CN110722863B - Preparation method of corrosion-resistant flexible packaging film for lithium battery - Google Patents
Preparation method of corrosion-resistant flexible packaging film for lithium battery Download PDFInfo
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- CN110722863B CN110722863B CN201910978146.6A CN201910978146A CN110722863B CN 110722863 B CN110722863 B CN 110722863B CN 201910978146 A CN201910978146 A CN 201910978146A CN 110722863 B CN110722863 B CN 110722863B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a preparation method of a corrosion-resistant flexible packaging film for a lithium battery, wherein the corrosion-resistant flexible packaging film for the lithium battery comprises a corrosion-resistant inner layer, a corrosion-resistant intermediate layer and a corrosion-resistant outer layer; adopting multi-layer polypropylene co-extrusion micro-crosslinking to form an inner-layer base film, and compounding the inner-layer base film with a polyethylene glycol terephthalate film and the like to form an inner-layer film; coating nano-scale titanium dioxide on the surface of the high-ductility aluminum foil to form a middle layer; the biaxially oriented nylon and the modified polyethylene glycol terephthalate film are compounded and coated with a silicon dioxide coating to prepare an outer layer; the outer layer, the middle layer and the inner layer are effectively compounded by adopting a dry compounding process, so that a high-corrosion-resistance multilayer film structure is integrally formed; the method has the advantages that the corrosion resistance effect of the film is achieved, the defect that a cross-linking agent in common composite is not resistant to an electrolyte solvent is overcome, and the characteristics of puncture resistance, high barrier, high insulation and high heat seal strength of the film are realized through a multi-layer structure.
Description
Technical Field
The invention relates to the field of polymers, in particular to a preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Background
With the development of microelectronic technology, the demand of lithium batteries is increasing day by day, and particularly in new energy vehicles, the flexible package of lithium ion batteries has the advantages of good safety performance, light weight, large capacity, small internal resistance, flexible design and the like compared with the traditional steel shell and aluminum shell packages, so that the flexible package research of the lithium ion batteries becomes popular. The flexible packaging material of the flexible packaging lithium ion battery is made of a multilayer film (substrate layer/aluminum foil layer/heat sealing layer). In the use process of the battery, electrochemical reaction is continuously carried out in the battery core, electrolyte in the battery core contains various organic solvents, the organic solvents can swell, dissolve and absorb flexible packaging materials in the use process of the battery, the bonding effect between composite layers is damaged, the concentration of each component in the electrolyte is changed, the electrical property of the battery is further influenced, and even expansion leakage of a lithium battery can be caused.
Chinese patent publication No. CN 108408245 a discloses a method for coating a corrosion-resistant organic coating and an inorganic oxide coating on the surface of an intermediate layer aluminum foil to improve the corrosion resistance of the film layer. However, the problem that the cross-linking agent in each layer of the composite in the method is not resistant to the corrosion of the electrolyte solvent is not solved.
Disclosure of Invention
The invention aims to provide a preparation method of a corrosion-resistant flexible packaging film for a lithium battery, wherein a crosslinking monomer containing a plurality of functional groups is added into a prepared corrosion-resistant inner layer, and the crosslinking monomer can perform free radical substitution crosslinking reaction with polypropylene under the action of an initiator, so that the functional groups of the crosslinking monomer are uniformly distributed in the polypropylene, the corrosion resistance of a polymer is improved through the synergistic effect of the functional groups, and the problem of insufficient corrosion resistance of the flexible packaging film for the lithium battery in the prior art is solved.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a corrosion-resistant flexible packaging film for a lithium battery is characterized in that the corrosion-resistant flexible packaging film for the lithium battery is prepared from a corrosion-resistant inner layer, a corrosion-resistant intermediate layer and a corrosion-resistant outer layer by a dry compounding method;
the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top in sequence, and the preparation steps are as follows:
s1: uniformly mixing 5-15 parts of ternary copolymer polypropylene, 0.1-3 parts of crosslinking monomer, 0.1-3 parts of initiator, 0.1-1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1-5 parts of graphene to obtain a layer A raw material, wherein the layer A is a heat sealing layer, the ternary copolymer polypropylene has a lower melting point, good hot melt property and a wider heat sealing temperature, so that the heat sealing strength of the material can be improved by selecting the ternary copolymer polypropylene as a layer A base material;
uniformly mixing 10-20 parts of homopolymerized polypropylene, 0.1-3 parts of crosslinking monomer, 0.1-3 parts of initiator, 0.1-1 part of N- (3-fluoro-5-carboxyl phenyl) maleimide and 1-5 parts of graphene to obtain a layer B raw material, wherein the layer B is a supporting layer and plays a role in supporting a film, and the homopolymerized polypropylene is selected as a layer B substrate so that the toughness and the stiffness of the film can be improved;
uniformly mixing 5-15 parts of mixed polypropylene, 0.1-3 parts of crosslinking monomer, 0.1-3 parts of initiator and 1-5 parts of graphene to obtain a C-layer raw material, wherein the C-layer is a corona outer layer, and the surface tension of the film layer can be improved by selecting the mixed polypropylene;
s2: respectively adding A, B, C mixed raw materials and 5-25 parts of nylon into A, B, C, D four double-screw extruders, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
s4: extruding and compounding the inner layer with 5-10 parts of polyethylene glycol terephthalate, coating a layer of polyvinyl alcohol or polyvinylidene chloride with the thickness of 1-5 mu m on the surface of the polyethylene glycol terephthalate to obtain a semi-finished inner layer film, and extruding and compounding 1-10 parts of ethylene-vinyl alcohol copolymer and 1-10 parts of polyvinyl butyral on the semi-finished inner layer film to obtain a corrosion-resistant inner layer; the polyethylene terephthalate has excellent physical and mechanical properties, can be used for a long time at the temperature of 100 ℃, and has excellent electrical insulation performance; the polyvinyl alcohol and the polyvinylidene chloride are easy to form a film, the mechanical property is excellent after the film is formed, and the film has good barrier effect on aprotic polar solvent, non-polar solvent and the like; the ethylene-vinyl alcohol copolymer and the polyvinyl butyral have good thermal stability, permeability resistance, water resistance and corrosion resistance, and also have good machining performance; the corrosion-resistant inner layer compounded by the materials can meet the performance required by the lithium battery;
the corrosion-resistant flexible packaging film for the lithium battery is prepared by a dry compounding method,
the method comprises the following steps: uniformly coating a layer of adhesive on the upper surface of the corrosion-resistant middle layer, drying by an oven, and then hot-pressing and attaching the corrosion-resistant outer layer on a composite roller to obtain a semi-finished film;
step two: and uniformly coating a layer of adhesive on the lower surface of the semi-finished film, drying by an oven, and then hot-pressing and attaching the adhesive to the corrosion-resistant inner layer on a composite roller to obtain the corrosion-resistant flexible packaging film.
As a further scheme of the invention, the crosslinking monomer is one or more of pentaerythritol tetraacrylate, glycerol triacrylate, divinylbenzene and triacrylate isocyanurate.
As a further scheme of the invention, the initiator is one or more of dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, dicumyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and di-o-methylbenzoyl peroxide.
As a further embodiment of the present invention, the N- (3-fluoro-5-carboxyphenyl) maleimide is prepared as follows:
(1) dissolving 2 parts by mass of maleic anhydride in a solvent of N, N-dimethylformamide and toluene at a volume ratio of 1: 3-1: 4 to prepare a maleic anhydride solution with the concentration of 5-7 mol/L;
(2) adding 1 part by mass of 3-fluoro-5-carboxyphenyl into the maleic anhydride solution in batches, and stirring for 1-3 hours;
(3) adding 0.01 part by mass of p-toluenesulfonic acid and 0.01 part by mass of hydroquinone into the solution (2), heating to 110-;
(4) and washing, drying and recrystallizing the crude product of the N- (3-fluoro-5-carboxyphenyl) maleimide to obtain the N- (3-fluoro-5-carboxyphenyl) maleimide.
As a further scheme of the invention, the mixed polypropylene is formed by mixing 0-20% by mass, 10-20% by mass and 60-90% by mass of binary polypropylene, ternary polypropylene and homo-polypropylene.
As a further scheme of the invention, the head temperature of the double-screw extruder is 150-220 ℃, and the rotating speed is 170-210 r/min.
As a further scheme of the invention, the corrosion-resistant intermediate layer is made of aluminum foil, and a titanium dioxide or silicon dioxide coating with the thickness of 10-200nm is coated on the surface of the aluminum foil.
As a further scheme of the invention, the corrosion-resistant outer layer is made of 10-25 parts of nylon as a main material, the nylon and 1-10 parts of modified polyethylene terephthalate are extruded and compounded, silica with the thickness of 10-200nm is coated on the modified polyethylene terephthalate layer, and the corrosion-resistant outer layer is obtained through cold stamping and forming.
In a further embodiment of the present invention, the modified polyethylene terephthalate film used in the corrosion-resistant outer layer is one of polyethylene terephthalate modified with adipic acid, polyethylene glycol, polyethylene adipate and epoxy resin.
As a further scheme of the invention, the adhesive uses one or more of polyurethane adhesive, epoxy resin adhesive, acrylic resin adhesive, polyester adhesive and acid modified resin adhesive, and the thickness of the coating is 1-10 μm; the drying temperature of the oven is 60-100 ℃.
Compared with the prior art, the invention has the beneficial effects that:
in the preparation of the corrosion-resistant inner layer: the ternary copolymer polypropylene is used as the innermost layer of the four-layer inner-layer base film, and the lower melting point of the ternary copolymer polypropylene is utilized, so that the heat sealing temperature can be properly reduced, and the heat sealing strength is improved; by adding graphene into the raw materials of each layer, the barrier property of the film layer can be effectively improved, and the copper wire or the aluminum wire in the battery can be prevented from puncturing the film layer; adding a crosslinking monomer, an initiator and N- (3-fluoro-5-carboxyphenyl) maleimide into a double-screw extruder together for extrusion compounding, so that micro-crosslinking reaction can be generated among polypropylene layers, the compounding of each layer is firmer, the crosslinking degree of the crosslinking monomer can be effectively controlled by adding the N- (3-fluoro-5-carboxyphenyl) maleimide, and an acid group is introduced into a crosslinking product, so that the corrosion resistance is improved to a certain extent, and the N- (3-fluoro-5-carboxyphenyl) maleimide is not added into the corona outer layer so as to ensure that the surface tension of the outer layer is not influenced; the inner base film is compounded with the polyethylene glycol terephthalate film, the ethylene-vinyl alcohol copolymer and the polyvinyl butyral, so that the defect that a cross-linking product in general compounding is not resistant to an electrolyte solvent can be avoided, and the corrosion resistance effect is effectively improved.
In the preparation of the corrosion-resistant intermediate layer, the surface of the aluminum foil is coated with a nano-scale titanium dioxide or silicon dioxide coating, and the reactive activity of the film layer to corrosive substances is greatly reduced by utilizing the passivation effect of the titanium dioxide and the silicon dioxide.
In the preparation of the corrosion-resistant outer layer, the biaxially oriented nylon and the modified polyethylene terephthalate film are compounded, so that the overall corrosion resistance of the flexible packaging film is further improved, and the silicon dioxide coating is coated on the film, so that the stronger pressure of a cold stamping forming process can be met.
The outer layer, the middle layer and the inner layer are effectively compounded by adopting a dry compounding process, so that a high-corrosion-resistance multilayer film structure is integrally formed.
Drawings
FIG. 1 is a cross-sectional view of a dispenser;
FIG. 2 is an enlarged view of area A of FIG. 1;
FIG. 3 is a schematic view of a feed hopper in the distributor;
FIG. 4 is a schematic view of a speed limiting plate in the dispenser;
FIG. 5 is a schematic view of the rear of the dispenser;
in the figure: 1. a housing; 2. a material channel; 3. a feed inlet; 4. an annular cover; 5. a feed hopper; 6. bolt holes; 7. a through hole; 8. an end cap; 9. a speed limiting plate; 10. rotating the block; 11. a threaded rod; 12. a chute; 13. a restrictor plate; 14. a fixing plate; 15. an annular plate; 16. a bolt; 17. a groove; 18. a seal ring; 19. a bump; 20. a threaded bore.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
With reference to FIGS. 1-5
Example 1
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top, and the preparation steps are as follows:
s1: uniformly mixing 5 parts of ternary copolymer polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer A raw material;
uniformly mixing 10 parts of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer B raw material;
uniformly mixing 5 parts of mixed polypropylene of 10% of ternary polypropylene and 90% of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide and 1 part of graphene by mass percent to obtain a layer C raw material;
s2: a, B, C, respectively adding the three well-mixed raw materials and 5 parts of nylon into A, B, C, D four double-screw extruders at the head temperature of 180 ℃ and the rotating speed of 190r/min, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
the distributor comprises a shell 1, four material channels 2 are arranged in the shell 1, one end of each material channel 2 is fixedly connected with a feed hopper 5, the feed hoppers 5 are communicated with the material channels 2, each feed hopper 5 is conical, the diameter of the end, communicated with the material channels 2, of each feed hopper 5 is smaller, the diameter of the end, far away from the material channels 2, of each feed hopper 5 is larger, a feed inlet 3 is arranged in each feed hopper 5, the feed hoppers 5 and the shell 1 are correspondingly provided with two annular plates 15, bolts 16 are fixed on the two annular plates 15, each feed hopper 5 is provided with a groove 17, each shell 1 is provided with a lug 19, each groove 17 is arranged corresponding to the lug 19, and a sealing ring 18 is fixedly arranged on the inner wall of each groove 17; the outer side wall of the feed hopper 5 is fixedly provided with an annular cover 4, and the annular cover 4 is provided with a plurality of bolt holes 6;
a speed limiting plate 9 is arranged at one end of the material channel 2, the speed limiting plate 9 is fixedly connected to the material channel 2, a fixing plate 14 is fixedly installed at one end of the speed limiting plate 9, four sliding grooves 12 are formed in the fixing plate 14, the sliding grooves 12 are communicated with the material channel 2, a flow limiting plate 13 is slidably installed in the sliding grooves 12, two threaded holes 20 are formed in the flow limiting plate 13, threaded rods 11 are connected with the threaded holes 20 in a threaded manner, a rotating block 10 is fixedly connected to the upper end of one threaded rod 11, an end cover 8 is fixedly connected to the tail portion, close to one end of the speed limiting plate 9, of the shell 1, and a plurality of through holes 7 are formed in the end cover 8;
when the distributor is used, firstly, the groove 17 of the feed hopper 5 and the bump 19 on the shell 1 are correspondingly arranged, the bolts 16 are screwed on the two annular plates 15 to fix the feed hopper 5, the feed hopper 5 of the distributor is communicated with the discharge hole of the extruder, the end cover 8 on the shell 1 is connected with the T-shaped die head, materials enter the material channel 2 through the feed hole 3 and reach the speed limiting plate 9 to be distributed, when the materials reach the speed limiting plate 9, the rotating block 10 is rotated to drive the threaded rod 11 to rotate, the flow limiting plate 13 in threaded connection with the threaded rod 11 moves upwards to cover part of the material channel 2 to achieve the purpose of flow limiting, and by adjusting the four rotating blocks 10, the four material channels 2 can be subjected to different flow limiting, so that the materials reach different proportions;
the dispenser has the advantages that: the shell 1 can be connected with four feed hoppers 5, at most four materials can be distributed, the shell 1 and the feed hoppers 5 can be detached, the distributor can be conveniently cleaned, the shell 1 and the feed hoppers 5 are respectively provided with a convex block 19 and a groove 17, the position of the feed hoppers 5 can be conveniently determined when the feed hoppers 5 are installed, and the sealing rings 18 on the inner walls of the grooves 17 can prevent the materials from leaking; the arrangement of the speed limiting plate 9 can facilitate material distribution, the outlet areas of different material channels 2 can be freely adjusted by arranging the speed limiting plate 9 on each material channel 2, the effect of limiting the flow and the speed of the material is achieved, and the arrangement of the end cover 8 facilitates the butt joint of the discharging position of the distributor and an extruder die.
S4: extruding and compounding the inner-layer base film and 5 parts of polyethylene glycol terephthalate, coating a layer of polyvinyl alcohol with the thickness of 1 mu m on the surface of the polyethylene glycol terephthalate to obtain a semi-finished inner-layer film, and extruding and compounding 2 parts of ethylene-vinyl alcohol copolymer and 2 parts of polyvinyl butyral on the semi-finished inner-layer film to obtain a corrosion-resistant inner layer;
in S1, the preparation method of the N- (3-fluoro-5-carboxyphenyl) maleimide is as follows:
(1) dissolving 2 parts by mass of maleic anhydride in a solvent of N, N-dimethylformamide and toluene at a volume ratio of 1: 4 to prepare a maleic anhydride solution with the concentration of 7 mol/L;
(2) adding 1 part by mass of 3-fluoro-5-carboxyphenyl into the maleic anhydride solution in batches, and stirring for 2 hours;
(3) adding 0.01 part by mass of p-toluenesulfonic acid and 0.01 part by mass of hydroquinone into the solution (2), heating to 110 ℃ for reaction for 3 hours, and then carrying out reduced pressure distillation to obtain a crude product of N- (3-fluoro-5-carboxyphenyl) maleimide;
(4) and washing, drying and recrystallizing the crude product of the N- (3-fluoro-5-carboxyphenyl) maleimide to obtain the N- (3-fluoro-5-carboxyphenyl) maleimide.
And then preparing a corrosion-resistant intermediate layer, wherein the corrosion-resistant intermediate layer is an aluminum foil, and titanium dioxide with the thickness of 10nm is coated on the surface of the aluminum foil.
And then, preparing a corrosion-resistant outer layer, wherein the corrosion-resistant outer layer is prepared by selecting 10 parts of nylon as a main material, extruding and compounding the nylon and 2 parts of adipic acid modified polyethylene terephthalate, coating silicon dioxide with the thickness of 10nm on the adipic acid modified polyethylene terephthalate layer, and performing cold stamping forming to obtain the corrosion-resistant outer layer.
Then, preparing the corrosion-resistant flexible packaging film by a dry compounding method,
the method comprises the following steps: uniformly coating a layer of polyurethane adhesive with the thickness of 1 mu m on the upper surface of the corrosion-resistant middle layer, drying the polyurethane adhesive by an oven at the temperature of 80 ℃, and then hot-pressing and attaching the polyurethane adhesive with the corrosion-resistant outer layer on a composite roller to obtain a semi-finished film;
step two: and uniformly coating a layer of epoxy resin adhesive with the thickness of 1 micrometer on the lower surface of the semi-finished film, drying by an oven at 80 ℃, and then hot-pressing and attaching the corrosion-resistant inner layer on a composite roller to obtain the corrosion-resistant flexible packaging film.
And finally, performing corrosion resistance test, wherein the test method comprises the following steps:
the flexible packaging film in the above examples was prepared by taking a 15mm wide strip of electrolyte (EC/DEC/DMC 1/1/1+1mol/L LiPF)6) Soaking for 12h, 24h and 48h, and observing the layering conditions of the outer layer, the middle layer and the inner layer after cleaning.
And (3) testing results: the flexible packaging film prepared by the embodiment has a fine layering phenomenon between the middle layer and the inner layer when being soaked for 48 hours.
Example 2
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top, and the preparation steps are as follows:
s1: uniformly mixing 10 parts of ternary copolymer polypropylene, 0.5 part of glycerol triacrylate, 0.5 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 2 parts of graphene to obtain a layer A raw material;
uniformly mixing 15 parts of homopolymerized polypropylene, 0.5 part of glycerol triacrylate, 0.5 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer B raw material;
uniformly mixing 10 parts of mixed polypropylene, 0.5 part of glycerol triacrylate, 0.5 part of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and 1 part of graphene to obtain a C-layer raw material,
the mixed polypropylene consists of 10 percent of binary polypropylene, 10 percent of ternary polypropylene and 80 percent of homopolymerized polypropylene in percentage by mass;
s2: a, B, C, respectively adding the three well-mixed raw materials and 10 parts of nylon into A, B, C, D four double-screw extruders at the head temperature of 180 ℃ and the rotating speed of 190r/min, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
the distributor comprises a shell 1, four material channels 2 are arranged in the shell 1, one end of each material channel 2 is fixedly connected with a feed hopper 5, the feed hoppers 5 are communicated with the material channels 2, each feed hopper 5 is conical, the diameter of the end, communicated with the material channels 2, of each feed hopper 5 is smaller, the diameter of the end, far away from the material channels 2, of each feed hopper 5 is larger, a feed inlet 3 is arranged in each feed hopper 5, the feed hoppers 5 and the shell 1 are correspondingly provided with two annular plates 15, bolts 16 are fixed on the two annular plates 15, each feed hopper 5 is provided with a groove 17, each shell 1 is provided with a lug 19, each groove 17 is arranged corresponding to the lug 19, and a sealing ring 18 is fixedly arranged on the inner wall of each groove 17; the outer side wall of the feed hopper 5 is fixedly provided with an annular cover 4, and the annular cover 4 is provided with a plurality of bolt holes 6;
a speed limiting plate 9 is arranged at one end of the material channel 2, the speed limiting plate 9 is fixedly connected to the material channel 2, a fixing plate 14 is fixedly installed at one end of the speed limiting plate 9, four sliding grooves 12 are formed in the fixing plate 14, the sliding grooves 12 are communicated with the material channel 2, a flow limiting plate 13 is slidably installed in the sliding grooves 12, two threaded holes 20 are formed in the flow limiting plate 13, threaded rods 11 are connected with the threaded holes 20 in a threaded manner, a rotating block 10 is fixedly connected to the upper end of one threaded rod 11, an end cover 8 is fixedly connected to the tail portion, close to one end of the speed limiting plate 9, of the shell 1, and a plurality of through holes 7 are formed in the end cover 8;
when the distributor is used, firstly, the groove 17 of the feed hopper 5 and the bump 19 on the shell 1 are correspondingly arranged, the bolts 16 are screwed on the two annular plates 15 to fix the feed hopper 5, the feed hopper 5 of the distributor is communicated with the discharge hole of the extruder, the end cover 8 on the shell 1 is connected with the T-shaped die head, materials enter the material channel 2 through the feed hole 3 and reach the speed limiting plate 9 to be distributed, when the materials reach the speed limiting plate 9, the rotating block 10 is rotated to drive the threaded rod 11 to rotate, the flow limiting plate 13 in threaded connection with the threaded rod 11 moves upwards to cover part of the material channel 2 to achieve the purpose of flow limiting, and by adjusting the four rotating blocks 10, the four material channels 2 can be subjected to different flow limiting, so that the materials reach different proportions;
the dispenser has the advantages that: the shell 1 can be connected with four feed hoppers 5, at most four materials can be distributed, the shell 1 and the feed hoppers 5 can be detached, the distributor can be conveniently cleaned, the shell 1 and the feed hoppers 5 are respectively provided with a convex block 19 and a groove 17, the position of the feed hoppers 5 can be conveniently determined when the feed hoppers 5 are installed, and the sealing rings 18 on the inner walls of the grooves 17 can prevent the materials from leaking; the arrangement of the speed limiting plate 9 can facilitate material distribution, the outlet areas of different material channels 2 can be freely adjusted by arranging the speed limiting plate 9 on each material channel 2, the effect of limiting the flow and the speed of the material is achieved, and the arrangement of the end cover 8 facilitates the butt joint of the discharging position of the distributor and an extruder die.
S4: extruding and compounding the inner-layer base film and 8 parts of polyethylene glycol terephthalate, coating a layer of polyvinyl alcohol with the thickness of 2 mu m on the surface of the polyethylene glycol terephthalate to obtain a semi-finished inner-layer film, and extruding and compounding 2 parts of ethylene-vinyl alcohol copolymer and 2 parts of polyvinyl butyral on the semi-finished inner-layer film to obtain a corrosion-resistant inner layer;
the preparation of N- (3-fluoro-5-carboxyphenyl) maleimide corresponds to that of example 1.
And then preparing a corrosion-resistant intermediate layer, wherein the corrosion-resistant intermediate layer is an aluminum foil, and titanium dioxide with the thickness of 50nm is coated on the surface of the aluminum foil.
And then, preparing an anti-corrosion outer layer, wherein the anti-corrosion outer layer is prepared by selecting 15 parts of nylon as a main material, extruding and compounding the nylon and 2 parts of adipic acid modified polyethylene terephthalate, coating silicon dioxide with the thickness of 10nm on the adipic acid modified polyethylene terephthalate layer, and performing cold stamping forming to obtain the anti-corrosion outer layer.
Then, preparing the corrosion-resistant flexible packaging film by a dry compounding method,
the method comprises the following steps: uniformly coating a layer of epoxy resin adhesive with the thickness of 1 mu m on the upper surface of the corrosion-resistant middle layer, drying the epoxy resin adhesive by an oven at 80 ℃, and then hot-pressing and attaching the epoxy resin adhesive with the corrosion-resistant outer layer on a composite roller to obtain a semi-finished film;
step two: and uniformly coating a layer of epoxy resin adhesive with the thickness of 1 micrometer on the lower surface of the semi-finished film, drying by an oven at 80 ℃, and then hot-pressing and attaching the corrosion-resistant inner layer on a composite roller to obtain the corrosion-resistant flexible packaging film.
Finally, a corrosion resistance test was performed, the test method being in accordance with example 1.
And (3) testing results: the flexible packaging film prepared by the embodiment has no delamination phenomenon after being soaked for 48 hours.
Example 3
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top, and the preparation steps are as follows:
s1: uniformly mixing 15 parts of ternary copolymer polypropylene, 1 part of pentaerythritol tetraacrylate, 1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 3 parts of graphene to obtain a layer A raw material;
uniformly mixing 20 parts of homopolymerized polypropylene, 1 part of pentaerythritol tetraacrylate, 1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 3 parts of graphene to obtain a layer B raw material;
uniformly mixing 15 parts of mixed polypropylene, 1 part of pentaerythritol tetraacrylate, 1 part of dicumyl peroxide and 1 part of graphene to obtain a C-layer raw material,
the mixed polypropylene consists of 20 percent of binary polypropylene, 20 percent of ternary polypropylene and 60 percent of homopolymerized polypropylene in percentage by mass;
s2: respectively adding A, B, C mixed raw materials and 20 parts of nylon into A, B, C, D four double-screw extruders at the head temperature of 180 ℃ and the rotating speed of 190r/min, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
the distributor comprises a shell 1, four material channels 2 are arranged in the shell 1, one end of each material channel 2 is fixedly connected with a feed hopper 5, the feed hoppers 5 are communicated with the material channels 2, each feed hopper 5 is conical, the diameter of the end, communicated with the material channels 2, of each feed hopper 5 is smaller, the diameter of the end, far away from the material channels 2, of each feed hopper 5 is larger, a feed inlet 3 is arranged in each feed hopper 5, the feed hoppers 5 and the shell 1 are correspondingly provided with two annular plates 15, bolts 16 are fixed on the two annular plates 15, each feed hopper 5 is provided with a groove 17, each shell 1 is provided with a lug 19, each groove 17 is arranged corresponding to the lug 19, and a sealing ring 18 is fixedly arranged on the inner wall of each groove 17; the outer side wall of the feed hopper 5 is fixedly provided with an annular cover 4, and the annular cover 4 is provided with a plurality of bolt holes 6;
a speed limiting plate 9 is arranged at one end of the material channel 2, the speed limiting plate 9 is fixedly connected to the material channel 2, a fixing plate 14 is fixedly installed at one end of the speed limiting plate 9, four sliding grooves 12 are formed in the fixing plate 14, the sliding grooves 12 are communicated with the material channel 2, a flow limiting plate 13 is slidably installed in the sliding grooves 12, two threaded holes 20 are formed in the flow limiting plate 13, threaded rods 11 are connected with the threaded holes 20 in a threaded manner, a rotating block 10 is fixedly connected to the upper end of one threaded rod 11, an end cover 8 is fixedly connected to the tail portion, close to one end of the speed limiting plate 9, of the shell 1, and a plurality of through holes 7 are formed in the end cover 8;
when the distributor is used, firstly, the groove 17 of the feed hopper 5 and the bump 19 on the shell 1 are correspondingly arranged, the bolts 16 are screwed on the two annular plates 15 to fix the feed hopper 5, the feed hopper 5 of the distributor is communicated with the discharge hole of the extruder, the end cover 8 on the shell 1 is connected with the T-shaped die head, materials enter the material channel 2 through the feed hole 3 and reach the speed limiting plate 9 to be distributed, when the materials reach the speed limiting plate 9, the rotating block 10 is rotated to drive the threaded rod 11 to rotate, the flow limiting plate 13 in threaded connection with the threaded rod 11 moves upwards to cover part of the material channel 2 to achieve the purpose of flow limiting, and by adjusting the four rotating blocks 10, the four material channels 2 can be subjected to different flow limiting, so that the materials reach different proportions;
the dispenser has the advantages that: the shell 1 can be connected with four feed hoppers 5, at most four materials can be distributed, the shell 1 and the feed hoppers 5 can be detached, the distributor can be conveniently cleaned, the shell 1 and the feed hoppers 5 are respectively provided with a convex block 19 and a groove 17, the position of the feed hoppers 5 can be conveniently determined when the feed hoppers 5 are installed, and the sealing rings 18 on the inner walls of the grooves 17 can prevent the materials from leaking; the arrangement of the speed limiting plate 9 can facilitate material distribution, the outlet areas of different material channels 2 can be freely adjusted by arranging the speed limiting plate 9 on each material channel 2, the effect of limiting the flow and the speed of the material is achieved, and the arrangement of the end cover 8 facilitates the butt joint of the discharging position of the distributor and an extruder die.
S4: extruding and compounding an inner-layer base film and 10 parts of polyethylene glycol terephthalate, coating a layer of polyvinylidene chloride with the thickness of 1 mu m on the surface of the polyethylene glycol terephthalate to obtain a semi-finished inner-layer film, and extruding and compounding 2 parts of ethylene-vinyl alcohol copolymer and 2 parts of polyvinyl butyral on the semi-finished inner-layer film to obtain a corrosion-resistant inner layer;
the preparation of N- (3-fluoro-5-carboxyphenyl) maleimide corresponds to that of example 1.
And then preparing a corrosion-resistant intermediate layer, wherein the corrosion-resistant intermediate layer is an aluminum foil, and titanium dioxide with the thickness of 50nm is coated on the surface of the aluminum foil.
And then, preparing an anti-corrosion outer layer, wherein the anti-corrosion outer layer is prepared by selecting 20 parts of nylon as a main material, extruding and compounding the nylon and 2 parts of adipic acid modified polyethylene terephthalate, coating silicon dioxide with the thickness of 10nm on the adipic acid modified polyethylene terephthalate layer, and performing cold stamping forming to obtain the anti-corrosion outer layer.
Then, preparing the corrosion-resistant flexible packaging film by a dry compounding method,
the method comprises the following steps: uniformly coating a layer of acrylic resin adhesive with the thickness of 1 mu m on the upper surface of the corrosion-resistant middle layer, drying the acrylic resin adhesive by an oven at 80 ℃, and then hot-pressing and attaching the acrylic resin adhesive with the corrosion-resistant outer layer on a composite roller to obtain a semi-finished film;
step two: and uniformly coating a layer of acrylic resin adhesive with the thickness of 1 mu m on the lower surface of the semi-finished film, drying the semi-finished film by an oven at 80 ℃, and then hot-pressing and attaching the semi-finished film and the corrosion-resistant inner layer on a composite roller to obtain the corrosion-resistant flexible packaging film.
Finally, a corrosion resistance test was performed, the test method being in accordance with example 1.
And (3) testing results: the flexible packaging film prepared by the embodiment has no delamination phenomenon after being soaked for 48 hours.
Comparative example 1
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery,
firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises the following preparation steps:
s1: uniformly mixing 5 parts of ternary copolymer polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer A raw material;
s2: respectively adding the A and 5 parts of nylon into A, B two double-screw extruders, wherein the head temperature is 180 ℃, the rotating speed is 190r/min, and extruding and plasticizing;
s3: the plasticized material in a molten state is subjected to T-shaped die head and tape casting cooling forming to obtain a base film with an inner layer of a two-layer structure;
s4: the inner-layer base film is firstly extruded and compounded with 5 parts of polyethylene glycol terephthalate, then a layer of polyvinyl alcohol with the thickness of 1 mu m is coated on the surface of the polyethylene glycol terephthalate to obtain a semi-finished inner-layer film, and then 2 parts of ethylene-vinyl alcohol copolymer and 2 parts of polyvinyl butyral are extruded and compounded on the semi-finished inner-layer film to obtain the corrosion-resistant inner layer.
The preparation of N- (3-fluoro-5-carboxyphenyl) maleimide corresponds to that of example 1.
The preparation of the corrosion resistant intermediate layer, the corrosion resistant outer layer and the corrosion resistant flexible packaging film was identical to example 1.
The test method was in accordance with example 1.
And (3) testing results: the flexible packaging film prepared by the embodiment has no delamination condition after being soaked for 24 hours, and the middle layer and the inner layer have obvious delamination phenomenon after 48 hours.
Comparative example 2
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top, and the preparation steps are as follows:
s1: uniformly mixing 5 parts of ternary copolymer polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer A raw material;
uniformly mixing 10 parts of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide, 0.1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1 part of graphene to obtain a layer B raw material;
uniformly mixing 5 parts of mixed polypropylene of 10% of ternary polypropylene and 90% of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide and 1 part of graphene by mass percent to obtain a layer C raw material;
s2: a, B, C, respectively adding the three well-mixed raw materials and 5 parts of nylon into A, B, C, D four double-screw extruders at the head temperature of 180 ℃ and the rotating speed of 190r/min, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
the distributor comprises a shell 1, four material channels 2 are arranged in the shell 1, one end of each material channel 2 is fixedly connected with a feed hopper 5, the feed hoppers 5 are communicated with the material channels 2, each feed hopper 5 is conical, the diameter of the end, communicated with the material channels 2, of each feed hopper 5 is smaller, the diameter of the end, far away from the material channels 2, of each feed hopper 5 is larger, a feed inlet 3 is arranged in each feed hopper 5, the feed hoppers 5 and the shell 1 are correspondingly provided with two annular plates 15, bolts 16 are fixed on the two annular plates 15, each feed hopper 5 is provided with a groove 17, each shell 1 is provided with a lug 19, each groove 17 is arranged corresponding to the lug 19, and a sealing ring 18 is fixedly arranged on the inner wall of each groove 17; the outer side wall of the feed hopper 5 is fixedly provided with an annular cover 4, and the annular cover 4 is provided with a plurality of bolt holes 6;
a speed limiting plate 9 is arranged at one end of the material channel 2, the speed limiting plate 9 is fixedly connected to the material channel 2, a fixing plate 14 is fixedly installed at one end of the speed limiting plate 9, four sliding grooves 12 are formed in the fixing plate 14, the sliding grooves 12 are communicated with the material channel 2, a flow limiting plate 13 is slidably installed in the sliding grooves 12, two threaded holes 20 are formed in the flow limiting plate 13, threaded rods 11 are connected with the threaded holes 20 in a threaded manner, a rotating block 10 is fixedly connected to the upper end of one threaded rod 11, an end cover 8 is fixedly connected to the tail portion, close to one end of the speed limiting plate 9, of the shell 1, and a plurality of through holes 7 are formed in the end cover 8;
when the distributor is used, firstly, the groove 17 of the feed hopper 5 and the bump 19 on the shell 1 are correspondingly arranged, the bolts 16 are screwed on the two annular plates 15 to fix the feed hopper 5, the feed hopper 5 of the distributor is communicated with the discharge hole of the extruder, the end cover 8 on the shell 1 is connected with the T-shaped die head, materials enter the material channel 2 through the feed hole 3 and reach the speed limiting plate 9 to be distributed, when the materials reach the speed limiting plate 9, the rotating block 10 is rotated to drive the threaded rod 11 to rotate, the flow limiting plate 13 in threaded connection with the threaded rod 11 moves upwards to cover part of the material channel 2 to achieve the purpose of flow limiting, and by adjusting the four rotating blocks 10, the four material channels 2 can be subjected to different flow limiting, so that the materials reach different proportions;
the dispenser has the advantages that: the shell 1 can be connected with four feed hoppers 5, at most four materials can be distributed, the shell 1 and the feed hoppers 5 can be detached, the distributor can be conveniently cleaned, the shell 1 and the feed hoppers 5 are respectively provided with a convex block 19 and a groove 17, the position of the feed hoppers 5 can be conveniently determined when the feed hoppers 5 are installed, and the sealing rings 18 on the inner walls of the grooves 17 can prevent the materials from leaking; the arrangement of the speed limiting plate 9 can facilitate material distribution, the outlet areas of different material channels 2 can be freely adjusted by arranging the speed limiting plate 9 on each material channel 2, the effect of limiting the flow and the speed of the material is achieved, and the arrangement of the end cover 8 facilitates the butt joint of the discharging position of the distributor and an extruder die.
S4: and extruding and compounding the inner base film and 5 parts of polyethylene glycol terephthalate to obtain the corrosion-resistant inner layer.
The preparation of N- (3-fluoro-5-carboxyphenyl) maleimide corresponds to that of example 1.
The preparation of the corrosion resistant intermediate layer, the corrosion resistant outer layer and the corrosion resistant flexible packaging film was identical to example 1.
Finally, a corrosion resistance test was performed, the test method being in accordance with example 1.
And (3) testing results: the soft packaging film prepared by the embodiment has a fine layering phenomenon on the middle layer and the inner layer when being soaked for 12 hours.
Comparative example 3
A preparation method of a corrosion-resistant flexible packaging film for a lithium battery.
Firstly, preparing a corrosion-resistant inner layer, wherein the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top, and the preparation steps are as follows:
s1: uniformly mixing 5 parts of ternary copolymer polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide and 1 part of graphene to obtain a layer A raw material;
uniformly mixing 10 parts of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide and 1 part of graphene to obtain a layer B raw material;
uniformly mixing 5 parts of mixed polypropylene of 10% of ternary polypropylene and 90% of homo-polypropylene, 0.1 part of pentaerythritol tetraacrylate, 0.1 part of dicumyl peroxide and 1 part of graphene by mass percent to obtain a layer C raw material;
s2: a, B, C, respectively adding the three well-mixed raw materials and 5 parts of nylon into A, B, C, D four double-screw extruders at the head temperature of 180 ℃ and the rotating speed of 190r/min, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
the distributor comprises a shell 1, four material channels 2 are arranged in the shell 1, one end of each material channel 2 is fixedly connected with a feed hopper 5, the feed hoppers 5 are communicated with the material channels 2, each feed hopper 5 is conical, the diameter of the end, communicated with the material channels 2, of each feed hopper 5 is smaller, the diameter of the end, far away from the material channels 2, of each feed hopper 5 is larger, a feed inlet 3 is arranged in each feed hopper 5, the feed hoppers 5 and the shell 1 are correspondingly provided with two annular plates 15, bolts 16 are fixed on the two annular plates 15, each feed hopper 5 is provided with a groove 17, each shell 1 is provided with a lug 19, each groove 17 is arranged corresponding to the lug 19, and a sealing ring 18 is fixedly arranged on the inner wall of each groove 17; the outer side wall of the feed hopper 5 is fixedly provided with an annular cover 4, and the annular cover 4 is provided with a plurality of bolt holes 6;
a speed limiting plate 9 is arranged at one end of the material channel 2, the speed limiting plate 9 is fixedly connected to the material channel 2, a fixing plate 14 is fixedly installed at one end of the speed limiting plate 9, four sliding grooves 12 are formed in the fixing plate 14, the sliding grooves 12 are communicated with the material channel 2, a flow limiting plate 13 is slidably installed in the sliding grooves 12, two threaded holes 20 are formed in the flow limiting plate 13, threaded rods 11 are connected with the threaded holes 20 in a threaded manner, a rotating block 10 is fixedly connected to the upper end of one threaded rod 11, an end cover 8 is fixedly connected to the tail portion, close to one end of the speed limiting plate 9, of the shell 1, and a plurality of through holes 7 are formed in the end cover 8;
when the distributor is used, firstly, the groove 17 of the feed hopper 5 and the bump 19 on the shell 1 are correspondingly arranged, the bolts 16 are screwed on the two annular plates 15 to fix the feed hopper 5, the feed hopper 5 of the distributor is communicated with the discharge hole of the extruder, the end cover 8 on the shell 1 is connected with the T-shaped die head, materials enter the material channel 2 through the feed hole 3 and reach the speed limiting plate 9 to be distributed, when the materials reach the speed limiting plate 9, the rotating block 10 is rotated to drive the threaded rod 11 to rotate, the flow limiting plate 13 in threaded connection with the threaded rod 11 moves upwards to cover part of the material channel 2 to achieve the purpose of flow limiting, and by adjusting the four rotating blocks 10, the four material channels 2 can be subjected to different flow limiting, so that the materials reach different proportions;
the dispenser has the advantages that: the shell 1 can be connected with four feed hoppers 5, at most four materials can be distributed, the shell 1 and the feed hoppers 5 can be detached, the distributor can be conveniently cleaned, the shell 1 and the feed hoppers 5 are respectively provided with a convex block 19 and a groove 17, the position of the feed hoppers 5 can be conveniently determined when the feed hoppers 5 are installed, and the sealing rings 18 on the inner walls of the grooves 17 can prevent the materials from leaking; the arrangement of the speed limiting plate 9 can facilitate material distribution, the outlet areas of different material channels 2 can be freely adjusted by arranging the speed limiting plate 9 on each material channel 2, the effect of limiting the flow and the speed of the material is achieved, and the arrangement of the end cover 8 facilitates the butt joint of the discharging position of the distributor and an extruder die.
S4: and extruding and compounding the inner base film and 5 parts of polyethylene glycol terephthalate to obtain the corrosion-resistant inner layer.
The preparation of the corrosion resistant intermediate layer, the corrosion resistant outer layer and the corrosion resistant flexible packaging film was identical to example 1.
Finally, a corrosion resistance test was performed, the test method being in accordance with example 1.
And (3) testing results: the flexible packaging film prepared by the embodiment has obvious layering phenomenon on the middle layer and the inner layer when being soaked for 12 hours.
The soft packaging film obtained in example 1 was finely delaminated in the middle layer and the inner layer after being soaked for 48 hours, the soft packaging films obtained in examples 2 to 3 were not delaminated after being soaked for 48 hours, while comparative examples 1, 2 and 3 were delaminated to different degrees after 48 hours, 12 hours and 12 hours, respectively, and the soft packaging film in comparative example 2 was less delaminated than comparative example 3 due to the addition of N- (3-fluoro-5-carboxyphenyl) maleimide. Therefore, the method for forming the inner-layer base film by utilizing the multi-layer polypropylene co-extrusion micro-crosslinking and compounding the inner-layer base film with the polyethylene glycol terephthalate film, the ethylene-vinyl alcohol copolymer and the polyvinyl butyral obviously improves the corrosion resistance effect of the flexible packaging film, improves the mass parts of the film layer raw materials to a certain extent, can improve the corrosion resistance of the flexible packaging film, and improves the corrosion resistance effect by adding the N- (3-fluoro-5-carboxyphenyl) maleimide into the corrosion-resistant inner-layer raw material.
Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.
Therefore, the above description is only a preferred embodiment of the present application, and is not intended to limit the scope of the present application; all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (10)
1. A preparation method of a corrosion-resistant flexible packaging film for a lithium battery is characterized in that the corrosion-resistant flexible packaging film for the lithium battery is prepared from a corrosion-resistant inner layer, a corrosion-resistant intermediate layer and a corrosion-resistant outer layer by a dry compounding method;
the corrosion-resistant inner layer comprises a layer A, a layer B, a layer C and a layer D from bottom to top in sequence, and the preparation steps are as follows:
s1: uniformly mixing 5-15 parts of ternary copolymer polypropylene, 0.1-3 parts of crosslinking monomer, 0.1-3 parts of initiator, 0.1-1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1-5 parts of graphene to obtain a layer A raw material;
uniformly mixing 15-20 parts of homo-polypropylene, 0.1-3 parts of a crosslinking monomer, 0.1-3 parts of an initiator, 0.1-1 part of N- (3-fluoro-5-carboxyphenyl) maleimide and 1-5 parts of graphene to obtain a layer B raw material;
uniformly mixing 5-15 parts of mixed polypropylene, 0.1-3 parts of crosslinking monomer, 0.1-3 parts of initiator and 1-5 parts of graphene to obtain a C-layer raw material;
s2: respectively adding A, B, C mixed raw materials and 5-25 parts of nylon into A, B, C, D four double-screw extruders, and extruding and plasticizing;
s3: feeding the plasticized material in a molten state into a distributor, and then carrying out T-shaped die head and tape casting cooling forming to obtain an inner base film with a four-layer structure;
s4: extruding and compounding the inner base film with 5-10 parts of polyethylene glycol terephthalate to form a layer of polyethylene glycol terephthalate film on the inner base film, coating a layer of polyvinyl alcohol or polyvinylidene chloride with the thickness of 1-5 mu m on the surface of the polyethylene glycol terephthalate film to obtain a semi-finished inner film, and extruding and compounding the semi-finished inner film with 1-10 parts of ethylene-vinyl alcohol copolymer and 1-10 parts of polyvinyl butyral to obtain a corrosion-resistant inner layer;
the corrosion-resistant flexible packaging film for the lithium battery is prepared by a dry compounding method,
the method comprises the following steps: uniformly coating a layer of adhesive on the upper surface of the corrosion-resistant middle layer, drying by an oven, and then hot-pressing and attaching the corrosion-resistant outer layer on a composite roller;
step two: and uniformly coating a layer of adhesive on the lower surface of the corrosion-resistant middle layer, drying by an oven, and then hot-pressing and attaching the corrosion-resistant middle layer and the corrosion-resistant inner layer on a composite roller to obtain the corrosion-resistant flexible packaging film.
2. The method for preparing a corrosion-resistant flexible packaging film for a lithium battery as claimed in claim 1, wherein the crosslinking monomer is one or more of pentaerythritol tetraacrylate, glycerol triacrylate, divinylbenzene, and triacrylate isocyanurate.
3. The method of claim 1, wherein the initiator is one or more selected from the group consisting of dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and bis (o-methylbenzoyl) peroxide.
4. The method of claim 1, wherein the method for preparing the N- (3-fluoro-5-carboxyphenyl) maleimide comprises the following steps:
(1) dissolving 2 parts by mass of maleic anhydride in a solvent of N, N-dimethylformamide and toluene at a volume ratio of 1: 3-1: 4 to prepare a maleic anhydride solution with the concentration of 5-7 mol/L;
(2) adding 1 part by mass of 3-fluoro-5-carboxyl aniline into a maleic anhydride solution and stirring for 1-3 hours;
(3) adding 0.01 part by mass of p-toluenesulfonic acid and 0.01 part by mass of hydroquinone into the solution (2), heating to 110-;
(4) and washing, drying and recrystallizing the crude product of the N- (3-fluoro-5-carboxyphenyl) maleimide to obtain the N- (3-fluoro-5-carboxyphenyl) maleimide.
5. The method for preparing the corrosion-resistant flexible packaging film for the lithium battery as claimed in claim 1, wherein the mixed polypropylene is prepared by mixing 0-20% by mass, 10-20% by mass and 60-90% by mass of binary polypropylene, ternary polypropylene and homo-polypropylene.
6. The method as claimed in claim 1, wherein the head temperature of the twin-screw extruder is 150-220 ℃, and the rotation speed is 170-210 r/min.
7. The method for preparing a corrosion-resistant flexible packaging film for a lithium battery as claimed in claim 1, wherein the corrosion-resistant intermediate layer is an aluminum foil, and a titanium dioxide or silicon dioxide coating layer with a thickness of 10-200nm is coated on the surface of the aluminum foil.
8. The method for preparing the corrosion-resistant flexible packaging film for the lithium battery as claimed in claim 1, wherein the corrosion-resistant outer layer is prepared by selecting 10-25 parts of nylon as a main material, extruding and compounding the nylon and 1-10 parts of modified polyethylene terephthalate, coating silica with the thickness of 10-200nm on the modified polyethylene terephthalate layer, and performing cold stamping molding.
9. The method as claimed in claim 8, wherein the modified polyethylene terephthalate film used in the corrosion-resistant outer layer is one of polyethylene terephthalate modified with adipic acid, polyethylene glycol, polyethylene adipate and epoxy resin.
10. The method for preparing the corrosion-resistant flexible packaging film for the lithium battery as claimed in claim 1, wherein the adhesive is one or more of a polyurethane adhesive, an epoxy resin adhesive, an acrylic resin adhesive, a polyester adhesive and an acid-modified resin adhesive, and the thickness of the coating of the adhesive is 1-10 μm; the drying temperature of the oven is 60-100 ℃.
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| CN112652844B (en) * | 2020-12-24 | 2022-04-29 | 界首市天鸿新材料股份有限公司 | Power lithium battery flexible packaging film |
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| CN113635578B (en) * | 2021-05-25 | 2023-07-18 | 浙江玖邦科技有限公司 | Preparation method of fuel cell protective film |
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