CN117936797A - Resin-graphite emulsion composite copper foil and preparation method and application thereof - Google Patents
Resin-graphite emulsion composite copper foil and preparation method and application thereof Download PDFInfo
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- CN117936797A CN117936797A CN202311863216.6A CN202311863216A CN117936797A CN 117936797 A CN117936797 A CN 117936797A CN 202311863216 A CN202311863216 A CN 202311863216A CN 117936797 A CN117936797 A CN 117936797A
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- copper foil
- emulsion
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 77
- 239000010439 graphite Substances 0.000 title claims abstract description 77
- 239000000839 emulsion Substances 0.000 title claims abstract description 51
- 239000011889 copper foil Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000007788 roughening Methods 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 8
- 238000005238 degreasing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 239000004816 latex Substances 0.000 claims 1
- 229920000126 latex Polymers 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 3
- 230000008020 evaporation Effects 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001755 magnetron sputter deposition Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Electroplating Methods And Accessories (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention discloses a resin-graphite emulsion composite copper foil and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1: after degreasing and roughening treatment, coating a graphite conducting layer on the surface of the resin film through graphite emulsion suspension, and drying to obtain a graphite-resin-graphite structure; s2, depositing copper foil on the graphite layer of the graphite-resin-graphite structure to form a copper-graphite-resin-graphite-copper structure; s3, performing antioxidation treatment on the copper-graphite-resin-graphite-copper structure body to obtain the resin-graphite emulsion composite copper foil, wherein the resin-graphite emulsion composite copper foil provided by the invention does not need expensive treatments such as evaporation, sputtering and the like, has the advantages of low cost and simple process and good conductivity, and increases the binding force of the electrodeposited copper foil on the surface of the graphite layer through the pinning effect of graphite and copper particles by conducting the resin through impregnating graphite emulsion.
Description
Technical Field
The invention relates to the technical field of composite copper foil, in particular to a resin-graphite emulsion composite copper foil, and a preparation method and application thereof.
Background
The composite copper foil is a film material with polymer-based film material as an intermediate layer and metal copper as a plating layer. The middle layer is generally PET/PP/PI, a metal material is coated on the surface of a base material by utilizing an evaporation/magnetron sputtering/water electroplating technology, and other functional metals are respectively used as coating layers on two sides of the base material to form an interlayer conductive film material.
The composite copper foil has soft texture, good ductility and good compression resistance, can be used for the negative electrode of a lithium battery to effectively inhibit lithium dendrite generation, reduce the risk of internal short circuit of the battery, reduce the weight of the battery and improve the energy density and safety of the battery. However, the thickness of the PET film roll of the composite copper foil is small, precise magnetron sputtering equipment is needed, and the equipment investment and equipment depreciation cost of the magnetron sputtering equipment are high; the thickness of the sputtered seed copper is small, the resistivity is high, and the electroplating thickness error of the copper foil layer is large; the PET film has small thickness and is easy to deform in the preparation process. The PET/PP composite copper foil has poor conductivity of the intermediate layer, good PI performance but high cost, and is difficult to deposit copper on a polymer, whether sputtering or vapor deposition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a resin-graphite emulsion composite copper foil and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The first aspect of the invention provides a preparation method of a resin-graphite emulsion composite copper foil, which comprises the following steps:
S1, conducting conductive treatment after degreasing and roughening treatment of the resin, namely enabling the surface of the resin film to be covered with a graphite conductive layer through graphite emulsion suspension, and drying and curing to obtain a graphite-resin-graphite structure;
S2, depositing copper foil on the graphite layer conductive layer of the graphite-resin-graphite structure to form a copper-graphite-resin-graphite-copper structure;
And S3, performing antioxidation treatment on the copper-graphite-resin-graphite-copper structure body to obtain the resin-graphite emulsion composite copper foil.
In some embodiments, the resin film degreasing and roughening treatment is: washing the resin film in sodium hydroxide solution with concentration of 5-10% and temperature of 40-65deg.C for 5-30min, and roughening with roughening solution with temperature of 50-60deg.C for 5-10min, wherein the roughening solution comprises sulfuric acid and oxidant, and the oxidant is at least one selected from chromic acid, chromic anhydride and potassium permanganate;
In some embodiments of the present invention, it is preferred that the roughening solution comprises 80-90% pure sulfuric acid and 4-6% pure chromic acid, with the balance being water; preferably, the roughening liquid contains 20-60% of pure sulfuric acid and 5-10% of pure potassium permanganate, and the balance of water.
In some embodiments, in step S1, the resin film has a thickness of 1.0 to 5.0 μm, and the resin film is at least one selected from ABS resin, polypropylene resin, PET resin, polyurethane, polytetrafluoroethylene resin, phenolic resin, and epoxy resin.
In some embodiments, in step S1, the graphite emulsion suspension contains a low-resistance conductive graphite emulsion or a graphite emulsion mixture; the graphite emulsion mixed solution comprises graphite emulsion and acrylic resin, wherein the mass ratio of the graphite emulsion to the acrylic resin is 85-95:5-15, wherein the graphite particle diameter D50 is 2-200nm, the density of the graphite emulsion is 1.9-2.3g/cm 3, the speed of the resin film passing through the graphite emulsion suspension is 0.1-2.5cm/s, and the thickness of the graphite-resin-graphite structure is 1.0-6.0 mu m.
In some embodiments, the graphite suspension further comprises copper powder, the mass ratio of graphite to copper powder being 20-250:1, the grain diameter of the copper powder is 15-500nm.
According to the invention, the suspension with uniformly dispersed graphite is used, and nanometer copper powder is added into the graphite emulsion solution, so that the resin film is uniformly covered with a layer of graphite/copper composite layer, and the graphite layer of the graphite-resin-graphite structure body is provided with nanometer copper particles, the nanometer copper particles can become the subsequent position for preferential deposition, and the binding force between the graphite and the copper deposition layer is enhanced through the pinning effect.
In some embodiments, in step S2, the copper foil layer has a thickness of 0.5-5 μm.
In some embodiments, in step S2, the deposition parameters include: the current density is 0.1-10A/dm 2, and the deposition solution is at least one selected from copper pyrophosphate and copper sulfate system copper plating solution; wherein, the concentration of copper ions in the copper plating solution of the copper sulfate system is 60-120g/L, and the concentration of sulfuric acid is 100-150g/L.
In some embodiments, the oxidation resistant treatment is an electrodeposition or a soaking treatment.
The antioxidation reagent used in the electrodeposition or soaking treatment is at least one selected from chromium trioxide, glucose, BTA, EDTA, triethanolamine and deionized water.
In some embodiments the oxidation resistant treatment is electrodeposited chromium, the electrodepositing step comprising: putting the copper-graphite-resin-graphite-copper structure body obtained in the step S2 into an antioxidant agent for electrodeposition treatment; wherein the current density is 1-6A/dm 2, the temperature of the antioxidant agent is 25-35 ℃, the concentration of the antioxidant agent is 0.4-10g/L, and the electrodeposition time is 3-10s.
In some other embodiments the antioxidation treatment is a soaking treatment, the soaking treatment step comprising: immersing the copper-graphite-resin-graphite-copper structure obtained in the step S2 into an antioxidant agent in a flat manner, and drying the copper-graphite-resin-graphite-copper structure without washing; wherein the soaking time is 3-15s, the temperature of the antioxidant agent is 20-40 ℃, the drying temperature is 50-110 ℃, and the hot air drying is carried out.
The second aspect of the present invention is to provide a resin-graphite emulsion composite copper foil.
The third aspect of the invention provides application of the resin-graphite emulsion composite copper foil in preparing negative current collectors of lithium batteries, sodium batteries, potassium batteries, magnesium batteries, calcium batteries and aluminum batteries.
The invention has the following beneficial effects:
(1) The composite copper foil provided by the invention has the advantages of good conductivity, easy preparation of an intermediate layer, low cost and wide thickness adjustable range, and the thickness of the composite copper foil can be further reduced, so that the process is simple, and expensive treatment methods such as evaporation, sputtering and the like are not needed.
(2) According to the preparation method provided by the invention, the resin is subjected to conductive treatment by dipping the graphite emulsion, the binding force of the electrodeposited copper foil on the surface of the graphite layer is increased by the pinning effect of graphite and copper particles, and the binding force of the graphite and copper is weaker when copper is directly plated on the graphite, so that the peeling strength between layers is low when the composite copper foil is used, and cracks and the like are easy to form. The mode of electroless copper plating and electroplating copper thickening easily causes low copper plating efficiency and unstable plating solution, and the invention utilizes the pinning effect of graphite and copper particles to increase the binding force of electrodeposited copper foil on the surface of a graphite layer, and does not need an electroless copper plating link.
Drawings
Fig. 1 is a schematic structural diagram of a resin-graphite emulsion composite copper foil provided by the invention, wherein 1 is a copper foil and 2 is a graphite-resin-graphite structure.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings, by way of which the embodiments are described for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Example 1
The preparation method of the resin-graphite emulsion composite copper foil comprises the following steps:
S1: conductive treatment of resin film
Selecting an ABS film with the thickness of 2.0 mu m, alkaline washing the resin film in a sodium hydroxide solution with the concentration of 5% and the temperature of 60 ℃ for 15min, roughening the resin film for 5min by using a roughening liquid with the temperature of 50 ℃, wherein the roughening liquid contains 80% of pure sulfuric acid, 4% of pure chromic acid and the balance of water, and conducting electric treatment after degreasing and roughening, namely, the treated resin film passes through a graphite emulsion suspension at the speed of 0.2cm/s, wherein the graphite emulsion suspension consists of calcium carbide emulsion, acrylic resin and copper powder, the mass ratio of graphite emulsion to acrylic resin in the graphite emulsion suspension is 95:5, and the mass ratio of graphite to copper powder is 22:1, graphite emulsion density is 2.2g/cm 3, particle size of copper powder is 200nm, particle size D50 of graphite is 180nm, two sides of a resin film are covered with a layer of graphite conducting layer, and a graphite-resin-graphite structure body is obtained after drying, wherein the thickness of the graphite-resin-graphite structure body is 2.5 mu m.
S2: electroplated copper
Copper foil is deposited on the two sides of a graphite layer of the graphite-resin-graphite structure body to form the copper-graphite-resin-graphite-copper structure body, the deposition current density is 1.0A/dm, the deposition current density is 1.0 mu m on one side, the deposition liquid is a copper sulfate sulfuric acid system plating liquid, the copper ion concentration is 90g/L, and the sulfuric acid concentration is 120g/L.
S3: electroplating antioxidant
And (3) performing antioxidation treatment on the copper-graphite-resin-graphite-copper structure to obtain the resin-graphite emulsion composite copper foil, wherein the antioxidation treatment is electrodeposited chromate, the current density of electrodeposited chromium is 2A/dm 2, the plating solution is a mixed solution of 0.2g/L of chromium trioxide and 4g/L of glucose, the plating solution temperature is 30 ℃, the plating solution concentration is 5g/L, and the electrodeposition time is 3s.
Example 2
The preparation procedure was the same as in example 1, except that the ABS resin was replaced with polypropylene resin (PP).
Comparative example 1
The preparation procedure was the same as in example 1, except that the graphite emulsion contained no nanoscale conductive copper powder.
Test example tensile Property test
For the 4.5 μm copper foil obtained above, the bonding force between the coating and the substrate was tested according to the standard test method of ASTM E345-16 metallic foil tensile test. Copper foil having a width of 0.5 inch was cut using a double-edged cutting knife (JDC, THWING-ALBERT), and then the tensile properties of the copper foil were tested using a single tensile tester (force test, LD 22.502). The test results are shown in Table 1, and it can be seen from the results that the bonding force and the tensile strength of the composite copper foil provided by the application in the example 1 and the example 2 are better than those of the comparative example 1.
TABLE 1
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the resin-graphite emulsion composite copper foil is characterized by comprising the following steps of:
S1, after degreasing and roughening treatment of a resin film, coating a graphite conductive layer on the surface of the resin film through graphite emulsion suspension, and drying to obtain a graphite-resin-graphite structure;
s2, depositing copper foil on the graphite conductive layer of the graphite-resin-graphite structure to form a copper-graphite-resin-graphite-copper structure;
And S3, performing antioxidation treatment on the copper-graphite-resin-graphite-copper structure body to obtain the resin-graphite emulsion composite copper foil.
2. The method for preparing a resin-graphite emulsion composite copper foil according to claim 1, wherein in the step S1, the degreasing and roughening treatment of the resin film is: washing resin film with sodium hydroxide solution at 40-65deg.C for 5-30min, and roughening with roughening solution at 50-60deg.C for 5-10min; the roughening liquid comprises pure sulfuric acid and an oxidant, wherein the oxidant is at least one selected from chromic acid, chromic anhydride and potassium permanganate.
3. The method for producing a resin-graphite emulsion composite copper foil according to claim 1, wherein in the step S1, the resin film thickness is 1.0 to 5.0 μm, and the resin film is at least one selected from the group consisting of ABS resin, polypropylene resin, PET resin, polyurethane, polytetrafluoroethylene resin, phenolic resin, and epoxy resin.
4. The method for preparing the resin-graphite emulsion composite copper foil according to claim 1, wherein in the step S1, the graphite emulsion suspension comprises graphite emulsion and acrylic resin, and the mass ratio of the graphite emulsion to the acrylic resin is 85-95:5-15, wherein the graphite particle diameter D50 is 2-200nm, the density of the graphite emulsion is 1.9-2.3g/cm 3, the speed of the resin film passing through the graphite emulsion suspension is 0.1-2.5cm/s, and the thickness of the graphite-resin-graphite structure is 1.0-6.0 mu m.
5. The method for preparing a resin-graphite emulsion composite copper foil as claimed in claim 4, wherein the graphite emulsion suspension further comprises copper powder, and the mass ratio of graphite to copper powder is 20-250:1, the grain diameter of the copper powder is 15-500nm.
6. The method for preparing a resin-graphite emulsion composite copper foil according to claim 1, wherein the thickness of the copper foil layer in the step S2 is 0.5-5 μm.
7. The method for preparing a resin-graphite emulsion composite copper foil according to claim 1, wherein in the step S2, the deposition parameters include: the current density is 0.1-10A/dm 2, and the deposition solution is at least one selected from copper pyrophosphate and copper sulfate system copper plating solution; the copper ion concentration in the copper plating solution of the copper sulfate system is 60-120g/L, and the sulfuric acid concentration is 100-150g/L.
8. The method for producing a resin-latex composite copper foil according to claim 1, wherein in the step S3, the antioxidation treatment is an electrodeposition or soaking treatment.
9. The resin-graphite emulsion composite copper foil produced by the production method according to any one of claims 1 to 8.
10. The use of the resin-graphite emulsion composite copper foil of claim 9 in the preparation of negative current collectors of lithium ion batteries, sodium batteries, potassium batteries, magnesium batteries, calcium batteries, and aluminum batteries.
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