CN105584151A - High-barrier and high-acid-resisting aluminum-plastic film and preparation method thereof - Google Patents
High-barrier and high-acid-resisting aluminum-plastic film and preparation method thereof Download PDFInfo
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- CN105584151A CN105584151A CN201510915853.2A CN201510915853A CN105584151A CN 105584151 A CN105584151 A CN 105584151A CN 201510915853 A CN201510915853 A CN 201510915853A CN 105584151 A CN105584151 A CN 105584151A
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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
- 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
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/32—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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0682—Silicides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/46—Sputtering by ion beam produced by an external ion source
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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
- B32B2439/00—Containers; Receptacles
Abstract
The invention relates to a high-barrier and high-acid-resisting aluminum-plastic film. The high-barrier and high-acid-resisting aluminum-plastic film sequentially comprises a modified polypropylene layer, a polypropylene and cycloolefin copolymer co-extrusion layer, a plasma treatment layer, an adhesive layer, a nano silicified layer, a nano titanized layer, an aluminum foil layer, a passivation layer, an adhesive layer, a plasma treatment layer, a polypropylene and cycloolefin copolymer co-extrusion layer and a nylon layer from inside to outside. A layer of polypropylene and cycloolefin copolymer co-extrudate is added to the inner polypropylene layer, a layer of polypropylene and cycloolefin copolymer co-extrudate is added to the outer nylon layer, and therefore the barrier property of the inner layer can be improved. Meanwhile, a titanium compound and silicide are successively deposited on the surface of aluminum foil in the aluminum foil layer through the double-cathode plasma sputtering deposition technology, the wear resisting and corrosion resisting performance of the aluminum foil can be effectively improved, and the high-barrier and high-acid-resisting aluminum-plastic film is excellent in performance and can be applied to polymer lithium ion batteries.
Description
Technical field
The present invention relates to battery packaging material field, particularly high anti-acid aluminum plastic film of a kind of high-barrier and preparation method thereof.
Background technology
Lithium ion battery because it is lightweight, the advantage of capacity large, have extended cycle life (being greater than 1000 times) and memory-less effect is very soon at the battery applications such as mobile phone, notebook computer field Quick Extended, due to the unique advantage of lithium ion battery, apply to some extent at electrokinetic cell and energy-storage battery field simultaneously.
Lithium ion battery can be divided into duricrust battery and polymer battery, because polymer lithium ion battery internal does not have movably electrolyte, battery can be made sheet and various shape as thin as a wafer simultaneously, even monolithic battery can accomplish that 0.6mm is thick, thereby to battery lightweight, small quantization or cell shapes is required to strict application, polymer battery has its unique advantage.
The erosion of water, the oxygen etc. that the flexible package aluminum plastic film of polymer battery application can intercept environment to battery electrolyte inside, protection battery electrolyte stable, extends service life of battery. owing to containing multiple organic solvent and lithium salts in polymer Li-ion battery, as ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), dimethoxy-ethane (DME), dimethyl carbonate (DMC), lithium hexafluoro phosphate (LiPF6), hexafluoroarsenate lithium (LiASF6) etc., these solvents have polarity and the strong feature of permeability, lithium salts in battery is very easily hydrolyzed simultaneously, chance water can produce rapidly hydrofluoric acid and other gases of severe corrosive, cause battery air-blowing, cycle life declines and other electrical property (capacity, insulating properties etc.) reduce, even cause battery rapid failure, therefore the barrier and stable operation and the permanent use of acidproof dissolubility to polymer Li-ion battery that how to improve aluminum plastic film are all very important.
Summary of the invention
For solving the problems of the technologies described above, the invention provides high anti-acid aluminum plastic film of a kind of high-barrier and preparation method thereof, this aluminum plastic film has excellent barrier property, heat sealability, ductility and decay resistance.
Technical scheme of the present invention is: high anti-acid aluminum plastic film of a kind of high-barrier and preparation method thereof. this aluminum plastic film comprises modified polypropene layer, polypropylene and cycloolefin analog copolymer coextruded layer, plasma treatment layer, adhesive layer, nanometer disilicide layer, nanometer titanizing layer, aluminium foil layer, passivation layer, adhesive layer, plasma treatment layer, polypropylene and cycloolefin analog copolymer coextruded layer, nylon layer, it is followed successively by modified polypropene layer from inside to outside, polypropylene and cycloolefin analog copolymer coextruded layer, plasma treatment layer, adhesive layer, nanometer disilicide layer, nanometer titanizing layer, aluminium foil layer, passivation layer, adhesive layer, plasma treatment layer, polypropylene and cycloolefin analog copolymer coextruded layer, nylon layer.
As a preferred embodiment of the present invention, the material of described nanometer disilicide layer is Cr3Si、Cr-Si-N、NiSi2/Ti5Si3In one or more.
As a preferred embodiment of the present invention, the thickness of described nanosilicon layer is 0.1-
100nm。
As a preferred embodiment of the present invention, the material of described nanometer titanizing layer is Ti5Si3、TiB、TiB2、TiO2In one or more.
As a preferred embodiment of the present invention, the thickness of described nanometer titanizing layer is 0.1-
100nm。
A preparation method for the high anti-acid aluminum plastic film of high-barrier, comprises the following steps:
1) adopt twin cathode plasma sputtering deposition technique at aluminium foil surface successively titanium deposition compound and silicide, the corresponding nylon composite surface of aluminium foil carries out chromaking processing, finally makes aluminium foil surface form many nanometers structural material;
2) modified polypropene and polypropylene and cycloolefin analog copolymer co-extrusion thing form layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
3) nylon and polypropylene and cycloolefin analog copolymer co-extrusion thing are formed to layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
4) modified polypropene layer laminates, many nanostructured layers aluminum foil material, modification of nylon layer laminates are carried out to lamination by adhesive compound, obtain clad aluminum plastic film;
5) to this aluminum plastic film be dried, slaking, rolling, obtain finished product composite packaging aluminum plastic film.
Adopt after technique scheme, the invention has the beneficial effects as follows: first, in this composite membrane, polypropylene layer internal layer and outer nylon layer internal layer increase one deck polypropylene and cycloolefin analog copolymer co-extrusion thing can improve the barrier property of internal layer; Secondly, in this composite membrane, aluminium foil layer adopts twin cathode plasma sputtering deposition technique at aluminium foil surface successively titanium deposition compound and silicide, can effectively improve the wear-resisting and decay resistance of aluminium foil, thereby realize the comprehensive raising of barrier and the decay resistance of aluminum plastic film.
Brief description of the drawings
Fig. 1 is structural representation of the present invention.
1. modified polypropene layer; 2. polypropylene and cycloolefin analog copolymer coextruded layer 3. plasma treatment layers; 4. adhesive layer; 5. nanometer disilicide layer; 6. nanometer titanizing layer; 7. aluminium foil layer; 8. passivation layer; 9. adhesive layer; 10. plasma treatment layer; 11. polypropylene and cycloolefin analog copolymer coextruded layer; 12. nylon layers.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further illustrate the present invention.
Embodiment
As shown in Figure 1, the invention provides high anti-acid aluminum plastic film of a kind of high-barrier and preparation method thereof, comprise 1. modified polypropene layers, 2. polypropylene and cycloolefin analog copolymer coextruded layer, 3. plasma treatment layer, 4. adhesive layer, 5. nanometer disilicide layer, 6. nanometer titanizing layer, 7. aluminium foil layer, 8. passivation layer, 9. adhesive layer, 10. plasma treatment layer, 11. polypropylene and cycloolefin analog copolymer coextruded layer, 12. nylon layers.
The material of described modified polypropene layer 1 is polypropylene and poly mixture, and wherein the accounting of polyethylene in gross weight is 10-30%, and rete is thick is 5-30 μ m.
The material of described polypropylene and cycloolefin analog copolymer coextruded layer 2 and layer 11 is that one or more in polypropylene and cyclopentene, ENB, dimethano octahydro naphthalene are carried out co-extrusion, wherein the accounting of cycloolefin analog copolymer in gross weight is 10-30%, and rete is thick is 5-30 μ m.
Described plasma treatment layer 3 and plasma treatment layer 10 adopt the one in air, oxygen, argon gas or ammonia to process.
Described adhesive layer 4 is chosen as one or more combinations in monocomponent polyurethane adhesive, bi-component polyurethane adhesive, polyacrylic resin adhesive, polyvinyl acetate adhesive, urea-formaldehyde resin adhesive, epoxyn.
The material of described nanometer disilicide layer 5 is Cr3Si、Cr-Si-N、NiSi2/Ti5Si3In one or more.
The thickness of described nanosilicon layer 5 is 0.1-100nm.
The material of described nanometer titanizing layer 6 is Ti5Si3、TiB、TiB2、TiO2In one or more.
The thickness of described nanometer titanizing layer 6 is 0.1-100nm.
The thickness of described aluminium foil layer 7 is 30-70 μ m.
The thickness of described aluminium foil passivation layer 8 is 0.1-100nm, and the passivation mode of employing is one or more in potassium chromate, potassium bichromate or chromic anhydride chemical oxidation.
The thickness of nylon layer is 30-70 μ m.
A preparation method for the high anti-acid aluminum plastic film of high-barrier, comprises the following steps:
1) adopt twin cathode plasma sputtering deposition technique at aluminium foil surface successively titanium deposition compound and silicide, the corresponding nylon composite surface of aluminium foil carries out chromaking processing, finally makes aluminium foil surface form many nanometers structural material;
2) modified polypropene and polypropylene and cycloolefin analog copolymer co-extrusion thing form layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
3) nylon and polypropylene and cycloolefin analog copolymer co-extrusion thing are formed to layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
4) modified polypropene layer laminates, many nanostructured layers aluminum foil material, modification of nylon layer laminates are carried out to lamination by adhesive compound, obtain clad aluminum plastic film;
5) to this aluminum plastic film be dried, slaking, rolling, obtain finished product composite packaging aluminum plastic film.
Product of the present invention reaches following index through measuring:
1. peel strength test: electrolyte soaks 85 DEG C, 7 days, and film interlaminar strength is more than or equal to 8N/15mm.
2. permeability resistance test: soak in the water of 60 DEG C 14 days, without layering, changes in weight is less than 0.05 gram.
3. deep drawability test, more than the deep-draw degree of depth reaches 6mm.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. the high anti-acid aluminum plastic film of high-barrier, it is characterized in that, modified polypropene layer, the first polypropylene and cycloolefin analog copolymer coextruded layer, the first plasma treatment layer, the first adhesive layer, nanometer disilicide layer, nanometer titanizing layer, aluminium foil layer, passivation layer, the second adhesive layer, the second plasma treatment layer, the second polypropylene and cycloolefin analog copolymer coextruded layer, nylon layer, it is followed successively by modified polypropene layer from inside to outside, the first polypropylene and cycloolefin analog copolymer coextruded layer, the first plasma treatment layer, the first adhesive layer, nanometer disilicide layer, nanometer titanizing layer, aluminium foil layer, passivation layer, the second adhesive layer, the second plasma treatment layer, the second polypropylene and cycloolefin analog copolymer coextruded layer, nylon layer.
2. according to the high anti-acid aluminum plastic film of the high-barrier described in claim 1, it is characterized in that, the material of described nanometer disilicide layer is Cr3Si、Cr-Si-N、NiSi2/Ti5Si3In one or more.
3. according to the high anti-acid aluminum plastic film of the high-barrier described in claim 2, it is characterized in that, the thickness of described nanosilicon layer is 0.1-100nm.
4. according to the high anti-acid aluminum plastic film of the high-barrier described in claim 1, it is characterized in that, the material of described nanometer titanizing layer is Ti5Si3、TiB、TiB2、TiO2In one or more.
5. according to the high anti-acid aluminum plastic film of the high-barrier described in claim 4, it is characterized in that, the thickness of described nanometer titanizing layer is 0.1-100nm.
6. a preparation method who prepares the high anti-acid aluminum plastic film of high-barrier described in claim 1~5 any one, is characterized in that, comprises the following steps:
1) adopt twin cathode plasma sputtering deposition technique at aluminium foil surface successively titanium deposition compound and silicide, the corresponding nylon composite surface of aluminium foil carries out chromaking processing, finally makes aluminium foil surface form many nanometers structural material;
2) modified polypropene and polypropylene and cycloolefin analog copolymer co-extrusion thing form layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
3) nylon and polypropylene and cycloolefin analog copolymer co-extrusion thing are formed to layer laminates and polypropylene and cycloolefin analog copolymer co-extrusion object plane are carried out to Cement Composite Treated by Plasma;
4) modified polypropene layer laminates, many nanostructured layers aluminum foil material, modification of nylon layer laminates are carried out to lamination by adhesive compound, obtain clad aluminum plastic film;
5) to this aluminum plastic film be dried, slaking, rolling, obtain finished product composite packaging aluminum plastic film.
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Cited By (6)
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CN106450046A (en) * | 2016-08-30 | 2017-02-22 | 无锡华盈锂能新材有限公司 | Water-resistant and anti-flatulence aluminum-plastic film for packaging lithium battery and preparation method of water-resistant and anti-flatulence aluminum-plastic film |
CN109263220A (en) * | 2018-11-02 | 2019-01-25 | 苏州锂盾储能材料技术有限公司 | Nonpolar physics anchoring method polymer soft-package battery aluminum plastic film and its manufacturing method |
CN110239194A (en) * | 2019-07-15 | 2019-09-17 | 哈尔滨工业大学 | A kind of preparation method of high Nb containing TiAl based alloy material |
CN114474926A (en) * | 2021-12-29 | 2022-05-13 | 深圳市力合科创股份有限公司 | Composite plastic hose |
CN114472108A (en) * | 2021-12-17 | 2022-05-13 | 惠州万极新能源材料有限公司 | Control process for residual solvent in aluminum-plastic film production |
CN114843664A (en) * | 2022-03-29 | 2022-08-02 | 佛山市中技烯米新材料有限公司 | Power battery aluminum plastic film |
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CN204558551U (en) * | 2015-02-06 | 2015-08-12 | 江阴骏驰光电科技有限公司 | A kind of lithium battery flexible packaging aluminum plastic film |
CN104966800A (en) * | 2015-07-13 | 2015-10-07 | 苏州锂盾储能材料技术有限公司 | Functional composite packaging aluminum plastic film for lithium battery |
CN205542907U (en) * | 2015-12-12 | 2016-08-31 | 苏州锂盾储能材料技术有限公司 | High resistant separates high acidproof type plastic -aluminum membrane |
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JP2015051525A (en) * | 2013-09-05 | 2015-03-19 | 出光ユニテック株式会社 | Biaxially stretched nylon film, laminated film, laminated packaging material, battery, and method for producing biaxially stretched nylon film |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106450046A (en) * | 2016-08-30 | 2017-02-22 | 无锡华盈锂能新材有限公司 | Water-resistant and anti-flatulence aluminum-plastic film for packaging lithium battery and preparation method of water-resistant and anti-flatulence aluminum-plastic film |
CN109263220A (en) * | 2018-11-02 | 2019-01-25 | 苏州锂盾储能材料技术有限公司 | Nonpolar physics anchoring method polymer soft-package battery aluminum plastic film and its manufacturing method |
CN110239194A (en) * | 2019-07-15 | 2019-09-17 | 哈尔滨工业大学 | A kind of preparation method of high Nb containing TiAl based alloy material |
CN110239194B (en) * | 2019-07-15 | 2021-03-12 | 哈尔滨工业大学 | Preparation method of high Nb-TiAl alloy material |
CN114472108A (en) * | 2021-12-17 | 2022-05-13 | 惠州万极新能源材料有限公司 | Control process for residual solvent in aluminum-plastic film production |
CN114474926A (en) * | 2021-12-29 | 2022-05-13 | 深圳市力合科创股份有限公司 | Composite plastic hose |
CN114843664A (en) * | 2022-03-29 | 2022-08-02 | 佛山市中技烯米新材料有限公司 | Power battery aluminum plastic film |
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