CN114388948A - Aluminum-plastic film for lithium battery packaging and preparation method thereof - Google Patents

Aluminum-plastic film for lithium battery packaging and preparation method thereof Download PDF

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Publication number
CN114388948A
CN114388948A CN202111443085.7A CN202111443085A CN114388948A CN 114388948 A CN114388948 A CN 114388948A CN 202111443085 A CN202111443085 A CN 202111443085A CN 114388948 A CN114388948 A CN 114388948A
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layer
aluminum
polypropylene
film
plastic film
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CN202111443085.7A
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CN114388948B (en
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毛建军
周明
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Jiangyin Shenmei Packaging Material Co ltd
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Jiangyin Shenmei Packaging Material Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/126—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers
    • H01M50/129—Primary casings; Jackets or wrappings characterised by the material having a layered structure comprising three or more layers with two or more layers of only organic material
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/32—Making multilayered or multicoloured articles
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/105—Pouches or flexible bags
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/14—Primary casings; Jackets or wrappings for protecting against damage caused by external factors
    • H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/008—Wide strips, e.g. films, webs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B29L2009/003—Layered products comprising a metal layer
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Plasma & Fusion (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses an aluminum plastic film for lithium battery packaging, which comprises an outer nylon composite layer, a polyurethane adhesive layer, an aluminum alloy foil layer, a polyolefin adhesive layer and a polypropylene composite layer which are sequentially arranged, wherein the polypropylene composite layer is a three-layer co-extrusion composite film, the middle layer of the co-extrusion composite film is polypropylene toughened by ultrahigh molecular weight polyethylene, the outer layer is co-polypropylene filled with nano filler, and the inner layer is co-polypropylene. The addition of the nano filler can improve the mechanical property of polypropylene, play a role in neutralizing hydrofluoric acid, improve the low-temperature heat sealing property of the inner layer film and improve the corrosion resistance of the aluminum plastic film. The invention also discloses a preparation method of the aluminum-plastic film, wherein the inner layer film of the aluminum-plastic film is manufactured by adopting a thermal compounding mode, the surface of the aluminum foil is firstly subjected to plasma cleaning treatment, and then the cleaned aluminum foil is subjected to plasma etching, so that the bonding property between the aluminum foil and the bonding agent can be increased, and the corrosion resistance and the humidity and heat resistance of the aluminum-plastic film are improved.

Description

Aluminum-plastic film for lithium battery packaging and preparation method thereof
Technical Field
The invention relates to the technical field of aluminum-plastic films, in particular to an aluminum-plastic film for lithium battery packaging and a preparation method thereof.
Background
With the development of the soft package battery and the popularization of the soft package battery in mobile phones and new energy automobiles, the safety and the energy density of the soft package battery are paid attention and paid attention by all parties. Compared with a hard-shell cylindrical battery and a square battery, the soft-package battery adopts the aluminum plastic film as a package, and gas generated by side reaction in the charging and discharging processes of the battery only enables the soft-package battery to bulge and not explode, so that the soft-package battery has great advantage in the aspect of safety. On the other hand, because the quality of aluminium foil is lighter, laminate polymer battery's energy density is also higher, can be fine satisfy the demands such as continuation of the journey of present lithium cell.
The aluminum plastic film for the soft package lithium battery is classified according to each layer, the base layers are respectively the outermost layer, the middle layer or the blocking layer and the innermost layer, and the base layers are mutually bonded into a film through bonding layers formed by bonding agents. The outermost layer material has the main functions of protecting the aluminum foil layer of the middle layer from being scratched and continuously operating in the processing process, so that the yield of products is ensured, and the internal battery is protected from impact shock and the like caused by falling and the like in the use process of the battery, so that the most main requirements of the outer layer material are good impact resistance, good puncture resistance, good heat resistance, good insulation performance and good friction resistance, and the most common outer layer material at present is a nylon film. The middle layer or the barrier layer for the lithium battery flexible packaging film is mainly aluminum foil and mainly functions in blocking the entry of water vapor and oxygen, so that the middle layer is required to have excellent water vapor resistance, excellent bonding strength, excellent pinhole resistance, stable processability and excellent double-sided composite property. The innermost layer has good heat sealing properties, solvent resistance and puncture resistance over a long period of time. On one hand, the main composition of the current electrolyte is carbonate, so that a series of physicochemical changes such as permeation of an inner layer material and the electrolyte are inevitably caused, and the cast polypropylene film can better meet the electrical performance of the lithium ion battery compared with other materials. On the other hand, the lithium ion battery may have a ballooning phenomenon during formation, because the lithium ion battery inevitably generates gas during formation, and therefore, the battery needs to be vacuumized, so that the aluminum mesh and the copper mesh on the electrode may pierce through the innermost layer material, and the innermost layer is in contact with the interlayer Al foil, so that the battery is short-circuited. The most mature inner layer material currently in use is cast polypropylene film.
With the common application of soft package lithium ion batteries in the fields of mobile phones, computers, cameras, electric vehicles and the like, people have higher and higher requirements on the safety performance of the aluminum plastic film for the soft package of the lithium batteries, and at present, the manufacturing difficulty of the high-performance aluminum plastic film is mainly shown in the following aspects: firstly, the puncture resistance of the external package needs to be further improved, mainly because the tab and the tab rubber block thereof need to be folded after being heat-sealed with the battery composite film in the assembly process of the battery, and the metal edge angle of the tab is easy to pierce the shell of the flexible package lithium ion battery, so that the tab is in contact with the aluminum foil layer. Secondly, as the packaging film is thinned, the barrier properties of the thin aluminum foil against water vapor and air are weakened, and when external water vapor enters the inside of the lithium ion battery, lithium hexafluorophosphate in the electrolyte reacts with water to generate harmful hydrofluoric acid, and when water vapor enters, PVDF used as an adhesive separator layer can undergo a dehydro-HF acid reaction under the catalytic action of NMP. The generation of strong acid causes the aluminum foil to dissolve and the battery packaging to fail. Third, the heat sealing properties of polypropylene materials are not very good, especially the low temperature heat sealing properties are poor, and the electrolyte inside the battery is easily decomposed at high temperature. Fourthly, the polypropylene is used as an inner layer material, the puncture resistance of the polypropylene also needs to be further improved, the main reason is that the copper net and the aluminum net are used as electrodes of the lithium ion battery cell, vacuumizing treatment is needed when the lithium ion battery cell is packaged and formed, and meanwhile, when the lithium ion battery cell is packaged and folded reversely, the copper net and the aluminum net possibly puncture the outermost layer material to enable the battery to be short-circuited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, the innermost membrane is replaced by a three-layer co-extrusion composite membrane, and the nano filler is added in the membrane close to the aluminum alloy foil to prevent hydrofluoric acid generated by the reaction of electrolyte and water from reacting with the aluminum alloy foil, so that the battery fails. When the aluminum plastic film is manufactured, plasma treatment and plasma etching are carried out on two surfaces of the aluminum alloy foil to increase the adhesive force between the aluminum alloy foil and the adhesive layer, so that the moisture and air are further prevented from entering, and the corrosion resistance of the aluminum plastic film is improved.
In order to achieve the purpose, the technical scheme of the invention is to provide an aluminum-plastic film for lithium battery packaging, which comprises an outermost nylon composite layer, a polyurethane adhesive layer, an aluminum alloy foil layer, a polyolefin adhesive layer and a polypropylene composite layer which are sequentially arranged, wherein the polypropylene composite layer is a three-layer co-extrusion composite film, the middle layer of the co-extrusion composite film is ultrahigh molecular weight polyethylene toughened polypropylene, the outermost layer is nano filler filled polypropylene copolymer, the innermost layer is polypropylene copolymer, and the mass ratio of the outermost layer, the middle layer and the innermost layer of the co-extrusion composite film is 2-4: 4: 1.
The further preferable technical scheme is that in the polypropylene toughened by the ultrahigh molecular weight polyethylene, the mass percentage of the ultrahigh molecular weight polyethylene is 15-25%.
According to a further preferable technical scheme, in the copolymerized polypropylene filled with the nano filler, the mass percentage of the nano filler is 3.5-4.5%, and the nano filler comprises any one of silicon oxide, aluminum oxide, magnesium oxide, boron oxide and zinc oxide.
The innermost layer of the aluminum plastic film for packaging the lithium battery is directly contacted with the electrolyte, because the main composition of the current electrolyte is carbonate, a series of physical and chemical changes such as permeation of the inner layer material and the electrolyte are inevitably caused, and the cast polypropylene film can better meet the electrical property of the lithium ion battery compared with other materials and is widely applied to the inner layer material of the aluminum plastic film. However, cast polypropylene films also have some disadvantages, such as poor low temperature heat sealability due to the high melting point of polypropylene, poor puncture resistance and solvent resistance, and the like, and thus, it is necessary to improve the performance by changing the inner layer structure of the packaging material.
In the technical scheme to be protected by the invention, the inner layer film of the aluminum-plastic film is manufactured in a three-layer composite mode, so that each layer can exert different performances. The middle layer adopts polypropylene toughened by ultra-high molecular weight polyethylene, the puncture resistance and the impact resistance of the polypropylene can be obviously improved, the main principle is that when the polypropylene is blended and toughened by the ultra-high molecular weight polyethylene, ultra-high molecular weight polyethylene molecules and long-chain polypropylene molecules jointly form a blending network, the rest polypropylene molecules form a polypropylene network, and the polypropylene network and the blending network are interwoven to form a linear interpenetrating network. The blending network plays a skeleton role in the material to provide mechanical strength for the material, and when the material is impacted by external force, the blending network can generate large deformation to absorb external energy to play a toughening role. The ultra-high molecular weight polyethylene is an engineering material with very strong comprehensive performance, high strength, good toughness, excellent mechanical property and good chemical stability, and the application of the ultra-high molecular weight polyethylene toughened polypropylene to an aluminum plastic film can increase the puncture resistance and impact resistance of an inner layer film and play a certain role in resisting the corrosion of electrolyte, and in addition, the heat-sealing performance of the polypropylene can be greatly improved due to the fact that the ultra-high molecular weight polyethylene has the heat deformation temperature of only 85 ℃ and the melting point of 130-136 ℃.
The outermost layer of the inner layer film of the aluminum-plastic film is made of a copolymerized polypropylene material filled with nano filler, the nano filler is any one of silicon oxide, aluminum oxide, magnesium oxide, boron oxide and zinc oxide, and the addition of the nano filler can improve the mechanical property of the polypropylene and also play a role in neutralizing hydrofluoric acid, so that the corrosion resistance of the aluminum-plastic film is improved. The inner layer film of the aluminum-plastic film is manufactured in a thermal compounding mode, and electrolyte resistance and hydrolysis resistance of the aluminum-plastic film can be further improved.
The further preferable technical scheme is that the nylon composite layer is a co-extrusion composite film of nylon and polyethylene glycol terephthalate, the polyethylene glycol terephthalate is an outermost layer of an outer layer material, and the mass ratio of the nylon to the polyethylene glycol terephthalate in the co-extrusion composite film is 3.5-4.5: 1.
In order to improve the puncture resistance of the outermost layer material of the aluminum-plastic film, the outermost layer of the aluminum-plastic film to be protected is a composite film formed by compounding nylon and polyethylene terephthalate together in a thermal compounding mode, wherein the polyethylene terephthalate is the outermost layer film. The film made of polyethylene terephthalate is a PET film, is a packaging film with comprehensive performance, has good transparency, luster, good air tightness and aroma retention, excellent mechanical performance, the toughness of the film is the best of all thermoplastic plastics, and the tensile strength and the impact strength of the film are much higher than those of the common films. In addition, the PET film has excellent heat resistance, cold resistance and good chemical resistance and oil resistance. The polyethylene glycol terephthalate material is added into the outermost layer of the aluminum-plastic film, so that the puncture resistance, the mechanical property and the damp and heat resistance of the aluminum-plastic film can be effectively improved.
Further preferably, the aluminum alloy foil layer is an aluminum alloy foil with an iron content of 2-5%. The presence of a small amount of Fe in the aluminum foil may increase the ductility, wear resistance, and corrosion resistance of the aluminum foil.
The further preferred technical scheme does, the nylon composite layer thickness is 20 ~ 40um, and the thickness of aluminium alloy foil is 40 ~ 60um, the thickness of polypropylene composite layer is 30 ~ 50um, the polyurethane tie coat with the thickness of polyolefin tie coat is 5 ~ 10 um.
The technical scheme of the invention also provides a preparation method of the aluminum-plastic film, which comprises the following steps:
(1) filling nano filler: weighing nano filler and co-polypropylene, adding the nano filler and co-polypropylene into a high-speed mixer, and uniformly stirring at a rotating speed of 250-400 r/min for 10-15 min during mixing;
(2) co-extrusion compounding of the inner layer film: respectively adding the polypropylene copolymer filled with the nano filler, the polypropylene toughened by the ultra-high molecular weight polyethylene and the polypropylene copolymer into three charging barrels of an extruder, setting the temperature of the extruder to melt three raw material resins, setting the extrusion melting temperatures of the three materials to be 200-230 ℃, 170-190 ℃ and 180-220 ℃, respectively, casting the molten resin onto a cooling roller with a smooth surface through a machine head to rapidly cool the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(3) co-extrusion compounding of the outermost layer: respectively weighing polyethylene glycol terephthalate, a compatibilizer and nylon, respectively adding the polyethylene glycol terephthalate, the compatibilizer and the nylon into two material cylinders of an extruder, setting the extrusion temperature of two groups of extruders to be 250-280 ℃, casting molten resin onto a cooling roller with a smooth surface through a machine head, and rapidly cooling the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(4) plasma treatment of aluminum alloy foil: first using Ar2As working gas, carrying out surface cleaning treatment on the aluminum foil, then increasing plasma power and treatment time, and carrying out surface roughening treatment on the aluminum foil;
(5) and (3) dry compounding of the aluminum plastic film: and respectively coating adhesives on two sides of the aluminum foil after the plasma treatment, and respectively compounding the aluminum foil with the outermost layer film and the innermost layer film.
In a further preferable technical scheme, in the step of plasma treatment of the aluminum alloy foil, during the surface cleaning treatment, the discharge power of plasma is 3 to 5kW, the treatment time is 30 to 60 seconds, and Ar is2The flow rates of the plasma discharge electrodes are respectively 180-220 sccm, the plasma discharge power is 6-8 kW during the surface roughening treatment, and the treatment time is 100-300 s.
In a further preferable technical scheme, in the step of co-extrusion compounding of the outermost layer, the content of the compatibilizer is 4.5-7%, and the compatibilizer comprises maleic anhydride or SEBS grafted maleic anhydride.
The aluminum plastic film is used as a carrier of electrolyte and a battery core of the flexible package lithium ion battery, and not only needs to prevent the permeation of impurities such as moisture, air and the like, but also has higher requirements on the humidity resistance and the heat resistance of an outer layer and the corrosion resistance of an inner layer because the environment where the lithium ion battery can be used is relatively complex. As for the inner layer, the inner layer is in direct contact with the electrolyte, and the situation of molecular permeation in the electrolyte inevitably occurs, so that the inner layer is corroded. For the outer layer, when the lithium battery is in a damp and hot environment for a long time, the aluminum-plastic film is easy to be layered due to the water and air, and the prior art indicates that the corrosion of the inner layer and the separation of the outer layer have a large relationship with the bonding performance of the adhesive, the aluminum foil and the composite film. When the aluminum-plastic film is manufactured, the surface of the aluminum foil is firstly subjected to plasma cleaning treatment, and Ar is used as working gas2Removing impurities such as grease and stains on the surface of the aluminum foil, then increasing the plasma power and the processing time, and carrying out plasma etching on the cleaned aluminum foil to form a point-shaped rough layer with closely arranged corrosion pits on the surface of the aluminum foil, so that the bonding between the point-shaped rough layer and the bonding layer is tighter, the bonding performance between the aluminum foil and the bonding agent is increased, and the corrosion resistance and the moisture and heat resistance of the aluminum-plastic film are improved.
The invention has the advantages and beneficial effects that:
1. the inner layer film of the aluminum-plastic film takes the copolymerized polypropylene filled with the nano filler as the outer layer of the inner layer film, and the polypropylene toughened by the ultra-high molecular weight polyethylene as the middle layer, so that the mechanical property of the polypropylene can be improved, the effect of neutralizing hydrofluoric acid can be achieved, the low-temperature heat sealing property of the inner layer film can be improved, and the corrosion resistance of the aluminum-plastic film can be further improved. The inner layer film of the aluminum-plastic film is manufactured in a thermal compounding mode, and electrolyte resistance and hydrolysis resistance of the aluminum-plastic film can be further improved.
2. The outermost layer of the aluminum-plastic film adopts a composite film of nylon and polyethylene glycol terephthalate and is manufactured in a co-extrusion compounding mode, so that the puncture resistance and the environmental stability of the aluminum-plastic film can be effectively improved. The presence of a small amount of Fe in the aluminum alloy foil may increase ductility, wear resistance and corrosion resistance of the aluminum foil.
3. When the aluminum-plastic film is manufactured, firstly, plasma cleaning treatment is carried out on the surface of the aluminum foil to remove impurities such as grease and stains on the surface of the aluminum foil, and then plasma etching is carried out on the cleaned aluminum foil, so that a point-shaped rough layer with closely arranged corrosion pits is formed on the surface of the aluminum foil, the bonding property between the aluminum foil and a bonding agent can be increased, and the corrosion resistance and the moisture resistance of the aluminum-plastic film are improved.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
An aluminum plastic film for packaging a lithium battery comprises an outermost polyethylene terephthalate and nylon composite layer, a polyurethane bonding layer, an aluminum alloy foil layer, a polyolefin bonding layer and a polypropylene composite layer. In the outermost composite film, the mass ratio of nylon to polyethylene glycol terephthalate is 3.5:1, in the middle aluminum alloy foil, the iron content in the aluminum alloy is 2%, the polypropylene composite layer is a three-layer co-extrusion composite film, wherein the middle layer is polypropylene toughened by ultrahigh molecular weight polyethylene, the mass percentage content of the ultrahigh molecular weight polyethylene is 15%, the outer layer is silicon oxide filled polypropylene copolymer, the content of silicon oxide is 3.5%, the inner layer is polypropylene copolymer, and the mass ratio of the materials of the outer layer, the middle layer and the inner layer is 2:4: 1. In this plastic-aluminum membrane, the nylon composite layer thickness is 20um, aluminum alloy foil's thickness is 60um, the thickness of polypropylene composite layer is 30um, the polyurethane tie coat with the thickness of polyolefin tie coat is 10 um.
A preparation method of an aluminum-plastic film comprises the following steps:
(1) filling nano filler: weighing 10.5g of nano silicon oxide and 300g of polypropylene copolymer, adding the nano silicon oxide and the polypropylene copolymer into a high-speed mixer, and uniformly stirring at a rotating speed of 250r/min for 15min during mixing;
(2) co-extrusion compounding of the inner layer film: respectively adding 150g of copolymerized polypropylene filled with nano silicon oxide, 300g of ultrahigh molecular weight polyethylene toughened polypropylene and 75g of copolymerized polypropylene into three charging barrels of an extruder, setting the temperature of the extruder to melt three raw material resins, setting the extrusion melting temperatures of the three materials to 230 ℃, 190 ℃ and 220 ℃, casting the molten resin onto a cooling roller with a smooth surface through a machine head to rapidly cool the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(3) co-extrusion compounding of the outermost layer: respectively adding 100g of polyethylene terephthalate, 7g of maleic anhydride and 350g of nylon into two material cylinders of an extruder, setting the extrusion temperature of the two groups of extruders to be 250 ℃, casting molten resin onto a cooling roller with a smooth surface through a machine head, and rapidly cooling the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the rear cooling roller temperature is 30 ℃;
(4) plasma treatment of aluminum alloy foil: first using Ar2As a working gas, surface cleaning treatment was performed on an aluminum foil, the discharge power of plasma was 3kW, the treatment time was 60s, and Ar was used2The flow rates of the aluminum foil and the aluminum foil were respectively 180sccm, then the discharge power of the plasma was increased to 6kW, and the surface roughening treatment was performed for 300 seconds.
(5) And (3) dry compounding of the aluminum plastic film: and respectively coating adhesives on two sides of the aluminum foil after the plasma treatment, and respectively compounding the aluminum foil with the outermost layer film and the innermost layer film.
Example 2
An aluminum plastic film for packaging a lithium battery comprises an outermost polyethylene terephthalate and nylon composite layer, a polyurethane bonding layer, an aluminum alloy foil layer, a polyolefin bonding layer and a polypropylene composite layer. In the outermost composite film, the mass ratio of nylon to polyethylene glycol terephthalate is 4.5:1, in the middle aluminum alloy foil, the iron content in the aluminum alloy is 5%, the polypropylene composite layer is a three-layer co-extrusion composite film, wherein the middle layer is polypropylene toughened by ultrahigh molecular weight polyethylene, the mass percentage content of the ultrahigh molecular weight polyethylene is 25%, the outer layer is copolymerized polypropylene filled with alumina, the content of the alumina is 4.5%, the inner layer is copolymerized polypropylene, and the mass ratio of the materials of the outer layer, the middle layer and the inner layer is 4:4: 1. In this plastic-aluminum membrane, the nylon composite layer thickness is 40um, aluminum alloy foil's thickness is 40um, the thickness of polypropylene composite layer is 50um, the polyurethane tie coat with the thickness of polyolefin tie coat is 5 um.
A preparation method of an aluminum-plastic film comprises the following steps:
(1) filling nano filler: weighing 13.5g of alumina and 300g of polypropylene copolymer according to the mass ratio, adding the alumina and the polypropylene copolymer into a high-speed mixer, and uniformly stirring at the rotating speed of 400r/min for 10 min;
(2) co-extrusion compounding of the inner layer film: respectively adding 300g of aluminum oxide filled polypropylene copolymer, 300g of ultrahigh molecular weight polyethylene toughened polypropylene and 75g of polypropylene copolymer into three charging barrels of an extruder, setting the temperature of the extruder to melt three raw material resins, setting the extrusion melting temperatures of the three materials to be 200 ℃, 170 ℃ and 180 ℃, casting the molten resin onto a cooling roller with a smooth surface through a machine head to rapidly cool the molten resin into a film, setting the casting roller temperature of the extruder to be 25 ℃, the annealing roller temperature to be 40 ℃ and the post-cooling roller temperature to be 30 ℃;
(3) co-extrusion compounding of the outermost layer: respectively adding 66.67g of polyethylene terephthalate, 3g of SEBS grafted maleic anhydride and 300g of nylon into two material cylinders of an extruder, setting the extrusion temperature of the two groups of extruders to be 280 ℃, casting molten resin onto a cooling roller with a smooth surface through a machine head, and rapidly cooling the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(4) plasma treatment of aluminum alloy foil: first using Ar2As a working gas, surface cleaning treatment was performed on an aluminum foil, the discharge power of plasma was 5kW, the treatment time was 30s, and Ar was used2The flow rates of the aluminum foil and the aluminum foil were respectively 200sccm, then the discharge power of the plasma was increased to 8kW, and the surface roughening treatment was performed for 100 seconds.
(5) And (3) dry compounding of the aluminum plastic film: and respectively coating adhesives on two sides of the aluminum foil after the plasma treatment, and respectively compounding the aluminum foil with the outermost layer film and the innermost layer film.
Comparative example 1
The composite membrane is prepared by selecting a nylon membrane, an aluminum foil and polypropylene copolymer prepared by an extrusion casting method as the outermost layer, the middle layer and the innermost layer of the aluminum-plastic membrane and adopting a dry-type compounding method, the structure of the composite membrane is sequentially a nylon membrane, a polyurethane adhesive layer, an aluminum foil, a polyolefin adhesive layer and polypropylene copolymer from outside to inside, and the thickness of each layer is sequentially 30um, 10um, 50um, 10um and 50um from outside to inside.
The performance test is carried out on the aluminum plastic film for lithium battery packaging prepared by the method, and the specific test method is as follows:
1. interlaminar peel strength test
The interlayer peeling strength of the aluminum foil layer and the inner layer is tested by referring to the test method operation specified in GB/T2792-2014 & lt 180 DEG peeling strength test method for pressure sensitive adhesive tape & gt. Wherein, the stripping angle is: 180 °, peeling speed: 150 mm/min.
2. Electrolyte resistance test
And (3) soaking the sample in the electrolyte at 85 ℃ for 15 days, and observing the appearance of the aluminum plastic film.
3. Test for Barrier Properties
The sample is made into a bag, the bag is sealed by injecting electrolyte, the bag is soaked in water at the temperature of 45 ℃ for 7 days, and the water content in the electrolyte is tested.
The test results are given in the following table:
Figure BDA0003383302480000101
according to the test results, the aluminum-plastic film prepared by the method has the advantages that the bonding performance of the aluminum alloy foil and the adhesive is good, the electrolyte corrosion resistance is improved, and the barrier performance to moisture and the like is improved greatly.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and improvements can be made without departing from the technical principle of the present invention, and these modifications and improvements should also be considered as the protection scope of the present invention.

Claims (9)

1. The aluminum-plastic film for packaging the lithium battery is characterized by comprising an outer nylon composite layer, a polyurethane adhesive layer, an aluminum alloy foil layer, a polyolefin adhesive layer and a polypropylene composite layer which are sequentially arranged, wherein the polypropylene composite layer is a three-layer co-extrusion composite film, the middle layer of the co-extrusion composite film is polypropylene toughened by ultrahigh molecular weight polyethylene, the outer layer is co-polypropylene filled with nano filler, and the inner layer is co-polypropylene, wherein the mass ratio of the outer layer material to the middle layer material to the inner layer material of the co-extrusion composite film is 2-4: 4: 1.
2. The aluminum-plastic film as recited in claim 1, wherein the ultrahigh molecular weight polyethylene-toughened polypropylene is 15-25% by mass.
3. The aluminum-plastic film of claim 2, wherein the co-polypropylene filled with the nano-filler is 3.5-4.5% by mass, and the nano-filler comprises any one of silicon oxide, aluminum oxide, magnesium oxide, boron oxide and zinc oxide.
4. The aluminum-plastic film of claim 3, wherein the nylon composite layer is a co-extruded composite film of nylon and polyethylene terephthalate, the polyethylene terephthalate is an outermost layer of the outer layer, and the mass ratio of the nylon to the polyethylene terephthalate in the co-extruded composite film is 3.5-4.5: 1.
5. The aluminum-plastic film of claim 4, wherein the aluminum alloy foil layer is an aluminum alloy foil with an iron content of 2-5%.
6. The aluminum-plastic film of claim 5, wherein the nylon composite layer has a thickness of 20-40 um, the aluminum alloy foil has a thickness of 40-60 um, the polypropylene composite layer has a thickness of 30-50 um, the polyurethane adhesive layer has a thickness of 5-10 um, and the polyolefin adhesive layer has a thickness of 5-10 um.
7. A method for manufacturing an aluminium-plastic film according to any one of claims 1 to 6, comprising the steps of:
(1) filling nano filler: weighing nano filler and co-polypropylene, adding the nano filler and co-polypropylene into a high-speed mixer, and uniformly stirring at a rotating speed of 250-400 r/min for 10-15 min during mixing;
(2) co-extrusion compounding of the inner layer film: respectively adding polypropylene copolymer filled with nano filler, polypropylene toughened by ultrahigh molecular weight polyethylene and polypropylene copolymer into three charging barrels of an extruder, setting the temperature of the extruder to melt three raw material resins, setting the extrusion melting temperatures of the three materials to be 200-230 ℃, 170-190 ℃ and 180-220 ℃, casting the molten resin onto a cooling roller with a smooth surface through a machine head to rapidly cool the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(3) co-extrusion compounding of the outer layer film: respectively weighing polyethylene glycol terephthalate, a compatibilizer and nylon, respectively adding the polyethylene glycol terephthalate, the compatibilizer and the nylon into two material cylinders of an extruder, setting the extrusion temperature of two groups of extruders to be 250-280 ℃, casting molten resin onto a cooling roller with a smooth surface through a machine head, and rapidly cooling the molten resin into a film, wherein the casting roller temperature of the extruder is 25 ℃, the annealing roller temperature is 40 ℃, and the post-cooling roller temperature is 30 ℃;
(4) plasma treatment of aluminum alloy foil: first using Ar2As working gas, cleaning the surface of the aluminum foil, increasing the plasma power and the processing time, and roughening the surface of the aluminum foil;
(5) and (3) dry compounding of the aluminum plastic film: and respectively coating adhesives on two sides of the aluminum foil after the plasma treatment, and respectively compounding the aluminum foil with the outermost layer film and the innermost layer film.
8. The production method according to claim 7, wherein in the step of plasma-treating the aluminum alloy foil, a discharge power of plasma is 3 to 5kW, a treatment time is 30 to 60s, and Ar is Ar in the surface cleaning treatment2The flow rates of the plasma discharge electrodes are respectively 180-220 sccm, the plasma discharge power is 6-8 kW during the surface roughening treatment, and the treatment time is 100-300 s.
9. The preparation method of the outer layer film according to claim 7, wherein in the co-extrusion compounding step of the outer layer film, the content of the compatibilizer is 4.5-7%, and the compatibilizer comprises maleic anhydride or SEBS (styrene-ethylene-butadiene-styrene) grafted maleic anhydride.
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