WO2020118794A1 - Aluminum plastic film for encapsulating lithium battery and aluminum foil passivating process for aluminum plastic film - Google Patents
Aluminum plastic film for encapsulating lithium battery and aluminum foil passivating process for aluminum plastic film Download PDFInfo
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- WO2020118794A1 WO2020118794A1 PCT/CN2018/125275 CN2018125275W WO2020118794A1 WO 2020118794 A1 WO2020118794 A1 WO 2020118794A1 CN 2018125275 W CN2018125275 W CN 2018125275W WO 2020118794 A1 WO2020118794 A1 WO 2020118794A1
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- Prior art keywords
- aluminum foil
- layer
- aluminum
- passivation
- plastic film
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 97
- 239000011888 foil Substances 0.000 title claims abstract description 78
- 239000002985 plastic film Substances 0.000 title claims abstract description 30
- 229920006255 plastic film Polymers 0.000 title claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 71
- 230000001070 adhesive effect Effects 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 5
- 238000002161 passivation Methods 0.000 claims description 56
- 238000004806 packaging method and process Methods 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000005025 cast polypropylene Substances 0.000 claims description 8
- 239000004840 adhesive resin Substances 0.000 claims description 7
- 229920006223 adhesive resin Polymers 0.000 claims description 7
- 229920006015 heat resistant resin Polymers 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- -1 polyethylene Polymers 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000010790 dilution Methods 0.000 abstract 1
- 239000012895 dilution Substances 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007718 adhesive strength test Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 3
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229940125846 compound 25 Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- 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
- B32B27/32—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
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- 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
Definitions
- the invention relates to the technical field of lithium battery packaging, in particular to an aluminum-plastic film and aluminum-plastic film aluminum foil passivation process for lithium battery packaging.
- the key packaging material of the soft pack lithium battery is an aluminum plastic film.
- the structure is a heat-resistant resin layer, an adhesive layer, an aluminum foil layer, an adhesive resin layer, and a heat seal layer. It must have high heat seal performance, interlayer adhesion performance, Corrosion resistance and ductility after shelling, especially after the shell of aluminum plastic film is stretched during shelling and after long-term electrolyte resistance, the aluminum foil layer and heat seal layer still need to have a high bonding strength.
- the aluminum foil layer still needs to have certain resistance to electrolyte and hydrofluoric acid corrosion, so it is necessary to chemically treat the surface of the aluminum foil layer to make the surface of the aluminum foil layer not only have good corrosion resistance, but also match the adhesive resin layer , Maintain the bonding strength between the aluminum foil layer and the heat seal layer, so the chemical treatment of the surface of the aluminum foil layer, that is, the passivation treatment technology is the key technology of the aluminum plastic film.
- European patent document WO2016/052294 discloses a battery packaging material, but after this packaging material is resistant to electrolyte for a long time, the adhesion between the heat seal layer and the aluminum foil layer is seriously reduced or the two are delaminated, making it difficult to meet the power soft Lithium battery requirements.
- the present invention provides a lithium battery Aluminum plastic film and aluminum plastic film aluminum foil passivation process for packaging.
- a passivation process of aluminum plastic film and aluminum foil for lithium battery packaging characterized in that it includes the following steps:
- step (2) Apply the finished passivation solution product obtained in step (1) to the surface of the aluminum foil through a micro concave roller in an environment of 25 to 35°C;
- step (3) Put the aluminum foil coated with the passivation solution product in step (2) into an oven at 50-80°C.
- the aluminum foil runs in the drying tunnel at a speed of 10m/min to maintain the tension and flatness of the aluminum foil to obtain the passivation. Layer of aluminum foil.
- the coating amount of the finished passivation liquid is 3 to 4.5 g/m2, and the thickness of the passivation layer after baking is ⁇ 1um.
- the mesh number of the micro concave roller is set to 300 to 350 mesh.
- the thickness of the aluminum foil is 20-80um.
- the finished passivation liquid product is set in a closed glue tank during coating to avoid contact of the finished passivation liquid product with air.
- the invention also provides an aluminum-plastic film for lithium battery encapsulation, which includes an outer heat-resistant resin layer, an intermediate aluminum foil layer and an inner heat-sealing layer.
- the heat-resistant resin layer is PA plastic with a thickness of 15 ⁇ m ⁇ 25 ⁇ m
- the aluminum foil layer is an aluminum foil with a passivation layer prepared by the passivation process according to any one of claims 1 to 5, and the heat seal layer is cast polypropylene (CPP film) or cast polymer Ethylene (CPE film) with a thickness of 30 ⁇ m to 80 ⁇ m
- the heat-resistant resin layer and the aluminum foil layer are fixedly connected by an adhesive layer
- the aluminum foil layer and the heat sealing layer are fixedly connected by an adhesive resin layer.
- the adhesive layer is a polyurethane adhesive, and the thickness of the adhesive layer after baking is 3 ⁇ m to 5 ⁇ m.
- the adhesive resin layer is a modified polyolefin adhesive, and the thickness of the adhesive layer after baking is 4 ⁇ m to 7 ⁇ m.
- the process of the present invention adopts a micro concave roller coating process to coat the finished passivation liquid on aluminum foil and dry it in an oven at 50-80°C, which improves the production efficiency of the passivation process, and improves the appearance quality of the aluminum foil layer and Service life
- the passivation liquid product is placed in a closed glue tank, and the passivation liquid product is in contact with air, which improves the resistance of the aluminum foil layer to electrolyte and hydrofluoric acid corrosion;
- the passivation liquid product provided by the process of the present invention improves the adhesion strength of the aluminum plastic film between the aluminum foil layer and the heat seal layer after being resistant to electrolyte and hydrofluoric acid through the adhesive resin layer;
- the aluminum-plastic film provided by the present invention is cross-linked by chemical bonds between layers, and the adhesion between the layers is enhanced, which solves the problem that the adhesion performance of the heat seal layer and the aluminum foil layer is seriously reduced or delaminated after long-term electrolyte resistance.
- a dry thickness of 3 ⁇ m polyurethane adhesive compound 25 ⁇ m PA film is coated on the other side, and a dry thickness of 4 ⁇ m modified polyolefin adhesive compound 40 ⁇ m CPP film is coated to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
- a dry thickness 4 ⁇ m polyurethane adhesive compound 25 ⁇ m PA film is coated on the other side, and a dry thickness 4 ⁇ m modified polyolefin adhesive compound 40 ⁇ m CPP film is coated on the other side to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
- a dry thickness 4 ⁇ m polyurethane adhesive compound 25 ⁇ m PA film is coated on the other side, and a dry thickness 4 ⁇ m modified polyolefin adhesive compound 40 ⁇ m CPP film is coated on the other side to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
- Adhesive strength of aluminum foil layer and heat seal layer cut the finished aluminum plastic film into 15mm wide splines, peel test the aluminum foil and heat seal layer, and record the adhesive strength test data.
- the packaging film is cut into 15mm wide splines and placed in the LiPF6 electrolyte at 85°C for 7 days.
- the aluminum foil and the heat seal layer are peeled off and the adhesive strength test data is recorded .
- Two-seal tensile test take a piece of finished aluminum-plastic film, inject 3 ⁇ 6g of electrolyte after heat-sealing the heavy shell, put it in an oven at 85°C for 7 days, take it out and re-heat-seal it, then cut into 15mm wide splines.
- CPP carries out a peeling test and records the adhesive strength test data.
- Boiling experiment Put the finished aluminum-plastic film into a 60°C water bath and boil for 24 to 72 hours, and observe whether the color of the PA film changes.
- Comparative Example 1 is a sample of existing technology at home and abroad.
- the structure is: PA film 25 ⁇ m/first adhesive layer 3 ⁇ m/aluminum foil layer with passivation layer 40 ⁇ m/second adhesive layer 5 ⁇ m/cast polypropylene 40 ⁇ m.
- the second seal refers to the heat seal layer and heat seal layer of the two aluminum-plastic films after the shell is punched.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
Abstract
Disclosed is an aluminum foil passivating process for an aluminum plastic film used for encapsulating a lithium battery, comprising the following steps: (1) mixing a passivating solution and a diluent in a ratio of (1-4) : (6-9) for dilution to obtain a finished product; (2) coating the finished product obtained in step (1) on the surface of the aluminum foil at 25-35°C using a slightly concave roll with a reverse coating method; (3) placing the aluminum foil coated with the finished product in step (2) into a drying oven at 50-80°C, the aluminum foil being operated in a drying path at a speed of 10m/min to maintain the tension and flatness of the aluminum foil, thereby obtaining an aluminum foil comprising a passivating layer. An aluminum foil layer in the aluminum plastic film for encapsulating a lithium battery is an aluminum foil with a passivating layer prepared by the described passivating process. The described process solves the problem of serious adhesive property degradation or lamination between the aluminum foil layer and the heat sealing layer after long-term electrolyte resistance, thereby prolonging the service life of the pouch lithium battery.
Description
本发明涉及锂电池包装技术领域，尤其涉及一种锂电池封装用铝塑膜及铝塑膜铝箔钝化工艺。The invention relates to the technical field of lithium battery packaging, in particular to an aluminum-plastic film and aluminum-plastic film aluminum foil passivation process for lithium battery packaging.
计算机、通信和消费类电子产品为代表的3C类电子产品带动了软包锂电池行业的快速发展，近两年，新能源汽车的迅猛发展，使得软包锂电池的应用量急剧增长。随着动力汽车的快速发展，软包锂电池各方面的应用研究均成为研究热点。作为软包锂电池关键材料之一的包装材料，如何使动力软包锂电池使用寿命达到10年，是目前锂电池包装材料研究的重要课题。The 3C electronic products represented by computers, communications and consumer electronics products have driven the rapid development of the soft pack lithium battery industry. In the past two years, the rapid development of new energy vehicles has led to a sharp increase in the application of soft pack lithium batteries. With the rapid development of power vehicles, application research in all aspects of soft pack lithium batteries has become a research hotspot. As a packaging material that is one of the key materials of soft pack lithium batteries, how to make the service life of power soft pack lithium batteries reach 10 years is an important topic of current research on lithium battery packaging materials.
软包锂电池关键封装材料是铝塑膜，结构为耐热树脂层、胶粘剂层、铝箔层、粘合树脂层、热封层，其必须具有较高的热封性能、层间粘接性能、耐腐蚀性能及冲壳后的延展性能，特别是冲壳时铝塑膜各层延展后和长时间耐电解液后，铝箔层与热封层间仍需具有较高的粘接强度。并且铝箔层仍需具有一定的耐电解液和耐氢氟酸腐蚀性能，因此需要对铝箔层表面进行化学处理，使铝箔层表面不仅具有良好的耐腐蚀性，同时还与粘合树脂层相匹配，保持铝箔层与热封层的粘接强度，所以铝箔层表面的化学处理即钝化处理技术是铝塑膜的关键技术。The key packaging material of the soft pack lithium battery is an aluminum plastic film. The structure is a heat-resistant resin layer, an adhesive layer, an aluminum foil layer, an adhesive resin layer, and a heat seal layer. It must have high heat seal performance, interlayer adhesion performance, Corrosion resistance and ductility after shelling, especially after the shell of aluminum plastic film is stretched during shelling and after long-term electrolyte resistance, the aluminum foil layer and heat seal layer still need to have a high bonding strength. And the aluminum foil layer still needs to have certain resistance to electrolyte and hydrofluoric acid corrosion, so it is necessary to chemically treat the surface of the aluminum foil layer to make the surface of the aluminum foil layer not only have good corrosion resistance, but also match the adhesive resin layer , Maintain the bonding strength between the aluminum foil layer and the heat seal layer, so the chemical treatment of the surface of the aluminum foil layer, that is, the passivation treatment technology is the key technology of the aluminum plastic film.
欧洲专利文献WO2016/052294公开了一种电池用包装材料，但此包装材料在长期耐电解液后，热封层与铝箔层之间的粘接力严重下降或两者分层，难以满足动力软包锂电池的要求。European patent document WO2016/052294 discloses a battery packaging material, but after this packaging material is resistant to electrolyte for a long time, the adhesion between the heat seal layer and the aluminum foil layer is seriously reduced or the two are delaminated, making it difficult to meet the power soft Lithium battery requirements.
发明内容Summary of the invention
为了解决上述铝箔层在具备长期耐电解液和氢氟酸腐蚀性能的同时，热封层与铝箔层之间不会出现粘接性能严重下降或分层的问题，本发明提供了一种锂电池封装用铝塑膜及铝塑膜铝箔钝化工艺。In order to solve the above problem that the aluminum foil layer has long-term corrosion resistance to electrolyte and hydrofluoric acid, and there is no problem that the adhesion between the heat seal layer and the aluminum foil layer will be seriously reduced or delaminated, the present invention provides a lithium battery Aluminum plastic film and aluminum plastic film aluminum foil passivation process for packaging.
本发明的技术方案是这样实现的：The technical solution of the present invention is implemented as follows:
一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于，包括如下步骤：A passivation process of aluminum plastic film and aluminum foil for lithium battery packaging, characterized in that it includes the following steps:
(1)将钝化液和稀释剂按(1～4)：(6～9)比例稀释后得到钝化液成品；(1) Dilute the passivation solution and diluent at the ratio of (1 to 4): (6 to 9) to obtain the finished passivation solution;
(2)在25～35℃环境中通过微凹辊将步骤(1)得到的钝化液成品涂布到铝箔表面上；(2) Apply the finished passivation solution product obtained in step (1) to the surface of the aluminum foil through a micro concave roller in an environment of 25 to 35°C;
(3)将步骤(2)中涂布了钝化液成品的铝箔放入50～80℃烘箱，该铝箔按照10m/min速度在烘道中运行，保持铝箔的张力及平坦性，得到含有钝化层的铝箔。(3) Put the aluminum foil coated with the passivation solution product in step (2) into an oven at 50-80°C. The aluminum foil runs in the drying tunnel at a speed of 10m/min to maintain the tension and flatness of the aluminum foil to obtain the passivation. Layer of aluminum foil.
上述步骤(1)中的钝化液和稀释剂均为现有技术得到的。The passivation liquid and diluent in the above step (1) are all obtained in the prior art.
进一步的，所述钝化液成品的涂布量为3～4.5g/㎡，钝化层烘烤后厚度＜1um。Further, the coating amount of the finished passivation liquid is 3 to 4.5 g/㎡, and the thickness of the passivation layer after baking is <1um.
进一步的，所述微凹辊目数设为300～350目。Further, the mesh number of the micro concave roller is set to 300 to 350 mesh.
进一步的，所述铝箔的厚度为20～80um。Further, the thickness of the aluminum foil is 20-80um.
进一步的，所述步骤(2)涂布时钝化液成品设置于密闭的胶槽中，可避免钝化液成品与空气接触。Further, in the step (2), the finished passivation liquid product is set in a closed glue tank during coating to avoid contact of the finished passivation liquid product with air.
本发明还提供了一种锂电池封装用铝塑膜，包括外层的耐热树脂层、中间的铝箔层和内层的热封层，所述耐热树脂层为PA塑料，厚度为15μm～25μm，所述铝箔层由权利要求1至5任一项所述的钝化工艺制备而成的带钝化层的铝箔，所述热封层为流延聚丙烯(CPP膜)或流延聚乙烯(CPE膜)，厚度为30μm～80μm，所述耐热树脂层与铝箔层通过胶粘剂层固定连接，所述铝箔层与热封层通过粘合树脂层固定连接。The invention also provides an aluminum-plastic film for lithium battery encapsulation, which includes an outer heat-resistant resin layer, an intermediate aluminum foil layer and an inner heat-sealing layer. The heat-resistant resin layer is PA plastic with a thickness of 15 μm～ 25 μm, the aluminum foil layer is an aluminum foil with a passivation layer prepared by the passivation process according to any one of claims 1 to 5, and the heat seal layer is cast polypropylene (CPP film) or cast polymer Ethylene (CPE film) with a thickness of 30 μm to 80 μm, the heat-resistant resin layer and the aluminum foil layer are fixedly connected by an adhesive layer, and the aluminum foil layer and the heat sealing layer are fixedly connected by an adhesive resin layer.
进一步的，所述胶粘剂层为聚氨酯胶粘剂，烘烤后胶粘剂层厚度为3μm～5μm。Further, the adhesive layer is a polyurethane adhesive, and the thickness of the adhesive layer after baking is 3 μm to 5 μm.
进一步的，所述粘合树脂层为改性聚烯烃胶粘剂，烘烤后胶粘剂层厚度为4μm～7μm。Further, the adhesive resin layer is a modified polyolefin adhesive, and the thickness of the adhesive layer after baking is 4 μm to 7 μm.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明工艺采用微凹辊涂布工艺将钝化液成品涂布于铝箔上，并于50～80℃烘箱内烘干，提高了钝化工艺生产效率，提高了铝箔层的外观质量及使用寿命；1. The process of the present invention adopts a micro concave roller coating process to coat the finished passivation liquid on aluminum foil and dry it in an oven at 50-80°C, which improves the production efficiency of the passivation process, and improves the appearance quality of the aluminum foil layer and Service life
2、本发明工艺将钝化液成品设置于密闭的胶槽中，钝化液成品与空气接触，提高了铝箔层耐电解液和耐氢氟酸腐蚀性能；2. In the process of the present invention, the passivation liquid product is placed in a closed glue tank, and the passivation liquid product is in contact with air, which improves the resistance of the aluminum foil layer to electrolyte and hydrofluoric acid corrosion;
3、本发明工艺提供的钝化液成品，通过粘合树脂层提高了铝塑膜在耐电解液和耐氢氟酸后的铝箔层与热封层间的粘接强度；3. The passivation liquid product provided by the process of the present invention improves the adhesion strength of the aluminum plastic film between the aluminum foil layer and the heat seal layer after being resistant to electrolyte and hydrofluoric acid through the adhesive resin layer;
4、本发明提供的铝塑膜，各层间通过化学键交联，层间粘接力增强，解决了长期耐电解液后热封层与铝箔层粘接性能严重下降或分层的问题。4. The aluminum-plastic film provided by the present invention is cross-linked by chemical bonds between layers, and the adhesion between the layers is enhanced, which solves the problem that the adhesion performance of the heat seal layer and the aluminum foil layer is seriously reduced or delaminated after long-term electrolyte resistance.
下面结合具体实施例对本发明作进一步说明。The present invention will be further described below with reference to specific embodiments.
实施例一：Example one:
将现有钝化液与稀释剂按4：9比例稀释后得到钝化液成品，在25℃环境中通过目数为300的微凹辊将上述钝化液成品涂布到清洗干净的基材厚40μm的铝箔表面上，将涂布了钝化液成品的铝箔放入50℃烘箱，该铝箔按照10m/min速度在烘道中运行，保持铝箔的张力及平坦性，得到干厚0.4μm的铝箔表面钝化层；Dilute the existing passivation liquid and diluent at a ratio of 4:9 to obtain the finished passivation liquid, and apply the finished passivation liquid to the cleaned substrate through a micro concave roller with a mesh number of 300 in a 25°C environment On the surface of the aluminum foil with a thickness of 40 μm, put the aluminum foil coated with the passivation solution into a 50°C oven. The aluminum foil runs in a drying tunnel at a speed of 10 m/min to maintain the tension and flatness of the aluminum foil to obtain a 0.4 μm dry aluminum foil Surface passivation layer;
于上述带钝化层的铝箔一面涂布干厚3μm聚氨酯胶粘剂复合25μmPA薄膜，另一面涂布干厚4μm的改性聚烯烃胶粘剂复合40μmCPP薄膜，得到锂电池包装用铝塑膜，经熟化后检测性能。On one side of the aluminum foil with a passivation layer, a dry thickness of 3 μm polyurethane adhesive compound 25 μm PA film is coated on the other side, and a dry thickness of 4 μm modified polyolefin adhesive compound 40 μm CPP film is coated to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
实施例二：Example 2:
将现有钝化液与稀释剂按2：7比例稀释后得到钝化液成品，在30℃环境中通过目数为320的微凹辊将上述钝化液成品涂布到清洗干净的基材厚40μm的铝箔表面上，将涂布了钝化液成品的铝箔放入60℃烘箱，该铝箔按照10m/min速度在烘道中运行，保持铝箔的张力及平坦性，得到干厚0.2μm的铝箔表面钝化层；Dilute the existing passivation solution and diluent at a ratio of 2:7 to obtain the finished passivation solution, and apply the finished passivation solution to the cleaned substrate through a micro concave roller with a mesh number of 320 at 30°C. On the surface of the aluminum foil with a thickness of 40 μm, put the aluminum foil coated with the passivation solution into a 60°C oven. The aluminum foil runs in a drying tunnel at a speed of 10 m/min to maintain the tension and flatness of the aluminum foil to obtain a 0.2 μm dry aluminum foil Surface passivation layer;
于上述带钝化层的铝箔一面涂布干厚4μm聚氨酯胶粘剂复合25μmPA薄膜，另一面涂布干厚4μm的改性聚烯烃胶粘剂复合40μmCPP薄膜，得到锂电池包装用铝塑膜，经熟化后检测性能。On the one side of the aluminum foil with the passivation layer, a dry thickness 4 μm polyurethane adhesive compound 25 μm PA film is coated on the other side, and a dry thickness 4 μm modified polyolefin adhesive compound 40 μm CPP film is coated on the other side to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
实施例三：Example three:
将现有钝化液与稀释剂按1：6比例稀释后得到钝化液成品，在35℃环境中通过目数为350的微凹辊将上述钝化液成品涂布到清洗干净的基材厚40μm的铝箔表面上，将涂布了钝化液成品的铝箔放入80℃烘箱，该铝箔按照10m/min速度在烘道中运行，保持铝箔的张力及平坦性，得到干厚0.5μm的铝箔表面钝化层；Dilute the existing passivation liquid and diluent at a ratio of 1:6 to obtain the finished passivation liquid, and apply the finished passivation liquid to the cleaned substrate through a micro concave roller with 350 mesh in a 35°C environment On the surface of the aluminum foil with a thickness of 40 μm, put the aluminum foil coated with the passivation solution into an oven at 80°C. The aluminum foil runs in a drying tunnel at a speed of 10 m/min to maintain the tension and flatness of the aluminum foil to obtain an aluminum foil with a thickness of 0.5 μm. Surface passivation layer;
于上述带钝化层的铝箔一面涂布干厚4μm聚氨酯胶粘剂复合25μmPA薄膜，另一面涂布干厚4μm的改性聚烯烃胶粘剂复合40μmCPP薄膜，得到锂电池包装用铝塑膜，经熟化后检测性能。On the one side of the aluminum foil with the passivation layer, a dry thickness 4 μm polyurethane adhesive compound 25 μm PA film is coated on the other side, and a dry thickness 4 μm modified polyolefin adhesive compound 40 μm CPP film is coated on the other side to obtain an aluminum plastic film for lithium battery packaging, which is tested after curing performance.
性能测试：Performance Testing:
1)铝箔层与热封层粘合强度：将成品铝塑膜切成15mm宽样条，对铝箔与热封层进行剥离测试，记录粘合强度检测数据。1) Adhesive strength of aluminum foil layer and heat seal layer: cut the finished aluminum plastic film into 15mm wide splines, peel test the aluminum foil and heat seal layer, and record the adhesive strength test data.
2)二封热封强度：热封条件：180℃，3s，0.4Mpa压力。将15mm宽样条进行剥离测试，记录粘合强度检测数据。2) Two-sealing heat-sealing strength: heat-sealing conditions: 180℃, 3s, 0.4Mpa pressure. The 15mm wide strips were subjected to peel test, and the adhesive strength test data was recorded.
3)铝箔与热封层耐电解液性能：将包装膜切成15mm宽样条，放置到85℃LiPF6电解液中保存7天，对铝箔与热封层进行剥离测试，记录粘合强度检测数据。3) The electrolyte resistance of the aluminum foil and the heat seal layer: the packaging film is cut into 15mm wide splines and placed in the LiPF6 electrolyte at 85°C for 7 days. The aluminum foil and the heat seal layer are peeled off and the adhesive strength test data is recorded .
4)二封拉力测试：取一块成品铝塑膜，重壳热封后注入3～6g电解液，放入85℃烘箱中7天，取出重新热封后切成15mm宽样条，对CPP与CPP进行剥离测试，记录粘合强度检测数据。4) Two-seal tensile test: take a piece of finished aluminum-plastic film, inject 3～6g of electrolyte after heat-sealing the heavy shell, put it in an oven at 85℃ for 7 days, take it out and re-heat-seal it, then cut into 15mm wide splines. CPP carries out a peeling test and records the adhesive strength test data.
5)水煮实验：将成品铝塑膜放入60℃水浴锅中水煮24～72小时，观察其PA薄膜颜色是否有变化。5) Boiling experiment: Put the finished aluminum-plastic film into a 60°C water bath and boil for 24 to 72 hours, and observe whether the color of the PA film changes.
对比例1为国内外现有技术样品，结构为：PA薄膜25μm/第一胶粘剂层3μm/带钝化层的铝箔层40μm/第二胶粘剂层5μm/流延聚丙烯40μm。Comparative Example 1 is a sample of existing technology at home and abroad. The structure is: PA film 25 μm/first adhesive layer 3 μm/aluminum foil layer with passivation layer 40 μm/second adhesive layer 5 μm/cast polypropylene 40 μm.
表1.实施例与对比例1的各性能检测结果。Table 1. Results of performance tests of Examples and Comparative Example 1.
从本发明实施例一、二、三与对比例1相比较，实施例一、二、三的检测性能均有了较大的提升。Compared with Examples 1, 2, and 3 of the present invention and Comparative Example 1, the detection performance of Examples 1, 2, and 3 has been greatly improved.
备注：二封是指冲壳后两层铝塑膜的热封层与热封层。Note: The second seal refers to the heat seal layer and heat seal layer of the two aluminum-plastic films after the shell is punched.
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, and substitutions can be made to these embodiments without departing from the principles and spirit of the present invention And variations, the scope of the invention is defined by the appended claims and their equivalents.
Claims (8)
- 一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于，包括如下步骤：A passivation process of aluminum plastic film and aluminum foil for lithium battery packaging, characterized in that it includes the following steps:(1)将钝化液和稀释剂按(1～4)：(6～9)比例稀释后得到钝化液成品；(1) Dilute the passivation solution and diluent at the ratio of (1 to 4): (6 to 9) to obtain the finished passivation solution;(2)在25～35℃环境中通过微凹辊使用逆涂的方式将步骤(1)得到的钝化液成品涂布到铝箔表面上；(2) Apply the finished passivation solution obtained in step (1) to the surface of the aluminum foil by micro-gravure rolls using reverse coating in an environment of 25 to 35°C;(3)将步骤(2)中涂布了钝化液成品的铝箔放入50～80℃烘箱，该铝箔按照10m/min速度在烘道中运行，保持铝箔的张力及平坦性，得到含有钝化层的铝箔。(3) Put the aluminum foil coated with the passivation solution product in step (2) into an oven at 50-80°C. The aluminum foil runs in the drying tunnel at a speed of 10m/min to maintain the tension and flatness of the aluminum foil to obtain the passivation. Layer of aluminum foil.
- 根据权利要求1所述的一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于：所述钝化液成品的涂布量为3～4.5g/㎡，钝化层烘烤后厚度＜1um。The passivation process of aluminum plastic film and aluminum foil for lithium battery packaging according to claim 1, characterized in that: the coating amount of the finished passivation liquid is 3 to 4.5 g/㎡, and the thickness of the passivation layer after baking ＜1um.
- 根据权利要求2所述的一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于：所述微凹辊目数设为300～350目。The passivation process of an aluminum-plastic film aluminum foil for lithium battery packaging according to claim 2, wherein the mesh number of the micro concave roller is set to 300-350 mesh.
- 根据权利要求1所述的一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于：所述铝箔的厚度为20～80um。The passivation process of aluminum plastic film aluminum foil for lithium battery packaging according to claim 1, wherein the thickness of the aluminum foil is 20-80um.
- 根据权利要求1所述的一种锂电池封装用铝塑膜铝箔钝化工艺，其特征在于：所述步骤(2)涂布时钝化液成品设置于密闭的胶槽中，可避免钝化液成品与空气接触。The passivation process of aluminum-plastic film and aluminum foil for lithium battery packaging according to claim 1, characterized in that: in the step (2), the finished passivation liquid is placed in a closed glue tank during coating to avoid passivation Liquid products come into contact with air.
- 一种锂电池封装用铝塑膜，包括外层的耐热树脂层、中间的铝箔层和内层的热封层，所述耐热树脂层为PA塑料，厚度为15μm～25μm，所述铝箔层由权利要求1至5任一项所述的钝化工艺制备而成的带钝化层的铝箔，所述热封层为流延聚丙烯或流延聚乙烯，厚度为30μm～80μm，所述耐热树脂层与铝箔层通过胶粘剂层固定连接，所述铝箔层与热封层通过粘合树脂层固定连接。An aluminum plastic film for lithium battery packaging includes an outer heat-resistant resin layer, an intermediate aluminum foil layer and an inner heat-sealing layer. The heat-resistant resin layer is PA plastic with a thickness of 15 μm to 25 μm. The aluminum foil The aluminum foil with a passivation layer prepared by the passivation process according to any one of claims 1 to 5, the heat-sealing layer is cast polypropylene or cast polyethylene with a thickness of 30 μm to 80 μm. The heat-resistant resin layer and the aluminum foil layer are fixedly connected by an adhesive layer, and the aluminum foil layer and the heat seal layer are fixedly connected by an adhesive resin layer.
- 根据权利要求6所述的一种锂电池封装用铝塑膜，其特征在于：所述胶粘剂层为聚氨酯胶粘剂，烘烤后胶粘剂层厚度为3μm～5μm。The aluminum-plastic film for lithium battery packaging according to claim 6, wherein the adhesive layer is a polyurethane adhesive, and the thickness of the adhesive layer after baking is 3 μm to 5 μm.
- 根据权利要求6所述的一种锂电池封装用铝塑膜，其特征在于：所述粘合树脂层为改性聚烯烃胶粘剂，烘烤后胶粘剂层厚度为4μm～7μm。The aluminum-plastic film for lithium battery packaging according to claim 6, wherein the adhesive resin layer is a modified polyolefin adhesive, and the thickness of the adhesive layer after baking is 4 μm to 7 μm.
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