CN113745525A - Flexible composite plastic film and preparation and test method thereof - Google Patents
Flexible composite plastic film and preparation and test method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
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- 239000002184 metal Substances 0.000 claims abstract description 52
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- 238000001035 drying Methods 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 14
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 11
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052755 nonmetal Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
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- 101150058243 Lipf gene Proteins 0.000 claims description 2
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- 239000010949 copper Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
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- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000001771 vacuum deposition Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Abstract
The invention discloses an electrolyte corrosion resistant flexible composite plastic film and a preparation and test method thereof. The middle enhancement layer is arranged on two sides of the plastic film, the metal layer is arranged on the outer side of the middle enhancement layer, and the surface tolerance layer is coated on the outer side of the metal layer. The tensile strength of the composite plastic film is 130-300Mpa, the elongation at break is 50-150%, and the elastic modulus is 3200-5500. The square meter has the surface mass of 6-12 g/square meter and the thickness of 4-20 mu m, and has good chemical stability. Good permeation resistance: water vapor transmission rate<0.15g/(m224h), oxygen transmission rate<0.002cm3/(. square meter. 24 h). Can resist the electrolyte soaking at normal temperature of 25 ℃, high temperature of 60 ℃ and 85 ℃. The surface of the composite plastic film is not easy to be corroded and has good toleranceNo volume expansion occurs; the metal/plastic composite film has good corrosion resistance, and the metal layer is protected from being corroded in an acid electrolyte system by the surface tolerance layer, so that the chemical stability of the original metal/plastic composite film is effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a flexible composite plastic film and a preparation and test method thereof.
Background
The development direction of the lithium battery in the future is high energy, low cost and high safety. The current collector not only plays a role of bearing active substances, but also collects electrons generated by electrochemical reaction and conducts the collected electrons to an external circuit, thereby realizing the process of converting chemical energy into electric energy. The current collector is one of indispensable constituent components in a lithium ion battery. The thickness of the current collector of the anode aluminum foil applied to the production of the battery cell is 10-20 um, the thickness of the current collector of the cathode copper foil is 6-8 um, the aluminum foil mainly adopts a rolled aluminum foil, and the copper foil mainly adopts an electrolytic copper foil. However, since the pure metal has the characteristics of low brittleness and low toughness, the lithium ion battery electrode material is easy to break and break when being used in the process flows of the lithium ion battery electrode material in the production process under the heating and tension environments such as coating, rolling, drying, slicing and the like. Therefore, material waste is easily caused, the product consistency is poor, and the influence of the production efficiency is reduced. Meanwhile, the pure metal current collector is not an optimal application carrier due to key factors in many aspects such as cost, safety, energy density and the like, so that a lot of researches are beginning to focus on replacing the traditional metal current collector with a light flexible metal/plastic composite film material so as to realize higher safety, higher volume energy density and higher mass energy density of the lithium battery. However, compared with the traditional metal foil, the thickness of the conductive metal Al layer of the composite current collector is thinner, so that the composite current collector has a more serious corrosion phenomenon in an electrolyte environment compared with the traditional metal aluminum foil.
The standard electrode potential of Al is 1.39V (vs. Li/Li +), while the operating potential of a lithium ion battery is much higher than 1.39V, and from a thermodynamic point of view, the current collector Al will be oxidized during the charging and discharging of the lithium ion battery, but in many cases Al is kinetically stable due to its surface being a dense passivation film (about 50nm), the main component of which is an oxide of Al. However, under the conditions of long-time storage in a charge state, multiple charge-discharge cycles, overcharge and the like, the original surface passivation film of Al is damaged and corroded, the separation of the metal layer and the plastic film is easily caused after the corrosion phenomenon occurs, a white film is exposed, the internal resistance is increased, and corrosion products passivate or attack the positive active material; corrosion solid products will also increase electrical resistance; corrosion soluble products will contaminate the electrolyte solution, increasing the self-discharge rate of the cell; soluble Al3+ will migrate to the negative electrode and reduce the deposition. All of the above causes the degradation of the battery capacity.
Disclosure of Invention
In order to overcome the problems, the invention designs a flexible composite plastic film and a preparation and test method thereof, and the invention coats a metal oxide tolerance layer on the surface of the original metal plating layer, thereby keeping the light, thin and excellent mechanical properties and simultaneously improving the electrolyte resistance of the metal oxide tolerance layer. The composite plastic film is prepared by adopting one or two process combination forms of vapor deposition coating and magnetron sputtering coating, has excellent physical and mechanical properties, ultralight weight, ultrathin property, good chemical stability and particularly good electrolyte resistance.
The technical scheme of the invention is as follows:
a flexible composite plastic film comprises a plastic film layer, an intermediate enhancement layer, a metal layer and a surface tolerance layer, wherein the intermediate enhancement layer is arranged on the plastic filmThe metal layer is arranged on the outer side of the middle reinforcing layer, the surface tolerance layer covers the outer side of the metal layer, the tensile strength of the composite plastic film is 300Mpa, the elongation at break is 50-150%, the elastic modulus is 3200, the surface mass is 6-12 g/square meter, the thickness is 4-20 mu m, and the water vapor permeability is<0.15g/(m224h), oxygen transmission rate<0.002cm3/(㎡·24h)。
Further, the plastic film is a biaxially oriented polypropylene film (OPP), a cast polypropylene film (CPP), a polyethylene terephthalate film (PET), a polyimide film (PI) or a polyethylene naphthalate film (PEN).
Furthermore, the thickness of the plastic film layer is 3-20 μm.
Further, the middle enhancement layer comprises a metal film layer and/or a non-metal film layer, the metal film layer comprises more than one of copper, nickel and nickel-chromium alloy, and the non-metal film layer comprises more than one of aluminum oxide, silicon oxide, titanium dioxide, silicon carbide, silicon nitride and graphite.
Further, the thickness of the middle enhancement layer is 10-500 nm.
Further, the metal layer is an aluminum metal layer, the metal layer is made of a material different from that of the middle enhancement layer, and the thickness of the metal layer is 50-3000 nm.
Further, the surface tolerance layer is a metal oxide layer and comprises one or two of aluminum oxide and titanium dioxide.
Further, the thickness of the surface tolerance layer is 10-500 nm.
The invention also aims to provide a preparation method of the flexible composite plastic film, which comprises the following steps:
(1) selecting a proper plastic film, and performing surface oil stain removal and drying pretreatment;
(2) carrying out plasma treatment on the dried plastic film;
(3) depositing on two sides of the plastic film layer by magnetron sputtering coating or evaporation coating
A middle enhancement layer;
(4) depositing a metal layer outside the middle reinforcing layer in an evaporation coating mode;
(5) and finally performing vacuum evaporation or magnetron sputtering on the upper surface and the lower surface of the metal layer to form a metal oxide resistant layer.
Further, the power of the surface plasma treatment of the step (2) is 3-15 kW.
Further, the evaporation coating machine for depositing the middle enhancement layer in the step (3) adopts resistance heating, and the resistance heating process parameters are as follows: the evaporation boat type wire feeding speed is 200-1200mm/min, the temperature of the cooling system is-30-10 ℃, and the film running speed is 5-20 m/s.
Further, the evaporation coating machine cavity for depositing the middle enhancement layer in the step (3) is vacuumized to 10 DEG-7mbar～10-3mbar, and vacuumizing time of 10-30 min.
Furthermore, the magnetron sputtering coating power for depositing the middle enhancement layer in the step (3) is less than or equal to 250kW, the transmission speed of the substrate is less than or equal to 25m/min, and the argon introducing speed is 10-30L/min.
Further, the evaporation coating machine for depositing the metal layer in the step (4) also adopts resistance heating, and the evaporation boat type wire feeding speed is as follows: 400-1500mm/min cooling temperature: -30-10 ℃, membrane run speed: 3-15 m/s.
Further, in the step (5), the deposition of the surface tolerance layer adopts a vacuum evaporation method, and the resistance heating process parameters are as follows: the evaporation boat type wire feeding speed is 200-1200mm/min, the temperature of the cooling system is-30-10 ℃, and the film running speed is 5-20 m/s.
Further, the magnetron sputtering method for depositing the surface tolerance layer in the step (5) comprises the following process parameters: the power is less than or equal to 250kW, the transmission speed of the substrate is less than or equal to 25m/min, and the argon introducing speed is 10-30L/min.
The method for testing electrolyte resistance provided by the invention comprises the following steps:
(1) placing the composite plastic film in an air-blast drying oven at 60 ℃ for drying for 24 hours in advance;
(2) taking out 5 x 5cm thin film sheet samples;
(3) packaging into clean 10 × 10cm aluminum plastic film;
(4) preparing an electrolyte solution containing mainly Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), and lithium hexafluorophosphate (LiPF)6)；
(5) The soaking experiments were carried out for 24h, with 25 ℃ and 60 ℃ and 85 ℃ set in a forced air drying oven.
Further, the injection amount of the electrolyte in the step four is more than 1.5 g.
The invention has the beneficial effects that:
1. the flexible composite plastic film with the four-layer structure has good ductility and strength, the tensile strength reaches 130-.
2. The flexible composite plastic film of the invention has the advantages of light weight, thinness and low cost, the mass of the surface texture is only 6-12 g/square meter, the thickness is 4-20 mu m, and the cost per square meter is expected to be reduced to below 3 yuan.
3. The permeability resistance of the four-layer structure flexible composite plastic film is higher than that of the original three-layer structure composite film, and the novel four-layer structure water vapor transmission rate<0.15g/(m224h), oxygen transmission rate<0.002cm3The water vapor transmission rate of the three-layer composite structure is 0.5 to 2 g/(m)224h), oxygen transmission rate of 0.01-0.03cm3/(㎡·24h)。
4. The electrolyte resistance of the four-layer structure flexible composite plastic film is greatly improved compared with that of the original three-layer structure, the original structure material swells at the high temperature of an electrolyte organic solvent, the volume expansion rate reaches 20 percent, and the surface metal layer is seriously corroded to cause bubbling and cracking phenomena; the material of the present invention exhibits good electrolyte resistance. The material can resist the electrolyte soaking at the normal temperature of 25 ℃, 60 ℃ and 85 ℃, the surface is not corroded, the material has good tolerance, the volume expansion is avoided, and the size and the thickness of the material are not changed; corrosion resistance, a resistant layer on the surface protects the metal layer from corrosion in an acid electrolyte system. Effectively improves the chemical stability of the original metal/plastic composite film.
Drawings
FIG. 1 is a schematic structural view of a flexible composite plastic film of the present invention;
FIG. 2 is a scanning electron microscope micrograph of a flexible composite plastic film of the present invention;
FIG. 3 shows the result of soaking the flexible composite plastic film in the electrolyte at 85 ℃ for 72 h;
FIG. 4 shows the result of soaking the flexible composite plastic film of example 2 in the electrolyte at 85 ℃ for 72 h;
FIG. 5 shows the result of soaking the flexible composite plastic film of example 2 in the electrolyte at 85 ℃ for 72 h;
FIG. 6 shows the result of soaking the original three-layer structure composite plastic film in the electrolyte at 85 ℃ for 72h in comparative example 1.
Wherein, 1-plastic film layer, 2-middle enhancement layer, 3-metal layer, 4-tolerance layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be specifically and clearly described below, but the present invention is not limited to the following embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The utility model provides a flexible composite plastic film, includes the thick PET plastic film layer of 6 mu m, enhancement layer in the middle of the aluminium oxide of PET layer both sides coating by vaporization 50nm, the metal aluminium layer of coating by vaporization 1um thick outside the aluminium oxide layer, surface coating by vaporization 100nm aluminium oxide tolerance layer about the metal aluminium layer at last. A preparation method of a flexible composite plastic film resistant to electrolyte erosion comprises the following steps:
(1) selecting a proper plastic film, and performing surface oil stain removal and drying pretreatment;
(2) carrying out plasma treatment on the dried plastic film, wherein the power of the surface plasma treatment is 8 kW;
(3) coating middle enhancement layers on two sides of the plastic film layer in a magnetron sputtering coating mode, wherein the coating power is 200kW, the transmission speed of the substrate is 15m/min, and the argon introducing speed is 25L/min;
(4) depositing a metal layer on the outer side of the middle enhancement layer in a vapor deposition coating mode, wherein the evaporation boat type wire feeding speed of a vacuum coating machine is 500 mm/min; the cooling temperature is-30 ℃, and the film running speed is 12 m/s;
(5) and finally performing vacuum evaporation on the upper surface and the lower surface of the metal layer to form metal oxide tolerance layers, wherein the evaporation boat type wire feeding speed in a vacuum coating machine is 850mm/min, the temperature of a cooling system is-30 ℃, and the film running speed is 10 m/s.
The method for testing the electrolyte resistance of the composite plastic film comprises the following steps:
(1) the composite plastic film is placed in an air-blast drying oven for drying for 24 hours at the temperature of 60 ℃.
(2) And taking out a 5 x 5cm thin film slice sample.
(3) Packaging into a clean 10 x 10cm size aluminum plastic film.
(4) The electrolyte component is 1M LiPF6 which is lithium salt, the solvent is EC: DEC which is 1:1Vol by volume ratio, and the injection amount in a sealed glove box is more than 1.5 g.
(5) The soaking experiments were carried out for 72h at 25 ℃ and 60 ℃ and 85 ℃.
(6) The soaked film was taken out and observed for phenomena.
The novel flexible composite plastic film based on the scheme has the tensile strength of 278Mpa, the elongation at break of 130 percent and the elastic modulus of 4780 percent. Water vapor transmission rate of 0.12g/(m2 & 24h) and oxygen transmission rate of 0.001cm3/(. square meter. 24 h). The film changes in size before and after soaking at 25 deg.c, 60 deg.c and 85 deg.c, and has smooth surface and no aluminum layer corrosion owing to the surface resisting layer, as shown in Table 1, Table 2 and attached figure 3.
Example 2
A flexible composite plastic film comprises an OPP film layer with the thickness of 4.5 microns, a silicon oxide middle enhancement layer with the thickness of 10nm is formed by magnetron sputtering on two sides of the OPP layer, a metal aluminum layer with the thickness of 500nm is formed by evaporation on the outside of the silicon oxide layer, and finally an aluminum oxide tolerance layer with the thickness of 20nm is formed by evaporation on the surface of the silicon oxide middle enhancement layer. A preparation method of a flexible composite plastic film resistant to electrolyte erosion comprises the following steps:
(1) carrying out surface oil stain removal and drying pretreatment on the OPP plastic film;
(2) carrying out plasma treatment on the dried plastic film, wherein the power of the surface plasma treatment is 5 kW;
(3) coating middle enhancement layers on two sides of the plastic film layer in a magnetron sputtering coating mode, wherein the coating power is 150kW, the transmission speed of the substrate is 10m/min, and the argon introducing speed is 20L/min;
(4) depositing a metal layer on the outer side of the middle enhancement layer in a vapor deposition coating mode, wherein the evaporation boat type wire feeding speed of a vacuum coating machine is 700 mm/min; the cooling temperature is-30 ℃, and the film running speed is 10 m/s;
(5) and finally performing vacuum evaporation on the upper surface and the lower surface of the metal layer to form metal oxide tolerance layers, wherein the evaporation boat type wire feeding speed in a vacuum coating machine is 850mm/min, the temperature of a cooling system is-30 ℃, and the film running speed is 10 m/s.
The method for testing the electrolyte resistance of the composite plastic film comprises the following steps:
(1) the composite plastic film is placed in an air-blast drying oven for drying for 24 hours at the temperature of 60 ℃.
(2) And taking out a 5 x 5cm thin film slice sample.
(3) Packaging into a clean 10 x 10cm size aluminum plastic film.
(4) The electrolyte component is 1M LiPF6 which is lithium salt, the solvent is EC: DEC which is 1:1Vol by volume ratio, and the injection amount in a sealed glove box is more than 1.5 g.
(5) The soaking experiments were carried out for 72h at 25 ℃ and 60 ℃ and 85 ℃.
(6) The soaked film was taken out and observed for phenomena.
The novel flexible composite plastic film based on the scheme has the tensile strength of 180Mpa, the elongation at break of 60 percent and the elastic modulus of 3400. Water vapor transmission rate of 0.14g/(m 2.24 h) and oxygen transmission rate of 0.0015cm3/(. square meter. 24 h). The film changes in size before and after soaking at 25 ℃, 60 ℃ and 85 ℃, and has a flat surface without aluminum layer corrosion due to the action of the surface tolerance layer, which is detailed in table 1, table 2 and attached figure 4.
Example 3
A flexible composite plastic film comprises a PI film layer with the thickness of 20 microns, an aluminum oxide middle enhancement layer with the thickness of 500nm is evaporated on the two sides of the PI layer, a metal aluminum layer with the thickness of 3000nm is evaporated outside the aluminum oxide layer, and finally an aluminum oxide tolerance layer with the thickness of 500nm is evaporated on the surface of the aluminum oxide middle enhancement layer. A preparation method of a flexible composite plastic film resistant to electrolyte erosion comprises the following steps:
(1) carrying out surface oil stain removal and drying pretreatment on the PI plastic film;
(2) carrying out plasma treatment on the dried plastic film, wherein the power of the surface plasma treatment is 15 kW;
(3) coating middle enhancement layers on two sides of the plastic film layer in an evaporation coating mode, wherein the evaporation boat type wire feeding speed is 800mm/min, the temperature of a cooling system is-30 ℃, and the film running speed is 8 m/s;
(4) depositing a metal layer on the outer side of the middle enhancement layer in a vapor deposition coating mode, wherein the evaporation boat type wire feeding speed of a vacuum coating machine is 1200 mm/min; the cooling temperature is-30 ℃, and the film running speed is 10 m/s;
(5) and finally carrying out magnetron sputtering on the upper surface and the lower surface of the metal layer to form metal oxide tolerance layers, wherein the power is 250kW, the transmission speed of the substrate is 15m/min, and the argon introducing speed is 30L/min.
The method for testing the electrolyte resistance of the composite plastic film comprises the following steps:
(1) the composite plastic film is placed in an air-blast drying oven for drying for 24 hours at the temperature of 60 ℃.
(2) And taking out a 5 x 5cm thin film slice sample.
(3) Packaging into a clean 10 x 10cm size aluminum plastic film.
(4) The electrolyte component is 1M LiPF6 which is lithium salt, the solvent is EC: DEC which is 1:1Vol by volume ratio, and the injection amount in a sealed glove box is more than 1.5 g.
(5) The soaking experiments were carried out for 72h at 25 ℃ and 60 ℃ and 85 ℃.
(6) The soaked film was taken out and observed for phenomena.
The novel flexible composite plastic film based on the scheme has the tensile strength of 450Mpa, the elongation at break of 130 percent and elasticityModulus of elasticity 5500. Water vapor transmission rate of 0.07g/(m2 & 24h), oxygen transmission rate of 0.0008cm3/(. square meter. 24 h). The film changes in size before and after soaking at 25 deg.c, 60 deg.c and 85 deg.c, and has smooth surface and no aluminum layer corrosion owing to the surface resisting layer, as shown in Table 1, Table 2 and attached figure 5.
Comparative example 1
A flexible composite plastic film comprises a 6 mu m thick PET plastic film layer, an aluminum oxide middle enhancement layer and a 1 mu m thick metal aluminum layer, wherein the aluminum oxide middle enhancement layer is formed on two sides of the PET layer through evaporation, and the metal aluminum layer is formed outside the aluminum oxide layer through evaporation. The preparation method comprises the following steps:
(1) selecting a proper plastic film, and performing surface oil stain removal and drying pretreatment;
(2) carrying out plasma treatment on the dried plastic film, wherein the power of the surface plasma treatment is 8 kW;
(3) coating middle enhancement layers on two sides of the plastic film layer in a magnetron sputtering coating mode, wherein the coating power is 200kW, the transmission speed of the substrate is 15m/min, and the argon introducing speed is 25L/min;
(4) depositing a metal layer on the outer side of the middle enhancement layer in a vapor deposition coating mode, wherein the evaporation boat type wire feeding speed of a vacuum coating machine is 500 mm/min; the cooling temperature is-30 ℃, and the film running speed is 12 m/s;
the method for testing the electrolyte resistance of the composite plastic film comprises the following steps:
(1) the composite plastic film is placed in an air-blast drying oven for drying for 24 hours at the temperature of 60 ℃.
(2) And taking out a 5 x 5cm thin film slice sample.
(3) Packaging into a clean 10 x 10cm size aluminum plastic film.
(4) The electrolyte component is 1M LiPF6 which is lithium salt, the solvent is EC: DEC which is 1:1Vol by volume ratio, and the injection amount in a sealed glove box is more than 1.5 g.
(5) The soaking experiments were carried out for 72h at 25 ℃ and 60 ℃ and 85 ℃.
(6) The soaked film was taken out and observed for phenomena.
The novel flexible composite plastic film based on the scheme has the tensile strength of 220Mpa, the elongation at break of 128% and the elastic modulus of 4500. The water vapor transmission rate is 0.75g/(m2 & 24h), and the oxygen transmission rate is 0.018cm 3/(. square meter & 24 h). The film has no obvious change in the soaking size and thickness at 25 ℃ and 60 ℃, but has no obvious change in the thickness after soaking at 85 ℃, but the shrinkage in size is 4.5 x 4.5cm, and the aluminum layer on the surface has the phenomena of cracking, peeling and white film exposure, which are detailed in tables 1 and 2 and attached figure 6.
It should be noted that, according to the disclosure and the explanation of the above description, the person skilled in the art to which the present invention pertains may make variations and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some equivalent modifications and variations of the present invention should be covered by the protection scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
TABLE 1 Experimental data
Table 2 electrolyte resistance performance data.
Claims (9)
1. A flexible composite plastic film characterized by: comprising a plastic film layer, an intermediateThe composite plastic film comprises a reinforcing layer, a metal layer and a surface tolerance layer, wherein the middle reinforcing layer is arranged on two sides of the plastic film, the metal layer is arranged on the outer side of the middle reinforcing layer, the surface tolerance layer covers the outer side of the metal layer, the tensile strength of the composite plastic film is 130-300Mpa, the elongation at break is 50-150%, the elastic modulus is 3200 5500, and the surface mass is 6-12g/m2The thickness is 4-20 μm; water vapor transmission rate<0.15g/(m224h), oxygen transmission rate<0.002cm3/(m2·24h)。
2. The composite plastic film of claim 1, wherein: the plastic film layer is a biaxially oriented polypropylene (OPP) film, a casting polypropylene (CPP) film, a polyethylene terephthalate (PET) film, a Polyimide (PI) film or a polyethylene naphthalate (PEN) film, and the thickness of the plastic film layer is 3-20 mu m.
3. The composite plastic film of claim 1, wherein: the middle enhancement layer comprises a metal film layer and/or a non-metal film layer, the metal film layer comprises more than one of copper, nickel and nickel-chromium alloy, and the non-metal film layer comprises more than one of aluminum oxide, silicon oxide, titanium dioxide, silicon carbide, silicon nitride and graphite.
4. The composite plastic film of claim 1, wherein: the thickness of the middle reinforcing layer is 10-500 nm.
5. The composite plastic film of claim 1, wherein: the metal layer is an aluminum metal layer, the metal layer is made of a material different from that of the middle enhancement layer, and the thickness of the metal layer is 50-3000 nm.
6. The composite plastic film of claim 1, wherein: the surface tolerance layer is a metal oxide layer and comprises one or two of aluminum oxide and titanium dioxide.
7. The composite plastic film of claim 1 or 6, wherein: the thickness of the surface tolerance layer is 10-500 nm.
8. A method for preparing a flexible composite plastic film as claimed in any one of claims 1 to 7, comprising the steps of:
(1) selecting a proper plastic film, and performing surface oil stain removal and drying pretreatment;
(2) carrying out plasma treatment on the dried plastic film;
(3) respectively carrying out vacuum evaporation or magnetron sputtering on the upper layer and the lower layer of the surface of the plastic film subjected to the plasma treatment to form a middle enhancement layer;
(4) performing vacuum evaporation or magnetron sputtering deposition on the surface of the middle reinforcing layer to deposit a metal layer;
(5) and finally performing vacuum evaporation or magnetron sputtering on the upper surface and the lower surface of the metal layer to form a metal oxide resistant layer.
9. A method of testing a flexible composite plastic film as claimed in claims 1-7, comprising the steps of:
(1) placing the composite plastic film in an air-blast drying oven at 60 ℃ for drying for 24 hours in advance;
(2) taking out 5 x 5cm thin film sheet samples;
(3) packaging into clean 10 × 10cm aluminum plastic film;
(4) injecting 1.5g of electrolyte, wherein the electrolyte mainly comprises but not limited to common Ethylene Carbonate (EC), Propylene Carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and Ethyl Methyl Carbonate (EMC) as solvent, and lithium hexafluorophosphate (LiPF)6) Is a conductive salt;
(5) the soaking experiment was carried out for 24h at normal temperature 25 ℃ and 60 ℃ and 85 ℃.
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