Anti-warping additive, electrolytic copper foil bath solution, copper foil and preparation method and application of copper foil

Abstract

The invention discloses an anti-warping additive, an electrolytic copper foil bath solution, a copper foil and a preparation method and application of the copper foil, and belongs to the technical field of electrolytic copper foils. The anti-warping additive comprises a nitrogen heterocyclic ring modified compound and a sulfur-containing organic compound, and the mass ratio of the nitrogen heterocyclic ring modified compound to the sulfur-containing organic compound is (10-40): 1. In addition, the invention also provides application of the anti-warping additive in preparation of electrolytic copper foil or electrolytic copper foil bath solution. In addition, the invention further provides an electrolytic copper foil bath solution which comprises the anti-warping additive, and the concentration of the anti-warping additive in the electrolytic copper foil bath solution is 5-20 ppm. In addition, the invention further provides a preparation method of the electrolytic copper foil bath solution. The anti-warping additive provided by the invention can effectively prevent the copper foil from warping from a copper foil manufacturing source.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic copper foil, and in particular to an anti-warping additive, an electrolytic copper foil bath solution, a copper foil, and a preparation method and application thereof. Background Art

[0002] Copper foil is the carrier of the negative electrode active material of the lithium-ion battery, and it is also the collector and transmitter of the negative electrode electron flow. Therefore, various performance indicators of copper foil such as warping, tensile strength, elongation, density, roughness and thickness have a great impact on the endurance and safety performance of lithium-ion batteries.

[0003] Electrolytic copper foil is prone to warping during the manufacturing process, especially in the production of high-tensile strength, ultra-thin copper foil. Copper foil warping not only reduces the contact area between the electrode and the electrolyte, affecting the battery's charging and discharging efficiency and service life; it also easily leads to problems such as internal short circuits and overheating in the battery, resulting in safety accidents such as battery spontaneous combustion and explosion. Currently, high-temperature annealing is often used in the production of electrolytic copper foil to reduce copper foil warping, but this method takes a long time and consumes a lot of energy. Therefore, it is crucial to develop an electrolytic copper foil anti-warping additive that can effectively improve the copper foil warping problem during the electrolytic foil production process. Summary of the invention

[0004] The purpose of the present invention is to overcome the above technical deficiencies, provide an anti-warping additive, an electrolytic copper foil bath, a copper foil and a preparation method and application thereof, and solve the technical problem of copper foil warping in the prior art.

[0005] In order to achieve the above technical objectives, the technical solution of the present invention provides an anti-warping additive, including: a nitrogen heterocyclic modified compound and a sulfur-containing organic compound, the mass ratio of the nitrogen heterocyclic modified compound to the sulfur-containing organic compound is (10-40):1; the nitrogen heterocyclic modified compound is one or more of chlorpromazine, imidazole-epichlorohydrin copolymer, 1-methylpyrazole-4-carboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, triglycidyl isocyanurate and pyrroloquinoline quinone acid.

[0006] In any embodiment, the sulfur-containing organic compound is one or more of sodium phenyl polydisulfide propane sulfonate, 2-tetrahydrothiazolidinethione, 2-imidazolethione, and sodium 3-mercaptopropane sulfonate.

[0007] In any embodiment, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-imidazolethione; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer and triglycidyl isocyanurate, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-tetrahydrothiazolidinethione; and / or, the nitrogen heterocyclic modified compound is The organic compound is an imidazole-epichlorohydrin copolymer and pyrroloquinoline quinone acid, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is 1-methylpyrazole-4-carboxylic acid and triglycidyl isocyanurate, and the sulfur-containing organic compound is sodium phenyl polydisulfide propane sulfonate; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer and 1H-pyrrole-2,5-dicarboxylic acid, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate.

[0008] In addition, the present invention also proposes the use of the above anti-warping additive in the preparation of electrolytic copper foil or electrolytic copper foil bath solution.

[0009] In addition, the present invention also provides an electrolytic copper foil bath solution, comprising the above-mentioned anti-warping additive, wherein the concentration of the anti-warping additive in the electrolytic copper foil bath solution is 5-20 mg / L.

[0010] In any embodiment, 280-400 g / L of copper sulfate, 100-130 g / L of sulfuric acid, 25-40 mg / L of chloride ions, 8-30 ppm of gelatin and 30-60 ppm of hydroxyethyl cellulose are further included.

[0011] In addition, the present invention also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0012] Heat water to 50-55°C, add copper sulfate and stir until dissolved, continue to add sulfuric acid and stir, then add chloride ions and stir to obtain the electrolytic copper foil basic bath solution;

[0013] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred with air, and kept warm at 50-55° C., and then an anti-warping additive, hydroxyethyl cellulose and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0014] In any embodiment, the stirring time for adding sulfuric acid is 30-40 min; and / or the stirring time for adding chloride ions is 10-20 min.

[0015] In addition, the present invention also provides a method for preparing a copper foil, comprising the following steps:

[0016] The iridium-tantalum coated titanium plate is used as the anode and the titanium plate is used as the cathode. The electrolytic copper foil bath solution or the electrolytic copper foil bath solution prepared by the above preparation method is stirred by air under the action of an electric field, and the cathode current density is 60-70A / dm 2 , and electrodeposition is performed for 1-2 minutes to obtain the copper foil.

[0017] In addition, the present invention also provides a copper foil prepared by the above preparation method.

[0018] Compared with the prior art, the beneficial effects of the present invention include: the anti-warping additive proposed by the present invention includes: a nitrogen heterocycle modified compound and a sulfur-containing organic compound, the mass ratio of the nitrogen heterocycle modified compound to the sulfur-containing organic compound is (10-40):1; the nitrogen heterocycle modified compound is one or more of chlorpromazine, imidazole-epichlorohydrin copolymer, 1-methylpyrazole-4-carboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, triglycidyl isocyanurate and pyrroloquinoline quinone acid; the additive can effectively prevent the copper foil from warping from the source of copper foil manufacturing, without the need for annealing treatment process, which not only reduces production energy consumption, but also greatly improves production efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 are photos of copper foils obtained in Examples 1-6 of the present invention;

[0020] Figure 2 This is a photograph of the copper foil prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0021] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and a given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, if a range of 60 to 120 and 80 to 110 is listed for a particular parameter, it is understood that a range of 60 to 110 and 80 to 120 is also expected. In addition, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4 and 5 are listed, the following ranges can all be expected: 1 to 3, 1 to 4, 1 to 5, 2 to 3, 2 to 4 and 2 to 5. In the present application, unless otherwise specified, the numerical range "a to b" represents an abbreviation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are listed in this document, and "0-5" is just an abbreviation of these numerical combinations. In addition, when a parameter is expressed as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0022] If there is no special explanation, the "include" and "comprising" mentioned in this application are open-ended or closed-ended. For example, the "include" and "comprising" may mean that other components not listed may also be included or only the listed components may be included or only the listed components may be included.

[0023] If not specifically stated, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0024] The present specific embodiment provides an anti-warping additive, comprising: a nitrogen heterocyclic modified compound and a sulfur-containing organic compound, wherein the mass ratio of the nitrogen heterocyclic modified compound to the sulfur-containing organic compound is (10-40):1; the nitrogen heterocyclic modified compound is one or more of chlorpromazine, imidazole-epichlorohydrin copolymer, 1-methylpyrazole-4-carboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, triglycidyl isocyanurate and pyrroloquinoline quinone acid; the sulfur-containing organic compound is one or more of sodium phenyl polydisulfide propane sulfonate, 2-tetrahydrothiazolidinethione, 2-imidazolethione, and sodium 3-mercaptopropane sulfonate; the sulfur-containing organic compound is one or more of sodium phenyl polydisulfide propane sulfonate, 2-tetrahydrothiazolidinethione, 2-imidazolethione, and sodium 3-mercaptopropane sulfonate.

[0025] In some embodiments, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-imidazolethione; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer and triglycidyl isocyanurate, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-tetrahydrothiazolidinethione; and / or, the nitrogen heterocyclic modified compound is The compound is an imidazole-epichlorohydrin copolymer and pyrroloquinoline quinone acid, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is 1-methylpyrazole-4-carboxylic acid and triglycidyl isocyanurate, and the sulfur-containing organic compound is sodium phenyl polydisulfide propane sulfonate; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer and 1H-pyrrole-2,5-dicarboxylic acid, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate.

[0026] This specific embodiment also proposes an application of the above-mentioned anti-warping additive in the preparation of electrolytic copper foil or electrolytic copper foil bath solution.

[0027] In addition, this specific embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 5-20 mg / L, 280-400 g / L of copper sulfate, 100-130 g / L of sulfuric acid, 25-40 mg / L of chloride ions, 8-30 ppm of gelatin and 30-60 ppm of hydroxyethyl cellulose.

[0028] In addition, this specific embodiment also proposes a method for preparing the above-mentioned electrolytic copper foil bath solution, comprising the following steps:

[0029] Heat water to 50-55°C, add copper sulfate and stir for 30-40 minutes until dissolved, continue to add sulfuric acid and stir, then add chloride ions and stir for 10-20 minutes to obtain the electrolytic copper foil basic bath solution;

[0030] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred with air, and kept warm at 50-55° C., and then a copper foil anti-warping additive, hydroxyethyl cellulose and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0031] In addition, this specific embodiment also proposes a method for preparing copper foil, comprising the following steps:

[0032] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution or the electrolytic copper foil bath solution prepared by the above preparation method is stirred by air under the action of an electric field, and the cathode current density is 60-70A / dm 2 , and electrodeposition is performed for 1-2 minutes to obtain the copper foil.

[0033] This specific implementation also provides a copper foil, which is made by the above-mentioned preparation method.

[0034] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0035] In the present invention, reference is made to “some embodiments”, “this embodiment”, examples, etc., which describe a subset of all possible embodiments, but it can be understood that “some embodiments” may be the same subset or different subsets of all possible embodiments and may be combined with each other without conflict.

[0036] If similar descriptions of "first / second" appear in the application documents, the following instructions are added. In the following description, the terms "first\second\third" are merely used to distinguish similar objects and do not represent a specific ordering of the objects. It is understandable that "first\second\third" can be interchanged in a specific order or sequence where permitted, so that the embodiments described herein can be implemented in an order other than that illustrated or described herein.

[0037] In this embodiment, the term "and / or" is merely a description of the association relationship between associated objects, indicating that three relationships may exist. For example, object A and / or object B may represent three situations: object A exists alone, object A and object B exist at the same time, and object B exists alone.

[0038] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0039] The model of the imidazole-epichlorohydrin copolymer in the following examples is CAS: 68797-57-9, molecular weight 160.601, purchased from Zhongshan Dixin Chemical Co., Ltd.

[0040] The chloride ions in the following examples are from commercially available concentrated hydrochloric acid with a concentration of 36%-38%.

[0041] Example 1

[0042] This embodiment provides an anti-warping additive, including an imidazole-epichlorohydrin copolymer and 2-imidazolethione, wherein the mass ratio of the imidazole-epichlorohydrin copolymer to the 2-imidazolethione is 20:1.

[0043] This embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 15 mg / L, the concentration of gelatin is 20 ppm, the concentration of hydroxyethyl cellulose is 45 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0044] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0045] According to the concentration of the above substances, water was heated to 55°C, copper sulfate was added and stirred for 35 minutes until dissolved, sulfuric acid was added and stirred, and then chloride ions were added and stirred for 15 minutes to obtain the electrolytic copper foil basic bath solution;

[0046] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 50° C. Then, a copper foil anti-warping additive, hydroxyethyl cellulose, and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0047] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0048] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 60A / dm 2 , the copper foil is obtained by electroplating for 1.5 minutes, and the warpage of the obtained copper foil is ≤1.5mm.

[0049] Example 2

[0050] This embodiment provides an anti-warping additive, including imidazole-epichlorohydrin copolymer, triglycidyl isocyanurate and sodium 3-mercaptopropane sulfonate, and the mass ratio of imidazole-epichlorohydrin copolymer, triglycidyl isocyanurate and sodium 3-mercaptopropane sulfonate is 20:5:1.

[0051] This embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 15 mg / L, the concentration of gelatin is 8 ppm, the concentration of hydroxyethyl cellulose is 60 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0052] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0053] According to the concentration of the above substances, water is heated to 50°C, copper sulfate is added and stirred for 40 minutes until dissolved, sulfuric acid is added and stirred, and then chloride ions are added and stirred for 10 minutes to obtain the electrolytic copper foil basic bath solution;

[0054] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 50° C. Then, a copper foil anti-warping additive, hydroxyethyl cellulose, and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0055] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0056] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 70A / dm 2 , the copper foil is obtained by electroplating for 1 minute, and the warpage of the obtained copper foil is ≤1.0mm.

[0057] Example 3

[0058] This embodiment provides an anti-warping additive, including an imidazole-epichlorohydrin copolymer and 2-thiazolidinethione, wherein the mass ratio of the imidazole-epichlorohydrin copolymer to the 2-thiazolidinethione is 40:1.

[0059] This embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 20 mg / L, the concentration of gelatin is 8 ppm, the concentration of hydroxyethyl cellulose is 45 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0060] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0061] According to the concentration of the above substances, water is heated to 55°C, copper sulfate is added and stirred for 30 minutes until dissolved, sulfuric acid is added and stirred, and then chloride ions are added and stirred for 20 minutes to obtain the electrolytic copper foil basic bath solution;

[0062] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 55° C., and then a copper foil anti-warping additive, hydroxyethyl cellulose and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0063] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0064] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 70A / dm 2 , the copper foil is obtained by electroplating for 1 minute, and the warpage of the obtained copper foil is ≤2.0mm.

[0065] Example 4

[0066] This embodiment provides an anti-warping additive, including imidazole-epichlorohydrin copolymer, pyrroloquinoline quinone acid and sodium 3-mercaptopropane sulfonate, and the mass ratio of imidazole-epichlorohydrin copolymer, pyrroloquinoline quinone acid and sodium 3-mercaptopropane sulfonate is 15:8:1.

[0067] This embodiment also proposes an electrolytic copper foil bath liquid, including the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 10 mg / L, the concentration of gelatin is 30 ppm, the concentration of hydroxyethyl cellulose is 30 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0068] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0069] According to the concentration of the above substances, water was heated to 50°C, copper sulfate was added and stirred for 35 minutes until dissolved, sulfuric acid was added and stirred, and then chloride ions were added and stirred for 15 minutes to obtain the electrolytic copper foil basic bath solution;

[0070] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 50° C. Then, a copper foil anti-warping additive, hydroxyethyl cellulose, and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0071] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0072] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 60A / dm 2 , the copper foil is obtained by electroplating for 1.5 minutes, and the warpage of the obtained copper foil is ≤0.5mm.

[0073] Example 5

[0074] This embodiment provides an anti-warping additive, including 1-methylpyrazole-4-carboxylic acid, triglycidyl isocyanurate and sodium phenyl polydisulfide propane sulfonate, and the mass ratio of 1-methylpyrazole-4-carboxylic acid, triglycidyl isocyanurate and sodium phenyl polydisulfide propane sulfonate is 15:10:1.

[0075] This embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 20 mg / L, the concentration of gelatin is 8 ppm, the concentration of hydroxyethyl cellulose is 30 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0076] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0077] According to the concentration of the above substances, water was heated to 50°C, copper sulfate was added and stirred for 40 minutes until dissolved, sulfuric acid was added and stirred, and then chloride ions were added and stirred for 15 minutes to obtain the electrolytic copper foil basic bath solution;

[0078] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 50° C. Then, a copper foil anti-warping additive, hydroxyethyl cellulose, and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0079] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0080] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 70A / dm 2 , the copper foil is obtained by electroplating for 1 minute, and the warpage of the obtained copper foil is ≤0.5mm.

[0081] Example 6

[0082] This embodiment provides an anti-warping additive, including imidazole-epichlorohydrin copolymer, 1H-pyrrole-2,5-dicarboxylic acid and sodium 3-mercaptopropane sulfonate, and the mass ratio of imidazole-epichlorohydrin copolymer to 1H-pyrrole-2,5-dicarboxylic acid and sodium 3-mercaptopropane sulfonate is 20:15:1.

[0083] This embodiment also proposes an electrolytic copper foil bath liquid, comprising the above-mentioned anti-warping additive for electrolytic copper foil, wherein the concentration of the anti-warping additive for electrolytic copper foil in the electrolytic copper foil bath liquid is 20 mg / L, the concentration of gelatin is 30 ppm, the concentration of hydroxyethyl cellulose is 45 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0084] This embodiment also provides a method for preparing the electrolytic copper foil bath solution, comprising the following steps:

[0085] According to the concentration of the above substances, water is heated to 55°C, copper sulfate is added and stirred for 30 minutes until dissolved, sulfuric acid is added and stirred, and then chloride ions are added and stirred for 20 minutes to obtain the electrolytic copper foil basic bath solution;

[0086] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 55° C., and then a copper foil anti-warping additive, hydroxyethyl cellulose and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

[0087] In addition, this embodiment also provides a method for preparing a copper foil, comprising the following steps:

[0088] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 70A / dm 2 , the copper foil is obtained by electroplating for 1 minute, and the warpage of the obtained copper foil is ≤0.5mm.

[0089] Comparative Example 1

[0090] The electrolytic copper foil bath solution of this comparative example is different from that of Example 1 in that no anti-warping additive is added. In the electrolytic copper foil bath solution, the concentration of gelatin is 20 ppm, the concentration of hydroxyethyl cellulose is 45 ppm, the concentration of copper sulfate is 320 g / L, the concentration of sulfuric acid is 120 g / L, and the concentration of chloride ions is 30 mg / L.

[0091] This comparative example also proposes a method for preparing the above electrolytic copper foil bath solution, comprising the following steps:

[0092] According to the concentration of the above substances, water was heated to 55°C, copper sulfate was added and stirred for 35 minutes until dissolved, sulfuric acid was added and stirred, and then chloride ions were added and stirred for 15 minutes to obtain the electrolytic copper foil basic bath solution;

[0093] The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred with air, and kept warm at 50° C., and then hydroxyethyl cellulose and gelatin are added and stirred to obtain the electrolytic copper foil bath solution.

[0094] In addition, this comparative example also proposes a method for preparing a copper foil, comprising the following steps:

[0095] The iridium-tantalum coated titanium plate is used as the anode and the pure titanium plate is used as the cathode. The electrolytic copper foil bath solution is stirred by air under the action of the electric field. The cathode current density is 60A / dm 2 , electroplating for 1.5 minutes to obtain the copper foil, the obtained copper foil is warped, specifically as follows Figure 2 shown.

[0096] Combination Figure 1-2 It can be seen that the copper foils prepared in Examples 1-6 have low warpage, especially the copper foils in Examples 2, 4, 5 and 6 have warpage as low as ≤0.5 mm. However, the copper foil in Comparative Example 1 without adding anti-warpage additives has obvious warpage.

[0097] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. An anti-warping additive, characterized in that: include: A nitrogen heterocyclic modified compound and a sulfur-containing organic compound, wherein the mass ratio of the nitrogen heterocyclic modified compound to the sulfur-containing organic compound is (10-40):1; the nitrogen heterocyclic modified compound is one or more of chlorpromazine, imidazole-epichlorohydrin copolymer, 1-methylpyrazole-4-carboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, triglycidyl isocyanurate and pyrroloquinoline quinone acid.

2. The anti-warpage additive according to claim 1, characterized in that The sulfur-containing organic compound is one or more of sodium phenyl polydisulfide propane sulfonate, 2-thiazolidinethione, 2-imidazolethione and sodium 3-mercaptopropane sulfonate.

3. The anti-warpage additive according to claim 2, characterized in that The nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-imidazolethione; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer and triglycidyl isocyanurate, and the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is an imidazole-epichlorohydrin copolymer, and the sulfur-containing organic compound is 2-thiazolidinethione; and / or, the nitrogen heterocyclic modified compound is Imidazole-epichlorohydrin copolymer and pyrroloquinoline quinone acid, the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate; and / or, the nitrogen heterocyclic modified compound is 1-methylpyrazole-4-carboxylic acid and triglycidyl isocyanurate, the sulfur-containing organic compound is sodium phenyl polydisulfide propane sulfonate; and / or, the nitrogen heterocyclic modified compound is imidazole-epichlorohydrin copolymer and 1H-pyrrole-2,5-dicarboxylic acid, the sulfur-containing organic compound is sodium 3-mercaptopropane sulfonate.

4. Use of the anti-warping additive according to any one of claims 1 to 3 in the preparation of electrolytic copper foil or electrolytic copper foil bath solution.

5. An electrolytic copper foil bath solution, characterized in that: The anti-warping additive comprises the anti-warping additive according to any one of claims 1 to 3, wherein the concentration of the anti-warping additive in the electrolytic copper foil bath is 5-20 mg / L.

6. The electrolytic copper foil bath according to claim 5, characterized in that: It also includes 280-400 g / L of copper sulfate, 100-130 g / L of sulfuric acid, 25-40 mg / L of chloride ions, 8-30 ppm of gelatin and 30-60 ppm of hydroxyethyl cellulose.

7. A method for preparing an electrolytic copper foil bath solution according to any one of claims 5 to 6, characterized in that: The following steps are involved: Heat water to 50-55°C, add copper sulfate and stir until dissolved, continue to add sulfuric acid and stir, then add chloride ions and stir to obtain the electrolytic copper foil basic bath solution; The electrolytic copper foil base bath solution is placed in an electrolytic copper foil bath, stirred in air, and kept warm at 50-55° C., and then an anti-warping additive, hydroxyethyl cellulose and gelatin are added and stirred to obtain an electrolytic copper foil bath solution.

8. The method for preparing the electrolytic copper foil bath according to claim 7, characterized in that: The stirring time for adding sulfuric acid is 30-40 minutes; and / or, the stirring time for adding chloride ions is 10-20 minutes.

9. A method for preparing a copper foil, characterized in that: The following steps are involved: The iridium-tantalum coated titanium plate is used as the anode and the titanium plate is used as the cathode. The electrolytic copper foil bath solution described in any one of claims 5 to 6 or the electrolytic copper foil bath solution prepared by the preparation method described in any one of claims 7 to 8 is stirred by air under the action of an electric field, and the cathode current density is 60-70A / dm 2 , and electrodeposition is performed for 1-2 minutes to obtain the copper foil.

10. A copper foil, characterized in that: Prepared by the preparation method described in claim 9.

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