A method for preparing a copper layer on the surface of mesophase pitch-based graphite foam by electroplating

Abstract

The application discloses a preparation method of a copper layer on the surface of mesophase pitch-based graphite foam prepared by electroplating, and belongs to the technical field of electroplating. The preparation method comprises the following steps: S1, pretreating mesophase pitch-based graphite foam to obtain mesophase pitch-based graphite foam with a clean surface; S2, placing the mesophase pitch-based graphite foam treated in the step S1 into an acidic copper electroplating solution to obtain mesophase pitch-based graphite foam with a uniform copper electroplating layer on the surface; and S3, sequentially subjecting the mesophase pitch-based graphite foam with the copper electroplating layer on the surface to micro-etching and anti-oxidation treatment to obtain mesophase pitch-based graphite foam with an anti-oxidation copper electroplating layer on the surface. The preparation method disclosed by the application does not contain a complexing agent, is environmentally friendly and simple, and provides a technical solution for solving the interface bonding force between a metal material and a nonmetal graphite foam material in the process of preparing a thermal management device by brazing the mesophase pitch-based graphite foam and a copper plate (or an aluminum plate).

Description

Technical Field

[0001] This invention belongs to the field of copper electroplating technology, specifically a method for preparing a copper electroplated layer on the surface of mesophase pitch-based graphite foam. Background Technology

[0002] Mesophase pitch-based graphite foam is a novel porous carbon material with excellent properties such as high porosity, low density, high compressive strength, and high thermal conductivity. It is widely used in heat transfer systems for aerospace vehicles, waste heat management devices for radar and laser equipment, and large heat exchangers in the chemical industry. It is a new material with great development potential and application prospects.

[0003] The use of mesophase pitch-based graphite foam in thermal management devices inevitably involves the bonding of non-metallic graphite materials with metallic materials such as copper and aluminum. The conventional method is to use brazing to connect the graphite and metal materials. However, due to the inconsistent expansion of the graphite and metal materials and the brazing filler under vacuum and high-temperature brazing conditions, and the uneven contraction after cooling, interfacial bonding problems easily arise. To address these issues, chemical vapor deposition (CVD) or electroless plating is commonly used to coat the graphite foam surface with a metallic coating to solve the interfacial bonding problem. However, both CVD and electroless plating layers are relatively thin, resulting in weak bonding. For example, electroless copper plating layers are typically only 2-3 micrometers thick, with poor bonding and easy oxidation. Thin coatings are also difficult to treat for oxidation. Furthermore, electroless plating solutions generally contain large amounts of complexing agents, making wastewater treatment extremely difficult and environmentally unfriendly. Additionally, CVD processes are complex and costly.

[0004] To achieve uniform metallization of the surface of mesophase pitch-based graphite foam, it is of great significance to develop a novel electroplating method that is simple to operate, low in cost, and environmentally friendly to solve the technical problem of electroplating an anti-oxidation metal layer on the surface of mesophase pitch-based graphite foam, thereby enhancing the bonding force of the brazing interface. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing an electroplated copper layer on the surface of mesophase pitch-based graphite foam, in order to solve the problems mentioned in the prior art, such as poor adhesion, easy oxidation, thin coating that is difficult to prevent oxidation, and the fact that chemical plating solutions generally contain a large amount of complexing agents, making wastewater treatment extremely difficult and detrimental to environmental protection. Chemical vapor deposition processes are also complex and costly.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing an electroplated copper layer on the surface of mesophase pitch-based graphite foam includes the following steps:

[0008] Step S1: The mesophase pitch-based graphite foam is subjected to ultrasonic-assisted cleaning with an oil removal solution, three water washes, an oxidation removal solution, and three water washes in sequence to obtain a clean mesophase pitch-based graphite foam.

[0009] In step S1, during the degreasing solution cleaning, the temperature needs to be controlled between 40°C and 50°C, and the treatment should be carried out for 10 minutes with ultrasonic assistance; during the deoxidation solution treatment, the temperature needs to be controlled between 30°C and 40°C, and the treatment should be carried out for 10 minutes with ultrasonic assistance.

[0010] Step S2: The pretreated mesophase pitch-based graphite foam from step S1 is placed in an acidic copper plating solution, a copper plating brightener is added, and electroplating is performed at a certain current density at room temperature for (60-120) min. After three water washes and drying, a mesophase pitch-based graphite foam with a uniform copper plating layer on the surface is obtained.

[0011] Step S3: The mesophase pitch-based graphite foam after copper electroplating in step S2 is sequentially treated with micro-etching roughening solution, washed with water 3 times, treated with anti-oxidation solution, washed with water 3 times, and then dried to prepare an anti-oxidation mesophase pitch-based graphite foam with copper electroplating layer on the surface.

[0012] In step S3, when treating with the micro-etching and roughening solution, the temperature needs to be controlled between 20°C and 30°C, and the treatment should be carried out for 5 minutes with ultrasonic assistance; when treating with the anti-oxidation solution, the temperature needs to be controlled between 30°C and 40°C, and the treatment should be carried out for 90 seconds with ultrasonic assistance.

[0013] According to the above technical solution, in step S1, the degreasing solution is an acidic degreasing solution, including one or more of sulfuric acid, phosphoric acid, and nitric acid, with a concentration of (10-200) ml / L, preferably (30-100) ml / L; the acidic degreasing solution also includes at least one of fatty alcohol polyether, nonylphenol polyether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and sodium methylene dinaphthalene sulfonate, with a concentration of (10-100) g / L, preferably (30-80) g / L.

[0014] According to the above technical solution, in step S1, the deoxidation solution is an acidic deoxidation solution, including one or more of sulfuric acid, phosphoric acid, and nitric acid, with a concentration of (10-100) ml / L, preferably (20-60) ml / L; the acidic deoxidation solution also includes at least one of hydrogen peroxide, sodium persulfate, ammonium persulfate, and peracetic acid, with a concentration of (10-120) g / L, preferably (30-90) g / L.

[0015] According to the above technical solution, in step S2, the acidic copper plating solution includes (30-150) g / L copper sulfate, (40-160) ml / L sulfuric acid, and (30-300) μL / L hydrochloric acid, preferably (60-90) g / L copper sulfate, (70-140) ml / L sulfuric acid, and (100-200) μL / L hydrochloric acid.

[0016] According to the above technical solution, in step S2, the copper plating brightener includes a surfactant, an electroplating inhibitor, and a grain refiner.

[0017] According to the above technical solution, the surfactant includes one or more of nonylphenol polyether, fatty alcohol polyether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and polyquaternary ammonium salt, and the concentration of the surfactant is (5-20) g / L; the preferred surfactant is at least one of fatty alcohol polyether, fatty alcohol polyoxyethylene ether, and polyquaternary ammonium salt, and the concentration is (8-15) g / L.

[0018] According to the above technical solution, the electroplating inhibitor includes one or more of polyethylene glycol, polyvinyl alcohol, polypropylene glycol, and polyethoxypropoxy ether, and the concentration of the electroplating inhibitor is (1-10) g / L, preferably (3-8) g / L.

[0019] According to the above technical solution, the grain refiner includes one or more of sodium mercaptopropane sulfonate, sodium polydisulfide dipropane sulfonate, and mercaptobenzimidazole, and the concentration of the grain refiner is (30-100) mg / L, preferably (40-70) mg / L.

[0020] According to the above technical solution, in step S2, the current density is (0.5-5) A / dm. 3 The preferred current density is (0.5-3) A / dm³. 3 .

[0021] According to the above technical solution, in step S3, the micro-etching roughening solution is an acidic etching solution, including a sulfuric acid solution of (10-100) ml / L, preferably a sulfuric acid solution of (20-80) ml / L; the micro-etching roughening solution also includes at least one of hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate, with a concentration of (10-100) g / L, preferably one or more of sodium persulfate and potassium persulfate, with a concentration of (30-70) g / L.

[0022] In step S3, the anti-oxidation solution includes one or more of formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and citric acid, with a concentration of (50-300) ml / L; preferably, it includes at least one of formic acid, acetic acid, and citric acid, with a concentration of (80-180) ml / L; the anti-oxidation solution also includes at least one of imidazole, benzylimidazolium, benzimidazole, benzylbenzimidazole, triazole, and benzotriazole, with a concentration of (5-50) g / L; preferably, it includes at least one of benzimidazole, benzylbenzimidazole, and benzotriazole, with a concentration of (10-30) g / L.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The preparation process is simple, environmentally friendly, and low-cost, making it easy to industrialize.

[0025] 2. The present invention first pre-treats the surface of mesophase pitch-based graphite foam by using degreasing solution and deoxidation solution; then obtains a substrate with a uniform copper plating layer and excellent adhesion by electroplating; and finally obtains an antioxidant copper layer by treating with micro-etching roughening solution and anti-oxidation solution.

[0026] 3. The prepared mesophase pitch-based graphite foam anti-oxidation electroplated copper layer significantly enhances the bonding force of the brazing interface and has good application prospects in the fabrication of thermal management devices. Attached Figure Description

[0027] Figure 1 Image of an anti-oxidation electroplated copper layer on mesophase pitch-based graphite foam;

[0028] Figure 2 Image of mesophase pitch-based graphite foam;

[0029] Figure 3 Scanning electron microscope image of mesophase pitch-based graphite foam;

[0030] Figure 4 Scanning electron microscope (SEM) image of the front side of the copper-plated anti-oxidation layer on mesophase pitch-based graphite foam.

[0031] Figure 5 Scanning electron microscope (SEM) image of a side cross-section of an anti-oxidation electroplated copper layer on mesophase pitch-based graphite foam.

[0032] Figure 6 Partial magnification of the front side of the copper-plated anti-oxidation layer of mesophase pitch-based graphite foam under scanning electron microscopy;

[0033] Figure 7 Partial magnification of the side profile of the mesophase pitch-based graphite foam anti-oxidation electroplated copper layer using scanning electron microscopy;

[0034] Figure 8Metallographic cross section of the mesophase pitch-based graphite foam anti-oxidation electroplated copper layer. Detailed Implementation

[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0038] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 mL / L sulfuric acid and 50 g / L nonylphenol polyoxyethylene ether, heat to (40-50) °C and treat under ultrasonic assistance for 10 min, then wash with water 3 times until neutral.

[0039] Step 2: Place the mesophase pitch-based graphite foam material that has undergone acid degreasing treatment in a solution of 30 ml / L sulfuric acid and 60 ml / L hydrogen peroxide, heat it to (30-40)℃ and treat it under ultrasonic assistance for 10 min, then wash it with water 3 times until it is neutral.

[0040] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 mL / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add 10 g / L fatty alcohol polyether, 5 g / L polyethylene glycol, and 50 mg / L sodium mercaptopropane sulfonate as copper plating brighteners. Maintain the solution at room temperature with an 0.5 A / dm³ concentration. 3 Electroplating for 120 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0041] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L sodium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0042] Step 5: Place the mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment in an anti-oxidation solution containing 100 ml / L formic acid and 20 g / L benzimidazole, treat it under ultrasonic assistance at (30-40)℃ for 90 s, then wash it with water 3 times and dry it to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0043] Example 2

[0044] This embodiment provides a specific implementation method. A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0045] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 ml / L sulfuric acid and 50 g / L fatty alcohol polyoxyethylene ether, heat to (40-50)℃ and treat under ultrasonic assistance for 10 min, then wash with water 3 times until neutral.

[0046] Step 2: Place the mesophase pitch-based graphite foam material that has undergone acid degreasing treatment in a solution of 30 ml / L sulfuric acid and 60 ml / L peracetic acid, heat it to (30-40)℃ and treat it under ultrasonic assistance for 10 min, then wash it with water 3 times until it is neutral.

[0047] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 mL / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add 10 g / L fatty alcohol polyoxyethylene ether, 6 g / L polyvinyl alcohol, and 50 mg / L sodium dithiodipropane sulfonate as copper plating brighteners. Maintain the solution at room temperature at 1 A / dm³. 3 Electroplating for 120 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0048] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L sodium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0049] Step 5: Place the mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment in an anti-oxidation solution containing 100 ml / L acetic acid and 15 g / L benzylbenzimidazole, treat it under ultrasonic assistance at (30-40)℃ for 90 s, then wash it with water 3 times and dry it to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0050] Example 3

[0051] This embodiment provides a specific implementation method. A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0052] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 ml / L phosphoric acid, 30 g / L fatty alcohol polyoxyethylene ether, and 20 g / L sodium methylene dinaphthalene sulfonate. Heat to (40-50)℃ and treat with ultrasound for 10 min. Then wash with water 3 times until neutral.

[0053] Step 2: Place the mesophase pitch-based graphite foam material that has undergone acid degreasing treatment in a solution of 30 ml / L phosphoric acid and 60 ml / L peracetic acid, heat it to (30-40)℃ and treat it under ultrasonic assistance for 10 min, then wash it with water 3 times until it is neutral.

[0054] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 ml / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add 10 g / L polyquaternary ammonium salt, 5 g / L polypropylene glycol, and 50 mg / L mercaptobenzimidazole as copper plating brighteners. Maintain the solution at room temperature with an A / dm³ ... 3 Electroplating for 90 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0055] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L potassium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0056] Step 5: The mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment is placed in an anti-oxidation solution containing 100g / L citric acid and 20g / L benzotriazole, and treated with ultrasonic assistance at (30-40)℃ for 90s. Then it is washed with water 3 times and dried to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0057] Example 4

[0058] This embodiment provides a specific implementation method. A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0059] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 ml / L phosphoric acid and 50 g / L sodium methylene dinaphthalene sulfonate, heat to (40-50) ℃ and treat under ultrasonic assistance for 10 min, then wash with water 3 times until neutral.

[0060] Step 2: Place the acid-treated mesophase pitch-based graphite foam material in a solution of 30 ml / L phosphoric acid and 60 ml / L hydrogen peroxide, heat to (30-40)℃ and treat with ultrasound for 10 min, then wash with water 3 times until neutral.

[0061] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 ml / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add 10 g / L polyquaternary ammonium salt, 5 g / L polyethoxypropoxy ether, and 50 mg / L sodium mercaptopropane sulfonate as copper plating brighteners. Maintain the solution at room temperature with a flow rate of 2 A / dm³. 3Electroplating for 90 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0062] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L potassium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0063] Step 5: Place the mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment in an anti-oxidation solution containing 100g / L citric acid and 20g / L benzimidazole, treat it under ultrasonic assistance at (30-40)℃ for 90s, then wash it with water 3 times and dry it to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0064] Example 5

[0065] This embodiment provides a specific implementation method. A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0066] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 ml / L nitric acid, 30 g / L fatty alcohol polyoxyethylene ether, and 20 g / L nonylphenol polyoxyethylene ether, heat to (40-50)℃ and treat under ultrasonic assistance for 10 min, then wash with water 3 times until neutral.

[0067] Step 2: Place the mesophase pitch-based graphite foam material that has undergone acid degreasing treatment in a solution of 30 ml / L nitric acid and 60 ml / L hydrogen peroxide, heat it to (30-40)℃ and treat it under ultrasonic assistance for 10 min, then wash it with water 3 times until it is neutral.

[0068] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 ml / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add 10 g / L fatty alcohol polyether, 3 g / L polyethylene glycol, 2 g / L polyvinyl alcohol, and 50 mg / L sodium dithiodipropane sulfonate as copper plating brighteners. Maintain the solution at room temperature with an A / dm³ / dt. 3 Electroplating for 60 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0069] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L ammonium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0070] Step 5: Place the mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment in an anti-oxidation solution containing 100 ml / L acetic acid and 20 g / L benzylbenzimidazole, treat it under ultrasonic assistance at (30-40)℃ for 90 s, then wash it with water 3 times and dry it to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0071] Example 6

[0072] This embodiment provides a specific implementation method. A method for preparing an anti-oxidation electroplated copper layer from mesophase pitch-based graphite foam includes the following steps:

[0073] Step 1: Place the prepared mesophase pitch-based graphite foam material in an acidic degreasing solution of 50 ml / L nitric acid, 30 g / L nonylphenol polyoxyethylene ether, and 20 g / L sodium methylene dinaphthalene sulfonate. Heat the solution to (40-50)℃ and treat it under ultrasonic assistance for 10 min. Then wash it with water three times until it is neutral.

[0074] Step 2: Place the mesophase pitch-based graphite foam material that has undergone acid degreasing treatment in a solution of 30 ml / L nitric acid and 60 ml / L peracetic acid, heat it to (30-40)℃ and treat it under ultrasonic assistance for 10 min, then wash it with water 3 times until it is neutral.

[0075] Step 3: Place the pretreated mesophase pitch-based graphite foam material into an electroplating solution containing 100 ml / L sulfuric acid, 75 g / L copper sulfate, and 150 μL hydrochloric acid. Add copper plating brighteners: 10 g / L fatty alcohol polyoxyethylene ether, 2 g / L polypropylene glycol, 3 g / L polyethoxypropoxy ether, and 50 mg / L mercaptobenzimidazole. Maintain the solution at room temperature at 3 A / dm³. 3 Electroplating for 60 minutes, followed by three water washes and drying, yields a mesophase pitch-based graphite foam with a uniformly electroplated copper layer on the surface.

[0076] Step 4: The mesophase pitch-based graphite foam after electroplating copper is treated with a micro-etching and roughening solution containing 40 ml / L sulfuric acid and 50 g / L ammonium persulfate at (20-30)℃ under ultrasonic assistance for 5 min, and then washed with water 3 times until neutral.

[0077] Step 5: The mesophase pitch-based graphite foam electroplated with copper layer material after micro-etching and roughening treatment is placed in an anti-oxidation solution containing 100 ml / L formic acid and 20 g / L benzotriazole, and treated with ultrasonic assistance at (30-40)℃ for 90 s. Then it is washed with water 3 times and dried to obtain an anti-oxidation mesophase pitch-based graphite foam with copper electroplated on the surface.

[0078] To facilitate understanding by those skilled in the art, the data from the corresponding Examples 1 to 6 are summarized below, as shown in Table 1.

[0079] Table 1 Test Data Statistics Table

[0080]

[0081] As can be seen from Table 1, the thickness of the mesophase pitch-based graphite foam anti-oxidation electroplated copper layer generally increases with the increase of current density. The increase of current density can, to some extent, compensate for the impact of reduced electroplating time.

[0082] contrast Figure 1 and Figure 2 It can be seen that, Figure 2 The sample of the mesophase pitch-based graphite foam with anti-oxidation electroplated copper layer prepared in Example 5 shows that after being electroplated with copper using the method of this invention, a relatively uniform copper layer was deposited on the surface of the mesophase pitch-based graphite foam, and no oxidation occurred when placed in a room temperature environment.

[0083] contrast Figure 3 and Figure 4 It can be seen that after electroplating, the anti-oxidation copper layer effectively covers the surface of the mesophase pitch-based graphite foam, and no graphite foam matrix is ​​observed.

[0084] contrast Figure 4 , Figure 5 , Figure 6 and Figure 7 As can be seen, the surface of the antioxidant copper layer prepared by the present invention is relatively flat and the texture is uniform. The presence of copper crystals can be clearly observed in the partial magnified SEM image, and the side section is generally dense with no obvious defects.

[0085] contrast Figure 5 , Figure 7 and Figure 8 It can be seen that the electroplating method used in this invention can not only prepare an antioxidant electroplated copper layer on the surface of mesophase pitch-based graphite foam, but also deposit a copper layer inside the shallow pores of graphite foam. This greatly enhances the bonding force between the electroplated copper layer and the graphite foam matrix, which is of great significance for enhancing the strength of the brazing interface in the future.

[0086] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0087] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an electroplated copper layer on the surface of mesophase pitch-based graphite foam, characterized in that: Includes the following steps: Step S1: The mesophase pitch-based graphite foam is subjected to ultrasonic-assisted cleaning with an oil-removing solution, three water washes, an oxidation-removing solution, and three water washes to obtain a clean mesophase pitch-based graphite foam. The oil-removing solution is an acidic oil-removing solution, including one or more of sulfuric acid, phosphoric acid, and nitric acid, with a concentration of (10-200) ml / L. The oxidation-removing solution is an acidic oxidation-removing solution, including one or more of sulfuric acid, phosphoric acid, and nitric acid, with a concentration of (10-100) ml / L. Step S2: The mesophase pitch-based graphite foam pretreated in step S1 is placed in an acidic copper electroplating solution. A surfactant, an electroplating inhibitor, and a grain refiner are added. Electroplating is performed at a certain current density for (60-120) min. After washing with water and drying, a mesophase pitch-based graphite foam with a uniform copper electroplated layer is obtained. The surfactant includes one or more of nonylphenol polyether, fatty alcohol polyether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and polyquaternary ammonium salt, and the concentration of the surfactant is (5-20) g / L. The electroplating inhibitor includes one or more of polyethylene glycol, polyvinyl alcohol, polypropylene glycol, and polyethoxypropoxy ether, and the concentration of the electroplating inhibitor is (1-10) g / L. The grain refiner includes one or more of sodium mercaptopropane sulfonate, sodium polydisulfide dipropane sulfonate, and mercaptobenzimidazole, and the concentration of the grain refiner is (30-100) mg / L. Step S3: The mesophase pitch-based graphite foam electroplated with copper in step S2 is subjected to micro-etching roughening solution treatment, three water washes, anti-oxidation solution treatment, and three water washes under ultrasonic assistance, and then dried to obtain an anti-oxidation mesophase pitch-based graphite foam with a copper-plated surface layer.

2. The method for preparing a copper-plated layer on the surface of mesophase pitch-based graphite foam according to claim 1, characterized in that: In step S1, the acidic degreasing solution also includes at least one of fatty alcohol polyether, nonylphenol polyether, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, and sodium methylene dinaphthalene sulfonate, with a concentration of (10-100) g / L.

3. The method for preparing a copper-plated layer on the surface of mesophase pitch-based graphite foam according to claim 1, characterized in that: In step S1, the deoxidation solution also includes one or more of hydrogen peroxide, sodium persulfate, ammonium persulfate, and peracetic acid, with a concentration of (10-120) g / L.

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