Continuous strip-shaped foamy copper-manganese alloy and preparation method thereof
By coating a copper foam substrate with manganese slurry and performing multi-stage heat treatment, the problems of closed pores and impurity residues in traditional methods were solved, and a high-purity copper foam alloy suitable for solid oxide fuel cells was prepared, realizing industrial continuous production and environmentally friendly manufacturing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-12
- Publication Date
- 2026-03-10
AI Technical Summary
Existing technologies struggle to produce high-purity, low-impurity foamed copper-manganese alloys, especially in fields like solid oxide fuel cells where electron conductivity and impurity content are critically low. Traditional methods suffer from closed-cell defects, foaming agent residue, and electroplating challenges, and are unsuitable for continuous industrial production.
A continuous strip-shaped copper foam substrate is used. After degreasing and activation treatment, a manganese-containing slurry is coated and subjected to multi-stage heat treatment under a protective atmosphere to form a copper-manganese alloy. This avoids closed pores and impurity residues, and achieves high purity and a three-dimensional interconnected structure.
A high-purity foamed copper-manganese alloy was prepared, which has excellent air permeability and high specific surface area, meeting the requirements of solid oxide fuel cells. Moreover, the process is environmentally friendly and suitable for large-scale continuous production.
Smart Images
Figure CN121629210A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of new energy material preparation technology, specifically relating to a continuous strip-shaped foamed copper-manganese alloy and its preparation method. Background Technology
[0002] Supported noble metal catalysts are widely used in industrial catalysis due to their excellent catalytic activity; however, noble metals are scarce and expensive. Metal-rich element catalysts, such as copper-manganese spinel, have shown potential to replace noble metal catalysts in areas such as the catalytic combustion of volatile organic compounds. However, when applying copper-manganese alloy materials to applications with extreme requirements for electron conductivity and impurity content, such as solid oxide fuel cells, traditional preparation methods face insurmountable technical bottlenecks.
[0003] Currently, one of the main methods for preparing foamed metals is the powder metallurgy foaming method. This method mixes metal powder with a foaming agent, which decomposes during heating to generate gas, thus forming a porous structure. However, this method has inherent drawbacks: firstly, it easily forms closed pores, affecting the connectivity and permeability of the pores; secondly, the foaming agent is difficult to completely decompose and remove, and its residue significantly degrades the material's electrical conductivity. Another feasible technical route is electrodeposition, but the standard electrode potentials of copper and manganese differ greatly (approximately 1.5V), making it technically extremely difficult to achieve uniform co-deposition of the two in an aqueous solution system. Furthermore, the electroplating process generates large amounts of wastewater containing heavy metals, causing severe environmental pollution.
[0004] Therefore, developing a method for preparing high-purity foamed copper-manganese alloy that can avoid closed-cell defects, eliminate residual impurities, circumvent electroplating problems, and is suitable for continuous industrial production has become an urgent technical problem to be solved in this field. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention aims to provide a continuous method for preparing strip-shaped foamed copper-manganese alloys and the resulting products. This method fundamentally avoids the closed-cell and foaming agent residue problems of traditional powder metallurgy methods, while also circumventing the technical barriers of copper-manganese electroplating co-deposition, thereby achieving the preparation of high-quality, low-impurity foamed copper-manganese alloys suitable for large-scale continuous production.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] In a first aspect, the present invention provides a method for preparing a continuous strip-shaped foamed copper-manganese alloy, comprising the following steps:
[0008] S100, providing continuous strip-shaped open-cell foamed copper substrate;
[0009] S200, Degreasing and activation treatment is performed on the foamed copper substrate;
[0010] S300. Under a protective atmosphere, a manganese-containing slurry is applied to the surface of an activated copper foam substrate.
[0011] S400. The coated substrate is dried and set under a protective atmosphere.
[0012] S500: Under a hydrogen atmosphere, the dried substrate is subjected to multi-stage heat treatment, so that manganese and copper can form an alloy through solid diffusion, thereby obtaining a continuous strip-shaped foamed copper-manganese alloy.
[0013] Furthermore, the specifications of the open-cell copper foam substrate are: 30-130 PPI pore count, 200-500 g / m² areal density, and 0.1-3.0 mm thickness. This specification of copper foam substrate ensures sufficient three-dimensional interconnected porosity and specific surface area, while also possessing good mechanical strength, making it suitable for subsequent continuous processing.
[0014] Furthermore, in step S200, the degreasing agent used in the degreasing treatment includes water, sodium hydroxide, sodium carbonate, OP-10 emulsifier, and sodium dodecyl sulfonate. The degreasing temperature is 60-70℃, and the degreasing time is 3-5 minutes. The sodium hydroxide in the degreasing agent is 10-30 g / L, the sodium carbonate is 100-150 g / L, the OP-10 emulsifier is 0.2-0.5 g / L, and the sodium dodecyl sulfonate is 0.5-0.8 g / L. This process can effectively remove grease and other stains from the surface of the foamed copper substrate.
[0015] Further, in step S200, the activation solution used in the activation treatment contains formic acid, acetic acid, and trivalent manganese salt (such as manganese triacetate), wherein, by mass percentage, the formic acid content in the activation solution is 5-8%, the acetic acid content is 0.5-1%, and the concentration of trivalent manganese salt is 0.5-1 g / L. The activation treatment time is 1-2 minutes. Because the manganese ions (Mn) in the trivalent manganese salt... 3 + It has strong oxidizing properties and can effectively remove the oxide layer (CuO) on the surface of copper foam substrates under acidic conditions. The reaction mechanism is: CuO + 2Mn 3+ +4H + →Cu 2+ +2Mn 2+ The process of adding 2H2O not only activates the surface of the foamed copper substrate and enhances its bonding with the subsequent manganese slurry, but also creates a clean metal interface for the subsequent alloying process.
[0016] Further, in step S300, the method for preparing the manganese-containing slurry includes:
[0017] S310. The manganese powder is acid-washed with a formic acid solution of 8-12% by mass for 5-10 seconds to remove the surface passivation layer, washed with water until neutral, dried at 60-80℃ under an inert atmosphere, ground and passed through a 5000-mesh sieve, and then kept for use under an inert atmosphere.
[0018] S320. Dissolve rosin in anhydrous ethanol to prepare a solution (wherein, the mass ratio of rosin to anhydrous ethanol is 1-2:3), mix it with the manganese powder treated in step S310 at a first preset ratio (mass ratio of (1-2):20), degas under vacuum, and then disperse it in methyl acrylate (wherein, the second preset ratio requires control: the amount of manganese powder added in 1L of methyl acrylate is 400-800g, and by controlling the amount of manganese powder added, the manganese content in the final copper-manganese alloy can be adjusted), and stir to make a uniform paste slurry.
[0019] In this step, the rosin-ethanol solution serves as the primary binder, and methyl acrylate serves as the secondary dispersion carrier and subsequent pyrolysis carbon source, together ensuring the uniform and firm adhesion of manganese powder to the foamed copper skeleton.
[0020] Furthermore, in step S500, the multi-stage heat treatment of the dried substrate is the core of this invention, specifically including:
[0021] S510, Decomposition of auxiliary materials and reduction of matrix copper: Keep warm in a hydrogen atmosphere at 230-250℃ for 4-5 hours. During this stage, organic components such as methyl acrylate and rosin in the slurry are fully decomposed into small molecule gases (such as CO, CO2, CH4, C3H6, HCHO) and volatilized. At the same time, hydrogen reduces the copper oxide that may exist on the surface of the foamed copper to active copper.
[0022] S520, Lattice Vacancy Formation: Heat to 380-420℃ and hold for 7-8 hours. This temperature is higher than the recrystallization temperature of copper, which helps to form a large number of vacancies in the copper lattice, providing a channel for the subsequent diffusion of manganese atoms and significantly reducing the diffusion activation energy.
[0023] S530, Copper-Manganese Atom Interdiffusion: Continue heating to 735-765℃ and hold for 2-3 hours. At this high temperature, copper and manganese atoms diffuse fully with vacancies as the medium, eventually forming a copper-manganese alloy phase with uniform composition, thus achieving bulk alloying of the material.
[0024] Furthermore, the protective atmosphere is a nitrogen atmosphere, a helium atmosphere, or an argon atmosphere. By coating and drying the manganese-containing slurry in the protective atmosphere, the oxidation of manganese powder during the coating and drying process can be effectively prevented, thus ensuring the activity of the raw materials.
[0025] Secondly, the present invention also provides a continuous strip-shaped foamed copper-manganese alloy prepared by the above method. The copper-manganese alloy has a three-dimensional interconnected open-cell structure and does not contain high-temperature harmful impurities such as halogens, sulfur, chromium, and silicon, which fully meets the stringent requirements of solid oxide fuel cells (SOFC) for connector materials.
[0026] Compared with the prior art, the present invention has the following beneficial technical effects:
[0027] (1) The present invention adopts a new technical path of “prefabricated open-cell foam copper skeleton + coating manganese powder + solid diffusion alloying”, which completely avoids the problems of closed cell and foaming agent residue in traditional powder metallurgy, as well as the problems of large potential difference, difficulty in co-deposition and environmental pollution in electroplating.
[0028] (2) No harmful impurities are introduced during the entire preparation process of this invention. The final product has extremely high purity and does not contain high-temperature harmful impurities that are strictly controlled by SOFC. Moreover, the product inherits the three-dimensional interconnected open-cell structure of the foamed copper substrate, which ensures excellent air permeability and high specific surface area.
[0029] (3) By adjusting the manganese powder content in the slurry, the coating thickness and the heat treatment process parameters, the present invention can accurately control the manganese content and microstructure in the final alloy. Furthermore, by introducing the winding and unwinding modes, it is easy to achieve large-scale continuous and automated production, which is highly efficient and low-cost.
[0030] (4) The entire process of this invention has no electroplating steps, does not generate heavy metal wastewater, and the organic components are decomposed into harmless gases during heat treatment, which meets the green manufacturing standards. Attached Figure Description
[0031] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0032] Figure 1 This is a flowchart of a continuous strip foam copper-manganese alloy preparation method according to the present invention;
[0033] Figure 2 This is a scanning electron microscope (SEM) image of the foamed copper-manganese alloy prepared in Example 1 under 100x magnification.
[0034] Figure 3 This is a scanning electron microscope (SEM) image of the foamed copper-manganese alloy prepared in Example 1 under 1000x magnification.
[0035] Figure 4This is a schematic diagram of the SEM-EDS analysis results of the foamed copper-manganese alloy prepared in Example 1, wherein, Figure 4 a corresponds to Figure 3 EDS scan analysis spectrum of the first point Figure 5 , Figure 4 b corresponds to Figure 3 EDS scan analysis spectrum of the second point in the middle (6);
[0036] Figure 5 This is a scanning electron microscope (SEM) image of the copper-manganese foam alloy prepared in Example 2 under 500x magnification. Detailed Implementation
[0037] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way.
[0038] Example 1
[0039] The preparation process of a continuous strip-shaped copper-manganese alloy foam for SOFC connectors is as follows: Figure 1 As shown.
[0040] S100, Provide a continuous strip of open-cell foamed copper substrate, specifically: take a continuous strip of open-cell foamed copper substrate with a hole count of 110 PPI, a surface density of 350 g / m², and a thickness of 0.5 mm, and unwind it;
[0041] S200. The foamed copper substrate is subjected to degreasing and activation treatment, wherein the degreasing treatment includes: immersing the foamed copper substrate in a solution containing NaOH (20g / L), Na2CO3 (120g / L), OP-10 emulsifier (0.3g / L), and sodium dodecyl sulfonate (0.6g / L) for 4 minutes at a temperature of 65°C, and then washing with pure water until pH=7; the activation treatment includes: immersing the degreased foamed copper in an activation solution (containing 6% formic acid, 0.8% acetic acid, and 0.8g / L manganese triacetate) for 1.5 minutes, and then washing with pure water until pH=7;
[0042] S300. Under a protective atmosphere, a manganese-containing slurry is coated onto the surface of an activated copper foam substrate. The preparation and coating of the manganese-containing slurry specifically includes: activating electrolytic manganese powder by acid washing with 10% formic acid for 8 seconds, washing and drying with water, then drying at 70°C for 20 hours in a nitrogen furnace, and grinding through a 5000-mesh sieve; then dissolving rosin and anhydrous ethanol at a mass ratio of 1:3, mixing this solution with the treated manganese powder at a mass ratio of 1:20, stirring, and placing the mixture in a vacuum furnace under vacuum to below 100 Pa for 2 hours to degas; subsequently, slowly adding the above mixture to methyl acrylate under stirring, controlling the amount of manganese powder added to 1L of methyl acrylate to be 600g, and continuing to stir until a uniform paste is formed; finally, vertically immersing the activated copper foam into the slurry, lifting it at a uniform speed, and controlling the draining time to be 5.5 minutes;
[0043] S400. Under a protective atmosphere, the coated substrate is dried and shaped. Specifically, the coated foamed copper is dried and shaped by rapidly blowing hot air at a temperature of 100°C and a wind speed of 30m / s in a nitrogen-protected drying tunnel.
[0044] S500. Under a hydrogen atmosphere, the dried substrate is subjected to multi-stage heat treatment, specifically: first, the temperature is increased to 240℃ at 5℃ / min and held for 4.5 hours; then the temperature is increased to 400℃ and held for 7.5 hours; then the temperature is increased to 750℃ and held for 2.5 hours.
[0045] After heat treatment, the S600 copper-manganese alloy product is naturally cooled to below 60°C in the furnace and then removed from the furnace. The cooled continuous strip foam copper-manganese alloy product is then coiled up.
[0046] The foamed copper-manganese alloy product obtained in Example 1 was analyzed by scanning electron microscopy, such as... Figure 2 , Figure 3 and Figure 4 As shown, Figure 2 The image shown is a scanning electron microscope (SEM) image of the foamed copper-manganese alloy prepared in Example 1 at 100x magnification. Figure 3 The image shown is a scanning electron microscope (SEM) image of the foamed copper-manganese alloy prepared in Example 1 under 1000x magnification. Figure 4 From Figure 3 Two corresponding spectra were obtained by performing EDS analysis on any two points in the electron microscopy scanning image. Figures 2-4 As can be seen from the results, the manganese content in the foamed copper-manganese alloy product prepared in Example 1 is uniform, and the atomic percentage of manganese content at any two points is 36.69%. Moreover, the three-dimensional open-cell structure is intact, and the content of harmful impurities such as sulfur, chlorine, and chromium is not detected, which fully meets the requirements for SOFC applications.
[0047] Example 2
[0048] The preparation process of a continuous strip-shaped copper-manganese alloy foam for SOFC connectors is as follows:
[0049] S100, Provide a continuous strip of open-cell foamed copper substrate, specifically: take a continuous strip of open-cell foamed copper substrate with a pore count of 30 PPI, an areal density of 200 g / m², and a thickness of 0.1 mm, and unwind it;
[0050] S200. The foamed copper substrate is subjected to degreasing and activation treatment, wherein the degreasing treatment includes: immersing the foamed copper substrate in a solution containing NaOH (10g / L), Na2CO3 (100g / L), OP-10 emulsifier (0.2g / L), and sodium dodecyl sulfonate (0.5g / L) for 5 minutes at a temperature of 60°C, and then washing with pure water until pH=7; the activation treatment includes: immersing the degreased foamed copper in an activation solution (containing 5% formic acid, 0.5% acetic acid, and 0.5g / L manganese triacetate) for 2 minutes, and then washing with pure water until pH=7;
[0051] S300. Under a protective atmosphere, a manganese-containing slurry is coated onto the surface of an activated copper foam substrate. The preparation and coating of the manganese-containing slurry specifically include: activating electrolytic manganese powder by acid washing with 8% formic acid for 10 seconds, washing and drying with water, drying at 60°C for 24 hours in a nitrogen furnace, and grinding through a 5000-mesh sieve; then dissolving rosin and anhydrous ethanol at a mass ratio of 1:2, mixing this solution with the treated manganese powder at a mass ratio of 3:40, stirring, and placing it in a vacuum furnace to be evacuated to below 100Pa for 2 hours to remove bubbles; subsequently, slowly adding the above mixture to methyl acrylate under stirring, controlling the amount of manganese powder added to 1L of methyl acrylate to be 400g, and continuing to stir until a uniform paste is formed; finally, vertically immersing the activated copper foam into the slurry, lifting it at a uniform speed, and controlling the draining time to be 6 minutes;
[0052] S400. Under a protective atmosphere, the coated substrate is dried and shaped. Specifically, the coated foamed copper is dried and shaped by rapidly blowing hot air at a temperature of 80°C and a wind speed of 20m / s in a nitrogen-protected drying tunnel.
[0053] S500. Under a hydrogen atmosphere, the dried substrate is subjected to multi-stage heat treatment, specifically: first, the temperature is increased to 230℃ at 5℃ / min and held for 5 hours; then the temperature is increased to 380℃ and held for 8 hours; then the temperature is increased to 735℃ and held for 3 hours.
[0054] After heat treatment, the S600 copper-manganese alloy product is naturally cooled to below 60°C in the furnace and then removed from the furnace. The cooled continuous strip foam copper-manganese alloy product is then coiled up.
[0055] The foamed copper-manganese alloy product obtained in Example 2 was subjected to electron microscopy scanning, such as... Figure 5 As shown, from Figure 5 As can be seen from the results, the foamed copper-manganese alloy prepared in Example 2 has a uniform manganese content and a complete three-dimensional open-cell structure; and EDS analysis under an electron microscope showed that the content of harmful impurities such as sulfur, chlorine, and chromium was not detected, which fully meets the requirements for SOFC applications.
[0056] Example 3
[0057] The preparation process of a continuous strip-shaped copper-manganese alloy foam for SOFC connectors is as follows:
[0058] S100, Provide a continuous strip of open-cell foamed copper substrate, specifically: take a continuous strip of open-cell foamed copper substrate with a hole count of 130 PPI, an areal density of 500 g / m², and a thickness of 3.0 mm, and unwind it;
[0059] S200. The foamed copper substrate is subjected to degreasing and activation treatment, wherein the degreasing treatment includes: immersing the foamed copper substrate in a solution containing NaOH (30g / L), Na2CO3 (150g / L), OP-10 emulsifier (0.5g / L), and sodium dodecyl sulfonate (0.8g / L) for 3 minutes at a temperature of 70°C, and then washing with pure water until pH=7; the activation treatment includes: immersing the degreased foamed copper in an activation solution (containing 8% formic acid, 1.0% acetic acid, and 1.0g / L manganese triacetate) for 1 minute, and then washing with pure water until pH=7;
[0060] S300. Under a protective atmosphere, a manganese-containing slurry is coated onto the surface of an activated copper foam substrate. The preparation and coating of the manganese-containing slurry specifically include: activating electrolytic manganese powder by acid washing with 12% formic acid for 5 seconds, washing and drying with water, drying at 80°C for 24 hours in a nitrogen furnace, and grinding through a 5000-mesh sieve; then dissolving rosin and anhydrous ethanol at a mass ratio of 2:3, mixing this solution with the treated manganese powder at a mass ratio of 1:10, stirring, and placing it in a vacuum furnace to be evacuated to below 100Pa for 2 hours to remove bubbles; subsequently, slowly adding the above mixture to methyl acrylate under stirring, controlling the amount of manganese powder added to 1L of methyl acrylate to be 800g, and continuing to stir until a uniform paste is formed; finally, vertically immersing the activated copper foam into the slurry, lifting it at a uniform speed, and controlling the draining time to be 5 minutes;
[0061] S400. Under a protective atmosphere, the coated substrate is dried and shaped. Specifically, the coated foamed copper is dried and shaped by rapidly blowing hot air at a temperature of 120°C and a wind speed of 40m / s in a nitrogen-protected drying tunnel.
[0062] S500. Under a hydrogen atmosphere, the dried substrate is subjected to multi-stage heat treatment, specifically: first, the temperature is increased to 250℃ at 5℃ / min and held for 4 hours; then the temperature is increased to 420℃ and held for 7 hours; then the temperature is increased to 765℃ and held for 2 hours.
[0063] After heat treatment, the S600 copper-manganese alloy product is naturally cooled to below 60°C in the furnace and then removed from the furnace. The cooled continuous strip foam copper-manganese alloy product is then coiled up.
[0064] Testing revealed that the foamed copper-manganese alloy prepared in Example 3 had a uniform manganese content and a complete three-dimensional open-cell structure; moreover, no harmful impurities such as sulfur, chlorine, and chromium were detected, fully meeting the requirements for SOFC applications.
[0065] Example 4
[0066] The process is basically the same as in Example 1, except that in the preparation step of the manganese-containing slurry, the concentration of manganese powder in methyl acrylate is adjusted to 400 g / L, while the other process parameters remain unchanged.
[0067] The copper-manganese alloy product obtained in Example 4 was analyzed by scanning electron microscopy, such as... Figure 5 As shown, from Figure 5 As can be seen from the results, the three-dimensional open-pore structure of the copper-manganese alloy product prepared in Example 4 remains intact, and the manganese content is uniform. Furthermore, EDS analysis under an electron microscope showed that the content of harmful impurities such as sulfur, chlorine, and chromium was not detected, which fully meets the requirements for SOFC applications.
[0068] Comparative Example 1
[0069] The traditional powder metallurgy foaming method is adopted: copper powder, manganese powder and 1 wt% CaCO3 foaming agent are mixed, pressed into a blank, and sintered and foamed in argon at 850℃.
[0070] Micro-CT scanning of the product prepared in Comparative Example 1 revealed a large number of closed pores (accounting for approximately 15% of the total pore volume); furthermore, elemental analysis of the product prepared in Comparative Example 1 showed that approximately 200 ppm of calcium residue was detected.
[0071] In summary, the continuous strip foam copper-manganese alloy preparation method and the copper-manganese alloy product prepared by the present invention have a complete three-dimensional interconnected open structure and uniform manganese content. At the same time, the prepared copper-manganese alloy product does not contain harmful impurities such as sulfur, chlorine, and chromium, and fully meets the requirements for SOFC applications.
[0072] The foregoing provides a detailed description of a continuous strip-shaped foamed copper-manganese alloy and its preparation method. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the embodiments above are merely for the purpose of helping to understand the core ideas of this application. It should be noted that those skilled in the art can make various improvements and modifications to this application without departing from its principles, and these improvements and modifications also fall within the protection scope of the claims of this application.
Claims
1. A continuous ribbon of foamed copper-manganese alloy production method, characterized by, The method comprises the following steps: S100, providing a continuous strip-shaped open-cell foam copper substrate; S200, performing oil removal and activation treatment on the foam copper substrate; S300, coating a manganese-containing slurry on the surface of the foam copper substrate after the activation treatment under a protective atmosphere; S400, performing drying and shaping on the coated substrate under a protective atmosphere; S500, performing multi-stage heat treatment on the dried substrate under a hydrogen atmosphere, so that manganese and copper form an alloy through solid-state diffusion, thereby obtaining a continuous strip-shaped foam copper-manganese alloy.
2. The continuous ribbon of foam copper-manganese alloy production method according to claim 1, characterized in that, The open-cell foam copper substrate has a specification of 30-130 PPI in terms of the number of pores, 200-500 g / m2 in terms of the area density, and 0.1-3.0 mm in terms of the thickness.
3. The continuous ribbon of foam copper-manganese alloy production method of claim 1, wherein, In the step S200, the oil removal agent used in the oil removal treatment includes water, sodium hydroxide, sodium carbonate, OP-10 emulsifier and sodium dodecyl sulfonate, the oil removal temperature is 60-70℃, and the oil removal time is 3-5 min, wherein the sodium hydroxide in the oil removal agent is 10-30 g / L, the sodium carbonate is 100-150 g / L, the OP-10 emulsifier is 0.2-0.5 g / L, and the sodium dodecyl sulfonate is 0.5-0.8 g / L.
4. The continuous ribbon of foam copper-manganese alloy production method of claim 3, wherein, In the step S200, the activation liquid used in the activation treatment contains formic acid, acetic acid and trivalent manganese salt, wherein the formic acid content in the activation liquid is 5-8% by mass percentage, the acetic acid content is 0.5-1%, and the concentration of the trivalent manganese salt is 0.5-1 g / L; the activation treatment time is 1-2 min. The trivalent manganese salt is manganese trisacetate.
5. The continuous ribbon of foam copper-manganese alloy production method according to claim 1, wherein, In the step S300, the preparation method of the manganese-containing slurry comprises: S310, preparing manganese powder by pickling, washing, drying, grinding and sieving under the protection of an inert atmosphere; S320, mixing the manganese powder treated in the step S310 with a solution prepared from rosin and anhydrous ethanol according to a first preset ratio, vacuum degassing, and then mixing with methyl acrylate according to a second preset ratio to prepare a paste-like slurry by stirring.
6. The continuous ribbon of foam copper-manganese alloy production method according to claim 5, wherein, In the step S310, the pickling uses a formic acid solution with a mass fraction of 8-12%, and the treatment time is 5-10 seconds; the sieving is through a 5000-mesh sieve.
7. The continuous ribbon of foam copper-manganese alloy production method according to claim 1, wherein, In the step S500, the multi-stage heat treatment on the dried substrate comprises: S510, maintaining at 230-250℃ for 4-5 hours to decompose and volatilize the organic carrier and reduce the surface oxide of the substrate; S520, maintaining at 380-420℃ for 7-8 hours to promote the formation of crystal lattice vacancies; S530, maintaining at 735-765℃ for 2-3 hours to make copper and manganese atoms fully interdiffuse to realize alloying.
8. The continuous ribbon of foam copper-manganese alloy production method according to claim 1, characterized in that, The protective atmosphere is a nitrogen atmosphere, a helium atmosphere or an argon atmosphere.
9. A continuous strip of foamed copper-manganese alloy, characterized in that, The foam copper-manganese alloy is prepared by the preparation method of any one of claims 1-8.
10. The continuous ribbon of foamed copper-manganese alloy of claim 9, wherein, The foam copper-manganese alloy has a three-dimensionally interconnected open-cell structure and does not contain any one or more of halogen, sulfur, chromium and silicon.