的设计，制备得到了性能优异的改性聚丙烯膜，聚合物膜(改性聚丙烯膜)与金属层之间的粘结力较大，为0.9～2.7N/cm，且制备得到的复合集流体上没有孔洞，且复合集流体的方阻较小，为17～18mΩ。It can be seen from the contents of the above table that in this application, a modified polypropylene film with excellent performance was prepared by designing the raw materials for preparing the modified polypropylene film. The bonding force between the polymer film (modified polypropylene film) and the metal layer is relatively large, which is 0.9 to 2.7 N/cm. There are no holes on the prepared composite current collector, and the square resistance of the composite current collector is relatively small, which is 17 to 18 mΩ.

与应用例1相比，若改性聚丙烯膜的制备原料中改性聚丙烯的含量过少(应用例4)，制备得到的复合集流体相较于复合集流体(对比应用例1)的性能提升有限，其粘结力较小、孔洞数量较多、方阻较大。 Compared with Application Example 1, if the content of modified polypropylene in the raw material for preparing the modified polypropylene film is too small (Application Example 4), the performance improvement of the prepared composite current collector is limited compared with the composite current collector (Comparative Application Example 1), and its adhesion is smaller, the number of pores is larger, and the square resistance is larger.

与应用例1相比，若改性聚丙烯中改性剂的接枝率较低(应用例9)，制备得到的复合集流体的粘结力较小、孔洞数量较多、方阻较大。Compared with Application Example 1, if the grafting rate of the modifier in the modified polypropylene is low (Application Example 9), the prepared composite current collector has a smaller bonding force, a larger number of pores, and a larger square resistance.

与应用例1相比，以聚丙烯膜制备得到的复合集流体(对比例1)的粘结力较小、孔洞数量较多、方阻较大；若选用其他改性剂改性的聚丙烯制备聚丙烯膜，进而得到的复合集流体(对比例2)的性能也较差。Compared with Application Example 1, the composite current collector prepared with polypropylene film (Comparative Example 1) has smaller adhesion, more pores, and larger square resistance; if polypropylene modified with other modifiers is used to prepare the polypropylene film, the performance of the composite current collector (Comparative Example 2) obtained is also poor.

综上所述，本申请中，通过对改姓聚丙烯膜制备原料的设计，制备得到了性能优异的改性聚丙烯膜，进而制备得到改性聚丙烯膜与金属层之间的粘结力较大、无孔洞且方阻较小的复合集流体。In summary, in this application, by designing the raw materials for preparing modified polypropylene film, a modified polypropylene film with excellent performance is prepared, and then a composite current collector with large adhesion between the modified polypropylene film and the metal layer, no holes and small square resistance is prepared.

申请人声明，本申请通过上述实施例来说明本申请的详细工艺流程，但本申请并不局限于上述详细工艺流程，即不意味着本申请必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。 The applicant declares that the present application uses the above-mentioned embodiments to illustrate the detailed process flow of the present application, but the present application is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present application must rely on the above-mentioned detailed process flow to be implemented. The technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the present application product, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Claims (10)

一种改性聚丙烯膜，所述改性聚丙烯膜的制备原料包括改性聚丙烯；A modified polypropylene film, wherein the raw material for preparing the modified polypropylene film comprises modified polypropylene; 所述改性聚丙烯的改性剂包括萜烯醇。The modifier for modifying the polypropylene includes terpene alcohol. 根据权利要求1所述的改性聚丙烯膜，其中，所述改性聚丙烯中萜烯醇的接枝率≥0.05％。The modified polypropylene film according to claim 1, wherein the grafting rate of terpene alcohol in the modified polypropylene is ≥ 0.05%. 根据权利要求1或2所述的改性聚丙烯膜，其中，所述萜烯醇包括4-萜烯醇、α-萜品醇、香芹醇、薰衣草醇、橙花醇、香叶醇中的任意一种或至少两种的组合。The modified polypropylene film according to claim 1 or 2, wherein the terpene alcohol comprises any one of 4-terpene alcohol, α-terpineol, carveol, lavandulol, nerol, and geraniol, or a combination of at least two thereof. 根据权利要求1-3任一项所述的改性聚丙烯膜，其中，所述改性聚丙烯中聚丙烯的熔融指数为3.0-4.0g/10min。The modified polypropylene film according to any one of claims 1 to 3, wherein the melt index of the polypropylene in the modified polypropylene is 3.0-4.0 g/10 min. 根据权利要求1-4任一项所述的改性聚丙烯膜，其中，所述改性聚丙烯中聚丙烯的分子量分布为4.5-5.5。The modified polypropylene film according to any one of claims 1 to 4, wherein the molecular weight distribution of the polypropylene in the modified polypropylene is 4.5-5.5. 根据权利要求1-5任一项所述的改性聚丙烯膜，其中，所述改性聚丙烯中聚丙烯的等规度≥95％。The modified polypropylene film according to any one of claims 1 to 5, wherein the isotacticity of the polypropylene in the modified polypropylene is ≥ 95%. 根据权利要求1-6任一项所述的改性聚丙烯膜，其中，以所述改性聚丙烯膜的制备原料的质量百分含量为100％计，所述改性聚丙烯的质量百分含量≥0.5％。The modified polypropylene film according to any one of claims 1 to 6, wherein the mass percentage of the modified polypropylene is ≥ 0.5%, based on the mass percentage of the raw material for preparing the modified polypropylene film being 100%. 一种如权利要求1-7任一项所述的改性聚丙烯膜的制备方法，所述制备方法包括如下步骤：A method for preparing a modified polypropylene film according to any one of claims 1 to 7, the method comprising the following steps: (1)将改性聚丙烯膜的制备原料熔融、过滤、挤出，得到熔融料；(1) melting, filtering and extruding the raw materials for preparing the modified polypropylene film to obtain a molten material; (2)将步骤(1)得到的熔融料流延到铸片辊上，冷却成型后，进行双向拉伸，得到所述改性聚丙烯膜。(2) Casting the molten material obtained in step (1) onto a casting roll, cooling and forming the molten material, and then biaxially stretching the molten material to obtain the modified polypropylene film. 一种复合集流体，所述复合集流体包括金属层和聚合物层；A composite current collector, comprising a metal layer and a polymer layer; 所述聚合物膜层为如权利要求1-7任一项所述的改性聚丙烯膜。 The polymer film layer is a modified polypropylene film as described in any one of claims 1 to 7. 一种电池，所述电池包括权利要求9所述的复合集流体。 A battery comprising the composite current collector according to claim 9.
PCT/CN2023/099589 2023-05-29 2023-06-12 Modified polypropylene film, preparation method therefor and use thereof Pending WO2024244050A1 (en)

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