Preparation method of copper foil with uniform nano-sized holes
Through electroplating, heat treatment and modified corrosion liquid treatment, the problems of uneven pore size and poor porosity of copper foil are solved, and the preparation of copper foil with uniform nano-sized pores is achieved, reducing costs and improving quality.
Patent Information
- Application Number
- CN202411938143.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-26
- Publication Date
- 2025-05-13
AI Technical Summary
In the prior art, the pore size of copper foil is uneven and the porosity is poor, resulting in complex preparation process, high cost and difficult to control quality.
The copper foil is electroplating and then heat treatment is performed to form a zinc-containing copper foil, and the modified corrosion solution is used to corrode to form a copper foil with uniform nano-size pores.
Through this method, copper foil with uniform pore size and excellent porosity was successfully obtained, which solved the problem of poor quality of copper foil in the prior art, reduced the preparation cost and improved the uniformity of the product.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of copper foil preparation, and in particular relates to a method for preparing copper foil with uniform nano-sized pores. Background Art
[0002] Nanoporous metals, with their unique nano-sized pore structure, not only inherit the excellent physical and chemical properties of metal materials, but also show the unique characteristics of nanomaterials. This combination makes nanoporous metals show great application potential in many high-tech fields, such as catalysts, electrode materials, sensors, surface enhanced Raman scattering substrates, and hydrogen storage. Among them, porous copper foil has attracted widespread attention from researchers due to its low cost, environmental friendliness, and excellent physical and chemical properties.
[0003] The preparation process of nanoporous copper foil is complex and challenging. Traditional preparation methods, such as melt electroplating, hydrogen bubble dynamic template electrodeposition, and organic slurry coating, can produce porous copper foil to a certain extent, but there are many shortcomings. For example, the melting process is complicated, has high requirements for equipment, and is prone to copper oxidation. The subsequent corrosion process also causes waste of resources and increases the preparation cost. Although the preparation process of hydrogen bubble dynamic template electrodeposition is relatively simple and low in cost, the mechanical properties of the porous copper obtained are poor, and it is difficult to control the particle size and pore size of the porous copper. Although the organic slurry coating method is simple to operate and low in cost, the quality of the porous copper obtained is poor, and the particle size, pore size and uniformity are difficult to control. Summary of the invention
[0004] The object of the present invention is to provide a method for preparing a copper foil having uniform nano-sized pores, so as to solve the technical problems of uneven pore size and poor porosity of the copper foil in the prior art.
[0005] In order to achieve the above object, the present invention adopts the following technical solutions: The present invention provides a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: hang the degreased and cleaned copper foil with a clip in the electroplating tank containing the electroplating solution, place it at the cathode position, immerse it completely, turn on the power supply for electroplating, and obtain the copper foil with zinc electroplating on the surface after the treatment; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain the zinc-containing copper foil, and placing the zinc-containing copper foil into a modified etching solution for etching to obtain a crude product; Step 3: Take out the crude product, wash it, and dry it to obtain a copper foil with uniform nano-sized pores.
[0006] Preferably, in step 1, the temperature during the degreasing treatment is 70-80°C, 70wt% sodium hydroxide is used as the degreasing solution, the plating solution is composed of 2-4 parts of zinc sulfate, 0.9-1.1 parts of sodium sulfate, 8-10 parts of boric acid, 1-1.5 parts of sodium chloride and 0.2-0.5 parts of brightener, and the current density during the treatment is 10-100mA / cm 2 , the processing time is 15-30min.
[0007] Preferably, the method for preparing the modified corrosive solution comprises the following steps: Q1: Add N-iodosuccinimide and diphenyl chlorophosphate into a container, then replace the air in the container with argon, then add aniline, benzyl alcohol and 1,4-dioxane in sequence, seal, and react in an oil bath; Q2: After the reaction is completed, cool it, add ethyl acetate, rotary evaporate, and purify to obtain a modified etching solution.
[0008] Preferably, in Q1, the dosage ratio of N-iodosuccinimide, diphenyl chlorophosphate, aniline, benzyl alcohol and 1,4-dioxane is (4.5-9) mg: (172-340) mg: (18-22) μL: (80-150) μL: (1.3-2.3) mL, the oil bath reaction temperature is 120-140°C, and the reaction time is 15-18 h.
[0009] Preferably, in Q2, during the purification process, a silica gel column is used for separation and purification, and the eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02.
[0010] Preferably, in step 2, the treatment temperature during the corrosion treatment is 30-50° C., and the treatment time is 2-8 hours.
[0011] Preferably, in step three, washing is performed with anhydrous ethanol and distilled water, and the drying temperature is 40-60° C. and the drying time is 8-12 h.
[0012] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: The present invention firstly uses an electroplating solution to treat the copper foil, then performs a heat treatment to obtain a zinc-containing copper foil, and then uses a modified etching solution to perform an etching treatment on the copper foil, and then obtains a copper foil with uniform nano-sized pores. The chemical components in the modified etching solution react chemically with the zinc-containing copper foil, and during the heat treatment process, zinc dissolves in copper to form solute atoms, forming nano-pores with uniform pore diameters, thereby obtaining a copper foil with uniform nano-sized pores. DETAILED DESCRIPTION
[0013] The following will be described clearly and completely in conjunction with the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0014] Example 1: This example discloses a method for preparing a modified corrosive solution, comprising the following steps: Q1: 6.7 mg N-iodosuccinimide and 270 mg diphenyl chlorophosphate were added to a container, and then the air in the container was replaced with argon. Subsequently, 20 μL aniline, 115 μL benzyl alcohol and 1.8 mL 1,4-dioxane were added in sequence, and the mixture was sealed and reacted in an oil bath at 140 °C for 16 h. Q2: After the reaction is completed, cool, add ethyl acetate, rotary evaporate, and purify. During the purification process, a silica gel column is used for separation and purification. The eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02 to obtain a modified corrosion solution.
[0015] This embodiment discloses a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: Hang the degreased (using 70wt% sodium hydroxide as degreasing solution at 70℃) and cleaned copper foil with a clip in a plating tank containing a plating solution (composed of 3 parts of zinc sulfate, 1 part of sodium sulfate, 9 parts of boric acid, 1.25 parts of sodium chloride and 0.35 parts of brightener), place it at the cathode position, completely immerse it, turn on the power supply for electroplating, and during the treatment, the current density is 50mA / cm 2 The treatment time is 30 minutes, and after the treatment, a copper foil with surface electrogalvanized is obtained; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain a zinc-containing copper foil, placing the zinc-containing copper foil into a modified etching solution, and etching at 50° C. for 6 hours to obtain a crude product; Step 3: Take out the crude product, wash it with anhydrous ethanol and distilled water, and dry it at 60° C. for 12 hours to obtain a copper foil with uniform nano-sized pores.
[0016] Example 2: This example discloses a method for preparing a modified corrosive solution, comprising the following steps: Q1: 4.5 mg N-iodosuccinimide and 172 mg diphenyl chlorophosphate were added to a container, and then the air in the container was replaced with argon. Subsequently, 22 μL aniline, 80 μL benzyl alcohol and 2.3 mL 1,4-dioxane were added in sequence, and the mixture was sealed and reacted in an oil bath at 140 °C for 16 h. Q2: After the reaction is completed, cool, add ethyl acetate, rotary evaporate, and purify. During the purification process, a silica gel column is used for separation and purification. The eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02 to obtain a modified corrosion solution.
[0017] This embodiment discloses a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: Hang the degreased (using 70wt% sodium hydroxide as degreasing solution at 70℃) and cleaned copper foil with a clip in a plating tank containing a plating solution (composed of 2 parts of zinc sulfate, 0.9 parts of sodium sulfate, 8 parts of boric acid, 1 part of sodium chloride and 0.2 parts of brightener), place it at the cathode position, completely immerse it, turn on the power supply for electroplating, and during the treatment, the current density is 50mA / cm 2 The treatment time is 30 minutes, and after the treatment, a copper foil with surface electrogalvanized is obtained; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain a zinc-containing copper foil, placing the zinc-containing copper foil into a modified etching solution, and etching at 50° C. for 6 hours to obtain a crude product; Step 3: Take out the crude product, wash it with anhydrous ethanol and distilled water, and dry it at 60° C. for 12 hours to obtain a copper foil with uniform nano-sized pores.
[0018] Embodiment 3: This embodiment discloses a method for preparing a modified corrosive solution, comprising the following steps: Q1: 9 mg N-iodosuccinimide and 340 mg diphenyl chlorophosphate were added to a container, and then the air in the container was replaced with argon. Then 18 μL aniline, 150 μL benzyl alcohol and 1.3 mL 1,4-dioxane were added in sequence, and the mixture was sealed and reacted in an oil bath at 140 °C for 16 h. Q2: After the reaction is completed, cool, add ethyl acetate, rotary evaporate, and purify. During the purification process, a silica gel column is used for separation and purification. The eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02 to obtain a modified corrosion solution.
[0019] This embodiment discloses a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: Hang the degreased (using 70wt% sodium hydroxide as degreasing solution at 70℃) and cleaned copper foil with a clip in a plating tank containing a plating solution (consisting of 4 parts of zinc sulfate, 1.1 parts of sodium sulfate, 10 parts of boric acid, 1.5 parts of sodium chloride and 0.5 parts of brightener), place it at the cathode position, completely immerse it, turn on the power supply for electroplating, and during the treatment, the current density is 50mA / cm 2The treatment time is 30 minutes, and after the treatment, a copper foil with surface electrogalvanized is obtained; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain a zinc-containing copper foil, placing the zinc-containing copper foil into a modified etching solution, and etching at 50° C. for 6 hours to obtain a crude product; Step 3: Take out the crude product, wash it with anhydrous ethanol and distilled water, and dry it at 60° C. for 12 hours to obtain a copper foil with uniform nano-sized pores.
[0020] Embodiment 4: This embodiment discloses a method for preparing a modified etching solution, comprising the following steps: Q1: 5 mg of N-iodosuccinimide and 195 mg of diphenyl chlorophosphate were added to a container, and then the air in the container was replaced with argon. Subsequently, 21 μL of aniline, 90 μL of benzyl alcohol and 1.5 mL of 1,4-dioxane were added in sequence, and the mixture was sealed and reacted in an oil bath at 140 °C for 16 h. Q2: After the reaction is completed, cool, add ethyl acetate, rotary evaporate, and purify. During the purification process, a silica gel column is used for separation and purification. The eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02 to obtain a modified corrosion solution.
[0021] This embodiment discloses a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: Hang the degreased (using 70wt% sodium hydroxide as degreasing solution at 70℃) and cleaned copper foil with a clip in a plating tank containing a plating solution (composed of 2.5 parts of zinc sulfate, 0.95 parts of sodium sulfate, 8.5 parts of boric acid, 1.1 parts of sodium chloride and 0.25 parts of brightener), place it at the cathode position, completely immerse it, turn on the power supply for electroplating, and during the treatment, the current density is 50mA / cm 2 The treatment time is 30 minutes, and after the treatment, a copper foil with surface electrogalvanized is obtained; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain a zinc-containing copper foil, placing the zinc-containing copper foil into a modified etching solution, and etching at 50° C. for 6 hours to obtain a crude product; Step 3: Take out the crude product, wash it with anhydrous ethanol and distilled water, and dry it at 60° C. for 12 hours to obtain a copper foil with uniform nano-sized pores.
[0022] Embodiment 5: This embodiment discloses a method for preparing a modified etching solution, comprising the following steps: Q1: 7 mg of N-iodosuccinimide and 325 mg of diphenyl chlorophosphate were added to a container, and then the air in the container was replaced with argon. Subsequently, 19 μL of aniline, 130 μL of benzyl alcohol and 2.4 mL of 1,4-dioxane were added in sequence, and the mixture was sealed and reacted in an oil bath at 140 °C for 16 h. Q2: After the reaction is completed, cool, add ethyl acetate, rotary evaporate, and purify. During the purification process, a silica gel column is used for separation and purification. The eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.02 to obtain a modified corrosion solution.
[0023] This embodiment discloses a method for preparing a copper foil having uniform nano-sized pores, comprising the following steps: Step 1: Hang the degreased (using 70wt% sodium hydroxide as degreasing solution at 70℃) and cleaned copper foil with a clip in a plating tank containing a plating solution (consisting of 3.5 parts of zinc sulfate, 1.05 parts of sodium sulfate, 9.5 parts of boric acid, 1.45 parts of sodium chloride and 0.45 parts of brightener), place it in the cathode position, completely immerse it, turn on the power supply for electroplating, and during the treatment, the current density is 50mA / cm 2 The treatment time is 30 minutes, and after the treatment, a copper foil with surface electrogalvanized is obtained; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain a zinc-containing copper foil, placing the zinc-containing copper foil into a modified etching solution, and etching at 50° C. for 6 hours to obtain a crude product; Step 3: Take out the crude product, wash it with anhydrous ethanol and distilled water, and dry it at 60° C. for 12 hours to obtain a copper foil with uniform nano-sized pores.
[0024] Comparative Example 1: Compared with Example 1, in the process of preparing the modified etching solution in Comparative Example 1, no diphenyl chlorophosphate was added, and other conditions remained unchanged.
[0025] Comparative Example 2: Compared with Example 1, in the process of preparing the copper foil in Comparative Example 2, no zinc sulfate is added, and other conditions remain unchanged.
[0026] Comparative Example 3: Compared with Example 1, in the process of preparing the copper foil in Comparative Example 3, sulfuric acid is used instead of the modified etching solution, and other conditions remain unchanged.
[0027] Experimental example: The size distribution of nano-sized pores of the sample was tested by gas adsorption and desorption method, and the porosity of the sample was tested by gas replacement method. The test results are shown in Table 1: Table 1
[0028] From the test results in Table 1, it can be seen that the copper foils prepared in Examples 1-5 of the present invention have uniform nano-size and excellent porosity. From the comparison between Comparative Example 1 and Examples 1-5, it can be seen that the addition of diphenyl chlorophosphate can effectively increase the nano-size and porosity of the copper foil; from the comparison between Comparative Example 2 and Examples 1-5, it can be seen that the use of zinc sulfate can effectively increase the nano-size and porosity of the copper foil; from the comparison between Comparative Example 3 and Examples 1-5, it can be seen that the use of modified etching solution can effectively increase the nano-size and porosity of the copper foil.
[0029] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.
[0030] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.
Claims
1. A method for preparing a copper foil having uniform nano-sized pores, characterized in that: The following steps are involved: Step 1: hang the degreased and cleaned copper foil with a clip in the electroplating tank containing the electroplating solution, place it at the cathode position, immerse it completely, turn on the power supply for electroplating, and obtain the copper foil with zinc electroplating on the surface after the treatment; Step 2: heat-treating the surface of the electrogalvanized copper foil to obtain the zinc-containing copper foil, and placing the zinc-containing copper foil into a modified etching solution for etching to obtain a crude product; Step 3: Take out the crude product, wash it, and dry it to obtain a copper foil with uniform nano-sized pores.
2. The method for preparing a copper foil having uniform nano-sized pores according to claim 1, characterized in that: In the step 1, the temperature during the degreasing treatment is 70-80°C, 70wt% sodium hydroxide is used as the degreasing solution, the electroplating solution is composed of 2-4 parts of zinc sulfate, 0.9-1.1 parts of sodium sulfate, 8-10 parts of boric acid, 1-1.5 parts of sodium chloride and 0.2-0.5 parts of brightener, and the current density during the treatment is 10-100mA / cm 2 , the processing time is 15-30min.
3. The method for preparing a copper foil having uniform nano-sized pores according to claim 1, characterized in that: The preparation method of the modified corrosive liquid comprises the following steps: Q1: Add N-iodosuccinimide and diphenyl chlorophosphate into a container, then replace the air in the container with argon, then add aniline, benzyl alcohol and 1,4-dioxane in sequence, seal, and react in an oil bath; Q2: After the reaction is completed, cool it, add ethyl acetate, rotary evaporate, and purify to obtain a modified etching solution.
4. The method for preparing a copper foil having uniform nano-sized pores according to claim 3, characterized in that: In the Q1, the dosage ratio of N-iodosuccinimide, diphenyl chlorophosphate, aniline, benzyl alcohol and 1,4-dioxane is (4.5-9) mg: (172-340) mg: (18-22) μL: (80-150) μL: (1.3-2.3) mL, the oil bath reaction temperature is 120-140° C., and the reaction time is 15-18 h.
5. The method for preparing a copper foil having uniform nano-sized pores according to claim 3, characterized in that: In Q2, during the purification process, a silica gel column is used for separation and purification, and the eluent is a mixed solution of petroleum ether: ethyl acetate: triethylamine in a volume ratio of 2:1:0.
02.
6. The method for preparing a copper foil having uniform nano-sized pores according to claim 1, characterized in that: In the step 2, the treatment temperature during the corrosion treatment process is 30-50° C., and the treatment time is 2-8 hours.
7. The method for preparing a copper foil having uniform nano-sized pores according to claim 1, characterized in that: In the step three, washing is performed with anhydrous ethanol and distilled water, and the drying temperature is 40-60° C. and the drying time is 8-12 hours.