A metal structure based on a polymer film and a method for manufacturing the same

Abstract

The application provides a metal structure based on a polymer film and a manufacturing method thereof, the metal structure comprising a film substrate made of a polymer material, and a first metal layer and a second metal layer formed on the film substrate; a surface of the film substrate is configured to have a certain roughness and a surface structure after activation treatment, the first metal layer is adhered to the surface of the film substrate and configured to have a nano structure, and the second metal layer completely covers the first metal layer and / or is configured to have a patterned structure on the first metal layer; thus, the copper foil current collector of the negative electrode of the new energy can be replaced, the polymer density of the metal structure is much lower than that of copper, the use amount of copper of the negative electrode is reduced, the battery capacity per unit weight can be significantly improved, the patterned treatment of each metal layer is exposed and developed by using a femtosecond laser or UV pulse light, the manufacturing process can be obviously simplified, and the damage of etching liquid to the metal is avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new energy batteries and integrated circuits, in particular to a metal structure based on a polymer film and a manufacturing method thereof. BACKGROUND

[0002] If the metal line in the traditional integrated circuit is made by sputtering method, it needs to be plated in vacuum, but the production equipment is expensive and the production efficiency is low. If it is made by electroplating method, the electroplating solution is easy to cause environmental burden, and it needs to be pre-plated with conductive material before electroplating, the uniformity of plating thickness is affected by pattern and current, and it is not easy to control. If it is made by electroless plating method, it usually needs to use palladium metal as catalyst to grow metal layer on the component by chemical reduction, but palladium metal is a rare metal and expensive.

[0003] In addition, if the metal layer is grown on a passive and smooth material, such as a polymer material, the traditional method has the problem of poor adhesion of the metal layer. If the component needs to form a pattern of the metal layer, it needs to increase the process to remove the places that are not needed, which is usually achieved by etching. Therefore, in the traditional new energy battery field, pure copper foil is used as the electrode, the metal consumption is large and the quality is heavy, which increases the material cost and reduces the battery capacity per unit weight. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a metal structure based on a polymer film and a manufacturing method thereof to solve the above problems.

[0005] The present application adopts the following scheme:

[0006] The present application provides a metal structure based on a polymer film, which comprises a film substrate composed of a polymer material, and a first metal layer and a second metal layer formed on the film substrate; the surface of the film substrate is configured to have a certain roughness and a surface structure subjected to activation treatment, the first metal layer is adhered to the surface of the film substrate and configured to have a nanostructure, and the second metal layer completely covers the first metal layer and / or is configured to have a patterned structure on the first metal layer.

[0007] As a further improvement, one of the first metal layer and the second metal layer is arranged on the upper surface of the film substrate, and the other of the first metal layer and the second metal layer is symmetrically arranged on the lower surface of the film substrate.

[0008] As a further improvement, the film substrate is a polyimide PI film substrate, and the polyimide PI film substrate is configured to have a low-activity passivation surface.

[0009] As a further improvement, the surface roughness of the polyimide PI film substrate is 0.01-1 μm.

[0010] As a further improvement, the film substrate is a polyethylene terephthalate PET, polypropylene PP, or polytetrafluoroethylene PTFE film substrate.

[0011] As a further improvement, the first metal layer is made of silver, and the ions of the first metal layer are silver ions; the second metal layer is made of copper or copper alloy, and the ions of the second metal layer are copper ions or other metal ions corresponding to the copper alloy.

[0012] As a further improvement, the ratio of the thickness of the second metal layer to the thickness of the first metal layer is 1-5000.

[0013] The application further provides a method for manufacturing a polymer film-based metal structure, which is used to manufacture the polymer film-based metal structure as described above, and comprises the following steps:

[0014] S1: providing a film substrate with a low-activity passivated surface, roughening at least one side surface of the film substrate to obtain a film substrate with a rough surface;

[0015] S2: performing surface activation treatment on the film substrate by using a plasma gas to obtain a film substrate with a surface-activated surface structure;

[0016] S3: immersing the film substrate in a coupling agent solution, then immersing the film substrate in a solution of a compound or complex with metal ions after cleaning, to obtain a film substrate with metal ions complexed on the surface;

[0017] S4: performing reduction treatment on the film substrate with metal ions complexed on the surface by using general light, femtosecond laser or UV pulse light to obtain a film substrate with a first metal layer with a nanostructure on the surface;

[0018] S5: placing the film substrate with the first metal layer on the surface in a chemical plating solution to perform chemical plating, forming a second metal layer above the first metal layer to constitute the entire metal structure, and obtaining a film substrate with a metal structure on the surface.

[0019] As a further improvement, in step S2, the plasma gas uses Ar / O2, so that the surface of the thin film substrate forms hydroxyl or carboxyl groups, and the coupling agent reacts with the hydroxyl or carboxyl groups on the surface of the surface-activated thin film substrate; wherein the concentration of the coupling agent is 3-10 vol%, the soaking time is 10-60 min, the soaking temperature is 20-35℃, after soaking, baking at a temperature of 60-100℃ for 30-90 min, and soaking in a compound containing metal ions of the first metal layer, the soaking time is 1-60 s, and the soaking temperature is 20-35℃, to obtain a thin film substrate with metal ions complexed on the surface.

[0020] As a further improvement, in step S2, the plasma gas uses Ar / H2, so that the surface of the thin film substrate is ring-opened, and the thin film substrate is reacted with a silver nitrate and polyvinylpyrrolidone mixed solution, a silver amine carbamate or diamine silver ion complex solution, the soaking time is 1-60 s, and the soaking temperature is 20-35℃, to obtain a thin film substrate with metal ions complexed on the surface.

[0021] As a further improvement, in step S1, the roughening treatment includes alkaline solution soaking treatment or femtosecond laser; wherein the alkaline solution is a KOH or NaOH solution with a pH of 12-14; wherein in step S4, the thin film substrate with metal ions complexed on the surface is selectively reduced by using a photosensitive reducing agent combined with femtosecond laser or UV pulse light for exposure development, to obtain a first metal layer with a patterned structure, and a second metal layer with the same pattern as the patterned structure is chemically plated on the first metal layer; wherein the photosensitive reducing agent is polyvinylpyrrolidone; and the wavelength range of the femtosecond laser is 133nm-400nm, the pulse time is 1-10ns, the frequency range is 1-100Hz, and the light flux is 0.1-1mJ / cm 2 ; and the pulse time of the UV pulse light for exposure development is 10-100us, the frequency range is 1-100Hz, and the light flux is 200mJ / cm 2 -18J / cm 2 .

[0022] By using the above technical solution, the present application can achieve the following technical effects:

[0023] The polymer film-based metal structure of the present application roughens and activates the surface of the film substrate of the polymer material, grows a first metal layer with nanostructure on the surface of the film substrate by reduction treatment, and grows a second metal layer by electroless plating, thereby canceling the use of palladium as a catalyst, greatly reducing the production cost, and having better adhesion between the metal structure and the film substrate, so that different metal patterning structures can be obtained. In particular, the metal structure is composite, and can be efficiently formed on both surfaces of the film substrate, thereby replacing the copper foil current collector of the negative electrode of the new energy, the polymer density of which is much lower than that of copper, thereby reducing the amount of copper used in the negative electrode, significantly improving the battery capacity per unit weight, and the patterning of each metal layer is exposed and developed by femtosecond laser or UV pulse light, which can significantly simplify the process and avoid damage to the metal by etching chemicals. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a structural schematic diagram of a polymer film-based metal structure according to an embodiment of the present application;

[0025] Figure 2 is Figure 1 a structural schematic diagram from another perspective;

[0026] Figure 3 is a flowchart of a manufacturing method of a polymer film-based metal structure according to an embodiment of the present application;

[0027] Figure 4 is a trend chart of the relative change between the thickness of the film substrate and the thickness of the metal structure of a polymer film-based metal structure according to an embodiment of the present application;

[0028] Figure 5 is a scanning electron microscope image of the surface of a polyimide film substrate in embodiment 1 of the present application;

[0029] Figure 6 is a scanning electron microscope image of the surface of a polyimide film substrate after roughening treatment in embodiment 1 of the present application;

[0030] Figure 7 is a scanning electron microscope image of the surface of a polyimide film substrate with silver nanostructure in embodiment 1 of the present application;

[0031] Figure 8 is a top view of a patterned sample before electroless copper plating in embodiment 5 of the present application;

[0032] Figure 9 is a top view of a patterned sample after electroless copper plating in embodiment 5 of the present application;

[0033] Figure 10 and Figure 11is a cross-sectional SEM analysis diagram of the patterned sample after electroless copper plating in Example 5 of the present application;

[0034] Figure 12 is a drawing of cross-sectional elements in Example 5 of the present application;

[0035] Figure 13 is a schematic diagram of the surface of a polyimide film substrate after immersion treatment in a basic solution in Example 6 of the present application.

[0036] Icon:

[0037] 1 - film substrate; 2 - first metal layer; 3 - second metal layer. DETAILED DESCRIPTION

[0038] In order to make the objects, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the scope of protection of the present application. Therefore, the following detailed description of the embodiments of the present application provided in the drawings is not intended to limit the scope of the claimed present application, but only represents selected embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the scope of protection of the present application.

[0039] In combination Figures 1 to 13 , the present embodiment provides a metal structure based on a polymer film, which includes a film substrate 1 composed of a polymer material, and a first metal layer 2 and a second metal layer 3 formed on the film substrate 1. The surface of the film substrate 1 is configured to have a surface structure with a certain roughness and is subjected to activation treatment, the first metal layer 2 is adhered to the surface of the film substrate 1 and is configured to have a nanostructure, and the second metal layer 3 completely covers the first metal layer 2 and / or is configured to have a patterned structure on the first metal layer 2.

[0040] In the above, the surface of the film substrate 1 of the high polymer material is subjected to roughening treatment and surface activation treatment, and the first metal layer 2 with nano structure is grown on the surface of the film substrate 1 by reduction treatment, and the second metal layer 3 is grown by chemical plating, so that the palladium metal as catalyst is cancelled, the production cost is greatly reduced, the adhesion between the metal structure and the film substrate 1 is better, different metal patterning structures can be obtained, especially, the metal structure is composite, efficient formation can be carried out on both surfaces of the film substrate 1, which can replace the copper foil current collector of the negative electrode of the new energy, the polymer density is much lower than that of copper, the use amount of copper of the negative electrode is reduced, the battery capacity per unit weight can be significantly improved, and the patterning treatment of each metal layer is exposed and developed by femtosecond laser or UV pulse light, which can obviously simplify the process and avoid damage to the metal by etching liquid.

[0041] As shown in Figure 1 and Figure 2 in the embodiment, one of the first metal layer 2 and the second metal layer 3 is arranged on the upper surface of the film substrate 1, and the other of the first metal layer 2 and the second metal layer 3 is symmetrically arranged on the lower surface of the film substrate 1. Thus, the metal structure can be efficiently formed on both surfaces of the film substrate 1, and the production efficiency of the product is greatly improved.

[0042] In an embodiment, the film substrate 1 is a polyimide PI film substrate 1, and the polyimide PI film substrate 1 is provided with a low-activity passivation surface. It should be noted that the low-activity passivation specifically refers to passivation of the surface of the substrate to make the surface into a state not easy to be oxidized, so as to delay the corrosion rate. The surface roughness of the polyimide PI film substrate 1 is 0.01-1 μm.

[0043] In other embodiments, the film substrate 1 is a polyethylene terephthalate PET, polypropylene PP, or polytetrafluoroethylene PTFE film substrate. The above-mentioned high polymer film falls within the protection scope of the present application.

[0044] In the embodiment, the first metal layer 2 is silver material, and the ions of the first metal layer 2 are silver ions. The second metal layer 3 is copper or copper alloy, and the ions of the second metal layer 3 are copper ions or other metal ions corresponding to the copper alloy. The purpose of the copper alloy is to add a small amount of other metal to modify the chemical stability and mechanical properties.

[0045] The ratio of the thickness of the second metal layer 3 to the thickness of the first metal layer 2 is 1-5000. Thus, the first metal layer 2 and the second metal layer 3 form an entire metal structure, which has a partially continuous and discontinuous metal pattern, and there is no first metal layer 2 under the part without the second metal layer 3 in the discontinuous metal pattern. With such a composite metal structure, the copper foil current collector of the negative electrode can be replaced, the polymer density is much lower than copper, and the use amount of copper in the negative electrode can be reduced to improve the battery capacity per unit weight.

[0046] As Figure 4 mentioned above, in the case of the same thickness of the negative electrode, the weight reduction per 100 m 2 The weight reduction per 100 m 2 The battery weight can be reduced as follows:

[0047] When the thickness of the polyimide film is 4 um and the thickness of the metal structure is 2 um, the weight reduction is 2.99 Kg / 100 m 2 .

[0048] When the thickness of the polyimide film is 5 um and the thickness of the metal structure is 1 um, the weight reduction is 3.74 Kg / 100 m 2 .

[0049] In combination Figure 3 , the embodiment further provides a method for manufacturing a polymer film-based metal structure, which is used to manufacture the polymer film-based metal structure as described above, and includes the following steps:

[0050] S1: providing a film substrate 1 with a low-activity passivated surface, roughening at least one side surface of the film substrate 1 to obtain a film substrate 1 with a rough surface;

[0051] S2: performing surface activation treatment on the film substrate 1 by using a plasma gas to obtain a film substrate 1 with a surface-activated surface structure;

[0052] S3: immersing the film substrate 1 in a coupling agent solution, then immersing it in a solution of a compound or complex with metal ions after cleaning to obtain a film substrate 1 with surface-complexed metal ions;

[0053] S4: performing reduction treatment on the film substrate 1 with surface-complexed metal ions by using general light, femtosecond laser or UV pulse light to obtain a film substrate 1 with a first metal layer 2 having a nanostructure on the surface;

[0054] S5: placing the film substrate 1 with the surface having the first metal layer 2 into a chemical plating solution to perform chemical plating, forming a second metal layer 3 above the first metal layer 2 to constitute an entire metal structure, and obtaining the film substrate 1 with the surface being the metal structure.

[0055] Specifically, in step S1, the roughening treatment includes an alkaline solution immersion treatment or a femtosecond laser. The alkaline solution is a KOH or NaOH solution with a pH of 12-14. In step S4, a photosensitive reducing agent is used in combination with a femtosecond laser or UV pulse light for exposure development to selectively reduce the film substrate 1 with the surface complexed with metal ions, to obtain the first metal layer 2 with a patterned structure, and to chemically plate the second metal layer 3 with the same pattern as the patterned structure on the first metal layer 2. The photosensitive reducing agent is polyvinylpyrrolidone. The wavelength of the femtosecond laser ranges from 133 nm to 400 nm, the pulse time is 1-10 ns, the frequency ranges from 1 Hz to 100 Hz, and the light flux is 0.1-1 mJ / cm 2 . The pulse time of the UV pulse light for exposure development is 10-100 us, the frequency ranges from 1 Hz to 100 Hz, and the light flux is 200 mJ / cm 2 -18 J / cm 2 .

[0056] In one embodiment, in step S2, the plasma gas is Ar / O2, so that the surface of the film substrate 1 forms hydroxyl or carboxyl groups, and the coupling agent reacts with the hydroxyl or carboxyl groups on the surface of the surface-activated film substrate 1. The concentration of the coupling agent is 3-10 vol%, the immersion time is 10-60 min, the immersion temperature is 20-35°C, the film substrate 1 is baked at a temperature of 60-100°C for 30-90 min after immersion, and then immersed in a compound containing metal ions (silver ions) in the first metal layer 2 for 1-60 s at an immersion temperature of 20-35°C, to obtain the film substrate 1 with the surface complexed with metal ions. The coupling agent is γ-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 10-aminopropyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, or 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane. The compound with metal ions is a mixed solution of silver nitrate and polyvinylpyrrolidone, silver amine carbamate, or diamine silver ions.

[0057] In another embodiment, in step S2, the plasma gas is Ar / H2, so that the surface of the thin film substrate 1 is opened, and the opened thin film substrate 1 is reacted with a silver nitrate and polyvinyl pyrrolidone mixed solution, a silver amine carbamate or a diamine silver ion complex solution, the soaking time is 1-60s, and the soaking temperature is 20-35℃, to obtain the thin film substrate 1 with metal ions (silver ions) complexed on the surface.

[0058] In order to distinguish the differences between different embodiments and comparative examples, please refer to the following.

[0059] In Example 1, as shown in Figure 5 , it is a scanning electron microscope image of the surface of the polyimide thin film substrate 1. The side surface of the polyimide thin film substrate 1 is roughened by femtosecond laser, wherein the wavelength range of the femtosecond laser is 266nm, the pulse time is 5ns, the frequency is 10Hz, and the light flux is 1.0mJ / cm 2 , to obtain the polyimide thin film substrate 1 with a rough surface, as shown in Figure 6 , it is a scanning electron microscope image of the surface of the polyimide thin film substrate 1 after roughening treatment. Thus, the femtosecond laser can effectively increase the roughness of the surface and increase the adhesion of the subsequent metal.

[0060] In addition, the polyimide thin film substrate 1 with a rough surface is subjected to surface activation treatment by Ar / O2 plasma gas, so that the surface of the polyimide thin film substrate 1 forms hydroxyl or carboxyl groups, to obtain the surface-activated polyimide thin film substrate 1.

[0061] In addition, the surface-activated polyimide thin film substrate 1 is sequentially soaked in diamine silver ions, the soaking temperature is 25℃, and the soaking time is 5min, so that the silver ions react with the imide ring on the surface of the polyimide thin film substrate 1, to obtain the polyimide thin film substrate 1 with silver ions complexed on the surface, and the substrate is subjected to 1000 lumen light for 30s to obtain a silver nanostructure.

[0062] In addition, the polyimide thin film substrate 1 with a silver nanostructure on the surface is placed in a chemical plating solution for soaking, the composition of the chemical plating solution is: formaldehyde (reducing agent), 2,2'-dipyridyl (stabilizing agent), the concentration of the reducing agent is 12ml / L, and the concentration of the stabilizing agent is 10ml / L. The formaldehyde in the chemical plating solution is used to reduce the polyimide thin film substrate 1 with silver ions complexed on the surface, to obtain the polyimide thin film substrate 1 with a silver nanostructure on the surface. The formaldehyde as the reducing agent not only reduces the silver, but also performs chemical plating process as the chemical plating solution. The reduced silver nanostructure completely covers the surface of the polyimide thin film substrate 1. As shown in Figure 7The scanning electron microscope image of the silver nanostructure on the surface of the polyimide film substrate 1 is shown. At the same time, the electroless plating solution is carried out on the surface of the polyimide film substrate 1 with silver nanostructure, at this time, the reaction temperature is 40℃, the PH value is 12.5, the reaction time is 15min, and finally a copper layer is formed on the silver nanostructure, and the copper layer completely covers the silver nanostructure. Among them, the patterned structure of the copper layer is designed according to specific requirements, which is not limited here.

[0063] In example 2, the implementation principle and the technical effects generated are the same as those of example 1 described above. For brief description, the contents not mentioned in example 2 can be referred to the corresponding contents in example 1 described above. Different from example 1, in example 2, the polyimide film substrate 1 with rough surface is subjected to surface activation treatment by Ar / H2 plasma gas, so that the imide ring on the surface of the polyimide film substrate 1 is opened, and the surface-activated polyimide film substrate 1 is obtained.

[0064] In example 3, the implementation principle and the technical effects generated are the same as those of example 2 described above. For brief description, the contents not mentioned in example 3 can be referred to the corresponding contents in example 2 described above. Different from example 2, in example 3, the surface-activated polyimide film substrate 1 is sequentially soaked in silver amine-based carbonate (complex solution of silver ions) with a soaking temperature of 25℃ and a soaking time of 30s, and then taken out and baked at 60℃ for 30min to obtain the polyimide film substrate 1 with silver ions complexed on the surface. In addition, the side surface of the polyimide film substrate 1 is subjected to reduction heat treatment by UV pulse light, the pulse time of the UV pulse light is 50us, the frequency range is 50Hz, and the light flux is 1J / cm 2 The imide ring on the surface of the polyimide film substrate 1 is closed, and the polyimide film substrate 1 with silver nanostructure on the surface is obtained, and the silver nanostructure completely covers the surface of the polyimide film substrate 1.

[0065] In embodiment 4, the principle and the resulting technical effects are the same as those of embodiment 1, and for brief description, the embodiment 4 is not mentioned, please refer to the corresponding content in embodiment 1. Different from embodiment 1, in embodiment 4, the surface-activated polyimide film substrate 1 is sequentially immersed in 3-aminopropyltrimethoxysilane solution and silver nitrate and polyvinylpyrrolidone mixed solution, 3-aminopropyltrimethoxysilane is used as a coupling agent, and silver nitrate and polyvinylpyrrolidone mixed solution is a compound with metal ions, the immersion temperature in the coupling agent with a concentration of 5 vol% is 25°C, the immersion time is 30 min, the immersion temperature in the compound with metal ions is 25°C, and the immersion time is 30 s. The coupling agent is an organic molecule with different functional groups at both ends, for example, one end is -OH group, and the other end is -NH group. The -OH group in the coupling agent reacts with the -OH group on the surface of the polyimide film substrate 1, and the compound with metal ions reacts with the -NH group in the coupling agent and replaces the metal ions to obtain the polyimide film substrate 1 with silver ions complexed on the surface. In addition, the surface of the obtained polyimide film substrate 1 is coated with an alkali-resistant photoresist, and a pattern is defined by exposure and development.

[0066] In embodiment 5, the principle and the resulting technical effects are the same as those of embodiment 2, and for brief description, the embodiment 5 is not mentioned, please refer to the corresponding content in embodiment 2. Different from embodiment 2, in embodiment 5, the surface-activated polyimide film substrate 1 is sequentially immersed in silver nitrate and polyvinylpyrrolidone mixed solution, silver nitrate and polyvinylpyrrolidone mixed solution is a compound with metal ions, the immersion temperature is 25°C, and the immersion time is 30 s, to obtain the polyimide film substrate 1 with silver ions complexed on the surface. As shown in FIG. 5, it is a top view of the patterned sample before electroless copper plating. As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements. Figure 8 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements. Figure 9 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements. Figure 10 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements. Figure 11 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements. Figure 12 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements.

[0067] In embodiment 6, the principle and the resulting technical effects are the same as those of embodiment 5, and for brief description, the embodiment 6 is not mentioned, please refer to the corresponding content in embodiment 5. Different from embodiment 5, in embodiment 6, the side surface of the polyimide film substrate 1 is roughened by alkaline solution immersion treatment, the alkaline solution is KOH or NaOH solution with pH 13.5, and the polyimide film substrate 1 with rough surface is obtained. As shown in FIG. 10, it is a schematic diagram of the surface of the polyimide film substrate 1 after alkaline solution immersion treatment. Figure 13 As shown in FIG. 6, it is a top view of the patterned sample after electroless copper plating. As shown in FIG. 7 and FIG. 8, they are cross-sectional SEM analysis diagrams of the patterned sample after electroless copper plating. As shown in FIG. 9, it is a drawing of the cross-sectional elements.

[0068] In the comparative example 1, the surface of the polyimide film substrate 1 is not roughened and plasma activated, only reduced silver and electroless copper plating processes are used, and the steps of the reduced silver and electroless copper plating processes are the same as those of the above-mentioned example 2.

[0069] In the comparative example 2, the surface of the polyimide film substrate 1 is activated by a conventional palladium metal and electroless plating process, and the electroless plating process is consistent with examples 1 to 6.

[0070] It should be noted that the crosshatch adhesion test is tested according to ASTM D3002 "Standard Guide for Evaluating Coated Plastics" and ASTM D3359 "Standard Test Method for Measuring Adhesion by Tape". Each example and comparative example is prepared with 3 samples of suitable area, and 3 crosshatch tests are performed, and the worst result of the 3 test results is taken as the test result. The crosshatch adhesion test results of the samples of the above-mentioned examples and comparative examples are as follows:

[0071] Crosshatch adhesion test table

[0072] Sample Crosshatch adhesion test metal layer flaking rating evaluation Example 1 4B Example 2 4B Example 3 4B Example 4 4B Example 5 4B Example 6 4B Comparative Example 1 The degree of flaking was less than 1B Comparative Example 2 4B

[0073] As can be seen from the above, the method for manufacturing a metal structure of a polyimide film of the present application does not need to use palladium metal as a catalyst, and can reduce production costs. On the surface of a passive and smooth polyimide film material, roughening and surface activation treatment can be performed to make it have the same good adhesion (crosshatch test ≧4B) as the palladium-containing activation and plating process, and at the same time, the metal pattern required by the assembly can be formed when growing the first metal layer 2 and the second metal layer 3. Suitable surface roughness can not only improve the adhesion of the film, but also improve the characteristics for applications that require to reduce the electrode interface resistance, such as the positive and negative electrode current collectors of lithium ion batteries. When the surface is activated, the photosensitive material is exposed to appropriate wavelength and energy, and the solubility or activity of the photosensitive material is different, so that the metal is selectively grown in the required place. Compared with the traditional yellow light etching process, the process can be significantly simplified.

[0074] The above is only a preferred embodiment of the present application, and the protection scope of the present application is not limited to the above-mentioned examples. Any technical solution that belongs to the idea of the present application is within the protection scope of the present application.

Claims

1. A polymer thin film-based metal structure, characterized by, The polymer film-based metal structure comprises a film substrate made of a polymer material, and a first metal layer and a second metal layer formed on the film substrate; a surface of the film substrate is configured to have a certain roughness and a surface structure after activation treatment, the first metal layer is adhered to the surface of the film substrate and configured to have a nanostructure, and the second metal layer completely covers the first metal layer and / or is configured to have a patterned structure on the first metal layer; wherein the polymer film-based metal structure is prepared by the following steps: S1: providing a film substrate with a low-activity passivated surface, roughening at least one side surface of the film substrate to obtain a film substrate with a rough surface; S2: performing surface activation treatment on the film substrate by using a plasma gas to obtain a film substrate with a surface-activated surface structure; wherein the plasma gas is Ar / O2, so that the surface of the film substrate forms hydroxyl or carboxyl groups, and the hydroxyl or carboxyl groups on the surface of the surface-activated film substrate react with a coupling agent; wherein the concentration of the coupling agent is 3-10 vol%, the soaking time is 10-60 min, the soaking temperature is 20-35°C, the film substrate is baked at a temperature of 60-100°C for 30-90 min after soaking, and the film substrate is soaked in a compound containing metal ions of the first metal layer for 1-60 s at a soaking temperature of 20-35°C to obtain a film substrate with surface complexation of metal ions; S3: soaking the film substrate in a coupling agent solution, and then soaking in a compound or complex solution with metal ions after cleaning to obtain a film substrate with surface complexation of metal ions; S4: reduction treatment in the way of general light, femtosecond laser or UV pulse light, to reduce the thin film substrate with metal ion complexed on the surface, to obtain the thin film substrate with the first metal layer having nanostructure on the surface; wherein, the thin film substrate with metal ion complexed on the surface is selectively reduced by using photosensitive reducing agent combined with femtosecond laser or UV pulse light for exposure and development, to obtain the first metal layer with patterned structure, and the second metal layer with the same pattern as the patterned structure is chemically plated on the first metal layer; wherein, the photosensitive reducing agent is polyvinylpyrrolidone; and the wavelength range of the femtosecond laser is 133nm-400nm, the pulse time is 1-10ns, the frequency range is 1-100Hz, and the light flux is 0.1-1mJ / cm 2 ; and the pulse time of the UV pulse light for exposure and development is 10-100us, the frequency range is 1-100Hz, and the light flux is 200mJ / cm 2 -18J / cm 2 ; S5: placing the thin film substrate with the first metal layer on the surface in the chemical plating solution for chemical plating, to form the second metal layer above the first metal layer to constitute the entire metal structure, to obtain the thin film substrate with the surface being the metal structure.

2. The polymer thin film-based metal structure according to claim 1, wherein One of the first metal layer and the second metal layer is arranged on the upper surface of the film substrate, and the other of the first metal layer and the second metal layer is symmetrically arranged on the lower surface of the film substrate.

3. The polymer thin film-based metal structure according to claim 1, wherein The film substrate is a polyimide (PI) film substrate, and the polyimide (PI) film substrate is configured to have a low-activity passivated surface.

4. The polymer thin film-based metal structure according to claim 3, wherein The surface roughness of the polyimide (PI) film substrate is 0.01-1 μm.

5. The polymer thin film-based metal structure according to claim 1, wherein The film substrate is a polyethylene terephthalate (PET) film substrate, a polypropylene (PP) film substrate, or a polytetrafluoroethylene (PTFE) film substrate.

6. The polymer thin film-based metallic structure according to claim 1, wherein The first metal layer is made of silver, and the ions of the first metal layer are silver ions; the second metal layer is made of copper or copper alloy, and the ions of the second metal layer are copper ions or other metal ions corresponding to the copper alloy.

7. The polymer thin film-based metallic structure according to claim 1, wherein In step S1, the roughening treatment includes alkaline solution soaking treatment or femtosecond laser; wherein the alkaline solution is a KOH or NaOH solution with a pH of 12-14.

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