CN117328111A - Composite aluminum foil and preparation method thereof - Google Patents
Composite aluminum foil and preparation method thereof Download PDFInfo
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- CN117328111A CN117328111A CN202311634160.7A CN202311634160A CN117328111A CN 117328111 A CN117328111 A CN 117328111A CN 202311634160 A CN202311634160 A CN 202311634160A CN 117328111 A CN117328111 A CN 117328111A
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- polymer substrate
- conductive layer
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 108
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000011888 foil Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 87
- 238000009713 electroplating Methods 0.000 claims abstract description 33
- 238000007772 electroless plating Methods 0.000 claims abstract description 25
- 238000003486 chemical etching Methods 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 238000000151 deposition Methods 0.000 claims abstract description 15
- 239000004020 conductor Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 43
- 238000007747 plating Methods 0.000 claims description 43
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- FQERWQCDIIMLHB-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CC[NH+]1CN(C)C=C1 FQERWQCDIIMLHB-UHFFFAOYSA-N 0.000 claims description 19
- -1 polyethylene terephthalate Polymers 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920001955 polyphenylene ether Polymers 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000005030 aluminium foil Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000007788 roughening Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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 & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a composite aluminum foil and a preparation method thereof. The preparation method of the composite aluminum foil comprises the following steps: providing a polymer substrate, and carrying out surface modification on at least one surface of the polymer substrate through a chemical etching solution to obtain a surface modified polymer substrate; coating at least one surface of the surface modified polymer substrate with a conductive material by electroless plating or coating to obtain a conductive layer coated polymer substrate; and placing the polymer substrate covered with the conductive layer in ionic liquid, and depositing an aluminum layer on the surface of the conductive layer by electroplating to obtain the composite aluminum foil. The preparation method of the composite aluminum foil has the advantages of low production cost, high yield and high production efficiency.
Description
Technical Field
The invention relates to the technical field of composite current collector production, in particular to a composite aluminum foil and a preparation method thereof, and more particularly relates to a method for preparing the composite aluminum foil based on an electro-aluminum plating technology and the composite aluminum foil prepared by the method.
Background
The anode composite current collector of the lithium ion battery is a composite material with a structure of aluminum-high polymer material-aluminum, and the material has the advantages of improving the safety, the energy density and the cycle life of the lithium ion battery, so the anode composite current collector is widely paid attention to the field of the lithium ion battery. At present, the preparation of the composite material mainly comprises the step of depositing an aluminum layer with a certain thickness on the upper surface and the lower surface of a high polymer substrate by a Physical Vapor Deposition (PVD) method, so that the sheet resistance of the aluminum layer reaches the standard required by a secondary battery.
However, the existing composite aluminum foil current collector production process has limitations. Physical vapor deposition has the technical characteristics of high temperature, and the polymer base material is easy to generate deformation, dissolution, bubbling and other phenomena, so that the quality of a current collector product is greatly influenced, and the production yield is low. In addition, vapor deposition generally requires the use of large equipment and a relatively high energy supply, and is therefore costly to produce. In addition, the vapor deposition process is slow in running speed, and the production efficiency is low.
In conclusion, development of a novel composite aluminum foil current collector preparation technology with high production efficiency, low production cost and excellent product quality is in need of pushing.
Disclosure of Invention
The invention aims to provide a preparation method of a composite aluminum foil and the composite aluminum foil prepared by the method, so as to solve the technical problems of low yield, high cost, low efficiency and the like in the production of the known composite aluminum foil in the prior art.
In order to achieve the above object, according to one aspect of the present disclosure, there is provided a method for preparing a composite aluminum foil, comprising the steps of: step S1: pretreatment of a polymer substrate: providing a polymer substrate, and carrying out surface modification on at least one surface of the polymer substrate through a chemical etching solution to obtain a surface modified polymer substrate, wherein the chemical etching solution comprises one or more of sulfuric acid, potassium permanganate, sodium hydroxide, potassium dichromate, chloric acid, nitric acid and hydrogen peroxide; step S2: preparing a conductive layer: coating at least one surface of the surface modified polymer substrate with a conductive material by electroless plating or coating to obtain a conductive layer coated polymer substrate; step S3: plating an aluminum layer: and (3) placing the polymer substrate covered with the conductive layer in an ionic liquid, and depositing an aluminum layer on the surface of the conductive layer through electroplating to obtain the composite aluminum foil, wherein the ionic liquid comprises anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, and the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 1-3:1.
Further, in step S1, the temperature of the pretreatment of the polymer substrate is 18-60 ℃ and the treatment time is 10-150S; in the step S2, the temperature of the covering conductive layer is 18-60 ℃ and the covering time is 40-300S; and in the step S3, the plating temperature of the aluminum layer is 18-60 ℃ and the plating time is 5-15 min.
Further, in step S1, the polymer substrate is one or more selected from polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polyamide, polyimide, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, and polyethylene glycol.
Further, in step S2, the conductive material is one or more selected from gold, nickel, aluminum, copper, silver, carbon, and graphene.
Further, in step S3,in step S3, electroplating is performed at a gradually increasing current density, and the current density is controlled to be 4-5A/(dm) 2 S) from 0 to 1.0A/dm 2 The initial value in the range is raised to 1-50A/dm 2 。
Further, in step S2, electroless plating solutions used in electroless plating of the conductive layer include chloroauric acid, sodium carbonate, and formaldehyde, or nickel sulfate, sodium hypophosphite, trisodium citrate, and sodium acetate; the conductive paint used in the coating of the conductive layer includes silver, graphene, or carbon.
Further, in the composite aluminum foil, the thickness D1 of the polymer base material satisfies: 1. d1 is less than or equal to 20 mu m; the thickness D2 of the conductive layer satisfies: 10 nm is less than or equal to D2 and less than or equal to 1000 nm; the thickness D3 of the aluminum layer satisfies: 1. d3 is less than or equal to 10 mu m.
Further, the process is carried out continuously or discontinuously.
Further, steps S1, S2 and S3 are continuously performed in a roll-to-roll manner, and the winding speeds of steps S1, S2 and S3 are each in the range of 1-50 m/min and the winding speeds of the three are the same.
According to another aspect of the present disclosure, there is provided a composite aluminum foil produced by any one of the above methods.
As described above, the known method for manufacturing the composite aluminum foil has technical problems of low production yield, high cost, low efficiency, and the like. According to the technical scheme of the disclosure, a method for preparing a composite aluminum foil is provided, wherein a polymer substrate is pretreated by adopting a chemical etching solution before electroless plating or coating of a conductive layer and electroplating of an aluminum layer, so that a roughening effect is achieved on the surface of the substrate of an organic polymer, hydrophilic groups are generated on the surface of the polymer substrate, and therefore, the interfacial binding force between the organic polymer substrate and the conductive layer and the aluminum layer which are plated or coated later is improved.
The method of the invention adopts a specific chemical etching solution to pretreat and modify the surface of the polymer substrate, thereby coarsening and activating the surface of the substrate. And then growing a conductive layer on the upper and/or lower surfaces of the polymer substrate by means of electroless plating or coating, thereby enabling the polymer substrate to meet electroplating conditions. And then depositing an aluminum layer on the surface of the conductive layer by electroplating, thereby obtaining the composite aluminum foil with a metal-polymer base material-metal structure.
In addition, by introducing specific types and molar ratios of ionic liquid, namely anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride with the molar ratio of 1-3:1, the polymer substrate plated or coated with the conductive layer is subjected to aluminum layer electroplating, so that the process limitations of high temperature damage, high energy consumption and low deposition speed caused by a deposition method such as a physical vapor deposition method in the prior art can be avoided, the deposition temperature required by the process method for electroplating the aluminum layer by the ionic liquid is low, large equipment is not required, the yield of a finished product can be remarkably improved, the production cost is reduced, and the process method also has the advantages of low energy consumption and high deposition speed.
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 specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
fig. 1 is a partial schematic structure of a composite aluminum foil prepared according to an embodiment of the present invention.
Wherein the above figures include the following reference numerals:
1: electroplating an aluminum layer; 2: a conductive layer; 3: a pretreated surface modification layer; 4: a polymeric substrate.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present disclosure will be described in detail with reference to examples.
In view of the deficiencies of the prior art mentioned in the background, one embodiment of the present disclosure provides a method for preparing a composite aluminum foil, comprising the steps of: step S1: pretreatment of a polymer substrate: providing a polymer substrate, and carrying out surface modification on at least one surface of the polymer substrate through a chemical etching solution to obtain a surface modified polymer substrate, wherein the chemical etching solution comprises one or more of sulfuric acid, potassium permanganate, sodium hydroxide, potassium dichromate, chloric acid, nitric acid and hydrogen peroxide; step S2: preparing a conductive layer: coating at least one surface of the surface modified polymer substrate with a conductive material by electroless plating or coating to obtain a conductive layer coated polymer substrate; step S3: plating an aluminum layer: and (3) placing the polymer substrate covered with the conductive layer in an ionic liquid, and depositing an aluminum layer on the surface of the conductive layer through electroplating to obtain the composite aluminum foil, wherein the ionic liquid comprises anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, and the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 1-3:1.
Preferably, the molar ratio of anhydrous aluminum chloride to 1-ethyl-3-methylimidazole chloride in the ionic liquid is 1:1, 1.5:1, 2:1, 2.5:1, 3:1, etc.
The method for preparing the composite aluminum foil disclosed herein performs roughening treatment on the surface of the polymer substrate by pre-treating the polymer substrate with a specific chemical etching solution, and simultaneously forms hydrophilic groups on the surface of the polymer substrate by chemical reaction, thereby improving the interfacial bonding force between the organic polymer substrate and the conductive layer and the aluminum layer which are plated or coated later. The methods disclosed herein also employ a process for electroplating an aluminum layer in a specific ionic liquid that allows deposition of the aluminum layer at a lower temperature, thereby avoiding the high temperature damage that can result from prior art high temperature deposition methods; the process method for electroplating the aluminum layer by using the ionic liquid does not need to input large equipment, and can realize the advantages of low energy consumption and high deposition speed. The ionic liquid containing the anhydrous aluminum chloride and the 1-ethyl-3-methylimidazole chloride in the molar ratio of 1-3:1 is adopted, so that the binding force between an electroplated aluminum layer and a polymer substrate is improved, the deposition speed is increased, the production efficiency is effectively improved, and the mass production is realized.
In a preferred embodiment of the invention, the chemical etching solution comprises one or more of sulfuric acid, potassium permanganate, potassium dichromate and sodium hydroxide. The chemical etching solution is in the scope of the present disclosure, and is beneficial to improving the roughening and activating efficiency of the surface of the polymer substrate, and to improving the formation of hydrophilic groups on the surface of the polymer substrate, so as to further improve the interfacial bonding force between the organic polymer substrate and the conductive layer and the aluminum layer which are plated or coated later, and further improve the yield.
In some embodiments of the invention, in the step of pre-treating the polymeric substrate, the temperature of the pre-treatment of the polymeric substrate is 18-60 ℃ and the treatment time is 10-150 s. For example, the treatment temperature is 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃ and the like, and the treatment time is 10 s, 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s, 130 s, 140 s, 150 s and the like. The treatment temperature and the treatment time of the polymer substrate are within the scope of the disclosure, which can help to accelerate the pretreatment speed of the surface of the polymer substrate, facilitate the coarsening reaction of the surface of the polymer substrate and the formation of hydrophilic groups, further improve the interfacial binding force between the organic polymer substrate and the conductive layer and the aluminum layer which are plated or coated later, and improve the yield.
In some embodiments of the invention, in the step of preparing the conductive layer, the temperature of the covering conductive layer is 18-60 ℃ and the covering time is 40-300 s. For example, the cover temperature is 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, etc., and the cover time is 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 150 s, 200 s, 250 s, 260 s, 270 s, 280 s, 290 s, 300 s, etc. The temperature and the coverage time of the conductive layer are within the scope of the disclosure, so that the coverage rate of the conductive layer can be accelerated, the yield is improved, and the production efficiency is improved.
In some embodiments of the invention, in the step of aluminum layer plating, the temperature of aluminum layer plating is 18-60 ℃ and the plating time is 5-15 min. For example, the plating temperature is 18 ℃, 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 34 ℃, 36 ℃, 38 ℃, 40 ℃, 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃ and the like, and the plating time is 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min and the like. The temperature and plating time of the aluminum layer plating are within the scope of the disclosure, the interfacial bonding force between the aluminum layer and the front cladding layer can be further improved, and the speed of the aluminum layer plating can be increased, so that the production efficiency is further improved compared with the physical vapor deposition process, and the high-temperature damage to the polymer substrate is further reduced.
In a further embodiment of the present invention, in the polymer substrate pretreatment step, the polymer substrate is one or more selected from polyethylene terephthalate, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, polyamide, polyimide, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, and polyethylene glycol.
In a further embodiment of the present invention, in the conductive layer preparation step, the conductive material is one or more selected from gold, nickel, aluminum, copper, silver, carbon, and graphene. Conductive materials within the scope of the present disclosure may impart good electrical conductivity to the polymeric substrate, thereby providing plating-enabling conditions for subsequent metal plating.
In some embodiments of the invention, the electroplating is performed at a gradually increasing current density in the aluminum layer plating step, the current density being controlled to be 4-5A/(dm) 2 S) from 0 to 1.0A/dm 2 The initial value in the range is raised to 1-50A/dm 2 。
During the electroplating of the aluminum layer, the current density of the electroplating process is applied in a gradually increasing manner. The plating layer can be prevented from being broken down by adopting smaller current density at the beginning of the electroplating process; with the progress of the electroplating process, the deposition of the aluminum layer on the material surface of the conductive layer is gradually thickened, and the current density is gradually increased, so that the electroplating efficiency can be improved, and the overall production efficiency of the composite aluminum foil is further improved.
In some embodiments of the present invention, in the conductive layer preparation step, electroless plating solutions used in electroless plating of the conductive layer include chloroauric acid, sodium carbonate, and formaldehyde, or include nickel sulfate, sodium hypophosphite, trisodium citrate, and sodium acetate; the conductive paint used in the coating of the conductive layer includes silver, graphene, or carbon. Specific types of electroless plating solutions and conductive coatings are within the scope of the present disclosure, which may increase the reaction rate of electroless plating or coating, thereby further increasing the overall production efficiency.
In some embodiments of the present invention, in the composite aluminum foil, the thickness D1 of the polymeric substrate satisfies: 1. d1 is less than or equal to 20 mu m; the thickness D2 of the conductive layer satisfies: 10 nm is less than or equal to D2 and less than or equal to 1000 nm; the thickness D3 of the aluminum layer satisfies: 1. d3 is less than or equal to 10 mu m.
In some embodiments of the invention, the process is performed continuously or discontinuously.
Preferably, the process is carried out continuously.
In a further embodiment of the present invention, steps S1, S2 and S3 are performed continuously in a roll-to-roll manner, the winding speeds of steps S1, S2 and S3 are each in the range of 1-50 m/min and the winding speeds of the three are the same.
The polymer substrate pretreatment step, the conductive layer preparation step and the aluminum layer plating step of the invention are performed in a roll-to-roll manner, so that the polymer substrate pretreatment, the conductive layer chemical plating or coating and the aluminum layer plating can be continuously performed. The roll-to-roll production mode can omit interruption, displacement, placement and waiting processes among various links, can avoid the problems of oxidation, deactivation, internal stress improvement and the like of the surface of a material caused by long-time placement while improving the production efficiency, further improves the yield of products, improves the yield, and is beneficial to realizing mass production.
According to another embodiment herein, there is provided a composite aluminum foil prepared by the above method.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Example 1
(1) Pretreatment of a polymer substrate: polyethylene terephthalate 5 μm thick was used as the polymer substrate. The polymer substrate was immersed in a chemical etching solution at a temperature of 22 ℃ for 60 a s a to roughen and activate the surface. The chemical etching solution is prepared from potassium permanganate, sulfuric acid and deionized water, wherein the concentration of the potassium permanganate in the prepared chemical etching solution is 100 g/L, and the concentration of the sulfuric acid is 200 g/L.
(2) Preparing a conductive layer: the pretreated polymeric substrate was placed in an electroless plating solution at a temperature of 22 ℃ and immersed in the electroless plating solution at 120 s. The chemical plating solution is prepared from chloroauric acid, sodium carbonate, formaldehyde and deionized water, wherein the concentration of the chloroauric acid in the prepared chemical plating solution is 33 g/L, the concentration of the sodium carbonate is 95 g/L, and the concentration of the formaldehyde is 60 mL/L. A gold layer of 200 a nm a thick was deposited on the upper and lower surfaces of the polymer substrate.
(3) Electroplating an aluminum layer: the polymer substrate coated with the conductive layer was used as a cathode, the aluminum plate was used as an anode, and the electrolytic aluminum plating treatment was performed at a temperature of 22 ℃ for 10 minutes. The electroplating solution is an ionic liquid system (room temperature molten salt system) and is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, wherein the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 2:1. The current density of the plating was applied in a gradually rising manner, and the current density was 4A/(dm) 2 S) from an initial value of 0.5. 0.5A/dm 2 Gradually rise to 20A/dm 2 An aluminum layer having a thickness of 2 μm was deposited on the upper and lower surfaces of the polymer substrate covered with the electroless plating layer.
Example 2
(1) Pretreatment of a polymer substrate: as polymer substrate, polypropylene 6 μm thick was used. The polymer substrate was immersed in a chemical etching solution at 25 ℃ at a concentration of 100 g/L, prepared from sodium hydroxide and deionized water, for roughening and activating the surface of the polymer substrate by immersing the polymer substrate in the chemical etching solution at 20 s.
(2) Preparing a conductive layer: the pretreated polymeric substrate was placed in an electroless plating solution at a temperature of 25 ℃ and immersed in the electroless plating solution at 60 s. The chemical plating solution is prepared from chloroauric acid, sodium carbonate, formaldehyde and deionized water, wherein the concentration of the chloroauric acid in the prepared chemical plating solution is 30 g/L, the concentration of the sodium carbonate is 105 g/L, and the concentration of the formaldehyde is 62 mL/L. A gold layer having a thickness of 400 a nm a was deposited on the upper and lower surfaces of the polymer substrate.
(3) Electroplating an aluminum layer: the polymer substrate coated with the conductive layer was used as a cathode, the aluminum plate was used as an anode, and the electrolytic aluminum plating treatment was performed at a temperature of 25 ℃ for 8 minutes. The electroplating solution is an ionic liquid system (room temperature molten salt system) and is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, wherein the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 2:1. The current density of the plating was applied in a gradually rising manner, and the current density was 5A/(dm) 2 S) from an initial value of 0A/dm 2 Gradually rise to 21A/dm 2 An aluminum layer having a thickness of 1 μm was deposited on the upper and lower surfaces of the polymer substrate covered with the electroless plating layer.
Example 3
(1) Pretreatment of a polymer substrate: using polytetrafluoroethylene with a thickness of 3 μm as a polymer substrate, immersing the polymer substrate in a chemical etching solution at a temperature of 18 ℃ for roughening and activating the surface of the polymer substrate, wherein the chemical etching solution is prepared from potassium dichromate, sulfuric acid and deionized water, and the concentration of the potassium dichromate in the prepared chemical etching solution is 200 g/L and the concentration of the sulfuric acid is 200 g/L.
(2) Preparing a conductive layer: the pretreated polymeric substrate was placed in an electroless plating solution at a temperature of 18 ℃ and immersed 300 s in the electroless plating solution. The chemical plating solution is prepared from nickel sulfate, sodium hypophosphite, trisodium citrate, sodium acetate and deionized water, wherein the concentration of the nickel sulfate in the prepared chemical plating solution is 30 g/L, the concentration of the sodium hypophosphite is 30 g/L, the concentration of the trisodium citrate is 5 g/L, and the concentration of the sodium acetate is 5 g/L. A nickel layer having a thickness of 600 a nm a was deposited on the upper and lower surfaces of the polymer substrate.
(3) Electroplating an aluminum layer: the polymer substrate coated with the conductive layer is used as a cathode, and the aluminum plate is used asAnd an anode, wherein the electroplating aluminum treatment is carried out at the temperature of 18 ℃ for 15 min. The electroplating solution is an ionic liquid system (room temperature molten salt system) and is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, wherein the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 1:1. The current density of the plating was applied in a gradually rising manner, and the current density was 4.5A/(dm) 2 S) from an initial value of 0.5. 0.5A/dm 2 Gradually rise to 18A/dm 2 An aluminum layer having a thickness of 1.2 μm was deposited on the upper and lower surfaces of the polymer substrate covered with the electroless plating layer.
Example 4
(1) Pretreatment of a polymer substrate: using polyamide with the thickness of 20 μm as a polymer substrate, soaking the polymer substrate in a chemical etching solution at the temperature of 60 ℃ for 150 s to roughen and activate the surface of the polymer substrate, wherein the chemical etching solution is prepared from potassium permanganate, sulfuric acid and deionized water, the concentration of the potassium permanganate in the prepared chemical etching solution is 100 g/L, and the concentration of the sulfuric acid is 200 g/L.
(2) And (3) conducting layer coating: and (3) coating graphene conductive paint on the surface of the pretreated polymer substrate at the temperature of 60 ℃, wherein the thickness of the coating is 1000 nm.
(3) Electroplating an aluminum layer: the polymer substrate coated with the conductive layer was used as a cathode, the aluminum plate was used as an anode, and an electrolytic aluminum plating treatment was performed at a temperature of 60 ℃ for 5 minutes. The electroplating solution is an ionic liquid system (room temperature molten salt system) and is prepared from anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, wherein the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 3:1. The current density of the plating was applied in a gradually rising manner, and the current density was 5A/(dm) 2 S) from an initial value of 0A/dm 2 Gradually rise to 50A/dm 2 An aluminum layer having a thickness of 10 μm was deposited on the upper and lower surfaces of the polymer substrate covered with the electroless plating layer.
Comparative example 1
The preparation of the composite aluminum foil was performed in the same manner as in example 1, except that the pretreatment step of the polymer substrate was not performed.
Comparative example 2
Preparation of composite aluminum foil was performed in the same manner as in example 1 except that AlCl was used in the aluminum layer electroplating process 3 The NaCl-KCl molten salt system is used as an electroplating solution, and the temperature of the aluminum layer electroplating is 120 ℃.
Comparative example 3
Preparation of a composite aluminum foil was performed in the same manner as in example 1 except that the molar ratio of anhydrous aluminum chloride to 1-ethyl-3-methylimidazole chloride used in preparing the plating solution was 4:1.
Comparative example 4
Preparation of a composite aluminum foil was performed in the same manner as in example 1, except that pretreatment of a polymer substrate, preparation of a conductive layer, and plating of an aluminum layer were performed at a temperature of 70 ℃.
Comparative example 5
Preparation of a composite aluminum foil was carried out in the same manner as in example 1 except that 50A/dm was applied at the time of plating the aluminum layer 2 Instead of being applied in a gradual rise.
Performance testing
Determination of surface sheet resistance
The surface sheet resistance was measured using a four-probe Fang Zuyi at a test temperature of 25 ℃.
Binding force measurement
The binding force is measured by using a universal tensile machine, the sample is cut into a rectangle with the width of 60 mm and the length of 150 mm, the sample is fixed with the universal tensile force by adopting a 3M adhesive tape, and the stripping speed is 10 mm min −1 The test temperature was 25 ℃.
TABLE 1
From the above results, it can be seen that examples 1 to 3 based on the method for preparing a composite aluminum foil of the present invention, by combining pretreatment of a polymer substrate, electroless plating or coating of a conductive layer, and electroplating of an aluminum layerThree steps, the surface sheet resistance of the obtained composite aluminum foil is lower than 58 omega sq -1 The binding force between the aluminum layer and the polymer base material is higher than 2.5 kg/mm 2 The yield of the product is higher than 80%. In contrast, although the surface sheet resistance of comparative example 1, in which pretreatment of the polymer substrate was not performed, was comparable to examples 1 to 3, the bonding force between the aluminum layer and the polymer substrate was only 1.3 kg/mm 2 The yield of the product is only 60%, which is obviously lower than the binding force and yield of the composite aluminum foil in the embodiment 1-3. Comparative example 2 the plating solution used in the aluminum layer plating process and the plating temperature were outside the scope of the present invention, and the entire process operation temperature of comparative example 4 was outside the scope of the present invention, resulting in melting of the polymer substrate and failure to form an advantageous shaped aluminum foil. Comparative example 3 the molar ratio of anhydrous aluminum chloride to 1-ethyl-3-methylimidazole chloride used during the plating of an aluminum layer was outside the scope of the present invention, and comparative example 5 used a constant current density applied current during the plating of an aluminum layer, resulting in significantly lower binding force between an aluminum layer and a polymer substrate and product yield.
The above embodiments are merely descriptions of technical solutions of the present disclosure, and are not intended to limit the scope thereof. While various modifications can be made by one of ordinary skill in the art with reference to the above examples, it should be within the scope of the present disclosure without departing from the spirit of the design of the present disclosure.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The foregoing description relates to specific embodiments of the present disclosure, and is not intended to limit the disclosure to the particular embodiments described, but rather to limit the disclosure to the wide variety of modifications and changes that may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (10)
1. A method for preparing a composite aluminum foil, comprising the steps of:
step S1: pretreatment of a polymer substrate: providing a polymer substrate, and carrying out surface modification on at least one surface of the polymer substrate through a chemical etching solution to obtain a surface modified polymer substrate, wherein the chemical etching solution comprises one or more of sulfuric acid, potassium permanganate, sodium hydroxide, potassium dichromate, chloric acid, nitric acid and hydrogen peroxide;
step S2: preparing a conductive layer: coating a conductive material on the at least one surface of the surface-modified polymer substrate by electroless plating or coating to obtain a conductive layer-coated polymer substrate;
step S3: plating an aluminum layer: and placing the polymer substrate covered with the conductive layer into an ionic liquid, and depositing an aluminum layer on the surface of the conductive layer through electroplating to obtain the composite aluminum foil, wherein the ionic liquid comprises anhydrous aluminum chloride and 1-ethyl-3-methylimidazole chloride, and the molar ratio of the anhydrous aluminum chloride to the 1-ethyl-3-methylimidazole chloride is 1-3:1.
2. The method according to claim 1, wherein in step S1, the polymer substrate is pretreated at a temperature of 18-60 ℃ for a treatment time of 10-150S; in the step S2, the temperature of covering the conductive layer is 18-60 ℃ and the covering time is 40-300S; and in the step S3, the plating temperature of the aluminum layer is 18-60 ℃ and the plating time is 5-15 min.
3. The method according to claim 1 or 2, wherein in step S1, the polymer substrate is one or more selected from polyethylene terephthalate, polypropylene, polyethylene, polyvinylchloride, polytetrafluoroethylene, polyamide, polyimide, polyoxymethylene, polyphenylene sulfide, polyphenylene ether and polyethylene glycol.
4. The method according to claim 1 or 2, wherein in step S2 the conductive material is one or more selected from gold, nickel, aluminum, copper, silver, carbon and graphene.
5. The method according to claim 1 or 2, characterized in that in the step S3 the electroplating is performed at a gradually increasing current density, wherein the current density is controlled to be 4-5A/(dm) 2 S) from 0 to 1.0A/dm 2 The initial value in the range is raised to 1-50A/dm 2 。
6. The method according to claim 1 or 2, characterized in that in the step S2, electroless plating solutions used in electroless plating of the conductive layer include chloroauric acid, sodium carbonate, and formaldehyde, or nickel sulfate, sodium hypophosphite, trisodium citrate, and sodium acetate; the conductive paint used in the coating of the conductive layer includes silver, graphene or carbon.
7. The method according to claim 1 or 2, wherein in the composite aluminium foil, the thickness D1 of the polymeric substrate satisfies: 1. d1 is less than or equal to 20 mu m; the thickness D2 of the conductive layer satisfies: 10 nm is less than or equal to D2 and less than or equal to 1000 nm; the thickness D3 of the aluminum layer satisfies the following conditions: 1. d3 is less than or equal to 10 mu m.
8. The process according to claim 1 or 2, characterized in that it is carried out continuously or discontinuously.
9. The method according to claim 8, wherein the steps S1, S2 and S3 are continuously performed in a roll-to-roll manner, the winding speeds of the steps S1, S2 and S3 are each in the range of 1-50 m/min and the winding speeds of the three are the same.
10. A composite aluminium foil, characterized in that it is produced by the method according to any one of claims 1-9.
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