CN113564572A - Preparation and application of novel electrolytic copper foil anti-oxidation liquid - Google Patents
Preparation and application of novel electrolytic copper foil anti-oxidation liquid Download PDFInfo
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- CN113564572A CN113564572A CN202110891276.3A CN202110891276A CN113564572A CN 113564572 A CN113564572 A CN 113564572A CN 202110891276 A CN202110891276 A CN 202110891276A CN 113564572 A CN113564572 A CN 113564572A
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
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- 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
Abstract
The invention belongs to the technical field of copper foil anti-oxidation treatment, and particularly relates to preparation and application of a novel electrolytic copper foil anti-oxidation liquid. The anti-oxidation liquid comprises an organic polymer, an inorganic film-forming aid, organic/inorganic acid and distilled water. Wherein the mass concentration of the organic polymer is 1-12 g/L, the mass concentration of the inorganic film-forming aid is 0.5-6 g/L, and the mass concentration of the organic/inorganic acid is 1-6 g/L. The anti-oxidation liquid provided by the invention does not contain heavy metal, does not need washing, does not need electrifying, is simple to operate, belongs to a polymer organic-inorganic composite anti-oxidation liquid, and can remarkably improve the high temperature resistance and the anti-oxidation performance of the electrolytic copper foil.
Description
Technical Field
The invention relates to the technical field of copper foil anti-oxidation treatment, in particular to preparation and application of a novel electrolytic copper foil anti-oxidation liquid.
Background
Copper has excellent thermal conductivity, electrical conductivity and easy workability, and is widely used for connection wires of various circuits and current collectors of battery electrodes. In recent years, with the rapid development of the electronic information industry, thinner electrolytic copper foil is increasingly used, so that the electrolytic copper foil is more easily oxidized, and particularly, surface discoloration easily occurs in a humid environment. In order to prevent the problem of susceptibility to oxidative discoloration of copper foil, a copper foil post-treatment method such as chromate impregnation is generally used to improve discoloration resistance and corrosion resistance during the production of electrolytic copper foil. However, in the chromate dipping treatment process, a large amount of hexavalent chromium is used, contains carcinogens and is listed as a priority pollutant by environmental protection authorities of various countries in the world, and such chromium surface treatment products are subject to international limits and regulations; meanwhile, chromium is prevented from oxidation and needs to be cleaned, so that a large amount of chromium-containing wastewater is generated, and the hidden trouble of environmental pollution exists. Therefore, the research on the non-toxic and harmless electrolytic copper foil anti-oxidation treatment process technology has important significance. At present, the electrolytic copper chromium-free antioxidant solution mainly comprises two types: one method is to use benzotriazole and derivatives thereof as film forming agents, inorganic salt is required to be added in the treatment process, and the method sometimes needs to be electrified to generate energy consumption; in addition, the high-temperature oxidation resistance can only reach 150 ℃; in another method, various carboxylic acids, phosphonic acid and derivatives thereof are used as film forming agents, and inorganic substances are added as film forming aids. The technologies have certain defects, so the invention researches a preparation method of the polymer organic-inorganic composite antioxidant liquid, which is used for improving the high temperature resistance and the antioxidant performance of the electrolytic copper foil.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a novel electrolytic copper foil anti-oxidation liquid, which meets the anti-oxidation requirement of the electrolytic copper foil under the condition of higher temperature. In order to achieve the purpose, the invention is realized by the following technical scheme:
the novel electrolytic copper foil anti-oxidation liquid comprises the following components: the mass concentration of the organic polymer is 1-12 g/L, the mass concentration of the inorganic film-forming additive is 0.5-6 g/L, and the mass concentration of the organic/inorganic acid additive is 1-6 g/L, and the specific preparation method comprises the following steps:
s10, weighing 1-12 g of organic polymer, adding into 500 ml of distilled water, stirring by a stirrer, and uniformly mixing to obtain solution A.
S20, weighing 0.5-6 g of inorganic film-forming aid, adding into 300 ml of distilled water, stirring by using a stirrer, and uniformly mixing to obtain solution B.
S30, weighing 1-6 g of organic/inorganic acid additive, dissolving in 200 ml of distilled water, stirring for 1-3 hours at the stirring temperature of 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for half an hour, adding the solution C, and continuously stirring for half an hour to prepare an anti-oxidation solution for anti-oxidation treatment of the electrolytic copper foil.
In the step S10, the organic polymer is one or a mixture of two of sodium polyacrylate emulsion (with a mass concentration of 500g/L), polyacrylamide emulsion (with a mass concentration of 420 g/L), polyacrylic acid emulsion (with a mass concentration of 500g/L), polyvinyl alcohol (solid), polyvinyl acetate emulsion (with a mass concentration of 450g/L) and Polytetrafluoroethylene (PTFE) emulsion (with a mass concentration of 600 g/L).
Further, the mass concentration of the organic polymer in the prepared electrolytic copper foil anti-oxidation liquid is 1-12 g/L.
Further, in the step S10, the stirring speed is 600-1200 rpm, the stirring temperature is 25-80 ℃, and the stirring time is 6-12 hours.
In the step S20, the inorganic film-forming aid is one or a mixture of two of sodium silicate sol (mass concentration 400 g/L), silicon dioxide sol (mass concentration 400 g/L), Graphene Oxide (GO) dispersion liquid (mass concentration 12 g/L) and alumina sol (mass concentration 250 g/L), and the sodium silicate sol, the silicon dioxide sol and the alumina sol are all purchased from the market.
Further, the mass concentration of the inorganic film-forming aid in the prepared electrolytic copper foil anti-oxidation liquid is 0.5-6 g/L.
Further, in the step S20, the stirring speed is 600-1200 rpm, the stirring temperature is 25-40 ℃, and the stirring time is 1-3 hours.
Further, the organic/inorganic acid additive in the step S30 is one of acetic acid, oxalic acid and phosphoric acid, and the mass concentration of the organic/inorganic acid additive in the prepared electrolytic copper foil anti-oxidation solution is 1-6 g/L.
Advantageous effects
Compared with the prior art, the invention has the beneficial effects that: the invention aims to provide preparation and application of a novel electrolytic copper anti-oxidation liquid, the method realizes the purposes of no heavy metal ions, low energy consumption and no washing for anti-oxidation, and the anti-oxidation temperature can reach 180 ℃ for 30 minutes. In particular, the organic polymer with multifunctional functional groups has more adsorption sites combined with the metal surface, thereby effectively covering the metal surface to obtain a more compact organic film on the surface and preventing the metal from being oxidized. Compared with other organic ligands, the polymer has better film forming property and high temperature resistance. And secondly, the organic polymers are easily compounded with inorganic nano materials, so that gaps of an organic polymer film are filled, a more compact structure is obtained, an organic-inorganic composite film is generated, and the high-temperature resistance and oxidation resistance of the copper foil are further enhanced.
Example 1
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the sodium polyacrylate emulsion (the mass concentration is 500g/L) is 1g/L, the mass concentration of the silica sol (the mass concentration is 400 g/L) is 0.5 g/L, and the mass concentration of the additive acetic acid is 1 g/L.
S10, weighing 1g of sodium polyacrylate emulsion (with the mass concentration of 500g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 6 hours, and uniformly mixing to obtain solution A.
S20, weighing 0.5 g of silica sol (with the mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 1 hour, and uniformly mixing to obtain solution B.
S30, 1g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 1 hour at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the electrolytic copper foil, namely selecting two pieces of electrolytic copper foil processed by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in a drying oven at 80 ℃, then baking the electrolytic copper foil in a drying oven at 180 ℃, baking one piece for 15 minutes, baking the other piece for 30 minutes, and observing the oxidation discoloration condition.
Example 2
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the sodium polyacrylate emulsion (the mass concentration is 500g/L) is 12g/L, the mass concentration of the silica sol (the mass concentration is 400 g/L) is 6g/L, and the mass concentration of the additive acetic acid is 6 g/L.
S10, weighing 12g of sodium polyacrylate emulsion (with the mass concentration of 500g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 1200rpm and the stirring temperature of 80 ℃ for 12 hours, and uniformly mixing to obtain solution A.
S20, weighing 6g of silica sol (the mass concentration is 400 g/L), adding the silica sol into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 1200rpm and the stirring temperature of 40 ℃ for 3 hours, and uniformly mixing to obtain solution B.
S30, 6g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 3 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the electrolytic copper foil, namely selecting two pieces of electrolytic copper foil processed by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in a drying oven at 80 ℃, then baking the electrolytic copper foil in a drying oven at 180 ℃, baking one piece for 15 minutes, baking the other piece for 30 minutes, and observing the oxidation discoloration condition.
Example 3
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the sodium polyacrylate emulsion (the mass concentration is 500g/L) is 6g/L, the mass concentration of the silica sol (the mass concentration is 400 g/L) is 3.5 g/L, and the mass concentration of the additive acetic acid is 4 g/L.
S10, weighing 6g of sodium polyacrylate emulsion (with the mass concentration of 500g/L), adding the sodium polyacrylate emulsion into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 1000rpm and the stirring temperature of 50 ℃ for 9 hours, and uniformly mixing to obtain solution A.
S20, weighing 3.5 g of silica sol (with the mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the speed of 900rpm and the temperature of 30 ℃ for 2 hours, and uniformly mixing to obtain solution B.
S30, 4g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 2 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 4
The copper foil anti-oxidation liquid comprises the following components: the mass concentration of polyacrylamide (mass concentration of 420 g/L) is 6g/L, the mass concentration of alumina sol (mass concentration of 250 g/L) is 3.5 g/L, and the mass concentration of oxalic acid as an additive is 3 g/L.
S10, weighing 6g of polyacrylamide emulsion (with the mass concentration of 420 g/L), adding the polyacrylamide emulsion into 500 ml of distilled water, stirring by using a stirrer at the stirring speed of 800rpm and the stirring temperature of 35 ℃ for 8 hours, and uniformly mixing to obtain solution A.
S20, weighing 3.5 g of alumina sol (the mass concentration is 250 g/L), adding into 300 ml of distilled water, stirring by using a stirrer at the stirring speed of 800rpm at the stirring temperature of 35 ℃ for 2.5 hours, and uniformly mixing to obtain a solution B.
S30, 3g of oxalic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 1.5 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 5
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the polyacrylic acid emulsion (the mass concentration is 500g/L) is 9g/L, the mass concentration of the sodium silicate sol (the mass concentration is 400 g/L) is 4g/L, and the mass concentration of the additive phosphoric acid is 5 g/L.
S10, weighing 9g of polyacrylic acid emulsion (with the mass concentration of 500g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 900rpm and the stirring temperature of 60 ℃ for 7 hours, and uniformly mixing to obtain solution A.
S20, weighing 4g of sodium silicate sol (with the mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 700rpm and the stirring temperature of 28 ℃ for 1.5 hours, and uniformly mixing to obtain solution B.
S30, 5g of phosphoric acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 2.5 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 6
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the polyvinyl alcohol is 4g/L, the mass concentration of the graphene oxide dispersion liquid (mass concentration is 12 g/L) is 4g/L, and the mass concentration of the additive phosphoric acid is 5 g/L.
S10, weighing 4g of polyvinyl alcohol, adding the polyvinyl alcohol into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 700rpm and the stirring temperature of 80 ℃ for 10 hours, and uniformly mixing to obtain solution A.
S20, weighing 4g of graphene oxide dispersion liquid (mass concentration is 12 g/L), adding the graphene oxide dispersion liquid into 300 ml of distilled water, stirring the mixture by using a stirrer at the stirring speed of 700rpm and the stirring temperature of 30 ℃ for 2 hours, and uniformly mixing to obtain liquid B.
S30, 4g of phosphoric acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 2.5 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 7
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the polyvinyl acetate emulsion (the mass concentration is 450g/L) is 8g/L, the mass concentration of the graphene oxide dispersion liquid (the mass concentration is 12 g/L) is 2g/L, the mass concentration of the sodium silicate sol (the mass concentration is 400 g/L) is 4g/L, and the mass concentration of the additive phosphoric acid is 1 g/L.
S10, weighing 8g of polyvinyl acetate emulsion (the mass concentration is 450g/L), adding the polyvinyl acetate emulsion into 500 ml of distilled water, stirring by using a stirrer at the stirring speed of 800rpm at the stirring temperature of 45 ℃ for 8 hours, and uniformly mixing to obtain solution A.
S20, weighing 1g of graphene oxide dispersion liquid (with the mass concentration of 12 g/L) and 4g of silica sol (with the mass concentration of 400 g/L), adding the mixture into 300 ml of distilled water, stirring the mixture by using a stirrer at the stirring speed of 900rpm and the stirring temperature of 30 ℃ for 2 hours, and uniformly mixing the mixture to obtain liquid B.
S30, 5g of oxalic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 3 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 8
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the polytetrafluoroethylene emulsion (mass concentration of 600g/L) is 3g/L, the mass concentration of the silica sol (mass concentration of 400 g/L) is 3g/L, the mass concentration of the sodium silicate sol (mass concentration of 400 g/L) is 3g/L, and the mass concentration of the additive acetic acid is 3 g/L.
S10, weighing 4g of polytetrafluoroethylene emulsion (with the mass concentration of 600g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 1000rpm and the stirring temperature of 40 ℃ for 12 hours, and uniformly mixing to obtain solution A.
S20, weighing 3g of silica sol (mass concentration of 400 g/L) and 3g of sodium silicate sol (mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 800rpm and the stirring temperature of 25 ℃ for 3 hours, and uniformly mixing to obtain solution B.
S30, 3g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 3 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Example 9
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the polyacrylic acid emulsion (the mass concentration of 500g/L) is 6g/L, the mass concentration of the polytetrafluoroethylene emulsion (the mass concentration of 600g/L) is 3g/L, the mass concentration of the graphene oxide dispersion liquid (the mass concentration of 12 g/L) is 4g/L, the mass concentration of the silica sol (the mass concentration of 400 g/L) is 1g/L, and the mass concentration of the additive phosphoric acid is 3 g/L.
S10, weighing 3g of polyacrylic acid emulsion (with the mass concentration of 500g/L) and 3g of polytetrafluoroethylene emulsion (with the mass concentration of 600g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 1000rpm and the stirring temperature of 30 ℃ for 12 hours, and uniformly mixing to obtain solution A.
S20, weighing 3g of graphene oxide dispersion liquid (mass concentration is 12 g/L) and 3g of silica sol (mass concentration is 400 g/L), adding into 300 ml of distilled water, stirring by using a stirrer at the stirring speed of 800rpm and the stirring temperature of 25 ℃ for 3 hours, and uniformly mixing to obtain solution B.
S30, 3g of phosphoric acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 3 hours at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Comparative example 1
The electrolytic copper foil oxidation preventing liquid comprises the following components: the silica sol (400 g/L) had a mass concentration of 0.5 g/L and the additive acetic acid had a mass concentration of 1 g/L.
S10, 500 ml of distilled water is recorded as A liquid.
S20, weighing 0.5 g of silica sol (with the mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 1 hour, and uniformly mixing to obtain solution B.
S30, 1g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 1 hour at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Comparative example 2
The electrolytic copper foil oxidation preventing liquid comprises the following components: the mass concentration of the sodium polyacrylate emulsion (the mass concentration is 500g/L) is 1g/L, and the mass concentration of the inorganic film-forming additive and the additive acetic acid is 1 g/L.
S10, weighing 1g of sodium polyacrylate emulsion (with the mass concentration of 500g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 6 hours, and uniformly mixing to obtain solution A.
S20, 300 ml distilled water, and marking as B liquid.
S30, 1g of acetic acid is weighed and dissolved in 200 ml of distilled water, and the solution is stirred for 1 hour at 25 ℃ to obtain solution C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
Comparative example 3
The copper foil anti-oxidation liquid comprises the following components: the mass concentration of the sodium polyacrylate emulsion (mass concentration of 500g/L) is 1g/L, the mass concentration of the silica sol (mass concentration of 400 g/L) is 0.5 g/L, and no organic/inorganic acid additive is added.
S10, weighing 1g of sodium polyacrylate emulsion (with the mass concentration of 500g/L), adding into 500 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 6 hours, and uniformly mixing to obtain solution A.
S20, weighing 0.5 g of silica sol (with the mass concentration of 400 g/L), adding into 300 ml of distilled water, stirring by a stirrer at the stirring speed of 600rpm and the stirring temperature of 25 ℃ for 1 hour, and uniformly mixing to obtain solution B.
S30, 200 ml of distilled water is marked as liquid C.
And S40, adding the solution B into the solution A, stirring for 0.5 hour, adding the solution C, and continuously stirring for 0.5 hour to prepare the electrolytic copper foil anti-oxidation solution.
And (3) testing the oxidation performance of the copper foil, namely selecting two pieces of electrolytic copper foil treated by 15cm x 6cm, immersing the electrolytic copper foil into an antioxidant for 8 seconds, taking out the electrolytic copper foil, drying the electrolytic copper foil in an oven at 80 ℃, baking the electrolytic copper foil in an oven at 180 ℃ for 15 minutes, baking the electrolytic copper foil in another oven for 30 minutes, and observing the oxidation discoloration condition of the electrolytic copper foil.
The copper foil oxidation resistance test data of each example and comparative example are shown in the following table 1:
TABLE 1 copper foil Oxidation resistance test data results
As can be seen from comparative examples 1-3, the lack of the polymer film-forming agent, the film-forming aid, or the organic/inorganic acid additive all causes the reduction of the high-temperature oxidation resistance of the copper foil. The lack of a polymeric film former has the greatest degree of oxidation, and the lack of an organic/inorganic acid additive causes a greater degree of reduction in oxidation resistance than the lack of an inorganic film-forming aid.
Claims (9)
1. The preparation method of the novel electrolytic copper foil anti-oxidation liquid is characterized by comprising an organic polymer, an inorganic film-forming assistant and an organic/inorganic acid additive.
2. The method for preparing the electrolytic copper foil oxidation preventing solution as claimed in claim 1, wherein the mass concentration of the organic polymer is 1 to 12g/L, the mass concentration of the inorganic film forming aid is 0.5 to 6g/L, and the mass concentration of the organic/inorganic acid additive is 1 to 6 g/L.
3. The method for preparing an electrolytic copper foil oxidation preventing liquid as claimed in claim 1, comprising the steps of:
s10, weighing 1-12 g of organic polymer, adding into 500 ml of distilled water, stirring by using a stirrer, and uniformly mixing to obtain solution A;
s20, weighing 0.5-6 g of inorganic film-forming aid, adding into 300 ml of distilled water, stirring by using a stirrer, and uniformly mixing to obtain solution B;
s30, weighing 1-6 g of organic/inorganic acid additive, dissolving in 200 ml of distilled water, stirring for 1-3 hours at the stirring temperature of 25 ℃ to obtain a solution C;
and S40, adding the solution B into the solution A, stirring for half an hour, adding the solution C, and continuously stirring for half an hour to prepare the electrolytic copper foil anti-oxidation solution.
4. The method for preparing an electrolytic copper foil oxidation preventing solution according to claim 1, wherein the organic polymer in step 1 is one or two of sodium polyacrylate emulsion (500 g/L by mass), polyacrylamide emulsion (420 g/L by mass), polyacrylic acid emulsion (500 g/L by mass), polyvinyl alcohol (solid), polyvinyl acetate emulsion (450 g/L by mass), and Polytetrafluoroethylene (PTFE) emulsion (600 g/L by mass).
5. The method for preparing an electrolytic copper foil oxidation preventing solution according to claim 1, wherein the inorganic film forming aid in the step 2 is one or two of sodium silicate sol (400 g/L by mass), silica sol (400 g/L by mass), Graphene Oxide (GO) dispersion (12 g/L by mass), and alumina sol (250 g/L by mass), and the sodium silicate sol, the silica sol, and the alumina sol are all commercially available.
6. The method for preparing an electrolytic copper foil oxidation preventing solution according to claim 1, wherein the organic/inorganic acid additive in step 3 is one of acetic acid, oxalic acid and phosphoric acid.
7. The method for preparing the electrolytic copper foil oxidation preventing liquid as claimed in claim 1, wherein in the step 1 of the preparation method, the stirring speed is 600 to 1200rpm, the stirring temperature is 25 to 80 ℃, and the stirring time is 6 to 12 hours.
8. The method for preparing the electrolytic copper foil oxidation preventing solution according to claim 1, wherein the stirring speed in the step 2 is 600 to 1200rpm, the stirring temperature is 25 to 40 ℃, and the stirring time is 1 to 3 hours.
9. The use of the novel electrolytic copper foil oxidation preventing liquid as defined in claim 1 for electrolytic copper foil.
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