WO2024108680A1 - 聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置 - Google Patents

聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置 Download PDF

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WO2024108680A1
WO2024108680A1 PCT/CN2022/138273 CN2022138273W WO2024108680A1 WO 2024108680 A1 WO2024108680 A1 WO 2024108680A1 CN 2022138273 W CN2022138273 W CN 2022138273W WO 2024108680 A1 WO2024108680 A1 WO 2024108680A1
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polymer
film
zinc
zinc oxide
layer
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PCT/CN2022/138273
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English (en)
French (fr)
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朱中亚
王帅
夏建中
李学法
张国平
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扬州纳力新材料科技有限公司
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Publication of WO2024108680A1 publication Critical patent/WO2024108680A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • 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
    • 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
    • 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

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  • the present application relates to the field of electrochemical technology, and in particular to a polymer composite film and a preparation method thereof, a composite current collector, a pole piece, a secondary battery and an electrical device.
  • composite current collectors based on polymer films have received widespread attention and application in the new energy industry.
  • Conventional composite current collectors usually include a polymer film layer and a metal (aluminum, copper, etc.) layer formed on the polymer film layer by methods such as physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • composite current collectors based on polymer films have the characteristics of low cost, light weight, and good internal insulation. These characteristics enable composite current collectors to reduce the cost of batteries and improve the energy density and safety of batteries when used in batteries.
  • the bonding force between the polymer film layer and the metal layer is usually weak, which can easily lead to the separation of the polymer film layer and the metal layer during the use of the composite current collector, affecting the normal use of the composite current collector.
  • conventional composite current collectors are usually prepared by vapor deposition, but the inventors have found that this method has the following problems: 1 The vapor deposition method has high energy consumption; 2 During the deposition of the adhesive layer on the film surface by vapor deposition, the condensation of the deposited atoms on the polymer film surface and the attenuation of the kinetic energy cause the film surface to have high heat, and the thin polymer film leads to the generation of hole defects.
  • the present application provides a polymer composite film and a preparation method thereof, a composite current collector, a pole piece, a secondary battery and an electrical device, which can enhance the bonding force between the polymer film layer and the metal layer, thereby enhancing the structural stability of the composite current collector.
  • the first aspect of the present application provides a polymer composite film, comprising:
  • a zinc oxide nano-deposition layer is formed on the surface of at least one side of the polymer base film, wherein the zinc oxide nano-deposition layer has a thickness of 50 nm to 150 nm.
  • the polymer composite film satisfies at least one of the following conditions:
  • the average particle size of the zinc oxide grains contained in the zinc oxide nano-deposition layer is 20 nm to 80 nm;
  • the thickness of the polymer base film is 2 ⁇ m to 20 ⁇ m.
  • the polymer includes one or more of polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene ether, polystyrene, polyamide and derivatives of the above polymers.
  • the second aspect of the present application provides a method for preparing a polymer composite membrane, comprising:
  • Zinc oxide nanoparticles are deposited on the surface of at least one side of the polymer base film to form a zinc oxide nano-deposition layer to obtain a polymer composite film, wherein the zinc oxide nano-deposition layer has a thickness of 50 nm to 150 nm.
  • the surface of the polymer film layer is subjected to dielectric barrier discharge plasma modification treatment,
  • the voltage of the alternating current input to the two electrodes of the dielectric barrier discharge plasma device is 10 kV to 16 kV;
  • the dielectric barrier discharge plasma modification treatment lasts for 5 s to 60 s.
  • the step of depositing zinc oxide nanoparticles on the surface of at least one side of the polymer base film comprises:
  • an alkaline agent is added to the aqueous solution of the zinc salt containing the polymer-based membrane until the concentration of the alkaline agent in the solution reaches a target value, so that the zinc salt and the alkaline agent react in contact to form the zinc oxide nanoparticles.
  • the method satisfies at least one of the following conditions:
  • the concentration of the aqueous solution of zinc nitrate is 0.05 mol/L to 0.25 mol/L;
  • reaction time is 0.5 min to 5.0 min
  • the target value is 0.02 mol/L to 0.25 mol/L;
  • the zinc salt comprises one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc bromide and zinc acetate;
  • the alkaline reagent includes one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water.
  • the method further comprises:
  • the aqueous solution is subjected to ultrasonic treatment.
  • the ultrasonic power of the ultrasonic treatment is 200W to 700W.
  • the third aspect of the present application provides a composite current collector, comprising the polymer composite film of the first aspect of the present application or the polymer composite film prepared according to the method of the second aspect of the present application.
  • the composite current collector further comprises:
  • a protective layer is formed on a surface of at least one side of the metal layer that is relatively far from the polymer composite film.
  • the composite current collector satisfies at least one of the following conditions:
  • the thickness of the polymer composite film is 2 ⁇ m to 20 ⁇ m;
  • the thickness of the metal layer is 500 nm to 2000 nm, and can be 700 nm to 1200 nm;
  • the thickness of the protective layer is 10 nm to 150 nm, and can be optionally 20 nm to 100 nm.
  • the composite current collector satisfies at least one of the following conditions:
  • the material of the metal layer includes one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver;
  • the material of the protective layer includes one or more of nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, carbon nano-quantum dots, carbon nanotubes, carbon nanofibers and graphene.
  • the fourth aspect of the present application provides a pole piece, comprising the composite current collector of the third aspect of the present application.
  • the electrode sheet includes a positive electrode sheet and/or a negative electrode sheet.
  • the fifth aspect of the present application provides a secondary battery, comprising the electrode sheet of the fourth aspect of the present application.
  • a sixth aspect of the present application provides an electrical device, comprising the secondary battery of the fifth aspect of the present application.
  • the electric device of the present application includes the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
  • FIG. 1 is a schematic structural diagram of a polymer composite membrane according to an embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of a composite current collector according to another embodiment of the present application.
  • any lower limit can be combined with any upper limit to form an unclearly recorded range; and any lower limit can be combined with other lower limits to form an unclearly recorded range, and any upper limit can be combined with any other upper limit to form an unclearly recorded range.
  • each point or single value between the range endpoints is included in the range.
  • each point or single value can be combined as its own lower limit or upper limit with any other point or single value or with other lower limits or upper limits to form an unclearly recorded range.
  • a list of items connected by the terms “at least one of,” “at least one of,” “at least one of,” or other similar terms may mean any combination of the listed items. For example, if items A and B are listed, the phrase “at least one of A and B” means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase “at least one of A, B, and C” means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C.
  • Item A may contain a single component or multiple components.
  • Item B may contain a single component or multiple components.
  • Item C may contain a single component or multiple components.
  • the inventors found that in the current conventional composite current collector, the bonding force between the polymer film and the metal layer is relatively poor, mainly because of the differences in the surface structure and chemical environment between the polymer film and the metal layer.
  • the conventional vapor deposition method for preparing the composite current collector has the following problems: 1 The vapor deposition method has high energy consumption; 2 During the deposition of the adhesive layer on the film surface by vapor deposition, the condensation of the deposited atoms on the polymer film surface and the attenuation of the kinetic energy cause the film surface to have high heat, and the thin polymer film leads to the generation of hole defects.
  • the inventors proposed the following technical solutions of this application from the perspective of surface modification of the polymer film and the metal layer.
  • a first aspect of an embodiment of the present application provides a polymer composite film, as shown in Figure 1, the polymer composite film 1 includes: a polymer base film 11; and a zinc oxide nano-deposition layer 12 formed on the surface of at least one side of the polymer base film, wherein the zinc oxide nano-deposition layer has a thickness of 50nm to 150nm.
  • the polymer composite film provided by the present application includes a polymer base film and a zinc oxide nano-deposition layer, wherein, since the zinc oxide nano-deposition layer is similar to the crystal structure of the metal, it is easy to embed the metal atoms into the zinc oxide crystal, thereby improving the bonding force between the polymer film layer and the metal layer.
  • the zinc oxide deposition layer also gives the polymer base film a moderately rough structure on the surface, enhancing the roughness of the polymer base film surface, thereby being riveted with the metal layer, thereby improving the performance of the polymer base film in adhering to metal atoms, and further improving the bonding force between the polymer base film and the metal layer.
  • the surface of the zinc oxide nano-deposition layer is rich in oxygen atoms, which can increase the surface tension, and the oxygen atoms are easy to interact with the metal atoms, thereby further promoting the improvement of the bonding force between the metal layer and the polymer film layer.
  • the zinc oxide nano-deposition layer can be set on the surface of one side of the polymer base film, or it can be set on the surfaces of the opposite sides of the polymer base film at the same time; when set at the same time, the thickness of the zinc oxide nano-deposition layer on both sides can be the same or different, and the specific setting method can be selected according to actual needs.
  • the thickness of the zinc oxide nano-deposition layer is 50 nm to 150 nm.
  • the thickness of the zinc oxide nano-deposition layer can be 70 nm, 90 nm, 110 nm, 130 nm, 150 nm or within the range of any of the above values.
  • the thickness of the zinc oxide nano-deposition layer is within a suitable range, which can effectively improve the surface structure and properties of the polymer base film, thereby enhancing the bonding force with the metal layer, and save raw material costs.
  • the average particle size of the zinc oxide crystals contained in the zinc oxide nano-deposition layer is 20 nm to 80 nm.
  • the average particle size of the zinc oxide crystals can be 30 nm, 40 nm, 50 nm, 60 nm, 70 nm or within the range of any of the above values.
  • the average particle size of the zinc oxide crystals is relatively large or relatively small, it may be unfavorable to achieve the improvement of the surface adhesion performance of the polymer base film.
  • the thickness of the polymer base film is 2 ⁇ m to 20 ⁇ m.
  • the thickness of the polymer base film can be 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m or within the range of any of the above values.
  • the thickness of the polymer base film is controlled within a suitable range, while taking into account the difficulty of production (the thinner the film, the greater the difficulty of production, the lower the yield), and can promote the improvement of the energy density of the composite current collector.
  • the type of polymer is not particularly limited and can be selected according to actual needs.
  • the polymer can include polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyimide, polypropylene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, polyphenylene sulfide, polyphenylene oxide, polystyrene, polyamide and one or more of the derivatives of the above polymers.
  • a second aspect of the present application provides a method for preparing a polymer composite film, which may include the following steps:
  • the surface polarity of the polymer film layer can be improved by firstly performing surface modification treatment on the polymer film layer, thereby promoting the deposition of zinc oxide nanoparticles on the surface of the polymer film layer; and then after the zinc oxide nanoparticles are deposited on the surface of the polymer base film, the surface structure and chemical environment of the polymer base film can be improved, thereby facilitating the enhancement of the bonding force with the metal layer.
  • the method has the advantages of being simple and easy to operate and easy to scale up.
  • the polymer film layer can be prepared by a process of melt extrusion to biaxial stretching.
  • the surface modification treatment of the polymer film layer in step S10 may include the following steps:
  • the polarity of the surface of the polymer film layer can be improved, and oxygen-containing functional groups can be generated on the surface, which can provide active reaction sites for the subsequent deposition of zinc oxide nanoparticles, thereby facilitating the deposition of zinc oxide nanoparticles on the surface of the polymer film layer in the subsequent steps.
  • the voltage of the alternating current input to the two electrodes of the dielectric barrier discharge plasma device is 10 kV to 16 kV.
  • the voltage of the alternating current can be 11 kV, 12 kV, 13 kV, 14 kV, 15 kV or within the range of any of the above values.
  • the dielectric barrier discharge plasma modification treatment time is 5s to 60s.
  • the dielectric barrier discharge plasma modification treatment time can be 10s, 20s, 30s, 40s, 50s or within the range of any of the above values.
  • the treatment time is relatively short, the effect of improving the surface polarity of the polymer film layer may not be obvious; when the treatment time is relatively long, the surface polarity of the polymer film layer cannot be further improved, and it may cause a decrease in the mechanical properties of the polymer film layer.
  • the device may include a power supply unit, a high-voltage transformer, upper and lower electrodes, dielectric glass, an air supply system, and a cabin.
  • the air supply system provides compressed air to the cabin.
  • the working pressure in the cabin can be 206.8 kPa, and the working temperature can be room temperature (25°C to 27°C);
  • the power supply unit outputs 220V, 50Hz AC, which can be converted into 10kV to 16kV, 325Hz AC through a high-voltage transformer.
  • the output AC is input to two electrodes for plasma treatment, and the distance between the electrodes can be 4mm.
  • depositing zinc oxide nanoparticles on the surface of at least one side of the polymer base film in step S20 may include the following steps:
  • an exemplary reaction process for obtaining a zinc oxide nanoparticle deposition layer after the zinc salt reacts with an alkaline reagent is as follows: first, after the polymer base film is treated with plasma, oxygen-containing functional groups, i.e., active reaction sites, are generated on the surface; then, the polymer base film enters an aqueous solution of zinc salt, and the oxygen-containing functional groups on the surface of the base film serve as active sites to complex with zinc ions in the solution to achieve fixed deposition of zinc ions on the surface of the base film, and the zinc ions fixed on the surface of the base film react with hydroxides in an alkaline reagent subsequently added to the solution to generate zinc hydroxide nanoparticles; finally, under the effect of ultrasonic cavitation, the zinc hydroxide nanoparticles generate instantaneous local high temperature and high pressure, thereby achieving dehydration and refinement of the zinc hydroxide nanoparticles to generate refined zinc oxide nanoparticles, thereby generating a zinc oxide nano
  • the concentration of the aqueous solution of the zinc salt is 0.05 mol/L to 0.25 mol/L.
  • the concentration of the aqueous solution of the zinc salt can be 0.10 mol/L, 0.15 mol/L, 0.20 mol/L, 0.25 mol/L or within the range of any of the above values.
  • the target value is 0.02 mol/L to 0.25 mol/L.
  • the target value can be 0.05 mol/L, 0.10 mol/L, 0.15 mol/L, 0.20 mol/L or within a range consisting of any of the above values.
  • the molar ratio of the zinc nitrate to the sodium hydroxide is (1.0 to 2.5):1.
  • the concentrations of zinc nitrate and sodium hydroxide will affect the deposition rate and particle size of the zinc oxide nano-deposition layer.
  • the concentration is relatively high, the growth rate may be high, and the size of the generated zinc oxide nano-ions is large, which will make the surface roughness of the zinc oxide nano-deposition layer larger, which may easily lead to a decrease in the adhesion between the formed polymer composite film and the metal layer.
  • the concentration is relatively low, the growth rate may be too low, which may result in a poor deposition effect of the zinc oxide nano-deposition layer, which may easily lead to a decrease in the adhesion between the formed polymer composite film and the metal layer.
  • the reaction time is 0.5 min to 5.0 min.
  • the reaction time can be 1.0 min, 1.5 min, 2.0 min, 2.5 min, 3.0 min, 3.5 min, 4.0 min, 4.5 min or within the range of any of the above values.
  • the reaction time will also affect the deposition rate and particle size of the zinc oxide nano-deposition layer. If the reaction time is relatively short, it is difficult to form a complete zinc oxide deposition layer, the modification effect is not good, and the bonding force between the formed polymer composite film and the metal layer is poor; if the reaction time is relatively long, the size of the zinc oxide nano-particles on the surface of the deposition layer is too large, which can easily lead to excessive roughness of the film surface, thereby causing the bonding force between the polymer composite film and the metal layer to decrease.
  • the type of the zinc salt is not specifically limited and can be selected according to actual needs, as long as it is water-soluble.
  • the zinc salt can include one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc bromide and zinc acetate.
  • the type of the alkaline agent is not specifically limited and can be selected according to actual needs, as long as it can undergo a replacement reaction with the zinc salt.
  • the alkaline agent can include one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water.
  • step S10 the following steps may also be included:
  • Ultrasonic treatment can cause the zinc hydroxide nanoparticles generated in step S20 to generate instantaneous local high temperature and high pressure under the effect of ultrasonic cavitation, thereby achieving dehydration and refinement of the zinc hydroxide nanoparticles, generating refined zinc oxide nanoparticles, and thus forming a zinc oxide nanoparticle deposition layer on the surface of the polymer base film.
  • the ultrasonic power of the ultrasonic treatment is 200W to 700W.
  • the ultrasonic power can be 300W, 400W, 500W, 600W or in the range of any of the above values.
  • Ultrasonic treatment also has an impact on the size of zinc oxide nanoparticles. If the ultrasonic power is relatively low, the size of the zinc oxide nanoparticles formed will be too large, which will easily make the roughness of the surface of the zinc oxide nano-deposition layer larger, thereby causing the bonding force between the polymer composite film and the metal layer to decrease. If the ultrasonic power is relatively high, the size of the zinc oxide nanoparticles formed will be too small, and the surface of the zinc oxide nano-deposition layer will be too smooth, causing the bonding force between the polymer composite film and the metal layer to decrease.
  • a cleaning and drying step of the generated polymer composite membrane may also be included.
  • the polymer-based film can be placed in a 0.05mol/L to 0.25mol/L zinc nitrate solution, and the ultrasonic system in the tank is turned on, the ultrasonic power is 200W to 700W, and the ultrasonic frequency is 37Hz. Then, a high concentration of sodium hydroxide solution is added to the solution until the concentration of sodium hydroxide in the solution is 0.025mol/L to 0.125mol/L, the concentration ratio of zinc nitrate to sodium hydroxide is 2:1, and the reaction time is 0.5min to 5.0min. Then, the film after the reaction treatment is completed is deliquified by an air knife, and enters pure water for cleaning for 1min to 5min. The cleaned film enters a blast oven and is dried at 70°C to obtain a polymer composite film with surface deposited zinc oxide.
  • a third aspect of the embodiments of the present application provides a composite current collector, comprising the polymer composite film of the first aspect of the present application or the polymer composite film prepared according to the method of the second aspect of the present application.
  • the composite current collector further includes: a metal layer 2 formed on at least one surface of the polymer composite film; and a protective layer 3 formed on at least one surface of the metal layer relatively away from the polymer composite film.
  • the thickness of the polymer composite film is 2 ⁇ m to 20 ⁇ m.
  • the thickness of the polymer composite film can be 5 ⁇ m, 8 ⁇ m, 11 ⁇ m, 14 ⁇ m, 17 ⁇ m or within the range of any of the above values.
  • the thickness of the polymer composite film can be set to meet the application requirements of the composite current collector while taking into account the difficulty and cost of the preparation process.
  • the thickness of the metal layer is 500 nm to 2000 nm, and can be 700 nm to 1200 nm.
  • the composite current collector can have a higher conductivity.
  • the material of the metal layer is not particularly limited and can be selected according to actual needs.
  • the material of the metal layer can include one or more of copper, copper alloy, aluminum, aluminum alloy, nickel, nickel alloy, titanium and silver.
  • the metal layer can be set on the surface of one side of the polymer composite film, or it can be set on the surfaces of both opposite sides of the polymer composite film at the same time; when set at the same time, the thickness of the metal layer on both sides can be the same or different, and the specific setting method can be selected according to actual needs.
  • the preparation method of forming the metal layer on the polymer composite film is not particularly limited and can be selected according to actual needs.
  • it can be prepared by physical vapor deposition (such as resistance heating vacuum evaporation, electron beam heating vacuum evaporation, laser heating vacuum evaporation or magnetron sputtering, etc.), electroplating, chemical plating, etc.
  • the thickness of the protective layer is 10 nm to 150 nm, and optionally 20 nm to 100 nm.
  • the thickness of the protective layer shall not exceed one tenth of the thickness of the metal layer.
  • the thickness of the protective layer is controlled within a suitable range to better prevent the metal layer from being chemically corroded or physically damaged.
  • the material of the protective layer is not particularly limited and can be selected according to actual needs.
  • the material of the protective layer may include one or more of nickel, chromium, nickel-based alloy, copper-based alloy, copper oxide, aluminum oxide, nickel oxide, chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, carbon nano quantum dots, carbon nanotubes, carbon nanofibers and graphene.
  • the protective layer can be set on the surface of one side of the polymer composite membrane, or it can be set on the surfaces of the opposite sides of the polymer composite membrane at the same time; when set at the same time, the thickness of the protective layers on both sides can be the same or different, and the specific setting method can be selected according to actual needs.
  • the preparation method of the protective layer formed on the metal layer is not particularly limited and can be selected according to actual needs.
  • it can include one or more methods such as physical vapor deposition, chemical vapor deposition, in-situ forming, coating, etc.
  • the 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 forming a metal oxide passivation layer in situ on the surface of the metal layer
  • the coating method is preferably die coating, blade coating and extrusion coating.
  • the composite current collector provided in the present application includes a polymer composite film with a zinc oxide nano-deposition layer deposited on the surface.
  • the zinc oxide nano-deposition layer can effectively improve the adhesion between the polymer composite film and the metal layer, and improve the structural stability of the composite current collector.
  • a fourth aspect of the embodiments of the present application provides a pole piece, comprising the composite current collector of the third aspect of the present application.
  • the electrode sheet includes a positive electrode sheet and/or a negative electrode sheet.
  • a fifth aspect of the embodiments of the present application provides a secondary battery, comprising the electrode sheet of the fourth aspect of the present application.
  • the secondary battery includes a positive electrode sheet, a negative electrode sheet, an electrolyte and a separator.
  • active ions are embedded and removed back and forth between the positive electrode sheet and the negative electrode sheet.
  • the electrolyte plays the role of conducting ions between the positive electrode sheet and the negative electrode sheet.
  • the separator is arranged between the positive electrode sheet and the negative electrode sheet, mainly to prevent the positive and negative electrodes from short-circuiting, while allowing ions to pass through.
  • the sixth aspect of the embodiment of the present application provides an electrical device, including the secondary battery of the fifth aspect of the present application.
  • the secondary battery can be used as a power source for the device, and can also be used as an energy storage unit for the device.
  • the device can be, but is not limited to, a mobile device, an electric vehicle, an electric train, a ship and a satellite, an energy storage system, etc.
  • it can be a laptop computer, a pen-input computer, a mobile computer, an e-book player, a portable phone, a portable fax machine, a portable copier, a portable printer, a head-mounted stereo headset, a video recorder, an LCD TV, a portable cleaner, a portable CD player, a mini CD, a transceiver, an electronic notepad, a calculator, a memory card, a portable recorder, a radio, a backup power supply, a motor, a car, a motorcycle, a power-assisted bicycle, a bicycle, a lighting fixture, a toy, a game console, a clock, an electric tool, a flashlight, a camera, a large household battery, etc.
  • a commercial 4.5 ⁇ m biaxially stretched PP film was placed in a dielectric barrier discharge plasma device, and the air supply system air inlet regulating valve was opened to introduce compressed air into the cabin to maintain the pressure in the cabin at 206.8kPa and the temperature at 25°C. Then the power supply unit was turned on to input 220V, 50Hz AC power to the high-voltage transformer, which was converted into 10kV, 325Hz AC power by the high-voltage transformer and input to two electrodes with a distance of 4mm, and the dielectric barrier discharge plasma treatment was started for 5s. After the treatment, a plasma-modified polymer-based film was obtained.
  • the plasma-modified polymer-based membrane was placed in a 0.05 mol/L zinc nitrate solution, and the ultrasonic system in the tank was turned on, with an ultrasonic power of 200 W and an ultrasonic frequency of 37 Hz.
  • a high-concentration sodium hydroxide solution was then added to the solution until the concentration of sodium hydroxide in the solution was 0.025 mol/L, and the reaction was continued for 0.5 min.
  • the membrane was dehydrated by an air knife and washed in pure water for 2 min. The washed membrane was placed in a blast oven and dried at 70 ° C to obtain a polymer composite membrane with zinc oxide deposited on the surface.
  • Preparation of the metal layer The polymer composite film prepared above is placed in a vacuum evaporation chamber, and the high-purity copper wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at a high temperature of 1500°C. The evaporated metal atoms pass through the cooling system in the vacuum coating chamber and are deposited on the two surfaces of the polymer base film to form a copper metal conductive layer with a thickness of 1 ⁇ m.
  • Preparation of protective layer 1 g of graphene was evenly dispersed in 999 g of nitrogen methyl pyrrolidone (NMP) solution by ultrasonic dispersion to prepare a coating solution with a solid content of 0.1 wt.%, and then the coating solution was evenly coated on the surface of the metal conductive layer by a die coating process, where the coating amount was controlled at 80 ⁇ m, and finally dried at 75°C.
  • NMP nitrogen methyl pyrrolidone
  • Example 2 The preparation method of Example 2 is similar to the preparation method of Example 1, except that during the dielectric barrier discharge plasma treatment, the voltage of the alternating current input to the two electrodes is 13 kV.
  • Example 3 The preparation method of Example 3 is similar to the preparation method of Example 1, except that during the dielectric barrier discharge plasma treatment, the voltage of the alternating current input to the two electrodes is 16 kV.
  • the preparation method of Example 2 is similar to the preparation method of Example 2, except that the treatment time of the dielectric barrier discharge plasma surface modification is 30 s.
  • the preparation method of Example 5 is similar to the preparation method of Example 2, except that the treatment time of the dielectric barrier discharge plasma surface modification is 60 seconds.
  • Example 6 The preparation method of Example 6 is similar to the preparation method of Example 2, except that the concentrations of zinc nitrate and sodium hydroxide are 0.15 mol/L and 0.075 mol/L, respectively.
  • Example 7 The preparation method of Example 7 is similar to the preparation method of Example 2, except that the concentrations of zinc nitrate and sodium hydroxide are 0.25 mol/L and 0.125 mol/L, respectively.
  • the preparation method of Example 8 is similar to the preparation method of Example 6, except that the ultrasonic power is 500W.
  • Example 9 The preparation method of Example 9 is similar to that of Example 6, except that the ultrasonic power is 700W.
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • the preparation method of Example 10 is similar to the preparation method of Example 8, except that the reaction time for preparing the zinc oxide deposition layer is 3.0 min.
  • Embodiment 11 is a diagrammatic representation of Embodiment 11:
  • the preparation method of Example 11 is similar to the preparation method of Example 8, except that the reaction time for preparing the zinc oxide deposition layer is 5.0 min.
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • Example 12 The preparation method of Example 12 is similar to the preparation method of Example 10, except that the 4.5 ⁇ m biaxially stretched PP film is replaced with a 4.5 ⁇ m biaxially stretched PET film.
  • Example 2 It is basically the same as Example 1, except that during the dielectric barrier discharge plasma treatment, the voltage of the alternating current input to the two electrodes is 9 kV.
  • Example 2 It is basically the same as Example 1, except that during the dielectric barrier discharge plasma treatment, the voltage of the alternating current input to the two electrodes is 17 kV.
  • Example 2 It is basically the same as Example 2, except that the treatment time of the dielectric barrier discharge plasma surface modification is 4s.
  • Example 2 It is basically the same as Example 2, except that the treatment time of the dielectric barrier discharge plasma surface modification is 61 s.
  • the method is substantially the same as Example 4, except that the concentrations of zinc nitrate and sodium hydroxide are 0.04 mol/L and 0.02 mol/L, respectively.
  • the method is substantially the same as Example 4, except that the concentrations of zinc nitrate and sodium hydroxide are 0.26 mol/L and 0.13 mol/L, respectively.
  • the method is substantially the same as Example 4, except that the concentrations of zinc nitrate and sodium hydroxide are 0.15 mol/L and 0.10 mol/L, respectively.
  • the method is substantially the same as Example 4, except that the concentrations of zinc nitrate and sodium hydroxide are 0.15 mol/L and 0.06 mol/L, respectively.
  • Example 6 It is basically the same as Example 6, except that the ultrasonic power is 190W.
  • Example 6 Basically the same as Example 6, except that the ultrasonic power is 710W.
  • Example 8 It is basically the same as Example 8, except that the reaction time for preparing the zinc oxide deposition layer is 0.4 min.
  • Example 8 It is basically the same as Example 8, except that the reaction time for preparing the zinc oxide deposition layer is 5.1 min.
  • the method is basically the same as Example 1, except that the 4.5 ⁇ m biaxially oriented PP film is not subjected to the dielectric barrier discharge plasma surface modification treatment.
  • the method is basically the same as Example 1, except that: the polymer composite membrane is prepared by chemical vapor deposition, that is, a 4.5 ⁇ m biaxially oriented PP film treated with plasma is placed in a chemical vapor deposition device, dimethyl zinc is used as the zinc source with a flow rate of 500 sccm, tert-butyl alcohol is used as the oxygen source with a flow rate of 50 sccm, the pressure in the reaction chamber is 5.0 ⁇ 10 -3 Pa, and a 50 nm zinc oxide layer is deposited on the membrane surface.
  • Adhesion A layer of Permacel P-94 double-sided tape was adhered to a 1 mm thick aluminum foil, and the sample (composite current collector or polymer composite film with surface zinc oxide deposition) was adhered on the double-sided tape. A layer of ethylene acrylic acid copolymer film (DuPont Nurcel0903, thickness of 50 ⁇ m) was covered on the sample, and then hot-pressed at 1.3 ⁇ 105 N/m 2 and 120°C for 10 seconds, cooled to room temperature, and cut into 150 mm ⁇ 15 mm strips. Finally, the ethylene acrylic acid copolymer film of the sample strip was fixed to the upper fixture of the tensile machine, and the rest was fixed to the lower fixture.
  • the two were peeled off at an angle of 180° and a speed of 100 mm/min to test the peeling force, that is, the adhesion between the polymer composite film and the metal layer in the composite current collector, and the adhesion between the zinc oxide nano-deposition layer and the polymer base film in the polymer composite film with surface zinc oxide deposition.
  • the prepared polymer composite film is placed in a surface quality detection system (micro-vision charge coupled device CCD), the surface is scanned, and then the optical signal is converted into an electrical signal and transmitted to a computer.
  • the number of surface holes with a pore size less than 100 ⁇ m per unit area of the finished composite copper current collector is counted (generally, the finished product is required not to have holes larger than 100 ⁇ m).
  • the adhesion between the zinc oxide nano-deposition layer and the polymer base film and the adhesion between the polymer composite film and the metal layer are significantly reduced, that is, the surface adhesion performance of the polymer composite film and the structural stability of the composite current collector deteriorate.
  • the adhesion between the zinc oxide nano-deposition layer and the polymer base film and the adhesion between the polymer composite film and the metal layer are significantly reduced, that is, the surface adhesion performance of the polymer composite film and the structural stability of the composite current collector deteriorate.
  • the concentration change has basically no effect on the performance of the polymer-based film obtained by the plasma surface modification process, and mainly affects the performance of the polymer composite film obtained after the deposition of zinc oxide nanoparticles, that is, when the concentration is increased, the surface roughness of the polymer composite film and the average particle size of the zinc oxide nanoparticles increase, and the surface tension first increases and then remains basically unchanged, which eventually causes the bonding force between the polymer composite film and the metal layer to first increase and then decrease.
  • the bonding force between the polymer composite film and the metal layer is significantly reduced, that is, the surface bonding performance of the polymer composite film and the structural stability of the composite current collector deteriorate.
  • the ultrasonic power mainly affects the performance of the polymer composite film obtained after the deposition of the nanoparticles, that is, when the ultrasonic power is increased, the surface roughness of the polymer composite film and the average particle size of the zinc oxide nanoparticles decrease, and the surface tension first increases and then decreases, which ultimately causes the bonding force between the polymer composite film and the metal layer to first increase and then decrease.
  • the bonding force between the polymer composite film and the metal layer is significantly reduced, that is, the surface bonding performance of the polymer composite film and the structural stability of the composite current collector deteriorate.
  • the deposition time mainly affects the performance of the polymer composite film obtained by the deposition of zinc oxide nanoparticles, that is, when the deposition time is increased, the surface roughness of the polymer composite film and the average particle size of the zinc oxide nanoparticles increase, and the surface tension first increases and then remains basically unchanged, which ultimately causes the bonding force between the polymer composite film and the metal layer to first increase and then decrease.
  • the bonding force between the polymer composite film and the metal layer is significantly reduced, that is, the surface bonding performance of the polymer composite film and the structural stability of the composite current collector deteriorate.
  • Example 10 By comparing Example 10 and Comparative Example 13, it can be seen that after surface zinc oxide deposition treatment, the surface adhesion performance of the polymer composite film is significantly improved, and in the composite current collector prepared in this way, the bonding force between the polymer composite film and the metal layer is significantly improved, that is, the structural stability of the composite current collector is effectively improved.

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Abstract

本申请提供一种聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置，聚合物复合膜包括：聚合物基膜和形成于聚合物基膜至少一侧的表面上的氧化锌纳米沉积层，其中，氧化锌纳米沉积层的厚度为50nm至150nm。

Description

聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置
相关申请
本申请要求2022年11月21日申请的，申请号为2022114784837，名称为“聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及电化学技术领域，特别是涉及一种聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置。
背景技术
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。常规的复合集流体通常包括高分子聚合物膜层，以及通过物理气相沉积(PVD)等方法在高分子聚合物膜层上形成的金属(铝、铜等)层。相比于传统的集流体，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。
然而，在目前常规的复合集流体中，高分子聚合物膜层与金属层间的结合力通常较弱，极易导致复合集流体在使用过程中发生高分子聚合物膜层与金属层的分离，影响复合集流体的正常使用。另外，常规的复合集流体通常采用气相沉积的方法制备，但是发明人发现这一方法存在如下问题：①气相沉积的方法能耗较高；②粘结层通过气相沉积在膜面沉积的过程中由于沉积原子在聚合物膜面的凝华及动能的衰减引发膜面热量较高，加上聚合物膜较薄，导致孔洞缺陷的生成。因此，为了解决上述问题，有必要提出一种低能耗且易操作的聚合物膜表面改性方法，以此改性方法开发一种表面粘附性能提升且无孔洞缺陷的聚合物膜，以此聚合物膜为基膜制备复合集流体，以提升基膜与金属层间的粘结力。
发明内容
基于此，本申请提供一种聚合物复合膜及其制备方法、复合集流体、极片、二次电池 和用电装置，可以提升聚合物膜层与金属层间的结合力，由此提升复合集流体的结构稳定性。
本申请的第一方面提供了一种聚合物复合膜，包括：
聚合物基膜；和
形成于所述聚合物基膜至少一侧的表面上的氧化锌纳米沉积层，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
在本申请的一些实施方式中，所述聚合物复合膜满足如下条件中的至少一者：
(1)所述氧化锌纳米沉积层中包含的氧化锌晶粒的平均粒径为20nm至80nm；
(2)所述聚合物基膜的厚度为2μm至20μm；和
(3)所述聚合物包括聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚丙乙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚苯硫醚、聚苯醚、聚苯乙烯、聚酰胺及上述聚合物的衍生物中的一种或多种。
本申请的第二方面提供了一种用于制备聚合物复合膜的方法，包括：
对聚合物膜层做表面改性处理，得到聚合物基膜；和
在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，形成氧化锌纳米沉积层，得到聚合物复合膜，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
在本申请的一些实施方式中，所述对聚合物膜层做表面改性处理，包括：
对所述聚合物膜层的表面做介质阻挡放电等离子体改性处理，
可选地，在所述介质阻挡放电等离子体改性处理过程中，输入到介质阻挡放电等离子装置的两个电极的交流电的电压为10kV至16kV；和
可选地，所述介质阻挡放电等离子体改性处理的时间为5s至60s。
在本申请的一些实施方式中，所述在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，包括：
将所述聚合物基膜置于锌盐的水溶液中；和
在超声作用下，向含有所述聚合物基膜的所述锌盐的水溶液中加入碱性试剂，至所述溶液中所述碱性试剂的浓度达到目标值，以使所述锌盐与所述碱性试剂接触反应后形成所述氧化锌纳米粒子。
在本申请的一些实施方式中，所述方法满足如下条件中的至少一者：
(1)所述硝锌盐的水溶液的浓度为0.05mol/L至0.25mol/L；
(2)所述锌盐与所述碱性试剂的摩尔比为(1.0至2.5):1；
(3)所述反应的时间为0.5min至5.0min；
(4)所述目标值为0.02mol/L至0.25mol/L；
(5)所述锌盐包括硝酸锌、氯化锌、硫酸锌、溴化锌和醋酸锌中的一种或多种；和
(6)所述碱性试剂包括氢氧化钠、氢氧化钾、碳酸钠和氨水中的一种或多种。
在本申请的一些实施方式中，在所述将所述聚合物基膜置于锌盐的水溶液中之后，还包括：
对所述水溶液做超声处理，
可选地，所述超声处理的超声功率为200W至700W。
本申请的第三方面提供了一种复合集流体，包括本申请第一方面的聚合物复合膜或根据本申请第二方面的方法制得的聚合物复合膜。
在本申请的一些实施方式中，所述复合集流体还包括：
形成于所述聚合物复合膜至少一侧表面上的金属层；和
形成于所述金属层相对远离所述聚合物复合膜的至少一侧的表面上的保护层。
在本申请的一些实施方式中，所述复合集流体满足如下条件中的至少一者：
(1)所述聚合物复合膜的厚度为2μm至20μm；
(2)所述金属层的厚度为500nm至2000nm，可选为700nm至1200nm；和
(3)所述保护层的厚度为10nm至150nm，可选为20nm至100nm。
在本申请的一些实施方式中，所述复合集流体满足如下条件中的至少一者：
(1)所述金属层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的一种或多种；和
(2)所述保护层的材料包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种。
本申请的第四方面提供了一种极片，包括本申请第三方面的复合集流体。
在本申请的一些实施方式中，所述极片包括正极极片和/或负极极片。
本申请的第五方面提供了一种二次电池，包括本申请第四方面的极片。
本申请的第六方面提供了一种用电装置，包括本申请第五方面的二次电池。
本申请的用电装置包括本申请提供的二次电池，因而至少具有与所述二次电池相同的优势。
本申请的一个或多个实施例的细节在下面的附图和描述中提出。本申请的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
为了更清楚地说明本申请实施例或传统技术中的技术方案，下面将对实施例或传统技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据公开的附图获得其他的附图。
图1为本申请一实施方式的聚合物复合膜的结构示意图。
图2为本申请另一实施方式的复合集流体的结构示意图。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
为了简便，本申请仅明确地公开了一些数值范围。然而，任意下限可以与任何上限组合形成未明确记载的范围；以及任意下限可以与其它下限组合形成未明确记载的范围，同样任意上限可以与任意其它上限组合形成未明确记载的范围。此外，尽管未明确记载，但是范围端点间的每个点或单个数值都包含在该范围内。因而，每个点或单个数值可以作为自身的下限或上限与任意其它点或单个数值组合或与其它下限或上限组合形成未明确记载的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。需要说明的是，除非另有说明，本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合，“以上”、“以下”为包含本数，“一种或多种”中的“多种”的含义是两种以上。
除非另有说明，本申请中使用的术语具有本领域技术人员通常所理解的公知含义。除非另有说明，本申请中提到的各参数的数值可以用本领域常用的各种测量方法进行测量(例如，可以按照在本申请的实施例中给出的方法进行测试)。
术语“中的至少一者”、“中的至少一个”、“中的至少一种”或其他相似术语所连接的项目的列表可意味着所列项目的任何组合。例如，如果列出项目A及B，那么短语“A及B中的至少一者”意味着仅A；仅B；或A及B。在另一实例中，如果列出项目A、B及C，那么短语“A、B及C中的至少一者”意味着仅A；或仅B；仅C；A及B(排除C)； A及C(排除B)；B及C(排除A)；或A、B及C的全部。项目A可包含单个组分或多个组分。项目B可包含单个组分或多个组分。项目C可包含单个组分或多个组分。
本申请的上述申请内容并不意欲描述本申请中的每个公开的实施方式或每种实现方式。如下描述更具体地举例说明示例性实施方式。在整篇申请中的多处，通过一系列实施例提供了指导，这些实施例可以以各种组合形式使用。在各个实例中，列举仅作为代表性组，不应解释为穷举。
发明人在研究过程中发现，目前常规的复合集流体中，聚合物膜与金属层间的结合力较差，主要是因为聚合物膜与金属层的表面结构及化学环境间存在差异，同时发明人还发现常规的制备复合集流体的气相沉积方法会存在如下问题：①气相沉积的方法能耗较高；②粘结层通过气相沉积在膜面沉积的过程中由于沉积原子在聚合物膜面的凝华及动能的衰减引发膜面热量较高，加上聚合物膜较薄，导致孔洞缺陷的生成。为解决上述技术问题，发明人从聚合物膜与金属层的表面改性的角度出发，提出了本申请如下的技术方案。
本申请实施方式的第一方面提供了一种聚合物复合膜，如图1所示，聚合物复合膜1包括：聚合物基膜11；和形成于所述聚合物基膜至少一侧的表面上的氧化锌纳米沉积层12，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
本申请提供的聚合物复合膜包括聚合物基膜和氧化锌纳米沉积层，其中，由于氧化锌纳米沉积层与金属的晶体结构类似，因而易使金属原子镶嵌到氧化锌晶体内部，由此可提升聚合物膜层与金属层间的结合力。此外，氧化锌沉积层还赋予了聚合物基膜表面适度粗糙的结构，增强了聚合物基膜表面的粗糙性，由此可与金属层铆合，从而提高聚合物基膜粘附金属原子的性能，进一步提升聚合物基膜与金属层间的结合力。此外，氧化锌纳米沉积层表面富含氧原子，可提升表面张力，且氧原子易与金属原子发生相互作用，从而进一步促进金属层与聚合物膜层间的粘结力的提升。
可以理解的是，氧化锌纳米沉积层可设置于聚合物基膜一侧的表面上，也可同时设置于聚合物基膜相对两侧的表面上；当同时设置时，两侧的氧化锌纳米沉积层的厚度可以相同，也可以不同，具体设置方式可根据实际需求进行选择。
在一些实施方式中，氧化锌纳米沉积层的厚度为50nm至150nm。例如，氧化锌纳米沉积层的厚度可以为70nm，90nm，110nm，130nm，150nm或处于以上任何数值所组成的范围内。氧化锌纳米沉积层的厚度在合适范围内，既可有效改善聚合物基膜的表面结构和性质，从而提升与金属层间的结合力，又可节省原料成本。
在一些实施方式中，所述氧化锌纳米沉积层中包含的氧化锌晶粒的平均粒径为20nm至80nm。例如，氧化锌晶粒的平均粒径可以为30nm，40nm，50nm，60nm，70nm或处于 以上任何数值所组成的范围内。当氧化锌晶粒的平均粒径相对较大或相对较小时，均可能不利于实现聚合物基膜表面粘附性能的提升。
在一些实施方式中，所述聚合物基膜的厚度为2μm至20μm。例如，聚合物基膜的厚度可以为5μm，10μm，15μm，20μm或处于以上任何数值所组成的范围内。聚合物基膜的厚度控制在合适范围内，在兼顾生产难度(膜越薄、生产难度越大、良品率越低)的同时，加可促进复合集流体能量密度的提升。
在一些实施方式中，聚合物的种类没有特别的限制，可根据实际需求进行选择。例如，所述聚合物可以包括聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚丙乙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚苯硫醚、聚苯醚、聚苯乙烯、聚酰胺及上述聚合物的衍生物中的一种或多种。
本申请实施方式的第二方面提供了一种用于制备聚合物复合膜的方法，可以包括如下步骤：
S10、对聚合物膜层做表面改性处理，得到聚合物基膜；和
S20、在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，形成氧化锌纳米沉积层，得到聚合物复合膜，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
本申请提供的方法中，首先通过对聚合物膜层做表面改性处理，可提高聚合物膜层表面的极性，从而促进氧化锌纳米粒子在聚合物膜层表面上的沉积；然后在聚合物基膜的表面上沉积氧化锌纳米粒子后，可改善聚合物基膜的表面结构和化学环境，由此有利于增强与金属层间的结合力。该方法具备工艺简单易行、易于放大的优点。
在一些实施例中，聚合物膜层可通过熔融挤出至双向拉伸的方法制备而得。
在一些实施方式中，步骤S10中对聚合物膜层做表面改性处理，可以包括如下步骤：
S100、对所述聚合物膜层的表面做介质阻挡放电等离子体改性处理。
通过对聚合物膜层的表面做介质阻挡放电等离子体改性处理，可提高聚合物膜层表面的极性，且表面可生成含氧官能团，可为后续氧化锌纳米粒子的沉积提供活性反应位点，从而有利于促进后续步骤中氧化锌纳米粒子在聚合物膜层表面上的沉积。
在一些实施例中，在所述介质阻挡放电等离子体改性处理过程中，输入到介质阻挡放电等离子装置的两个电极的交流电的电压为10kV至16kV。例如，交流电的电压可以为11kV，12kV，13kV，14kV，15kV或处于以上任何数值所组成的范围内。输入到两个电极的交流电的电压相对较低时，易使改性处理的效果不明显；输入到两个电极的交流电的电压相对较高时，可能不会达到提高聚合物膜层表面极性的效果，并且可能会引起聚合物膜层力学性能的降低。
在一些实施例中，所述介质阻挡放电等离子体改性处理的时间为5s至60s。例如，介质阻挡放电等离子体改性处理的时间可以为10s，20s，30s，40s，50s或处于以上任何数值所组成的范围内。处理时间相对较短时，聚合物膜层表面极性的提升效果可能不明显；处理时间相对较长时，聚合物膜层表面极性并不能进一步提高，而且可能会引起聚合物膜层力学性能的降低。
作为介质阻挡放电等离子装置的一个非限制性示例，所述装置可包括供电单元、高压变压器、上下电极、介电玻璃、供气系统及舱体。其中，供气系统向舱体内提供压缩空气，通入气体后，舱体内的工作压力可为206.8kPa，工作温度可为室温(25℃至27℃)；供电单元输出220V、50Hz的交流电，经高压变压器可转换为10kV至16kV、325Hz的交流电，输出的交流电输入到两个电极进行等离子处理，电极之间的距离可为4mm。
在一些实施方式中，步骤S20中在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，可以包括如下步骤：
S200、将所述聚合物基膜置于锌盐的水溶液中；和
S210、在超声作用下，向含有所述聚合物基膜的所述锌盐的水溶液中加入碱性试剂，至所述溶液中所述碱性试剂的浓度达到目标值，以使所述锌盐与所述碱性试剂接触反应后形成所述氧化锌纳米粒子。
通过将聚合物基膜置于锌盐的水溶液中，并加入碱性试剂，可实现在聚合物基膜的表面上的原位沉积，然后获得氧化锌纳米粒子沉积层，并实现氧化锌纳米粒子的均匀沉积。
需要说明的是，锌盐与碱性试剂反应后获得氧化锌纳米粒子沉积层的示例性反应过程如下：首先，聚合物基膜经等离子体处理后，表面会生成含氧官能团即活性反应位点；然后，聚合物基膜进入到锌盐的水溶液中，以基膜表面的含氧官能团为活性位点，与溶液中的锌离子发生络合作用，实现锌离子在基膜表面的固定沉积，固定在基膜表面的锌离子与随后加入到溶液中的碱性试剂中的氢氧根进行反应，生成氢氧化锌纳米颗粒；最后，氢氧化锌纳米颗粒在超声空化的效应下，产生瞬间局部高温高压，实现氢氧化锌纳米颗粒的脱水及细化，生成细化的氧化锌纳米颗粒，从而在聚合物基膜表面生成一层氧化锌纳米粒子沉积层。
在一些实施方式中，所述锌盐的水溶液的浓度为0.05mol/L至0.25mol/L。例如，锌盐的水溶液的浓度可以为0.10mol/L，0.15mol/L，0.20mol/L，0.25mol/L或处于以上任何数值所组成的范围内。
在一些实施方式中，所述目标值为0.02mol/L至0.25mol/L。例如，所述目标值可以为0.05mol/L，0.10mol/L，0.15mol/L，0.20mol/L或处于以上任何数值所组成的范围内。
在一些实施方式中，所述硝酸锌与所述氢氧化钠的摩尔比为(1.0至2.5):1。
本申请实施方式中，硝酸锌及氢氧化钠的浓度会影响氧化锌纳米沉积层的沉积速率及颗粒尺寸。浓度相对较高时，生长速率可能会较高，生成的氧化锌纳米离子的尺寸较大，会使得氧化锌纳米沉积层表面的粗糙度较大，易导致形成的聚合物复合膜与金属层间的粘结力降低。浓度相对较低时，生长速率可能会过低，会使氧化锌纳米沉积层的沉积效果不佳，易导致形成的聚合物复合膜与金属层的粘结力降低。
在一些实施方式中，所述反应的时间为0.5min至5.0min。例如，反应的时间可以为1.0min，1.5min，2.0min，2.5min，3.0min，3.5min，4.0min，4.5min或处于以上任何数值所组成的范围内。
本申请实施方式中，反应的时间也会影响氧化锌纳米沉积层的沉积速率及颗粒尺寸。若反应时间相对较短，则不易形成完整的氧化锌沉积层，改性效果不佳，形成的聚合物复合膜与金属层间的粘结力较差；若反应时间相对较长，则沉积层表面的氧化锌纳米颗粒尺寸过大，易导致膜面粗糙度过大，进而引起聚合物复合膜与金属层的粘结力降低。
在一些实施方式中，所述锌盐的种类不做具体的限定，可根据实际需求进行选择，只要具备水溶性即可。例如，锌盐可包括硝酸锌、氯化锌、硫酸锌、溴化锌和醋酸锌中的一种或多种。
在一些实施方式中，所述碱性试剂的种类不做具体的限定，可根据实际需求进行选择，只要可与锌盐发生置换反应即可。例如，碱性试剂可以包括氢氧化钠、氢氧化钾、碳酸钠和氨水中的一种或多种。
在一些实施方式中，在步骤S10之后，还可以包括如下步骤：
S30、对所述水溶液做超声处理。
超声处理可使步骤S20中生成的氢氧化锌纳米颗粒在超声空化的效应下，产生瞬间局部高温高压，实现氢氧化锌纳米颗粒的脱水及细化，生成细化的氧化锌纳米颗粒，从而在聚合物基膜表面生成一层氧化锌纳米粒子沉积层。
在一些实施例中，所述超声处理的超声功率为200W至700W。例如，超声功率可以为300W，400W，500W，600W或处于以上任何数值所组成的范围内。超声处理也会对氧化锌纳米粒子的尺寸造成影响。若超声功率相对较低，则形成的氧化锌纳米离子尺寸会过大，易使得氧化锌纳米沉积层表面的粗糙度较大，进而引起聚合物复合膜与金属层间的粘结力降低。若超声功率相对较高，则形成的氧化锌纳米粒子尺寸会过小，氧化锌纳米沉积层的表面过于平整，导致聚合物复合膜与金属层间的粘结力降低。
在一些实施方式中，在步骤S20之后，还可以包括对生成的聚合物复合膜的清洗烘干 步骤。
作为上述步骤S20的一个非限制性示例，可将聚合物基膜置于0.05mol/L至0.25mol/L硝酸锌溶液中，并开启槽体内的超声系统，超声功率为200W至700W，超声频率为37Hz。然后向溶液中加入高浓度的氢氧化钠溶液至溶液中氢氧化钠的浓度为0.025mol/L至0.125mol/L，硝酸锌与氢氧化钠二者浓度比为2:1，反应时间为0.5min至5.0min。然后将反应处理完成后的膜经风刀除液，进入到纯水中清洗1min至5min，清洗后的膜进入到鼓风烘箱内，于70℃下烘干，即得到表面沉积氧化锌的聚合物复合膜。
本申请实施方式的第三方面提供了一种复合集流体，包括本申请第一方面的聚合物复合膜或根据本申请第二方面的方法制得的聚合物复合膜。
在一些实施方式中，如图2所示，所述复合集流体还包括：形成于所述聚合物复合膜至少一侧表面上的金属层2；和形成于所述金属层的相对远离所述聚合物复合膜的至少一侧的表面上的保护层3。
在一些实施方式中，所述聚合物复合膜的厚度为2μm至20μm。例如，聚合物复合膜的厚度可以为5μm，8μm，11μm，14μm，17μm或处于以上任何数值所组成的范围内。聚合物复合膜的厚度设置既可满足复合集流体的应用要求，同时还可兼顾制备工艺的难度和成本的高低。
在一些实施方式中，所述金属层的厚度为500nm至2000nm，可选为700nm至1200nm。金属层的厚度控制在合适范围内，可使复合集流体具备较高的导电性。
在一些实施方式中，所述金属层的材料不做特别的限定，可根据实际需求进行选。例如，金属层的材料可以包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的一种或多种。
可以理解的是，金属层可设置于聚合物复合膜一侧的表面上，也可同时设置于聚合物复合膜相对两侧的表面上；当同时设置时，两侧的金属层的厚度可以相同，也可以不同，具体的设置方式可根据实际需求进行选择。
在一些实施方式中，金属层形成于聚合物复合膜上的制备方法不做特别的限定，可根据实际需求进行选择。例如，可通过物理气相沉积(如电阻加热真空蒸镀、电子束加热真空蒸镀、激光加热真空蒸镀或磁控溅射等)、电镀、化学镀等方法制备。
在一些实施方式中，所述保护层的厚度为10nm至150nm，可选为20nm至100nm。可选地，所述保护层的厚度不得超过金属层厚度的十分之一。保护层的厚度控制在合适范围内，可更好地防止金属层被化学腐蚀或物理损坏。
在一些实施例中，所述保护层的材料不做特别的限定，可根据实际需求进行选。所述 保护层的材料可以包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种。
可以理解的是，保护层可设置于聚合物复合膜一侧的表面上，也可同时设置于聚合物复合膜相对两侧的表面上；当同时设置时，两侧的保护层的厚度可以相同，也可以不同，具体的设置方式可根据实际需求进行选择。
在一些实施方式中，保护层形成于金属层上的制备方法不做特别的限定，可根据实际需求进行选择。例如，可包括物理气相沉积、化学气相沉积、原位成型、涂布等方法中的一种或多种。其中，气相沉积法优选真空蒸镀和磁控溅射；化学气相沉积优选常压化学气相沉积和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、刮刀涂布和挤压涂布。
本申请提供的复合集流体包括表面沉积有氧化锌纳米沉积层的聚合物复合膜，氧化锌纳米沉积层可有效提升聚合物复合膜与金属层间的粘结力，提升复合集流体的结构稳定性。
本申请实施方式的第四方面提供了一种极片，包括本申请第三方面的复合集流体。
在一些实施方式中，所述极片包括正极极片和/或负极极片。
本申请实施方式的第五方面提供了一种二次电池，包括本申请第四方面的极片。
在一些实施方式中，二次电池包括正极极片、负极极片、电解质和隔离膜。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。电解质在正极极片和负极极片之间起到传导离子的作用。隔离膜设置在正极极片和负极极片之间，主要起到防止正负极短路的作用，同时可以使离子通过。
本申请实施方式的第六方面提供了一种用电装置，包括本申请第五方面的二次电池。所述二次电池可以用作所述装置的电源，也可以用作所述装置的能量存储单元。所述装置可以但不限于是移动设备、电动车辆、电气列车、船舶及卫星、储能系统等。例如，可以为笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池等。
实施例
以下为具体实施例，下述实施例更具体地描述了本申请公开的内容，这些实施例仅仅用于阐述性说明，因为在本申请公开内容的范围内进行各种修改和变化对本领域技术人员 来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
实施例1
聚合物复合膜的制备
将商业化的4.5μm双向拉伸PP膜置于介质阻挡放电等离子体装置中，打开供气系统进气调节阀，向舱体内通入压缩空气，使舱体内的压力维持在206.8kPa，温度为25℃。然后打开供电单元向高压变压器输入220V、50Hz的交流电，经高压变压器转换为10kV、325Hz的交流电，输入到距离为4mm的两个电极，开始进行介质阻挡放电等离子体处理，处理时间为5s。处理完成后即得到等离子体改性的聚合物基膜。
将上述等离子体改性的聚合物基膜置于0.05mol/L硝酸锌溶液中，并开启槽体内的超声系统，超声功率为200W，超声频率为37Hz。然后向溶液中加入高浓度的氢氧化钠溶液至溶液中氢氧化钠的浓度为0.025mol/L，反应0.5min。反应处理完成后的膜经风刀除液，进入到纯水中清洗2min。清洗后的膜进入到鼓风烘箱内，于70℃下烘干，即得到表面氧化锌沉积的聚合物复合膜。
复合集流体的制备
金属层的制备：将上述制备的聚合物复合膜置于真空蒸镀的舱体内，以1500℃的高温将金属蒸发室内的高纯铜丝(纯度大于99.99％)熔化蒸发，蒸发后的金属原子经过真空镀膜室内的冷却系统，沉积在高分子基膜的两个表面，形成厚度为1μm的铜金属导电层。
保护层的制备：通过超声分散的方法将1g石墨烯均匀分散到999g氮甲基吡咯烷酮(NMP)溶液中，配制成固含量为0.1wt.％的涂布液，然后通过模头涂布的工艺将涂布液均匀涂覆到金属导电层的表面，其中涂覆量控制在80μm，最后在75℃下进行烘干。
实施例2
实施例2的制备方法与实施例1的制备方法相似，不同之处在于：介质阻挡放电等离子体处理时，输入到两个电极的交流电的电压为13kV。
实施例3
实施例3的制备方法与实施例1的制备方法相似，不同之处在于：介质阻挡放电等离子体处理时，输入到两个电极的交流电的电压为16kV。
实施例4
实施例2的制备方法与实施例2的制备方法相似，不同之处在于：介质阻挡放电等离子体表面改性的处理时间为30s。
实施例5
实施例5的制备方法与实施例2的制备方法相似，不同之处在于：介质阻挡放电等离子体表面改性的处理时间为60s。
实施例6
实施例6的制备方法与实施例2的制备方法相似，不同之处在于：硝酸锌及氢氧化钠的浓度分别为0.15mol/L、0.075mol/L。
实施例7
实施例7的制备方法与实施例2的制备方法相似，不同之处在于：硝酸锌及氢氧化钠的浓度分别为0.25mol/L、0.125mol/L。
实施例8
实施例8的制备方法与实施例6的制备方法相似，不同之处在于：超声功率为500W。
实施例9
实施例9的制备方法与实施例6的制备方法相似，不同之处在于：超声功率为700W。
实施例10：
实施例10的制备方法与实施例8的制备方法相似，区别在于：制备氧化锌沉积层时的反应时间为3.0min。
实施例11：
实施例11的制备方法与实施例8的制备方法相似，区别在于：制备氧化锌沉积层时的反应时间为5.0min。
实施例12：
实施例12的制备方法与实施例10的制备方法相似，区别在于：4.5μm双向拉伸PP膜换成4.5μm双向拉伸PET膜。
对比例1：
与实施例1基本相同，区别在于：介质阻挡放电等离子体处理时，输入到两个电极的交流电的电压为9kV。
对比例2：
与实施例1基本相同，区别在于：介质阻挡放电等离子体处理时，输入到两个电极的交流电的电压为17kV。
对比例3：
与实施例2基本相同，区别在于：介质阻挡放电等离子体表面改性的处理时间为4s。
对比例4：
与实施例2基本相同，区别在于：介质阻挡放电等离子体表面改性的处理时间为61s。
对比例5：
与实施例4基本相同，区别在于：硝酸锌及氢氧化钠的浓度分别为0.04mol/L、0.02mol/L。
对比例6：
与实施例4基本相同，区别在于：硝酸锌及氢氧化钠的浓度分别为0.26mol/L、0.13mol/L。
对比例7：
与实施例4基本相同，区别在于：硝酸锌及氢氧化钠的浓度分别为0.15mol/L、0.10mol/L。
对比例8：
与实施例4基本相同，区别在于：硝酸锌及氢氧化钠的浓度分别为0.15mol/L、0.06mol/L。
对比例9：
与实施例6基本相同，区别在于：超声功率为190W。
对比例10：
与实施例6基本相同，区别在于：超声功率为710W。
对比例11：
与实施例8基本相同，区别在于：制备氧化锌沉积层时的反应时间为0.4min。
对比例12：
与实施例8基本相同，区别在于：制备氧化锌沉积层时的反应时间为5.1min。
对比例13：
与实施例1基本相同，区别在于：4.5μm双向拉伸PP膜不做介质阻挡放电等离子体表面改性处理。
对比例14：
与实施例1基本相同，区别在于：聚合物复合膜的制备采用化学气相沉积的方法，即将经过等离子体处理后的4.5μm双向拉伸PP膜置于化学气相沉积装置中，气体源以二甲基锌为锌源，流量为500sccm，以叔丁醇为氧源，流量为50sccm，反应舱体内的压力为5.0×10 -3Pa，在膜面沉积一层50nm的氧化锌层。
将实施例1至12及对比例1至14制得的聚合物复合膜或复合集流体进行相关的性能测试，测试结果如下表1所示；其中，对比例13中的表面张力及粗糙度代表的是未改性的PP膜表面张力及粗糙度。
测试部分
(1)表面张力：按照GB/T 14216-2008对介质阻挡放电等离子体表面改性后的聚合物基膜以及纳米氧化锌沉积后的聚合物复合膜的表面张力进行测试。
(2)表面粗糙度：按照GB/T 31227-2014对介质阻挡放电等离子体表面改性后的聚合物基膜以及纳米氧化锌沉积后的聚合物复合膜的表面粗糙度进行测试。
(3)面晶粒平均粒径：首先，按照广角X射线衍射仪(WAXD)的制样标准，对上述制备的聚合物复合膜进行制样，然后，将制好的样品置于WAXD中，以Cu Kα为X射线源，在10°～80°的2θ角范围内以1°min -1的扫描速度进行持续扫描，得到X射线衍射谱图，从谱图上读出不同衍射峰对应的2θ角，代入到谢乐(Scherrer)公式中，计算出不同衍射峰对应的晶体粒径，对不同衍射峰对应的晶体粒径求平均值，即得到晶粒平均粒径。
(4)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样品(复合集流体或表面氧化锌沉积的聚合物复合膜)，在样品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/m 2、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，即复合集流体中聚合物复合膜与金属层间的粘结力，以及表面氧化锌沉积的聚合物复合膜中氧化锌纳米沉积层与聚合物基膜间的粘结力。
(5)孔洞数量：将制备的聚合物复合膜置于表面质量检测系统(微觉视电荷耦合器件CCD)中，对表面进行扫描，然后将光信号转换为电信号输送到计算机上，对单位面积复合铜集流体成品孔径小于100μm的表面孔洞数进行统计(一般要求成品不能有超过100μm的孔洞)。
表1
Figure PCTCN2022138273-appb-000001
Figure PCTCN2022138273-appb-000002
对比实施例1至3及对比例1至2，可以看出：在输入到两个电极的交流电的电压在本申请保护范围内，提升电压，等离子改性后的聚合物基膜表面张力及粗糙度升高，导致氧化锌纳米沉积层与聚合物基膜间的粘结力先升高后降低，并导致氧化锌纳米颗粒沉积后，聚合物复合膜的表面张力及粗糙度升高、氧化锌纳米颗粒的平均粒径增大，最终引起聚合物复合膜与金属层间的粘结力先升高后降低。超出本申请的保护范围后，氧化锌纳米沉积层与聚合物基膜间的粘结力以及聚合物复合膜与金属层间的粘结力明显降低，即聚合物复合膜的表面粘结性能及复合集流体的结构稳定性变差。
对比实施例2、4、5以及对比例3至4，可以看出：等离子体表面处理的时间在本申请的保护范围内时，延长处理时间，等离子改性后的聚合物基膜的表面张力及粗糙度升高，导致氧化锌纳米沉积层与聚合物基膜间的粘结力先升高后降低，氧化锌纳米颗粒沉积后，聚合物复合膜的表面张力先升高后基本不变、及粗糙度升高、氧化锌纳米颗粒的平均粒径增大，最终引起聚合物复合膜与金属层间的粘结力先升高后降低。超出本申请的保护范围后，氧化锌纳米沉积层与聚合物基膜间的粘结力以及聚合物复合膜与金属层间的粘结力明显降低，即聚合物复合膜的表面粘结性能及复合集流体的结构稳定性变差。
对比实施例4、6、7以及对比例5至8，可以看出：硝酸锌与氢氧化钠浓度及二者比例在本申请保护的范围内时，浓度变化对等离子体表面改性处理工艺得到的聚合物基膜的性能基本没有影响，主要对氧化锌纳米颗粒沉积后得到的聚合物复合膜的性能有影响，即提升浓度，聚合物复合膜的表面粗糙度及氧化锌纳米颗粒的平均粒径增大，表面张力先升高后基本不变，最终引起聚合物复合膜与金属层间的粘结力先升高后降低。超出本申请的保护范围后，聚合物复合膜与金属层间的粘结力明显降低，即聚合物复合膜的表面粘结性能及复合集流体的结构稳定性变差。
对比实施例6、8、9及对比例9至10，可以看出：超声功率在本申请的保护范围内时，超声功率主要对纳米颗粒沉积后得到的聚合物复合膜的性能有影响，即提升超声功率，聚合物复合膜的表面粗糙度及氧化锌纳米颗粒的平均粒径降低，表面张力先升高后降低，最 终引起聚合物复合膜与金属层间的粘结力先升高后降低。超出本申请的保护范围后，聚合物复合膜与金属层间的粘结力明显降低，即聚合物复合膜的表面粘结性能及复合集流体的结构稳定性变差。
对比实施例8、10、11及对比例11至12，可以看出：沉积反应的时间在本申请的保护范围内时，沉积时间主要对氧化锌纳米颗粒沉积得到的聚合物复合膜的性能有影响，即提升沉积时间，聚合物复合膜的表面粗糙度及氧化锌纳米颗粒的平均粒径增大，表面张力先升高后基本不变，最终引起聚合物复合膜与金属层间的粘结力先升高后降低。超出本申请的保护范围后，聚合物复合膜与金属层间的粘结力明显降低，即聚合物复合膜的表面粘结性能及复合集流体的结构稳定性变差。
对比实施例10及对比例13，可以看出：经过表面氧化锌沉积处理后，聚合物复合膜的表面粘附性能明显提升，由此制备的复合集流体中，聚合物复合膜与金属层间的粘结力明显提升，即复合集流体的结构稳定性得到有效改善。
对比实施例1至12与对比例14，可以看出，与化学气相沉积制备方法相比，使用本申请提供的方法制备的聚合物复合膜，其表面空洞数量明显降低。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (15)

  1. 一种聚合物复合膜，包括：
    聚合物基膜；和
    形成于所述聚合物基膜至少一侧的表面上的氧化锌纳米沉积层，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
  2. 根据权利要求1所述的聚合物复合膜，其中，所述聚合物复合膜满足如下条件中的至少一者：
    (1)所述氧化锌纳米沉积层中包含的氧化锌晶粒的平均粒径为20nm至80nm；
    (2)所述聚合物基膜的厚度为2μm至20μm；和
    (3)所述聚合物包括聚丙烯、聚乙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚酰亚胺、聚丙乙烯、聚氯乙烯、聚偏氟乙烯、聚四氟乙烯、聚苯硫醚、聚苯醚、聚苯乙烯、聚酰胺及上述聚合物的衍生物中的一种或多种。
  3. 一种用于制备聚合物复合膜的方法，包括：
    对聚合物膜层做表面改性处理，得到聚合物基膜；和
    在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，形成氧化锌纳米沉积层，得到聚合物复合膜，其中，所述氧化锌纳米沉积层的厚度为50nm至150nm。
  4. 根据权利要求3所述的方法，其中，所述对聚合物膜层做表面改性处理，包括：
    对所述聚合物膜层的表面做介质阻挡放电等离子体改性处理，
    可选地，在所述介质阻挡放电等离子体改性处理过程中，输入到介质阻挡放电等离子装置的两个电极的交流电的电压为10kV至16kV；和
    可选地，所述介质阻挡放电等离子体改性处理的时间为5s至60s。
  5. 根据权利要求3或4所述的方法，其中，所述在所述聚合物基膜至少一侧的表面上沉积氧化锌纳米粒子，包括：
    将所述聚合物基膜置于锌盐的水溶液中；和
    在超声作用下，向含有所述聚合物基膜的所述锌盐的水溶液中加入碱性试剂，至所述溶液中所述碱性试剂的浓度达到目标值，以使所述锌盐与所述碱性试剂接触反应后形成所述氧化锌纳米粒子。
  6. 根据权利要求5所述的方法，其中，所述方法满足如下条件中的至少一者：
    (1)所述锌盐的水溶液的浓度为0.05mol/L至0.25mol/L；
    (2)所述锌盐与所述碱性试剂的摩尔比为(1.0至2.5):1；
    (3)所述反应的时间为0.5min至5.0min；
    (4)所述目标值为0.02mol/L至0.25mol/L；
    (5)所述锌盐包括硝酸锌、氯化锌、硫酸锌、溴化锌和醋酸锌中的一种或多种；和
    (6)所述碱性试剂包括氢氧化钠、氢氧化钾、碳酸钠和氨水中的一种或多种。
  7. 根据权利要求5或6所述的方法，其中，在所述将所述聚合物基膜置于锌盐的水溶液中之后，还包括：
    对所述水溶液做超声处理，
    可选地，所述超声处理的超声功率为200W至700W。
  8. 一种复合集流体，包括权利要求1或2所述的聚合物复合膜或根据权利要求3至7任一项所述的方法制得的聚合物复合膜。
  9. 根据权利要求8所述的复合集流体，其中，所述复合集流体还包括：
    形成于所述聚合物复合膜至少一侧表面上的金属层；和
    形成于所述金属层相对远离所述聚合物复合膜的至少一侧的表面上的保护层。
  10. 根据权利要求9所述的复合集流体，其中，所述复合集流体满足如下条件中的至少一者：
    (1)所述聚合物复合膜的厚度为2μm至20μm；
    (2)所述金属层的厚度为500nm至2000nm，可选为700nm至1200nm；和
    (3)所述保护层的厚度为10nm至150nm，可选为20nm至100nm。
  11. 根据权利要9或10所述的复合集流体，其中，所述复合集流体满足如下条件中的至少一者：
    (1)所述金属层的材料包括铜、铜合金、铝、铝合金、镍、镍合金、钛和银中的一种或多种；和
    (2)所述保护层的材料包括镍、铬、镍基合金、铜基合金、氧化铜、氧化铝、氧化镍、氧化铬、氧化钴、石墨、炭黑、乙炔黑、科琴黑、碳纳米量子点、碳纳米管、碳纳米纤维和石墨烯中的一种或多种。
  12. 一种极片，包括权利要求8至11任一项所述的复合集流体。
  13. 根据权利要求12所述的极片，其中，所述极片包括正极极片和/或负极极片。
  14. 一种二次电池，包括权利要求12或13所述的极片。
  15. 一种用电装置，包括权利要求14所述的二次电池。
PCT/CN2022/138273 2022-11-21 2022-12-12 聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置 WO2024108680A1 (zh)

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