A method for producing a foamed copper-manganese alloy

Abstract

The application belongs to the technical field of foam metal material preparation, and particularly relates to a preparation method of foam copper-manganese alloy, which comprises the following steps: taking foam copper as a cathode, immersing the cathode and an anode into an electroplating solution for electroplating treatment, and then performing heat treatment to obtain the foam copper-manganese alloy; the electroplating solution comprises the following components in the following contents: copper sulfate 0.48-0.72 mol / L, manganese sulfate 0.4-0.6 mol / L, sodium citrate 0.05-0.15 mol / L, boric acid 0.2-0.5 mol / L, sodium sulfite 0.25-0.5 g / L, sodium dodecyl sulfate 0.05-0.2 g / L, ammonium sulfate 10-20 g / L, cerium sulfate 0.01-0.1 g / L, sodium saccharin 1-2 g / L, and sodium chloride 2-5 g / L; the application realizes copper-manganese co-electrodeposition, reduces the cracking degree of the plating layer, effectively improves the mechanical properties of the foam copper-manganese alloy, and reduces the resistance.

Description

Technical Field

[0001] This invention belongs to the field of foam metal material preparation technology, specifically relating to a method for preparing foam copper-manganese alloy. Background Technology

[0002] Copper-manganese alloys, as important functional materials, have broad application prospects in electronic devices, catalyst supports, and battery current collectors due to their excellent electrical conductivity, wear resistance, and oxidation resistance. In particular, in recent years, with the rapid development of industries such as new energy and artificial intelligence, the demand for high-performance copper-manganese alloy materials has been increasing.

[0003] Electrodeposition technology, as a mature surface treatment process, boasts advantages such as simplicity, low cost, and high controllability, making it one of the main methods for preparing copper-manganese alloy thin films and coatings. By precisely controlling the electrodeposition parameters, copper-manganese alloy coatings with uniform composition and dense structure can be obtained, meeting the performance requirements of various application scenarios.

[0004] However, the preparation of copper-manganese alloys by electrodeposition presents the following technical challenges: 1. Difficulty in controlling composition: The standard electrode potentials of copper and manganese differ greatly (Cu²⁺). + / Cu: +0.34V, Mn² + / Mn: -1.18V), which makes it difficult for the two to co-deposit in aqueous solution, making it difficult to obtain an alloy coating with uniform composition.

[0005] 2. Difficulty in controlling coating quality: Manganese is chemically active in aqueous solution and is easily oxidized; at the same time, the lattice constants of manganese and copper are quite different, which can easily generate large internal stress in the coating during electrodeposition, leading to cracking and brittleness of the coating, which seriously affects the mechanical properties and service life of the material. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a method for preparing foamed copper-manganese alloy, which realizes the co-electrodeposition of copper and manganese, reduces the degree of coating cracking, effectively improves the mechanical properties of foamed copper-manganese alloy, and reduces resistance.

[0007] This invention provides a method for preparing a foamed copper-manganese alloy, using foamed copper as the cathode, immersing the cathode and anode in an electroplating solution for electroplating, and then performing heat treatment to obtain the foamed copper-manganese alloy; The electroplating solution comprises the following components in the following amounts: copper sulfate 0.48-0.72 mol / L, manganese sulfate 0.4-0.6 mol / L, sodium citrate 0.05-0.15 mol / L, boric acid 0.2-0.5 mol / L, sodium sulfite 0.25-0.5 g / L, sodium dodecyl sulfate 0.05-0.2 g / L, ammonium sulfate 10-20 g / L, cerium sulfate 0.01-0.1 g / L, sodium saccharin 1-2 g / L, and sodium chloride 2-5 g / L.

[0008] Preferably, the electroplating solution comprises the following components in the following amounts: copper sulfate 0.55-0.65 mol / L, manganese sulfate 0.45-0.55 mol / L, sodium citrate 0.08-0.12 mol / L, boric acid 0.3-0.4 mol / L, sodium sulfite 0.25-0.35 g / L, sodium dodecyl sulfate 0.08-0.12 g / L, ammonium sulfate 13-17 g / L, cerium sulfate 0.03-0.08 g / L, sodium saccharin 1-2 g / L, and sodium chloride 3-4 g / L.

[0009] Preferably, the pH value of the electroplating solution is 5.3-5.7.

[0010] Preferably, the electroplating temperature is 30-35℃.

[0011] Preferably, the current density for electroplating is 4-10 A / dm². 2 .

[0012] Preferably, the areal density of the copper foam is 200-500 g / m³. 2 The PPI is 50-130 and the thickness is 0.1-5mm.

[0013] Preferably, the heat treatment is performed by heating the electroplated material to 180-220°C at a rate of 1-2°C / min in a reducing atmosphere, holding it at that temperature for 30-60 minutes, and then heating it to 750-850°C at a rate of 4-6°C / min and holding it at that temperature for 1-2 hours.

[0014] Preferably, the heat treatment is performed by heating the electroplated material to 200°C at a rate of 1°C / min in a reducing atmosphere, holding it at that temperature for 30 min, and then heating it to 800°C at a rate of 5°C / min and holding it at that temperature for 1.5 h.

[0015] Preferably, the reducing atmosphere is a mixture of hydrogen and nitrogen.

[0016] Preferably, the volume ratio of hydrogen to nitrogen is 1:3.

[0017] The beneficial effects of this invention are that, by employing a specific electroplating solution system comprising copper sulfate, manganese sulfate, sodium citrate, boric acid, sodium sulfite, sodium dodecyl sulfate, ammonium sulfate, cerium sulfate, sodium saccharin, and sodium chloride, it effectively overcomes the challenge of the significant difference in standard electrode potentials between copper and manganese, successfully achieving uniform co-deposition of copper and manganese on a foamed copper substrate. In particular, the synergistic effect of the components in the electroplating solution (especially sodium saccharin, cerium sulfate, and sodium chloride) significantly reduces the internal stress of the coating, avoiding problems such as cracking and brittleness, and resulting in an alloy coating with a dense structure and excellent surface quality.

[0018] By combining the specific two-stage heat treatment process of this invention, the final foamed copper-manganese alloy exhibits excellent mechanical properties. As shown in Example 1 and the comparative example data, the average tensile strength of the product of this invention reaches 16.28 N / 2cm*10cm, and the average elongation reaches 1.16%. Its strength and toughness are significantly better than those of the comparative example with changes in key additives or heat treatment processes, effectively solving the technical bottleneck of high brittleness and easy cracking of traditional electrodeposited copper-manganese alloys.

[0019] The copper-manganese foam alloy prepared by this invention has fine and uniform grains, exhibiting low resistivity. The average resistivity of Example 1 is 288.6 mΩ, significantly lower than that of the comparative examples, which can meet the stringent requirements for material conductivity in fields such as electronic devices and battery current collectors.

[0020] The preparation method of this invention has clear process parameters and is easy to operate. By precisely controlling the electroplating solution formula, electroplating conditions and heat treatment regime, high-performance foamed copper-manganese alloys can be prepared stably and repeatedly, which has good prospects for industrial application. Attached Figure Description

[0021] Figure 1 The images are scanning electron microscope (SEM) images of the foamed copper-manganese alloy prepared in Example 1 at different magnifications. (a), (b), and (c) correspond to 200x, 500x, and 1000x magnification, respectively.

[0022] Figure 2 Scanning electron microscope (SEM) image of the foamed copper-manganese alloy prepared for Comparative Example 1.

[0023] Figure 3 The images show the scanning electron microscope (SEM) morphology of the foamed copper-manganese alloy prepared in Comparative Example 2 at different magnifications. (a) and (b) correspond to 1000x and 3000x magnification, respectively. Detailed Implementation

[0024] Example 1: A method for preparing a foamed copper-manganese alloy, comprising the following steps: Matrix preparation: A matrix with an areal density of 350 g / m³ was selected. 2Using copper foam with a PPI of 110 and a thickness of 1.5 mm as the matrix, the preparation method of the copper foam is as follows: 1) A polyurethane open-cell sponge with dimensions of 1.5mm × 110ppi × 1m was selected as the foam substrate and conductively treated by physical vapor deposition (PVD) with a resistance of 185Ω / m. The conductive polyurethane open-cell sponge was then activated in 5% sulfuric acid for 3 seconds. Copper was then electroplated onto the activated polyurethane open-cell sponge using a pre-prepared copper pyrophosphate plating solution at a temperature of 35℃ and a current density of 4A / dm³. 2 The electroplating time was 40 minutes, the pH value was 8.5, and foamed copper was obtained. The composition and ratio of the copper pyrophosphate plating solution were as follows: Copper pyrophosphate (Cu2P2O7): 70 g / L Potassium pyrophosphate (K4P2O7·3H2O): 300g / L Ammonium citrate [(NH4)3C6H5O7]: 25 g / L Ammonia (NH4OH): 2 mL / L; 2) The obtained foamed copper was placed in an incinerator at 700℃ for 5 minutes to remove the polyurethane open-cell sponge from the foamed copper; the incinerated foamed copper was then sent to a reduction furnace at 850℃ under a hydrogen atmosphere for high-temperature reduction for 5 minutes to reduce the copper oxidized during the incineration process; the reduced foamed copper was then activated in 5% hydrochloric acid for 3 seconds; finally, the activated foamed copper was rinsed with pure water for 2 seconds.

[0025] Preparation of electroplating solution: Prepare 1L of electroplating solution according to the following concentration: Copper sulfate (CuSO4·5H2O) 150 g, manganese sulfate (MnSO4·H2O) 85 g, sodium citrate 0.1 mol, boric acid 0.35 mol, sodium sulfite 0.3 g, sodium dodecyl sulfate 0.1 g, ammonium sulfate 15 g, cerium sulfate (Ce2(SO4)3) 0.05 g, sodium saccharin 1.5 g, sodium chloride 3.5 g.

[0026] Dissolve in deionized water and bring the volume to 1L, then adjust the pH to 5.5.

[0027] Electrodeposition: A copper foam was used as the cathode, and a copper plate containing 4% phosphorus was used as the anode (anode to cathode area ratio of 1.5:1), both immersed in the above electroplating solution. Electrodeposition was performed at a temperature of 32°C and a current density of 6 A / dm² for 40 min.

[0028] Heat treatment: The electrodeposited sample was placed in a tube furnace and a hydrogen / nitrogen mixture (volume ratio 1:3) was introduced. The heat treatment procedure was as follows: the temperature was increased from room temperature to 200°C at a rate of 1°C / min and held for 30 minutes; then the temperature was increased to 800°C at a rate of 5°C / min and held for 90 minutes, and then cooled to room temperature in the furnace to obtain a foamed copper-manganese alloy.

[0029] Morphological diagram of foamed copper-manganese alloy as shown in the figure. Figure 1 As shown.

[0030] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the electroplating solution formulation does not contain sodium chloride. All other steps and conditions are the same as in Example 1.

[0031] The results are as follows Figure 2 As shown, it can be seen that the electroplating layer was not successfully obtained; the plating layer was loose and had poor adhesion.

[0032] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that sodium saccharin in the electroplating solution formulation was replaced with an equimolar amount of sodium benzenesulfinate. All other steps and conditions were the same as in Example 1.

[0033] The results are as follows Figure 3 As shown, a large number of microcracks are generated on the surface of the coating.

[0034] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that cerium sulfate in the electroplating solution formulation was replaced with an equimolar amount of lanthanum carbonate. All other steps and conditions were the same as in Example 1.

[0035] Result: The obtained alloy has poor physical properties and is unqualified.

[0036] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that sodium saccharin in the electroplating solution was replaced with an equimolar amount of sodium benzenesulfinate, and cerium sulfate was replaced with an equimolar amount of lanthanum carbonate. All other steps and conditions were the same as in Example 1.

[0037] Comparative Example 5 Compared to Example 1, Comparative Example 5 differs in that the heat treatment was as follows: the electrodeposited sample was placed in a tube furnace, and a hydrogen / nitrogen mixture (volume ratio 1:3) was introduced. The heat treatment procedure was as follows: the temperature was increased from room temperature to 250°C at a rate of 5°C / min and held for 30 minutes; then increased to 450°C at a rate of 5°C / min and held for 60 minutes; then increased to 750°C at a rate of 5°C / min and held for 60 minutes; and then cooled to room temperature in the furnace to obtain a foamed copper-manganese alloy. The remaining steps and conditions were the same as in Example 1.

[0038] The physical properties of the samples prepared in Example 1 and Comparative Examples 2-5 were tested, and the results are shown in Table 1 below. Five parallel samples were tested for each sample, and the average value was taken.

[0039] Table 1 Performance Test Results

[0040] Note: The resistance test sample size is 2cm*10cm, and the measurement is taken in the length direction (10cm direction).

[0041] As can be seen from the performance test results in Table 1, the foamed copper-manganese alloy prepared in Example 1 of the present invention is significantly better than that of comparative examples 2-5 in all physical properties, which fully proves the effectiveness of the technical solution of the present invention.

[0042] Example 1 exhibits an average tensile strength of 16.28 N / 2cm*10cm and an average elongation of 1.16%, demonstrating excellent overall mechanical properties. In contrast, the properties of all comparative examples show varying degrees of decline. Comparative Example 2 showed that the tensile strength and elongation decreased to 8.41 N / 2cm*10cm and 0.64%, respectively, indicating that sodium saccharin plays an irreplaceable role in reducing internal stress and improving toughness of the coating.

[0043] Comparative Example 3 showed a more severe performance degradation, with tensile strength and elongation decreasing to 4.14 N / 2cm*10cm and 0.20%, respectively, demonstrating the crucial role of cerium sulfate as a grain refiner in improving alloy strength.

[0044] Comparative Example 4 showed inferior performance (tensile strength 6.16 N / 2cm*10cm, elongation 0.37%) compared to Comparative Examples 2 and 3, which only replaced a single component. This indicates that sodium saccharin and cerium sulfate have a synergistic effect in improving mechanical properties, and the absence of either component will lead to a significant decrease in performance.

[0045] Comparative Example 5 showed a significant decrease in performance, with tensile strength and elongation of only 1.95 N / 2cm*10cm and 0.06%, respectively. This highlights the decisive role of the specific two-stage heat treatment process of this invention in optimizing the microstructure of the alloy, releasing internal stress, and improving mechanical properties.

[0046] The average resistance of Example 1 was 288.6 mΩ, significantly lower than all comparative examples. The resistance values ​​of Comparative Examples 2 through 5 increased sequentially, with Comparative Example 5 exhibiting the worst performance at a resistance of 531 mΩ. This indicates that the present invention, through optimized electroplating solution formulation and heat treatment process, not only improved mechanical properties but also effectively reduced the alloy's resistance, resulting in a superior conductive network.

[0047] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of protection of this application is limited to these examples; within the framework of this application, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of different aspects of one or more embodiments of this application as described above, which are not provided in detail for the sake of brevity.

[0048] One or more embodiments in this application are intended to cover all such substitutions, modifications, and variations that fall within the broad scope of this application. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of one or more embodiments in this application should be included within the protection scope of this application.

Claims

1. A method of producing a foamed copper-manganese alloy, characterized by, Using copper foam as the cathode, the cathode and anode are immersed in an electroplating solution for electroplating treatment, followed by heat treatment to obtain a copper foam manganese alloy. The electroplating solution comprises the following components in the following amounts: copper sulfate 0.48-0.72 mol / L, manganese sulfate 0.4-0.6 mol / L, sodium citrate 0.05-0.15 mol / L, boric acid 0.2-0.5 mol / L, sodium sulfite 0.25-0.5 g / L, sodium dodecyl sulfate 0.05-0.2 g / L, ammonium sulfate 10-20 g / L, cerium sulfate 0.01-0.1 g / L, sodium saccharin 1-2 g / L, and sodium chloride 2-5 g / L.

2. The preparation method according to claim 1, characterized in that, The electroplating solution comprises the following components in the following amounts: copper sulfate 0.55-0.65 mol / L, manganese sulfate 0.45-0.55 mol / L, sodium citrate 0.08-0.12 mol / L, boric acid 0.3-0.4 mol / L, sodium sulfite 0.25-0.35 g / L, sodium dodecyl sulfate 0.08-0.12 g / L, ammonium sulfate 13-17 g / L, cerium sulfate 0.03-0.08 g / L, sodium saccharin 1-2 g / L, and sodium chloride 3-4 g / L.

3. The preparation method according to claim 1, characterized in that, The pH value of the electroplating solution is 5.3-5.

7.

4. The preparation method according to claim 1, characterized in that, The electroplating temperature is 30-35℃.

5. The preparation method according to claim 1, characterized in that, The current density of the electroplating treatment is 4-10 A / dm 2 .

6. The preparation method according to claim 1, characterized in that, The areal density of the foamed copper is 200-500 g / m 2 , the PPI is 50-130, and the thickness is 0.1-5 mm.

7. The preparation method according to claim 1, characterized in that, The heat treatment involves heating the electroplated material to 180-220°C at a rate of 1-2°C / min in a reducing atmosphere, holding it at that temperature for 30-60 minutes, and then heating it to 750-850°C at a rate of 4-6°C / min and holding it at that temperature for 1-2 hours.

8. The preparation method according to claim 7, characterized in that, The heat treatment is as follows: in a reducing atmosphere, the electroplated material is heated to 200°C at a rate of 1°C / min, held at that temperature for 30 min, and then heated to 800°C at a rate of 5°C / min, and held at that temperature for 1.5 h.

9. The preparation method according to claim 7, characterized in that, The reducing atmosphere is a mixture of hydrogen and nitrogen.

10. The preparation method according to claim 9, characterized in that, The volume ratio of hydrogen to nitrogen is 1:3.

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