Copper foil passivation solution and treatment method thereof

Abstract

The application provides a copper foil passivation solution, which comprises 4-7 ml / L of bis-1,6-hexylene triamine penta(methylene) phosphonic acid, 3-5 g / L of 1,2-vinyl diphosphonic acid, 0.5-1.5 g / L of sodium 2-hydroxyl citrate, 0.05-0.1 g / L of 2-(ethylamino) ethyl-1-alcohol, 5-7 g / L of modified aluminum nitride, and the rest is water; the modified aluminum nitride is coated by decanoic acid and 5-decyne-4,7-diol-2,4,7,9-tetramethyl, so that the hydrolysis problem of the aluminum nitride is solved; the copper foil passivation solution can be used for realizing the passivation of the aluminum nitride film on the copper foil by using a direct immersion method, the heat dissipation is good, the parameter requirement of the electronic copper foil is met, the process is simple, the raw materials are safe and environmentally friendly, and the copper foil passivation solution can be used as a replacement agent of a chromium salt passivation solution.

Description

Technical Field

[0001] This project is designed for the field of copper foil processing, specifically a copper foil passivation treatment solution and its treatment method. Background Technology

[0002] Electrolytic copper foil is widely used in PCBs and lithium batteries due to its excellent conductivity, tensile strength, and surface roughness. The performance of electrolytic copper foil plays a decisive role in the development of the electronics field, especially as a negative electrode carrier for lithium batteries. With the development of new energy vehicles in recent years, there are more stringent requirements for the performance of lithium batteries, which has led to higher demands on the performance of copper foil. The traditional manufacturing process of electrolytic copper foil mainly includes: copper foil generation, copper foil peeling, drying, passivation treatment, washing, water squeezing, drying, and winding.

[0003] In the passivation process, two methods are generally used. One is zinc plating and chromium plating. This process consumes a large amount of pure water, resulting in high water treatment costs. The finished product contains metallic zinc and environmentally harmful hexavalent chromium. Under high temperature conditions, metallic zinc can penetrate into the copper layer, causing a sharp increase in the resistance of the copper foil, making it unsuitable for lithium batteries used in new energy vehicles. The other method is direct immersion, using acidic chromate as the passivating agent. This method works by causing partial dissolution of the surface of the metal after contact with the chromate passivating agent, which then redeposits as metal-chromium oxide. Neither of these methods can avoid the presence of hexavalent chromium, affecting the performance of lithium batteries. Furthermore, due to the high toxicity of chromium and its significant environmental pollution, many countries have strictly restricted the use and emission of chromates. With the implementation of EU directives, the use of chromates in metal surface treatment has been greatly restricted. Therefore, developing copper foil passivation treatment towards a more environmentally friendly, lower energy consumption, and more stable direction is one of the main research directions in this industry.

[0004] However, although chromium is highly toxic and causes serious pollution, chromium plating or chromate immersion in the passivation process of electrolytic copper foil utilizes chromium's corrosion resistance and, more importantly, its high thermal conductivity, almost identical to that of copper. This plays a crucial role in the heat dissipation of the passivated copper foil, enabling it to withstand temperatures above 400°C or even 500°C, meeting current performance requirements for copper foil. While there are reports in literature and patents of chromium-free passivation solutions, these merely replace chromium's anti-oxidation properties with non-polluting metal or polymer coatings, eliminating chromium's environmental pollution, but failing to compensate for the poor heat dissipation caused by the absence of chromium. This is one of the main reasons why the industry, despite knowing the high toxicity of chromium, cannot replace it. Summary of the Invention

[0005] Aluminum nitride (AlN) has high thermal conductivity (theoretical thermal conductivity is 320 W / (m·K), and the actual value can reach 260 W / (m·K), making it a thermally conductive alternative to chromium. However, due to its susceptibility to hydrolysis, most current research focuses on its use as a composite material, pressing it with copper foil to form a composite plate to utilize its thermal conductivity. There are no reports on its direct use as a copper foil passivation agent. Existing research shows that modifying aluminum nitride with organic acid (+organic matter) coating can effectively solve its hydrolysis problem. However, aluminum nitride treated by this method has poor dispersibility, is prone to agglomeration, and has high porosity, making it impossible to directly passivate copper foil using the immersion method. Feasible methods are all based on vacuum sputtering coating. Moreover, this method requires a first aluminum layer as a base layer; otherwise, the directly sputtered aluminum nitride layer is prone to peeling off, resulting in poor film formation, high investment costs, and complex processes.

[0006] The purpose of this application is, based on the above background, to provide a passivation solution of aluminum nitride doped with copper foil that can be directly treated by immersion.

[0007] Another object of the present invention is to provide a method for treating copper foil using the above-mentioned passivation solution.

[0008] The technical solution for achieving the objective of this invention is as follows:

[0009] A copper foil passivation solution comprises 4-7 ml / L of bis(1,6-hexanetriamine)pentamethylenephosphonic acid, 3-5 g / L of 1,2-vinyldiphosphonic acid, 0.5-1.5 g / L of sodium 2-hydroxycitrate, 0.05-0.1 g / L of 2-(ethylamino)ethyl-1-ol, 5-7 g / L of modified aluminum nitride, and the balance being water.

[0010] The preparation method of modified aluminum nitride is as follows: Dissolve 0.5-1 parts of triacontanic acid in anhydrous ethanol in a water bath at 50-60℃, add 20-30 parts of nano-aluminum nitride powder, stir with a magnetic stirrer until evenly dispersed, then let it cool naturally to room temperature and stand for 0.5-1 h, then add 2-5 parts of 5-decyn-4,7-diol-2,4,7,9-tetramethyl, stir in a water bath at 40-45℃ for 1-2 h, let it stand, evaporate the solvent in a water bath at 70℃ or centrifuge to filter out the precipitate, and dry at 70℃ to obtain the product.

[0011] A method for passivating copper foil includes the following steps:

[0012] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0013] (2) Horizontal passivation treatment: At room temperature, the copper foil is horizontally immersed in the passivation treatment solution. Under 20KHz ultrasound, after each passivation treatment of 5-10s, it is horizontally lifted, left to stand for 3-5s, rotated 180° and then immersed in the passivation treatment solution again. This process is repeated until both sides of the copper foil are immersed 5 times.

[0014] (3) Rotational passivation treatment: Turn off the ultrasonic treatment, rotate the copper foil that has been immersed in the inverted cycle in the passivation solution in a direction perpendicular to the copper foil surface at a speed of 0.5 r / min, and take it out after 10 min;

[0015] (4) The product is obtained by drying, winding and slitting, with the drying temperature being 50-70℃.

[0016] Advantages of this invention:

[0017] 1) 1,6-Hexyltriaminepentimidephosphonic acid and 1,2-vinyldiphosphonic acid are both excellent chelating agents. Combined with the complexing effect of sodium 2-hydroxycitrate, the film-forming properties are stronger. 2-(ethylamino)ethyl-1-ol is a weakly basic organic compound that can form a buffer system in aqueous solution to maintain the pH of the solution within a certain range, regulate the film-forming rate, and thus improve the uniformity and density of the film.

[0018] 2) Triacontanic acid is an organic acid, while 5-decyn-4 and 7-diol-2,4,7,9-tetramethyl are organic compounds. 5-decyn-4 and 7-diol-2,4,7,9-tetramethyl coat the surface of aluminum nitride, preventing water molecules from contacting the surface and enhancing the hydrolysis resistance of aluminum nitride. Triacontanic acid has unsaturated bonds, which can form a conjugated system in the system. During curing, a smooth surface can be formed. The improved surface smoothness of aluminum nitride can increase specular reflection of light and improve the gloss of aluminum nitride. In addition, the long flexible chain of triacontanic acid can allow -CC and -CO bonds to rotate internally, increasing the flexibility of aluminum nitride. Furthermore, the introduction of flexible groups further increases the flexibility of aluminum nitride.

[0019] 3) 5-Decyne-4,7-diol-2,4,7,9-tetramethyl not only possesses defoaming properties, effectively reducing bubble generation during aluminum nitride modification and decreasing the porosity of the modified aluminum nitride, thus further improving its density and gloss, but more importantly, because it lacks a cloud point, it effectively enhances the stability of subsequent film formation—a property not found in other surfactants. Simultaneously, 5-Decyne-4,7-diol-2,4,7,9-tetramethyl exhibits excellent self-leveling properties. This invention utilizes this property in conjunction with its passivation method, first achieving horizontal static film formation followed by dynamic rotational filling, effectively improving film uniformity. This allows for direct impregnation to achieve aluminum nitride film loading on copper foil surfaces, a simple process with significant implications for the copper foil processing industry. Detailed Implementation

[0020] Example 1: Preparation method of modified aluminum nitride: 0.8 parts of triacontanic acid were dissolved in anhydrous ethanol in a water bath at 55°C. 25 parts of nano-aluminum nitride powder were added and stirred with a magnetic stirrer until evenly dispersed. After naturally cooling to room temperature and standing for 0.5 h, 3 parts of 5-decyn-4,7-diol-2,4,7,9-tetramethyl were added. The mixture was stirred in a water bath at 40°C for 1.5 h and then allowed to stand. The precipitate was centrifuged and filtered out. After drying at 70°C, it was ready for use.

[0021] A copper foil passivation solution comprises 6 ml / L of bis(1,6-hexanetriaminepentimidephosphonic acid), 4 g / L of 1,2-vinyldiphosphonic acid, 1 g / L of sodium 2-hydroxycitrate, 0.08 g / L of 2-(ethylamino)ethyl-1-ol, 6 g / L of modified aluminum nitride, and the balance being water.

[0022] A method for passivating copper foil includes the following steps:

[0023] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0024] (2) Horizontal passivation treatment: The copper foil is horizontally immersed in the passivation solution at room temperature, and the circulation rate of the passivation solution is 13m³. 3 / h; passivation under 20KHz ultrasound;

[0025] First time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0026] Second time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0027] Third time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0028] Fourth time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 4 seconds, then rotate it 180° and continue to immerse it in the passivation solution.

[0029] Fifth time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 5 seconds, then rotate it 180° and continue to immerse it in the passivation solution;

[0030] Sixth time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0031] Seventh time: After passivation treatment for 6 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0032] Eighth time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0033] Ninth time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0034] Tenth time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0035] (3) Rotational passivation treatment: Turn off the ultrasonic treatment, rotate the copper foil that has been immersed in the inverted cycle in the passivation solution in a direction perpendicular to the copper foil surface at a speed of 0.5 r / min, and take it out after 10 min;

[0036] (4) The product is then dried at 55°C, rolled up and cut.

[0037] Example 2: Preparation method of modified aluminum nitride: 0.5 parts of triacontanic acid were dissolved in anhydrous ethanol in a water bath at 60°C. 20 parts of nano-aluminum nitride powder were added and stirred with a magnetic stirrer until evenly dispersed. After naturally cooling to room temperature and standing for 1 hour, 5 parts of 5-decyn-4,7-diol-2,4,7,9-tetramethyl were added. The mixture was stirred at 45°C in a water bath for 2 hours and then allowed to stand. The solvent was evaporated at 70°C in a water bath for later use.

[0038] A copper foil passivation solution comprises 4 ml / L of bis(1,6-hexanetriaminepentimidephosphonic acid), 5 g / L of 1,2-vinyldiphosphonic acid, 1.5 g / L of sodium 2-hydroxycitrate, 0.1 g / L of 2-(ethylamino)ethyl-1-ol, 5 g / L of modified aluminum nitride, and the balance being water.

[0039] A method for passivating copper foil includes the following steps:

[0040] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0041] (2) Horizontal passivation treatment: The copper foil is horizontally immersed in the passivation solution at room temperature, and the circulation rate of the passivation solution is 12m³. 3 / h; passivation under 20KHz ultrasound;

[0042] First time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0043] Second time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0044] Third time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0045] Fourth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0046] Fifth time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 5 seconds, then rotate it 180° and continue to immerse it in the passivation solution;

[0047] Sixth time: After passivation treatment for 6 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0048] Seventh time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0049] Eighth time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0050] Ninth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0051] Tenth time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0052] (3) Rotational passivation treatment: Turn off the ultrasonic treatment, rotate the copper foil that has been immersed in the inverted cycle in the passivation solution in a direction perpendicular to the copper foil surface at a speed of 0.5 r / min, and take it out after 10 min;

[0053] (4) After drying at 50°C, the product is rolled up and cut.

[0054] Example 3: Preparation method of modified aluminum nitride: 1 part of triacontanic acid was dissolved in anhydrous ethanol in a water bath at 50°C. 30 parts of nano-aluminum nitride powder were added and stirred with a magnetic stirrer until evenly dispersed. After naturally cooling to room temperature and standing for 0.5 h, 2 parts of 5-decyn-4,7-diol-2,4,7,9-tetramethyl were added. The mixture was stirred in a water bath at 40°C for 1 h and then allowed to stand. The precipitate was centrifuged and filtered out. After drying at 70°C, it was ready for use.

[0055] A copper foil passivation solution comprises 7 ml / L of bis(1,6-hexanetriaminepentamethylphosphonic acid), 3 g / L of 1,2-vinyldiphosphonic acid, 0.5 g / L of sodium 2-hydroxycitrate, 0.05 g / L of 2-(ethylamino)ethyl-1-ol, 7 g / L of modified aluminum nitride, and the balance being water.

[0056] A method for passivating copper foil includes the following steps:

[0057] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0058] (2) Horizontal passivation treatment: The copper foil is horizontally immersed in the passivation solution at room temperature, and the circulation rate of the passivation solution is 15m³. 3 / h; passivation under 20KHz ultrasound;

[0059] First time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0060] Second time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0061] Third time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0062] Fourth time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 5 seconds, then rotate it 180° and continue to immerse it in the passivation solution.

[0063] Fifth time: After passivation treatment for 6 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0064] Sixth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0065] Seventh time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0066] Eighth time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0067] Ninth time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0068] Tenth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0069] (3) Rotational passivation treatment: Turn off the ultrasonic treatment, rotate the copper foil that has been immersed in the inverted cycle in the passivation solution in a direction perpendicular to the copper foil surface at a speed of 0.5 r / min, and take it out after 10 min;

[0070] (4) After drying at 70℃, the product is rolled up and cut.

[0071] Comparative Example 1:

[0072] A method for passivating copper foil includes the following steps:

[0073] Preparation method of modified aluminum nitride: Dissolve 0.8 parts of stearic acid in anhydrous ethanol in a water bath at 55°C, add 25 parts of nano aluminum nitride powder, stir with a magnetic stirrer until evenly dispersed, then let it cool naturally to room temperature and stand for 0.5 h, then add 3 parts of 5-decyn-4,7-diol-2,4,7,9-tetramethyl, stir in a water bath at 40°C for 1.5 h, let stand, centrifuge and filter out the precipitate, dry at 70°C for later use; the rest is the same as in Example 1.

[0074] Comparative Example 2:

[0075] A method for passivating copper foil includes the following steps:

[0076] Preparation method of modified aluminum nitride: Dissolve 0.8 parts of triacontanic acid in anhydrous ethanol in a water bath at 55°C, add 25 parts of nano aluminum nitride powder, stir with a magnetic stirrer until evenly dispersed, then let it cool naturally to room temperature and stand for 0.5 h, add 3 parts of 8-hydroxyquinoline, stir at 40°C in a water bath for 1.5 h, let stand, centrifuge and filter out the precipitate, dry at 70°C for later use; the rest is the same as in Example 1.

[0077] Comparative Example 3:

[0078] A method for passivating copper foil includes the following steps:

[0079] Preparation method of modified aluminum nitride: Dissolve 0.8 parts of palmitic acid in anhydrous ethanol in a water bath at 55°C, add 25 parts of nano aluminum nitride powder, stir with a magnetic stirrer until evenly dispersed, then let it cool naturally to room temperature and stand for 0.5 h, add 3 parts of Tween 80, stir at 40°C in a water bath for 1.5 h, let stand, centrifuge and filter out the precipitate, dry at 70°C for later use; the rest is the same as in Example 1.

[0080] Comparative Example 4:

[0081] A method for passivating copper foil includes the following steps:

[0082] The passivation solution includes 6 ml / L of hydroxyethylidene diphosphonic acid, 4 g / L of 1,2-vinyl diphosphonic acid, 1 g / L of sodium 2-hydroxycitrate; 0.08 g / L of 2-(ethylamino)ethyl-1-ol; 6 g / L of modified aluminum nitride, with the balance being water; the rest is the same as in Example 1.

[0083] Comparative Example 5:

[0084] A method for passivating copper foil includes the following steps:

[0085] The passivation solution includes 6 ml / L of bis(1,6-hexyltriaminepentamethylphosphonic acid), 4 g / L of hydroxyethylidene diphosphonic acid, 1 g / L of sodium 2-hydroxycitrate; 0.08 g / L of 2-(ethylamino)ethyl-1-ol; 6 g / L of modified aluminum nitride, with the balance being water; the rest is the same as in Example 1.

[0086] Comparative Example 6:

[0087] A method for passivating copper foil includes the following steps:

[0088] The passivation solution includes 6 ml / L of bis(1,6-hexyltriaminepentimidephosphonic acid), 4 g / L of 1,2-vinyldiphosphonic acid, 1 g / L of sodium citrate; 0.08 g / L of 2-(ethylamino)ethyl-1-ol; 6 g / L of modified aluminum nitride, with the balance being water; the rest is the same as in Example 1.

[0089] Comparative Example 7:

[0090] A method for passivating copper foil includes the following steps:

[0091] The passivation solution includes 6 ml / L of bis(1,6-hexyltriaminepentimidephosphonic acid), 4 g / L of 1,2-vinyldiphosphonic acid, and 1 g / L of sodium 2-hydroxycitrate; 6 g / L of modified aluminum nitride, with the remainder being water; the rest is the same as in Example 1.

[0092] Comparative Example 8:

[0093] A method for passivating copper foil includes the following steps:

[0094] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0095] (2) Horizontal passivation treatment: The copper foil is horizontally immersed in the passivation solution at room temperature, and the circulation rate of the passivation solution is 13m³. 3 / h; passivation under 20KHz ultrasound; after passivation treatment for 2min, lift horizontally, let stand for 3-5s, rotate 180° and continue to immerse in passivation solution, continue passivation treatment for 2min;

[0096] (3) Rotational passivation treatment: Turn off the ultrasonic treatment, rotate the copper foil that has been immersed in the inverted cycle in the passivation solution in a direction perpendicular to the copper foil surface at a speed of 0.5 r / min, and take it out after 10 min;

[0097] (4) After drying at 70℃, the product is rolled up and cut.

[0098] Comparative Example 9:

[0099] A method for passivating copper foil includes the following steps:

[0100] (1) Copper foil pretreatment: The copper foil obtained by stripping is dried using a hot air drying device;

[0101] (2) Horizontal passivation treatment: The copper foil is horizontally immersed in the passivation solution at room temperature, and the circulation rate of the passivation solution is 13m³. 3 / h; passivation under 20KHz ultrasound;

[0102] First time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0103] Second time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0104] Third time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0105] Fourth time: After passivation treatment for 8 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0106] Fifth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0107] Sixth time: After passivation treatment for 6 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0108] Seventh time: After passivation treatment for 10 seconds, lift it horizontally, let it stand for 4 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0109] Eighth time: After passivation treatment for 9 seconds, lift it horizontally, let it stand for 3 seconds, turn it 180° and continue to immerse it in the passivation solution;

[0110] Ninth time: After passivation treatment for 7 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0111] Tenth time: After passivation treatment for 5 seconds, lift it horizontally, let it stand for 5 seconds, turn it 180° and continue to immerse it in the passivation treatment solution;

[0112] (3) Take it out and dry it at 70℃, then roll it up and cut it to get the product.

[0113] experiment:

[0114] The above-described embodiments and comparative examples were used to passivate 8μm and 12μm electrolytic copper foils produced by our company, with 4 pieces of each specification.

[0115] Experiment 1: One piece of each of the two specifications was used. The surface roughness of the copper foil was tested using an SJ57 series 3d probe contact roughness profiler according to the GB29847-2013 method. The data were recorded as shown in Table 1 below.

[0116] Experiment 2: Two pieces of each of the two specifications were placed in a forced-air drying oven at 150℃ and 200℃ respectively. Every 10 minutes, the discoloration of the copper foil surface was observed. If oxidation discoloration occurred, it was marked with "+" and otherwise "-". The records are shown in Table 2 below.

[0117] Experiment 3: One piece of each of the two specifications was used. The thermal conductivity of each sample was measured using a GYDR-3030 thermal conductivity meter. The data were recorded as shown in Table 1 below.

[0118]

[0119] .

Claims

1. A copper foil passivation treatment solution, characterized by: The composition comprises 4-7 ml / L of bis-1,6-hexamethylene triamine penta(methylene phosphonic acid), 3-5 g / L of 1,2-vinyl diphosphonic acid, 0.5-1.5 g / L of sodium 2-hydroxy citrate, 0.05-0.1 g / L of 2-(ethylamino)ethyl-1-alcohol, 5-7 g / L of modified aluminum nitride, and the rest is water; The modified aluminum nitride is prepared by the following method: 0.5-1 parts of triacontanoic acid is dissolved in anhydrous ethanol under water bath at 50-60 DEG C, 20-30 parts of nano aluminum nitride powder is added, and the mixture is stirred until uniformly dispersed by a magnetic stirrer, and then naturally cooled to room temperature, and then 2-5 parts of 5-decyne-4,7-diol-2,4,7,9-tetramethyl is added, and the mixture is stirred under water bath at 40-45 DEG C for 1-2 h, and then the mixture is left to stand, and the precipitate is obtained by centrifugal filtration after the solvent is evaporated under water bath at 70 DEG C, and the precipitate is dried at 70 DEG C to obtain the modified aluminum nitride.

2. A method of passivation treatment using the treatment liquid according to claim 1, characterized by: The method comprises the following steps: (1) copper foil pretreatment: the copper foil obtained by peeling is dried by a hot air drying device; (2) horizontal passivation treatment: the copper foil is horizontally immersed in a passivation treatment solution under normal temperature, and after 5-10 s of passivation treatment under 20 kHz ultrasonic, the copper foil is horizontally lifted, and after 3-5 s of standing, the copper foil is turned over by 180 DEG and then continuously immersed in the passivation treatment solution, and the process is repeated until the copper foil is immersed for 5 times with both sides upward; (3) rotary passivation treatment: after the completion of the immersion and turning over, the copper foil is rotated in the passivation treatment solution with the direction perpendicular to the surface of the copper foil, and the rotation speed is 0.5 r / min, and the copper foil is taken out after 10 min of treatment; (4) drying, winding and slitting are performed to obtain the copper foil, and the drying temperature is 50-70 DEG C.

3. The method of processing of claim 2, wherein: The circulation amount of the passivation treatment liquid in the step (2) and the step (3) is 12-15 m 3 / h.

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