CN114551896A - Preparation method of composite current collector - Google Patents
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- CN114551896A CN114551896A CN202210102551.3A CN202210102551A CN114551896A CN 114551896 A CN114551896 A CN 114551896A CN 202210102551 A CN202210102551 A CN 202210102551A CN 114551896 A CN114551896 A CN 114551896A
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- H—ELECTRICITY
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Abstract
The invention relates to the technical field of new materials, in particular to a preparation method of a composite current collector. According to the invention, through performing laser femtosecond etching on the polymer film, a large number of etching holes can be formed on the surface of the polymer film, so that the polarity of the surface of the nonpolar polymer film is improved, the bonding force between the nonpolar polymer film and a metal layer with stronger polarity plated subsequently is enhanced, and the activation liquid in the next step can be better adsorbed, thereby smoothly completing activation; the polymer film is treated by contact treatment with activating liquid of specific composition and concentration under ultraviolet light, and due to laser effect, bivalent copper ions in the activating liquid are H-substituted2PO2 ‑The copper is reduced into a simple substance, so that a layer of nano-scale copper layer is formed on the surface of the polymer film, a certain sheet resistance is achieved, subsequent chemical plating or electroplating can be carried out, the physical vapor deposition step for preparing the composite current collector in the traditional technology is replaced, the energy consumption and the production cost are effectively reduced, and the production efficiency is improved.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a preparation method of a composite current collector.
Background
The composite current collector is a novel current collector material, is made of metal plated on two sides of a polymer substrate layer, and is of a sandwich structure. At present, the preparation method of the composite current collector mainly comprises the steps of depositing a metal layer with a certain thickness on the upper surface and the lower surface of a polymer base material by a Physical Vapor Deposition (PVD) method in a vacuum state so as to enable the metal layer to reach a certain sheet resistance and further reach the standard of electroplating or chemical plating, and then electroplating or chemical plating the material with metal deposited on the two sides so as to thicken the metal layer and enable the sheet resistance of the material to reach the standard required by a secondary battery.
However, the vacuum physical vapor deposition has high equipment requirements and is accompanied by high temperature, and the polymer substrate is easily deformed, wrinkled, blown, perforated, embrittled, and the like at high temperature, and even if the polymer material is cooled in real time during the deposition process, the above problems cannot be completely avoided, so that the yield of the composite current collector product prepared by using the physical gas is low, and is usually lower than 50%. In addition, the physical vapor deposition speed is low, and the production efficiency is low; and the physical vapor deposition needs to gasify the metal, so the consumed energy is high, and meanwhile, the cooling of the polymer substrate also needs high energy, so that energy mutual impact is formed, great energy loss is caused, and carbon peak reaching and carbon neutralization are not facilitated.
Disclosure of Invention
Therefore, a preparation method of the composite current collector with low energy consumption, low cost, high production efficiency and high yield is needed.
In one aspect of the present invention, a method for preparing a composite current collector is provided, which includes the steps of:
performing laser femtosecond etching on the polymer film to obtain a polymer film substrate; contacting the polymer film substrate with an activating solution, drying, and carrying out ultraviolet irradiation treatment to obtain an activated substrate; electroless copper plating the activated substrate;
wherein the activating solution comprises CuSO with the concentration of 10 g/L-20 g/L4And NaH with a concentration of 30g/L to 40g/L2PO2Or KH2PO2。
In some embodiments, the laser femtosecond etching has the wavelength of 150nm to 350nm, the power of 10mW to 50mW and the time of 10fs to 60 fs.
In some embodiments, the wavelength of the ultraviolet light treatment is 157nm to 353nm, and the time of the ultraviolet light treatment is 5ms to 100 ms.
In some embodiments, the contacting treatment is to apply the activating solution to the polymer film substrate to form an activated coating film with a thickness of 20nm to 60 nm.
In some embodiments, the drying is at a temperature of 75 ℃ to 85 ℃ for 2min to 5 min.
In some embodiments, the material of the polymer film is one or more of polyethylene terephthalate, polyethylene, polypropylene, polyimide, polyetheretherketone, and polymethylmethacrylate.
In some embodiments, the polymer film has a thickness of 2 μm to 10 μm.
In some embodiments, the electroless copper plating is alkaline electroless copper plating, and the electroless copper plating results in a copper layer thickness of 100nm to 1000 nm.
In some embodiments, the electroless copper plating is followed by electrolytic copper plating, the electrolytic copper plating being acid electrolytic copper plating, the electrolytic copper plating resulting in a copper layer thickness of 900nm to 1100 nm.
In some embodiments, the electroless copper plating further comprises electroplating with a chromium layer of 1nm to 2 nm.
By carrying out laser femtosecond etching on the polymer film, a large number of etching holes can be formed on the surface of the polymer film, so that the polarity of the surface of the nonpolar polymer film is improved, the bonding force between the nonpolar polymer film and a metal layer with stronger polarity which is plated later is enhanced, a latch effect can be formed between the nonpolar polymer film and the metal layer, the bonding strength between the nonpolar polymer film and the metal layer is further improved, in addition, the improvement of the polarity means better hydrophilicity, and the activation liquid in the next step can be better adsorbed, so that the activation can be smoothly completed; the polymer film is treated by contact treatment with activating liquid of specific composition and concentration under ultraviolet light, and due to laser effect, bivalent copper ions in the activating liquid are H-substituted2PO2 -Reducing the copper into a simple substance to form a layer of nano-copper layer on the surface of the polymer film, thereby achieving a certain sheet resistance, and being capable of carrying out subsequent chemical plating or electroplating to replace the preparation of a complex material in the traditional technologyThe physical vapor deposition step of the fluid collection effectively reduces energy consumption and production cost and improves production efficiency. In addition, the femtosecond etching time is extremely short, and the polymer film material cannot be macroscopically damaged, so that the physical strength and the performance of the polymer film material cannot be influenced, and the product yield is effectively improved.
Drawings
FIG. 1 is a schematic view of a scanning electron microscope illustrating a process and a scanning electron microscope after each step of the process according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution including the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In one aspect of the present invention, a method for preparing a composite current collector is provided, which includes the steps of:
performing laser femtosecond etching on the polymer film to obtain a polymer film substrate; contacting a polymer film substrate with an activating solution, drying, and carrying out ultraviolet irradiation treatment to obtain an activated substrate; carrying out chemical copper plating on the activated base material;
wherein the activating solution comprises CuSO with the concentration of 10 g/L-20 g/L4And NaH with a concentration of 30g/L to 40g/L2PO2Or KH2PO2。
Since the beginning of mass commercialization in the 1990's or so, the specific energy density of lithium ion batteries has increased at a rate of about 3% per year, and it is desired that lithium ion batteries be lighter and safer while increasing the energy density. Lithium batteries primarily store energy in the electrode material, and therefore, a common idea for increasing the energy density is to optimize and develop the electrode material, or to directly increase the proportion of active material in the battery. However, the change of these active ingredients has a great influence on the battery performance, and thus the operation is complicated and the development cost is high. In order to solve the problem, research and development personnel split the structure of the whole battery and try to find a new idea. It is found that the traditional metal current collector accounts for 15% or even higher of the proportion of the lithium battery, is composed of a metal foil film, has large weight and single function, is mainly used as a conduction carrier of electrons, is the only component part in the battery without influencing the lithium ion transmission, and has large development space, so that the energy density of the battery can be further improved by optimizing the current collector. Therefore, the composite current collector with a sandwich structure is produced by taking a light polymer material as a support body, and compounding high-purity metal films on two sides of the polymer, and the total thickness of the prepared composite current collector is reduced by 80% compared with the original pure metal current collector under the condition that the total thickness is not increased (about 9 microns) because the organic polymer is greatly lighter than metal; and because the weight ratio of the current collector is reduced, the energy density of the battery can be improved by 8-26% (the specific data are different according to different battery types).
Copper is a metal with good conductivity and low price, so the copper is widely used as a conductive material, and is also very suitable for preparing a composite current collector naturally. However, the boiling point of the elemental copper is as high as 2835K, and if the copper-containing composite current collector is prepared by physical vapor deposition, even though the copper itself is very cheap, the physical vapor deposition still causes high production cost due to high requirements on equipment and temperature. Besides, copper plating on the surface of the polymer needs to reach certain sheet resistance, a catalytic active center is also needed, and in the traditional technology, precious metals such as silver or palladium are usually adopted as catalytic active metals, so that the production cost is further increased.
The invention can form a large amount of etching holes on the surface of the polymer film by performing laser femtosecond etching on the polymer film, so that the polymer film is nonpolarThe polarity of the surface of the polymer film is improved, the bonding force between the polymer film and a metal layer with stronger polarity plated subsequently is enhanced, a latch effect can be formed between the polymer film and the metal layer, the bonding strength between the polymer film and the metal layer is further improved, in addition, the improvement of the polarity means that the hydrophilicity is better, and the polymer film is favorable for better adsorbing an activating solution in the next step, so that the activation is smoothly completed; the polymer film is treated by contact treatment with activating liquid of specific composition and concentration under ultraviolet light, and due to laser effect, bivalent copper ions in the activating liquid are H-substituted2PO2 -The copper is reduced into a simple substance, so that a layer of nano-scale copper layer is formed on the surface of the polymer film, a certain sheet resistance is achieved, the subsequent chemical plating or electroplating can be carried out, the physical vapor deposition step for preparing the composite current collector in the traditional technology is replaced, the deposition is not required to be carried out in a vacuum environment, the cold and hot energy hedging is basically avoided, the energy consumption and the production cost are effectively reduced, and the production efficiency is improved; moreover, the nano-scale copper layer has the catalytic activity of electroless copper plating, so that noble metal catalysts such as silver or palladium and the like adopted in the traditional technology can be saved, and the production cost is further reduced. In addition, the femtosecond etching time is extremely short, and the polymer film material cannot be macroscopically damaged, so that the physical strength and the performance of the polymer film material cannot be influenced, and the product yield is effectively improved.
Optionally, activating CuSO in the liquid4The concentration of (b) may be, for example, 12g/L, 13g/L, 14g/L, 15g/L, 16g/L, 17g/L, 18g/L or 19 g/L.
Optionally, NaH in the activating solution2PO2Or KH2PO2The concentration of (b) may be, for example, 32g/L, 33g/L, 34g/L, 35g/L, 36g/L, 37g/L, 38g/L or 39 g/L.
Preferably, the reducing agent is NaH2PO2。
In some embodiments, the solvent of the activation solution is water, preferably deionized water.
The selection and concentration of the solute in the activation liquid are of great importance for achieving the technical effect of the invention. The copper salt is matched with the oxidation-reduction potential of a reducing agent, and the oxidation-reduction reaction can be generated, which is the most basic requirement; in addition, the rate of the redox reaction and the type of ions in the reaction system also directly affect the formation effect of the nano copper layer. The concentration is set in a proper range, the reaction speed is high, the production efficiency is high, and meanwhile, the crystal grains are not grown too large due to the too high reaction speed, so that the formed nano copper layer structure is too loose, and the mechanical strength and the conductive effect of the composite current collector are influenced.
Preferably, the composite current collector prepared by the invention is a composite negative electrode current collector.
In some embodiments, the laser femtosecond etching has a wavelength of 150nm to 350nm, a power of 10mW to 50mW, and a time of 10fs to 60 fs. Alternatively, the wavelength of the laser femtosecond etching may be, for example, 160nm, 165nm, 170nm, 175nm, 180nm, 185nm, 190nm, 195nm, 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, or 340 nm. Alternatively, the power of the laser femtosecond etching may be, for example, 15mW, 20mW, 25mW, 30mW, 35mW, 40mW, or 45 mW. Alternatively, the time of the laser femtosecond etching may be, for example, 15fs, 20fs, 25fs, 30fs, 35fs, 40fs, 45fs, 50fs, or 55 fs. The size and density of holes formed by etching can be moderate due to proper laser femtosecond etching parameter setting, the bonding force between the polymer film and the metal layer is improved as much as possible on the premise of not influencing the physical property of the polymer film, the hydrophilicity of the polymer film is improved, and the activating liquid can be better adsorbed subsequently.
In some embodiments, the uv light treatment is performed at a wavelength of 157nm to 353nm, and the uv light treatment is performed for 5ms to 100ms after the contact treatment of the polymer film substrate. Alternatively, the wavelength of the ultraviolet light may be, for example, 160nm, 165nm, 170nm, 175nm, 180nm, 185nm, 190nm, 195nm, 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, 340nm, or 350 nm. Alternatively, the time of the ultraviolet light treatment may be, for example, 10ms, 20ms, 30ms, 40ms, 50ms, 60ms, 70ms, 80ms, or 90 ms. Exposing the polymer film substrate after contact treatment to ultraviolet light for ultraviolet irradiation treatment, wherein a large amount of cellular particles are generated on the surface of the substrate, and divalent copper ions are coated by H2PO2 -Is reduced to copper simple substance, therebyThe nano-scale copper layer grows on the surface of the base material, so that the surface of the polymer film can reach the square resistance of electroplating or chemical plating, has chemical plating catalytic activity, can directly replace the steps of adopting physical vapor deposition and adding noble metals such as palladium or silver and the like as catalysts in the traditional technology, effectively reduces the production cost and improves the yield. Suitable ultraviolet wavelengths have suitable energy to control the redox reaction rate within a suitable range.
In some embodiments, the contacting treatment is to apply an activating solution to the polymer film substrate to form an activated coating film having a thickness of 20nm to 60 nm. Alternatively, the thickness of the activation coating film may be, for example, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, or 55 nm. The appropriate coating film thickness can provide a raw material sufficient for forming a nano copper layer while making the cost lower.
In some embodiments, the drying temperature is from 75 ℃ to 85 ℃ for 2min to 5 min. Preferably, the temperature of drying is 70 ℃ and the time is 3 min.
In some embodiments, the material of the polymer film is one or more of polyethylene terephthalate, polyethylene, polypropylene, polyimide, polyetheretherketone, and polymethylmethacrylate. It is understood that the polymer film may be prepared by various film-making processes commonly used in the art, such as one or more of a blown film-making process, a cast film-making process, and a biaxially oriented film-making process.
In some embodiments, the intrinsic viscosity of the polymer solution in preparing the polymer membrane is from 0.5dL/g to 0.8dL/g, alternatively, the intrinsic viscosity may be, for example, 0.6dL/g or 0.7 dL/g. Films made from polymer solutions in a range of intrinsic viscosities are more suitable for use in the process of the present application.
In some embodiments, the polymer film has a thickness of 2 μm to 10 μm. Alternatively, the thickness of the polymer film may be, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, or 9 μm. The thickness of the polymer film is set within a proper range, so that the preparation method is particularly suitable for the preparation process of the invention, the mechanical strength of the etched current collector is not damaged due to over-thinness, and the conductivity of the current collector or the bonding force between composite layers is not influenced due to over-thicknesss.
In some embodiments, the electroless copper plating is alkaline electroless copper plating, and the electroless copper plating results in a copper layer thickness of 100nm to 1000 nm. It can be understood that before electroless copper plating, deionized water can be adopted to clean the activated substrate, so that the influence on the electroless copper plating can be avoided. The electroless copper plating is mainly used for forming a thickened copper layer so that the sheet resistance of the composite current collector can meet the standard required by the secondary battery, and any alkaline electroless copper plating solution which is conventional and commonly used in the field can be adopted for carrying out the copper plating. The thickness of the electroless copper plating layer may be adjusted as necessary, and may be, for example, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, or 900 nm.
In some embodiments, the electroless copper plating is followed by electrolytic copper plating, the electrolytic copper plating being acid electrolytic copper plating, the electrolytic copper plating resulting in a copper layer thickness of 900nm to 1100 nm. It can be understood that before the electro-coppering, deionized water can be adopted to clean the activated substrate after the electroless copper plating, so that the influence on the electro-coppering can be avoided. The electrolytic copper plating is mainly to further thicken the copper layer to meet the use requirement of the secondary battery, and any acid electrolytic copper plating solution which is conventional and commonly used in the field can be adopted for copper plating. The thickness of the electroplated copper layer can be adjusted as desired, and can be, for example, 910nm, 920nm, 930nm, 940nm, 950nm, 960nm, 970nm, 980nm, 990nm, 1000nm, 1010nm, 1020nm, 1030nm, 1040nm, 1050nm, 1060nm, 1070nm, 1080nm or 1090 nm.
In some embodiments, the electroless copper plating further comprises electroplating with a 1nm to 2nm chromium layer. It can be understood that before the chromium electroplating, the activated substrate after the copper electroplating can be cleaned by using deionized water, so that the influence on the chromium electroplating can be avoided. The chromium electroplating is mainly to form an anti-oxidation protective layer so as to prolong the service life of the composite current collector, and trivalent chromium or hexavalent chromium solution can be adopted for chromium plating.
It is understood that the process for preparing the composite current collector substrate may include both the steps of electroplating copper and electroplating chromium, or only either one of them. For example, when both copper and chromium electroplating steps are included, the structure of the composite current collector is: polymer film layer-chemical copper plating layer-electric chromium plating layer; if only the chromium electroplating layer is included and the copper electroplating step is not included, the structure of the composite current collector is as follows: polymer film layer-electroless copper layer-electroplated chromium layer.
In some embodiments, after electroless, electrolytic or chromium plating, the copper is dried at 75-85 ℃ for 2-5 min, preferably 80 ℃ for 3 min.
The present invention will be described in further detail with reference to specific examples and comparative examples. Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer. It is understood that the following examples are specific to the particular apparatus and materials used, and in other embodiments, are not limited thereto; the weight of the related components mentioned in the embodiments of the present specification may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the embodiments of the present specification according to the present specification. Specifically, the weight described in the description of the embodiment of the present invention may be a mass unit known in the chemical engineering field such as μ g, mg, g, kg, etc.
The source of the instrument is as follows:
laser femtosecond etching equipment: newport femtosecond laser processing system, usa;
an ultraviolet light processing device: shenzhen Baoliwang Shanghai DK-8-KZ laser engraving machine working platform.
Example 1
Preparing a polyethylene terephthalate film with the thickness of 2 mu m by a blow molding film-making process from a polyethylene terephthalate solution with the intrinsic viscosity of 0.6 dL/g; setting the wavelength of laser femtosecond etching equipment to be 190nm and the power to be 25mW, and etching the polyethylene terephthalate film for 15fs to obtain a polyethylene terephthalate substrate; activating solution (composition: CuSO)4The concentration is 15g/L，NaH2PO235g/L of solvent deionized water) is coated on a polyethylene terephthalate substrate to form an activated coating film with the thickness of 50nm, and after drying for 3min at the temperature of 80 ℃, the activated coating film is treated for 50ms under the ultraviolet light of 180nm to obtain an activated polyethylene terephthalate substrate;
cleaning an activated polyethylene glycol terephthalate substrate by deionized water, and placing the substrate in an alkaline chemical copper plating solution (a copper sulfate-formaldehyde system) for chemical copper plating to thicken a copper layer to 1000 nm; taking out, washing with deionized water, and electroplating copper (current density 5A/dm) in acidic copper electroplating solution (sulfuric acid-copper sulfate-chloride ion system)2) Thickening the copper layer to 1000 nm; taking out, washing with deionized water, and electroplating in trivalent chromium electroplating solution (current density of 30A/dm)2) Forming an anti-oxidation chromium layer with the thickness of 2nm, and then drying for 3min at the temperature of 80 ℃ to obtain the polyethylene terephthalate-copper composite current collector.
Example 2
Essentially the same as in example 1, except that the polymer was selected to be a polypropylene having an intrinsic viscosity of 0.5 dL/g.
Example 3
The procedure was as in example 1 except that the polymer was a polyimide having an intrinsic viscosity of 0.8 dL/g.
Example 4
Substantially the same as in example 1 except that the thickness of the polyethylene terephthalate film was 10 μm.
Comparative example 1
Substantially the same as in example 1 except that CuSO was added to the activating solution4To CuCl2(Cu in activating solution)2+Constant concentration of (c).
Comparative example 2
The same as example 1 except that the reducing agent in the activating solution was formaldehyde, and the content was 37%.
Comparative example 3
The same as example 1 except that CuSO was added to the activating solution4Has a concentration of 30g/L, NaH2PO2The concentration of (3) is 60 g/L.
Comparative example 4
Substantially the same as in example 1 except that the thickness of the polyethylene terephthalate film was 0.5. mu.m.
The composite current collectors prepared in the respective examples and comparative examples were subjected to the following tests, and the results are shown in table 1.
(1) Sheet resistance test
The test method comprises the following steps: measuring the resistance of the front and back diaphragm surfaces of the electroplated copper film by using a four-probe tester;
(2) tensile strength at break and elongation at break test
The test method comprises the following steps: a tensile machine: stretching speed is 50mm/min, 3-4 circles of samples are unfolded, 5 pieces of samples are taken from each sample, and the average value is taken as a test result. The length direction is required to be parallel to the axis of the clamp during measurement, and the sample is kept linear;
MD: longitudinal direction; TD: and (4) transverse direction.
TABLE 1
| Group of | Sheet resistance/m omega/□ | Elongation at break/% | Tensile strength at break/MPa |
| Example 1 | 22 | MD 22TD 8 | MD 145,TD 160 |
| Example 2 | 26 | MD 21TD 7 | MD 145,TD 160 |
| Example 3 | 38 | MD 33TD 16 | MD 145,TD 160 |
| Example 4 | 32 | MD 36TD 20 | MD 180,TD 167 |
| Comparative example 1 | 46 | MD 20TD 6 | MD 135,TD 148 |
| Comparative example 2 | 44 | MD 16TD 4 | MD 115,TD 130 |
| Comparative example 3 | 56 | MD 19TD 6 | MD 132,TD 145 |
| Comparative example 4 | 35 | MD 16TD 5 | MD 102TD 108 |
As can be seen from table 1, the composite current collectors prepared in the embodiments of the present invention have good conductivity and elongation at break, so that not only can the most basic conductive function be achieved, but also the safety is ensured, and the composite current collectors are not easily broken when being impacted or squeezed by external force, and the yield is significantly improved compared with the conventional technology; and the preparation method is simple, the energy consumption is low, and the cost can be greatly reduced compared with the traditional physical vapor deposition method.
Compared with example 1, in comparative example 1, because the activating solution contains chloride ions, the growth of the nano copper layer is influenced, and the formed nano copper layer is loose, the conductivity is reduced, the bonding force between the metal layer and the polymer layer is also reduced, and the elongation at break is influenced to a certain extent; in the comparative example 2, formaldehyde is used as a reducing agent, and hydrogen is generated, so that the formation of the nano copper layer is greatly influenced, holes are formed in the nano copper layer structure, and the conductivity and the elongation at break are greatly reduced; in comparative example 3, the concentration of copper sulfate and reducing agent is too high, the oxidation-reduction reaction speed is too fast, so that the deposition speed of nano-copper is too fast, the crystal grains are large, the formed copper layer is not compact enough, and the conductivity and the elongation at break are both reduced; in comparative example 4, the polymer film is too thin, and when the etching process disclosed by the invention is adopted for etching, the physical properties of the polymer film can be influenced, so that the elongation at break of the prepared composite current collector is obviously reduced, and the yield of the product is also obviously reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (10)
1. The preparation method of the composite current collector is characterized by comprising the following steps of:
performing laser femtosecond etching on the polymer film to obtain a polymer film substrate; contacting the polymer film substrate with an activating solution, drying, and carrying out ultraviolet irradiation treatment to obtain an activated substrate; electroless copper plating the activated substrate;
wherein the activating solution comprises CuSO with the concentration of 10 g/L-20 g/L4And NaH with a concentration of 30g/L to 40g/L2PO2Or KH2PO2。
2. The preparation method of claim 1, wherein the laser femtosecond etching has a wavelength of 150nm to 350nm, a power of 10mW to 50mW, and a time of 10fs to 60 fs.
3. The method for preparing a polycarbonate according to claim 1, wherein the wavelength of the ultraviolet light treatment is 157nm to 353nm, and the time of the ultraviolet light treatment is 5ms to 100 ms.
4. The production method according to claim 1, wherein the contact treatment is carried out by applying the activating solution to the polymer film substrate to form an activated coating film having a thickness of 20nm to 60 nm.
5. The method according to claim 1, wherein the drying temperature is 75-85 ℃ and the drying time is 2-5 min.
6. The method according to any one of claims 1 to 5, wherein the polymer film is made of one or more of polyethylene terephthalate, polyethylene, polypropylene, polyimide, polyetheretherketone, and polymethyl methacrylate.
7. The production method according to any one of claims 1 to 5, wherein the polymer film has a thickness of 2 μm to 10 μm.
8. The production method according to any one of claims 1 to 5, wherein the electroless copper plating is alkaline electroless copper plating, and the thickness of a copper layer obtained by the electroless copper plating is 100nm to 1000 nm.
9. The production method according to any one of claims 1 to 5, further comprising electroplating copper after the electroless copper plating, wherein the electroplating copper is acid electrolytic copper plating, and the thickness of a copper layer obtained by the electroplating copper is 900nm to 1100 nm.
10. The preparation method according to any one of claims 1 to 5, wherein the electroless copper plating further comprises electroplating with a chromium layer of 1nm to 2 nm.
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| CN202210102551.3A CN114551896A (en) | 2022-01-27 | 2022-01-27 | Preparation method of composite current collector |
| PCT/CN2022/094820 WO2023142320A1 (en) | 2022-01-27 | 2022-05-25 | Preparation method for composite current collector |
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| CN114678534A (en) * | 2022-05-30 | 2022-06-28 | 合肥国轩高科动力能源有限公司 | Preparation method of negative electrode composite current collector and product prepared by preparation method |
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| CN107313030B (en) * | 2017-07-18 | 2020-10-23 | 西南科技大学 | Method for non-metal substrate chemical plating palladium-free activation and chemical plating low-activity metal |
| JP2019026879A (en) * | 2017-07-27 | 2019-02-21 | 株式会社クオルテック | Production method of electronic component, and electronic component |
| CN109599563A (en) * | 2018-11-22 | 2019-04-09 | 欣旺达电子股份有限公司 | Affluxion body in lithium ion batteries and preparation method thereof |
| CN113363499A (en) * | 2019-05-31 | 2021-09-07 | 宁德时代新能源科技股份有限公司 | Negative current collector, negative pole piece, electrochemical device and electric automobile and electronic product containing electrochemical device |
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