CN115195234A - High-barrier aluminum-foil-free soft package lithium battery packaging film and preparation method thereof - Google Patents
High-barrier aluminum-foil-free soft package lithium battery packaging film and preparation method thereof Download PDFInfo
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- CN115195234A CN115195234A CN202210743460.8A CN202210743460A CN115195234A CN 115195234 A CN115195234 A CN 115195234A CN 202210743460 A CN202210743460 A CN 202210743460A CN 115195234 A CN115195234 A CN 115195234A
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- 239000012785 packaging film Substances 0.000 title claims abstract description 38
- 229920006280 packaging film Polymers 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010410 layer Substances 0.000 claims abstract description 98
- 239000011256 inorganic filler Substances 0.000 claims abstract description 35
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 35
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 32
- 230000004888 barrier function Effects 0.000 claims abstract description 31
- 239000012790 adhesive layer Substances 0.000 claims abstract description 28
- 239000004743 Polypropylene Substances 0.000 claims abstract description 19
- -1 polypropylene Polymers 0.000 claims abstract description 17
- 229920001155 polypropylene Polymers 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000003292 glue Substances 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 229920006284 nylon film Polymers 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- OIIYIFJVTVSNLY-UHFFFAOYSA-A octadecalithium hexaphosphate Chemical compound P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+].[Li+] OIIYIFJVTVSNLY-UHFFFAOYSA-A 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
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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
- 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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K9/04—Ingredients treated with organic substances
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- B32B2262/0261—Polyamide fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention provides a high-barrier aluminum-foil-free soft-package lithium battery packaging film which sequentially comprises a supporting layer, a first adhesive layer, a barrier layer, a second adhesive layer and a heat sealing layer from outside to inside; the barrier layer is selected from AlO x NY layer or AlO x -a layer of PET or AlO x -any of the OPP layers; the heat sealing layer is a modified polypropylene film, and the raw materials of the heat sealing layer comprise the following materials in parts by weight: 60-100 parts of copolymerized polypropylene particles; 0-40 parts of propylene-olefin copolymer; 5-20 parts of inorganic filler. The invention also provides a preparation method. The aluminum foil-free structure is designed, so that the cost is reduced, the weight is reduced, and the environment is protected. The polypropylene has good extensibility, when the packaging film structure is applied to a soft package lithium battery, the polypropylene is gradually extended in a stamping stress process, a stress point film is gradually thinned, and the inorganic filler is added into the raw material of the heat sealing layer. The inorganic filler has good resistance to elongation to ensure the integrity of the structural appearance of the packaging film.
Description
Technical Field
The invention relates to the technical field of films, in particular to a high-barrier aluminum-foil-free soft package lithium battery packaging film and a preparation method thereof.
Background
The aluminum plastic film for the soft package lithium battery generally consists of three layers of materials: the aluminum foil comprises an outer layer nylon (NY for short), an intermediate layer aluminum foil (AL for short) and an inner layer polypropylene layer (PP for short), wherein the layers are bonded through adhesive or bonding resin. The nylon layer is used as a supporting layer, plays a role in protecting in the cold stamping process, and is used for placing aluminum foil to break or generate pinholes; the aluminum foil is mainly made of barrier materials, has good water and air blocking functions and prevents the reaction of outside air to the contents of the soft package lithium battery; the PP layer has good heat sealing performance and electrolyte resistance, and the package integrity of the soft package lithium battery is guaranteed. In each layer of material, the weight and cost of the aluminum foil account for more than 40% of the whole packaging material, so how to remove the aluminum foil on the premise of ensuring the barrier property is not changed is one of the research focuses in the industry.
At present, different types of high-barrier coatings are available on the market, such as aluminum plating, aluminum oxide plating, PVDC coating and other materials of different substrates, and the water resistance (WVTR) and oxygen resistance (OTR) of the high-barrier coatings can respectively meet the requirements of less than 0.1 g/(m) 2 *24 hrs) and 0.1 cc/(m) 2 *0.1mpa × 24hrs). However, the soft package lithium battery packaging material needs to be formed by cold stamping in the using process, and after the barrier layer of the material is stamped, the barrier performance of the material is linearly reduced, so that if the barrier material is used simply, the soft package lithium battery packaging material cannot well meet the requirements of application of the soft package lithium battery packaging.
Disclosure of Invention
In order to achieve the above purpose, the invention is realized by the following technical scheme.
The invention aims to provide a high-barrier aluminum-foil-free soft-package lithium battery packaging film which sequentially comprises a supporting layer, a first adhesive layer, a barrier layer, a second adhesive layer and a heat sealing layer from outside to inside; wherein the barrier layer is selected from AlO x NY layer or AlO x -a layer of PET or AlO x -any of the OPP layers;
the heat sealing layer is a modified polypropylene film, and the raw materials of the heat sealing layer comprise the following materials in parts by weight:
60-100 parts of copolymerized polypropylene particles;
0-40 parts of propylene-olefin copolymer;
5-20 parts of inorganic filler.
Preferably, the inorganic filler is selected from at least one of nano alumina, layered montmorillonite, wollastonite and graphene.
Preferably, the mesh number of the inorganic filler is 800 to 1000 meshes.
Preferably, the inorganic filler also comprises 2 to 20 percent of silane coupling agent by weight of the inorganic filler for surface modification of the inorganic filler.
Preferably, the support layer is selected from at least one of a nylon film layer and an NY-PET co-extrusion film layer; the thickness of the supporting layer is 15-35 μm.
Preferably, the thickness of the barrier layer is 10-30 μm; the thickness of the heat sealing layer is 30-100 μm.
Preferably, the first adhesive layer and the second adhesive layer are both selected from a polyurethane glue layer or a polyolefin glue layer.
The second purpose of the invention is to provide a preparation method of the high-barrier aluminum-foil-free soft-package lithium battery packaging film, wherein the preparation of the heat-sealing layer comprises the following steps:
s1, weighing the raw materials in percentage by weight;
s2, sucking the raw materials into a hopper of a double-screw extruder through a vacuum suction machine for melt extrusion;
and S3, forming a film through upward blowing cold and downward blowing cold or performing casting co-extrusion to form a film, thus obtaining the heat seal layer.
Preferably, the length-diameter ratio of the screw of the double-screw extruder is 22-38, and the processing temperature is 130-200 ℃.
Preferably, the method further comprises the step of carrying out surface modification on the inorganic filler, wherein the steps are as follows: the inorganic filler and the silane coupling agent are premixed at normal temperature, then added into a high-speed mixer to be stirred for 15-30min, and dried at 80-100 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a high-barrier aluminum-foil-free soft package lithium battery packaging film, which is designed into an aluminum-foil-free structure, reduces the cost, lightens the weight and is environment-friendly. The polypropylene has good extensibility, after the packaging film structure is applied to the soft-package lithium battery, in the process of stamping stress, the polypropylene is gradually extended, the stress point film is gradually thinned, the heat sealing layer is improved, the inorganic filler is added into the raw materials of the heat sealing layer, and due to the physical separation of the inorganic filler, the gas passing path is increased, so that the separation performance of the heat sealing layer is improved, and in the process of cold stamping and forming after the subsequent soft-package lithium battery is packaged, the packaging film structure is prevented from being too much reduced in separation performance due to stamping, and the packaging use performance of the packaging film structure is not influenced. In addition, the inorganic filler has good resistance to elongation to ensure the integrity of the appearance of the packaging film structure.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood and to be implemented according to the content of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and do not constitute a limitation of the invention. In the drawings:
FIG. 1 is a schematic structural view of a packaging film structure of the present invention;
FIG. 2 is a flow chart of the steps of the preparation method of the present invention.
In the figure:
100. a packaging film structure; 10. a support layer; 20. a first adhesive layer; 30. a barrier layer; 40. a second adhesive layer; 50. and (6) heat sealing the layer.
Detailed Description
The foregoing and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings, which will enable those skilled in the art to practice the present invention with reference to the accompanying specification. In the drawings, the shape and size may be exaggerated for clarity, and the same reference numerals will be used throughout the drawings to designate the same or similar components. In the following description, terms such as center, thickness, height, length, front, back, rear, left, right, top, bottom, upper, lower, and the like are used based on the orientation or positional relationship shown in the drawings. In particular, "height" corresponds to the dimension from top to bottom, "width" corresponds to the dimension from left to right, and "depth" corresponds to the dimension from front to back. These relative terms are for convenience of description and generally are not intended to require a particular orientation. Terms concerning attachments, coupling and the like (e.g., "connected" and "attached") refer to a relationship wherein structures are secured or attached, either directly or indirectly, to one another through intervening structures, as well as both movable or rigid attachments or relationships, unless expressly described otherwise.
The present invention is further described with reference to the accompanying drawings and the detailed description, and it should be noted that, in the case of no conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The invention provides a high-barrier packaging film for a lithium battery without aluminum foil soft package, which comprises a packaging film structure 100, wherein the packaging film structure 100 sequentially comprises a supporting layer 10, a first adhesive layer 20, a barrier layer 30, a second adhesive layer 40 and a heat sealing layer 50 from outside to inside; wherein the barrier layer 30 is selected from AlO x NY layer or AlO x -a layer of PET or AlO x -any of the OPP layers;
the heat sealing layer 50 is a modified polypropylene film, and the raw materials of the heat sealing layer comprise the following materials in parts by weight:
60-100 parts of copolymerized polypropylene particles;
0-40 parts of propylene-olefin copolymer;
5-20 parts of inorganic filler.
In this embodiment, the packaging film structure 100 is designed to be an aluminum foil-free structure, which reduces the cost, reduces the weight and protects the environment. The polypropylene has good extensibility, after the packaging film structure 100 is applied to a soft package lithium battery, in the process of stamping stress, the polypropylene gradually extends, the stress point film becomes thinner gradually, the heat sealing layer 50 is improved, and inorganic filler is added in raw materials of the heat sealing layer, and due to physical separation of the inorganic filler, a gas passing path is increased, so that the separation performance of the heat sealing layer 50 is improved, and in the process of cold stamping and forming after the subsequent soft package lithium battery is packaged, the packaging film structure 100 is prevented from being too much reduced in separation performance due to stamping, and the packaging use performance of the packaging film structure is not affected. In addition, the inorganic filler has good resistance to elongation to ensure the integrity of the appearance of the packaging film structure 100.
In one embodiment, the inorganic filler is selected from at least one of nano alumina, layered montmorillonite, wollastonite, and graphene. The nano aluminum oxide, the layered montmorillonite, the wollastonite and the graphene have good size stability and large specific surface area, and can be better fused with polypropylene particles in double-screw processing. In the polypropylene film, the addition of the nano material or the layered material has good barrier property, and the process path of gas passing through the film is improved.
Furthermore, the mesh number of the inorganic filler is 800-1000 meshes, and the particle size distribution is more uniform.
In one embodiment, the inorganic filler further comprises 2-20% of silane coupling agent by weight of the inorganic filler for surface modification of the inorganic filler. Specifically, the surface modification is carried out on the inorganic filler through the silane coupling agent, the agglomeration phenomenon of the inorganic filler is improved, and the inorganic filler can be uniformly dispersed during melt extrusion to form good physical barrier.
In one embodiment, the support layer 10 is at least one selected from a nylon film layer, a NY-PET co-extruded film layer; the thickness of the support layer 10 is 15-35 μm.
In one embodiment, the barrier layer 30 is 10-30 μm thick; the thickness of the heat-sealing layer 50 is 30-100 μm.
Further, the barrier properties of the barrier layer 30 provide a water blocking WVTR of less than 0.1 g/(m) 2 *24 hrs) and oxygen blocking OTR performance of less than 0.1 g/(m) 2 *24 hrs) and 0.1 cc/(m) 2 *0.1MPa*24hrs)。
In one embodiment, the first adhesive layer 20 and the second adhesive layer 40 are both selected from a polyurethane glue layer or a polyolefin glue layer.
The invention also provides a preparation method of the high-barrier aluminum-foil-free soft-package lithium battery packaging film, as shown in fig. 2, the preparation of the heat sealing layer 50 comprises the following steps:
s1, weighing the raw materials in percentage by weight;
s2, sucking the raw materials into a hopper of a double-screw extruder through a vacuum suction machine for melt extrusion;
and S3, forming a film through upward air blowing and downward air blowing, or forming a film through casting and co-extrusion to obtain the heat seal layer.
In this embodiment, the heat-sealing layer 50 has a simple processing process and is easy to operate.
Furthermore, the length-diameter ratio of the screw of the double-screw extruder is 22-38, and the processing temperature is 130-200 ℃.
Further, the method also comprises the step of carrying out surface modification on the inorganic filler, and the steps are as follows: the inorganic filler and the silane coupling agent are premixed at normal temperature, then added into a high-speed mixer to be stirred for 15-30min, and dried at 80-100 ℃.
Further, step S2 further includes the steps of: the surface of the film is subjected to corona treatment at 2000-4000 Hz.
The following is set forth in specific examples, which should be understood as being for illustrative purposes only and not to be construed as limiting the invention in any way.
Example 1
The invention provides a high-barrier aluminum-foil-free soft-package lithium battery packaging film which sequentially comprises a supporting layer 10, a first adhesive layer 20, a barrier layer 30, a second adhesive layer 40 and a heat sealing layer 50 from outside to inside;
wherein the supporting layer 10 is NY25, and the barrier layer 30 is AlO x -NY30；
The raw materials of the heat sealing layer 50 comprise 100 parts by weight of CPP40 and 20 parts by weight of nano-alumina; the nano alumina is subjected to surface modification by a silane coupling agent accounting for 2-20% of the weight of the nano alumina; the thickness of the heat-seal layer 50 is 50 μm;
the first adhesive layer 20 and the second adhesive layer 40 are polyurethane glue layers.
Example 2
The invention provides a high-barrier aluminum-foil-free soft-packaged lithium battery packaging film which sequentially comprises a supporting layer 10, a first adhesive layer 20, a barrier layer 30, a second adhesive layer 40 and a heat sealing layer 50 from outside to inside;
wherein the supporting layer 10 is NY25, and the barrier layer 30 is AlO x -PET25；
The raw materials of the heat sealing layer 50 comprise 100 parts by weight of CPP40 and 20 parts by weight of nano-alumina; the nano aluminum oxide is subjected to surface modification by a silane coupling agent accounting for 2-20% of the weight of the nano aluminum oxide; the thickness of the heat-seal layer 50 is 50 μm;
the first adhesive layer 20 and the second adhesive layer 40 are polyurethane glue layers.
Example 3
The invention provides a high-barrier aluminum-foil-free soft-package lithium battery packaging film which sequentially comprises a supporting layer 10, a first adhesive layer 20, a barrier layer 30, a second adhesive layer 40 and a heat sealing layer 50 from outside to inside;
wherein the supporting layer 10 is NY25, and the barrier layer 30 is AlO x -NY30；
The raw materials of the heat-sealing layer 50 comprise 100 parts by weight of CPP40, 10 parts by weight of nano-alumina and 10 parts by weight of layered montmorillonite; the nano aluminum oxide is subjected to surface modification by a silane coupling agent accounting for 2-20% of the weight of the nano aluminum oxide; the thickness of the heat-seal layer 50 is 50 μm;
the first adhesive layer 20 and the second adhesive layer 40 are polyurethane glue layers.
Comparative example 1
According to a commercial product, the packaging film sequentially comprises a PA layer, an AL layer and a CPP layer from outside to inside, and the thicknesses of the PA layer, the AL layer and the CPP layer are respectively 25 micrometers, 40 micrometers and 40 micrometers.
Comparative example 2
The packaging film sequentially comprises an NY25 layer, a polyurethane glue layer and AlO from outside to inside x NY30 layer, polyurethane glue layer and CPP50 layer.
Comparative example 3
The packaging film comprises an NY25 layer, a polyurethane glue layer, an NY30 layer, a polyurethane glue layer and a CPP50 layer from outside to inside in sequence; the CPP50 layer has a thickness of 50 μm.
Example 4
Examples 1 to 3 and comparative examples 1 to 3 were subjected to barrier property tests in which oxygen and water blocking tests were conducted in accordance with ASTM F1249-90, ASTM D3985-95.
The test results are shown in table one.
Watch 1
Typical lithium battery aluminum plastic films have barrier requirements: the WVTR and the OTR can respectively meet the requirements of less than 0.1 g/(m) 2 *24 hrs) and 0.1 cc/(m) 2 *0.1mpa × 24hrs). As can be seen from Table one, comparative example 1 is a normal commercial product, using 40 μm thick aluminumThe foils, the embodiment of the invention, the embodiment 2 and the embodiment 3 have the same barrier property to the standard commercial products, the cost is reduced, and the barrier property is not obviously reduced after stamping.
The punching performance tests of examples 1 to 3 and comparative examples 1 to 3 were carried out, and the product was judged for when the bubble was broken by using a mold size of 50mm × 80mm.
The electrolyte resistance test was performed for examples 1 to 3 and comparative examples 1 to 3, and the film was put into a 1mol/L carbonate solution of lithium hexaphosphate, to which 2000ppm of water was additionally added. Soaking in 90 deg.C environment for 7 days, and observing whether there is delamination.
The results of the stamping performance test and the electrolyte resistance test are shown in the second table.
Watch two
As can be seen from table two, examples 1, 2, and 3 have good punching press performance and electrolyte resistance.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; one of ordinary skill in the art can readily practice the present invention as illustrated and described herein with reference to the accompanying drawings; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A high-barrier aluminum-foil-free soft-packaged lithium battery packaging film is characterized by sequentially comprising a supporting layer (10), a first adhesive layer (20), a barrier layer (30), a second adhesive layer (40) and a heat sealing layer (50) from outside to inside; wherein the barrier layer (30) is selected fromAlO x NY layer or AlO x -a layer of PET or AlO x -any of the OPP layers;
the heat sealing layer (50) is a modified polypropylene film, and the raw materials of the heat sealing layer comprise the following materials in parts by weight:
60-100 parts of copolymerized polypropylene particles;
0-40 parts of propylene-olefin copolymer;
5-20 parts of inorganic filler.
2. The high-barrier aluminum-foil-free soft-pack lithium battery packaging film as claimed in claim 1, wherein the inorganic filler is at least one selected from nano alumina, layered montmorillonite, wollastonite and graphene.
3. The high-barrier aluminum-foil-free soft-package lithium battery packaging film as claimed in claim 1, wherein the mesh number of the inorganic filler is 800-1000 meshes.
4. The high-barrier aluminum-foil-free soft-package lithium battery packaging film as claimed in claim 2, further comprising a silane coupling agent in an amount of 2-20% by weight of the inorganic filler for surface modification of the inorganic filler.
5. The high-barrier aluminum-foil-free soft-package lithium battery packaging film as claimed in claim 1, wherein the support layer (10) is at least one selected from a nylon film layer and an NY-PET co-extrusion film layer; the thickness of the support layer (10) is 15-35 μm.
6. The high-barrier aluminum-foil-free soft-packed lithium battery packaging film as claimed in claim 1, wherein the thickness of the barrier layer (30) is 10-30 μm; the thickness of the heat sealing layer (50) is 30-100 mu m.
7. The high-barrier packaging film for lithium ion batteries without aluminum foil and soft packages as claimed in claim 1, wherein the first adhesive layer (20) and the second adhesive layer (40) are both selected from polyurethane glue layers or polyolefin glue layers.
8. The method for preparing the packaging film of the high-barrier lithium battery pack without aluminum foil according to any one of claims 1 to 7, wherein the preparation of the heat sealing layer (50) comprises the following steps:
s1, weighing the raw materials in percentage by weight;
s2, sucking the raw materials into a hopper of a double-screw extruder through a vacuum suction machine for melt extrusion;
and S3, forming a film through upward air blowing and downward air blowing, or forming a film through casting and co-extrusion to obtain the heat seal layer.
9. The method of claim 8, wherein the twin-screw extruder has a screw length-diameter ratio of 22 to 38 and a processing temperature of 130 to 200 ℃.
10. The method according to claim 8, further comprising surface-modifying the inorganic filler by: the inorganic filler and the silane coupling agent are premixed at normal temperature, then added into a high-speed mixer to be stirred for 15-30min, and dried at 80-100 ℃.
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