CN115719811A - Online coating composite copper foil film and preparation method thereof - Google Patents
Online coating composite copper foil film and preparation method thereof Download PDFInfo
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- CN115719811A CN115719811A CN202211112771.0A CN202211112771A CN115719811A CN 115719811 A CN115719811 A CN 115719811A CN 202211112771 A CN202211112771 A CN 202211112771A CN 115719811 A CN115719811 A CN 115719811A
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Abstract
The invention discloses an online coating composite copper foil film and a preparation method thereof. The online coating layer is formed by uniformly mixing acrylic resin, metal copper nanoparticles with the particle size of 5-10nm, 1,4-dioxane, polyethylene oxide and ethylene-vinyl acetate copolymer into a primer solution and then performing online coating and curing. The preparation method comprises the following steps: preparing a substrate layer from a polyester film added with polyester functional master batch; forming an online coating layer on two sides of the base material layer by an online coating process while forming the base material layer; and finally forming the conductive layer on the outer side of the on-line coating layer. This application has replaced corona layer and barrier layer through online coating layer, has simplified processing technology, has reduced the equipment demand to can obtain the performance effect equivalent with corona layer and barrier layer.
Description
Technical Field
The application relates to a current collector for electric conduction in a lithium ion battery, in particular to a composite copper foil film capable of being used as a negative current collector of the lithium ion battery, and particularly relates to an online coating composite copper foil film and a preparation method thereof.
Background
The current collector in the lithium ion battery consists of a metal foil film for conducting electricity, and is mainly used for bearing electrode materials of a positive electrode and a negative electrode, and collecting current and conducting electrons at the same time. The common positive current collector adopts aluminum foil, and the common negative current collector adopts copper foil. The aluminum foil and the copper foil used as current collectors are mainly used for conduction and do not participate in active reactions, so that the thickness of the aluminum foil and the copper foil is reduced to the strength limit and no space for continuous thinning exists under the requirement of improving the energy density of the battery. By referring to the composite metal thin film in the prior art, a composite metal thin film has appeared in which a non-metal insulating material is used as a base material and conductive layers are formed on both sides thereof.
CN 114481080A discloses a vacuum plating and water plating integrated equipment and a production method of an ultrathin copper foil, wherein the equipment comprises a vacuum cavity, a winding device and an electroplating device, the winding device is used for winding a film, the vacuum cavity is used for carrying out vacuum evaporation on the film in the winding device, and the electroplating device is used for electroplating the evaporated film. The copper foil in the prior art needs to evaporate the target material into gas at high temperature and then adhere to the surface of the nonmetallic substrate layer, and the higher the evaporation temperature of the target material is, the more easily the substrate layer has defects such as fusing or scalding. Therefore, the prior art generally produces composite aluminum foil by evaporation, and the situation of preparing composite copper foil by evaporation is rare because the evaporation temperature of copper is higher. The higher the evaporation temperature of the target material is, the higher the running speed of the substrate layer is required to be, so that the thinner the copper layer formed by evaporation is, the correspondingly worse the conductivity of the copper foil is, and the target material is not suitable for being used as a current collector of a lithium ion battery. In addition, because the evaporation coating needs to operate the film at a higher speed, the thickness of the copper layer obtained by the evaporation coating is difficult to increase, and the copper layer has poor compactness and uniformity and is easy to fall off. In addition, the sheet resistance is very large due to the defects of the thickness, compactness and the like of the evaporated copper layer, and the energy consumption of the subsequent electroplating process is also very high.
In addition, another reason why the metal layer of the aluminum laminate foil is easily peeled off is that the surface structure of the nonmetallic base material layer for receiving the metal layer is not uniform, resulting in insufficient adhesion of the metal layer to the base material layer. In order to relieve the influence of long-time high-temperature baking on the surface performance of the base material layer, the base material layer needs to be gradually stacked at intervals to form a metal layer, and the defects of various structural properties of the base material layer can be gradually amplified by the stacked metal layer, so that the conventional composite metal foil and the preparation process thereof are difficult to be applied to the production and preparation of the composite copper foil film capable of being used as a current collector.
Disclosure of Invention
The technical problem to be solved by the present application is to provide an on-line coated composite copper foil film and a method for preparing the same, so as to reduce or avoid the aforementioned problems.
In order to solve the technical problem, the application provides an online coating composite copper foil film, which comprises a base material layer, online coating layers formed on two sides of the base material layer and a conductive layer attached to the outer side of the online coating layers, wherein the online coating layers are formed by uniformly mixing acrylic resin, metal copper nanoparticles with the particle size of 5-10nm, 1,4-dioxane, polyethylene oxide and ethylene-vinyl acetate copolymer into a primer solution and then performing online coating and curing.
Preferably, the mass ratio of each component of the on-line coating layer is, respectively, acrylic resin: metallic copper nanoparticles: 1,4-dioxane: polyethylene oxide: the ethylene-vinyl acetate copolymer is 100: (5-10): (20 to 30): (10-15): (5-10).
Preferably, the thickness of the in-line coating layer is 0.3 to 0.5 μm.
Preferably, the conductive layer comprises a metal copper sputtering layer, a metal copper electroplating layer and a protective layer in sequence from inside to outside; the metal copper sputtering layer is a layer of metal copper with the thickness of 5-15nm formed on the two side surfaces of the base material layer by adopting a vacuum sputtering process, the metal copper electroplating layer is a layer of metal copper with the thickness of 100-500nm formed on the outer surface of the metal copper sputtering layer by adopting a water electroplating process, and the protective layer is a compact protective layer formed after the outer surface of the metal copper electroplating layer is passivated; the protective layer is a metal chromium protective layer with the thickness of 5-15nm formed by an electroplating process.
Preferably, the thickness of the metal copper sputtering layer is 5-8nm, the thickness of the metal copper electroplating layer is 300-400nm, and the thickness of the metal chromium protective layer is 5-8nm.
Preferably, the substrate layer is made of a polyester film added with a polyester functional master batch, the polyester film is a single-layer polyester film containing 5-20 wt% of the polyester functional master batch, or a polyester film with a three-layer structure including an A layer, a B layer and a C layer, wherein the A layer and the C layer contain 5-20 wt% of the polyester functional master batch, and the polyester functional master batch is prepared from the following raw materials in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1,4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.
The application further provides a preparation method of the online coating composite copper foil film, the online coating composite copper foil film is composed of a base material layer, online coating layers formed on two sides of the base material layer and a conducting layer attached to the outer side of the online coating layers, and the preparation method comprises the following steps: preparing a substrate layer from a polyester film added with polyester functional master batch; forming an online coating layer on two sides of the base material layer by an online coating process while forming the base material layer; and finally forming the conductive layer on the outer side of the on-line coating layer.
Preferably, the preparation method further comprises the preparation step of the polyester functional masterbatch: at normal temperature, adding 50-100 parts by weight of powdered PET, 20-30 parts by weight of nano silicon dioxide, 30-50 parts by weight of powdered poly (m-xylylene diamide), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutylhydroxytoluene and 5-10 parts by weight of powdered 1,4-diiodobenzene into a high-speed mixer for pre-dispersion and mixing, wherein the rotating speed is 1500-2000 rpm, and the mixing time is 30-60 minutes to form a mixture; and then carrying out melt extrusion through a double-screw extruder, and then carrying out water-cooling granulation or slicing to obtain the polyester functional master batch.
Preferably, the conductive layer comprises a metal copper sputtering layer, a metal copper electroplating layer and a protective layer in sequence from inside to outside; wherein the forming of the conductive layer comprises: forming a metal copper sputtering layer on the outer side of the online coating layer by adopting a vacuum sputtering process; growing a metal copper electroplating layer on the outer surface of the metal copper sputtering layer by adopting a water electroplating process; and forming a protective layer on the outer surface of the metal copper electroplating layer through an electroplating process.
This application has replaced corona layer and barrier layer through online coating layer, has simplified processing technology, has reduced the equipment demand to can obtain the performance effect equivalent with corona layer and barrier layer.
Drawings
The drawings are only for purposes of illustrating and explaining the present application and are not to be construed as limiting the scope of the present application.
Fig. 1 shows a schematic structural diagram of a composite copper foil film according to an embodiment of the present application.
Fig. 2 is a schematic diagram showing a structure of a composite copper foil film according to another embodiment of the present application.
Fig. 3 shows a schematic structure of an in-line coated composite copper foil film according to yet another embodiment of the present application.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present application, embodiments of the present application will now be described with reference to the accompanying drawings. Wherein like parts are given like reference numerals.
As shown in the figure, the invention provides a composite copper foil film capable of being used as a negative current collector of a lithium ion battery, the composite copper foil film is composed of a base material layer 1 and conducting layers 2 attached to two sides of the base material layer 1, and the conducting layers 2 are mainly composed of metal copper. As described above, since the evaporation temperature of metal copper is high, if it is attached to the surface of the base material layer 1 made of a polymer material by vapor deposition, uniformity of the surface structure of the base material layer 1 is deteriorated, and it is difficult to obtain a thickness necessary for sufficient electrical performance, and the larger the thickness of the stack is, the more easily the powder falls off, and it is not suitable for use as a negative electrode current collector.
In view of this, the present application proposes a composite copper foil film, wherein the conductive layer 2 adopts a multi-layer conductive structure, and in the illustrated embodiment, the conductive layer 2 comprises a metal copper sputtering layer 21, a metal copper electroplating layer 22 and a protective layer 23 in sequence from inside to outside. The metal copper sputtering layer 21 is a layer of metal copper with the thickness of 5-15nm, which is formed on the two side surfaces of the base material layer 1 by adopting a vacuum sputtering process, the metal copper electroplating layer 22 is a layer of metal copper with the thickness of 100-500nm, which is formed on the outer surface of the metal copper sputtering layer 21 by adopting a water and electricity plating process, the protective layer 23 is a compact protective layer formed by passivating the outer surface of the metal copper electroplating layer 22 by an electroplating or chemical corrosion process, and preferably, the protective layer 23 is a metal chromium protective layer with the thickness of 5-15nm, which is formed by an electroplating process. More preferably, the thickness of the metal copper sputtering layer 21 is 5-8nm, the thickness of the metal copper electroplating layer 22 is 300-400nm, and the thickness of the protective layer 23 is 5-8nm.
In the composite copper foil film, the compactness and the adhesive force of a metal copper sputtering layer formed by vacuum sputtering are far superior to those of an evaporation process, and the running speed of the base material layer can be fast due to the fact that the required thickness is very thin, so that the possibility that the base material layer is fused or scalded is basically eliminated. The thickness of the metal copper sputtering layer is very thin, but basic conductive performance can be provided, so that a thicker metal copper layer can be further grown on the surface of the metal copper sputtering layer by means of water electroplating. Through the combination of the vacuum sputtering process and the water electroplating process, the application can obtain excellent electrical performance and adhesive force on the premise of not damaging the surface structure of the base material layer, which will be further explained later.
In addition, in order to avoid the problem of insufficient adhesion of the metal copper layer caused by uneven surface structure of the substrate layer, the present application also proposes an improved substrate layer 1, in a specific embodiment of the present application, the substrate layer 1 of the present application is made of a polyester film added with a polyester functional masterbatch, and the substrate layer 1 may be a polyester film with a single-layer structure (fig. 1) added with the polyester functional masterbatch, or a polyester film with a three-layer structure (fig. 2) including a layer a, a layer B and a layer C, the surface layer of which is added with the polyester functional masterbatch.
The polyester referred to in the present invention is a polyester comprising one or more selected from polybasic carboxylic acids containing dibasic acids and their ester-forming derivatives, and one or more selected from polyhydric alcohols containing dibasic alcohols; or a polyester formed from a hydroxycarboxylic acid or an ester-forming derivative thereof; or a polyester formed from a cyclic ester. The polyester can be produced by a conventionally known method. For example, taking the preparation of PET as an example, it can be obtained by: a method of performing polycondensation after esterification of terephthalic acid and ethylene glycol; or a method in which an alkyl ester of terephthalic acid such as dimethyl terephthalate is subjected to ester exchange reaction with ethylene glycol and then subjected to polycondensation. The polyester of the present invention is preferably PET.
In a specific embodiment, the polyester film forming the substrate layer 1 is a single-layer polyester film containing 5 to 20wt% of polyester functional master batch, or is a three-layer polyester film containing an a layer, a B layer and a C layer, wherein the a layer and the C layer contain 5 to 20wt% of polyester functional master batch, and the polyester functional master batch is prepared from the following raw materials in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1,4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.
The polyester functional master batch of the present invention can be prepared in a pellet or chip form, and added to a common polyester in the process of producing a polyester film to prepare the substrate layer 1 of the present invention. For example, 80 to 95wt% of polyester without other components and 5 to 20wt% of the polyester functional master batch of the present invention may be melt-blended, and then the substrate layer 1 of the single-layer structure may be obtained by a process such as stretching, or the surface layer structure of the substrate layer 1 of the present invention may be obtained by a multilayer co-extrusion process.
The raw material components of the polyester functional master batch can be uniformly mixed in the form of granules, and then the polyester functional master batch can be obtained by extrusion and granulation by using equipment such as an extruder.
In one embodiment, at room temperature, 50-100 parts by weight of powdered PET, 20-30 parts by weight of nano-silica, 30-50 parts by weight of powdered poly (m-xylylene diamide), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutyl hydroxy toluene and 5-10 parts by weight of powdered 1,4-diiodobenzene are added into a high-speed mixer to be pre-dispersed and mixed, and the rotating speed is 1500-2000 rpm and the mixture is mixed for 30-60 minutes to form a mixture. And then carrying out melt extrusion through a double-screw extruder, and then carrying out water-cooling granulation or slicing to obtain the polyester functional master batch.
In another embodiment, for example, after preparing the chip for obtaining the polyester functional master batch, 5 to 20wt% of the polyester functional master batch is added to 80 to 95wt% of PET particles for uniform mixing, the two are melt blended, and finally the substrate layer 1 with a single-layer structure is obtained through a process such as stretching, or the surface layer structure of the substrate layer 1 with a three-layer structure is obtained through a multilayer co-extrusion process.
The preparation method of the polyester film for the composite copper foil film of the present invention is further described below by taking a single-layer polyester film as an example. The preparation method of the polyester film for the composite copper foil film comprises the following steps:
the components with the following weight ratio: 80-95 wt% of PET resin and 5-20 wt% of polyester functional master batch are respectively metered by an electronic scale and enter a mixing bunker to be mixed to prepare a mixture.
Then the mixture enters an exhaust type double-screw extruder, and the temperature of the double-screw extruder is adjusted to be 270-280 ℃.
After the materials are melted in an extruder, the materials are filtered and extruded to be made into thick sheets. The thickness and the profile of the slab can be adjusted by the extrusion amount of an extruder, the rotating speed of a casting sheet roller and the opening degree of a die head.
Preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching ratio is 4.0, thus obtaining the stretched sheet.
Preheating the stretching sheet at the temperature of 90-120 ℃, and transversely stretching the stretching sheet at the temperature of 100-160 ℃, wherein the transverse stretching ratio is 3.8. Then the mixture is shaped at the temperature of 160-240 ℃, and then is cooled at the temperature of 100-50 ℃ to prepare the polyester film for the composite copper foil film.
The thickness of the polyester film is 6-10 μm.
The preparation method of the polyester film for the composite copper foil film of the present invention is further described below by taking a three-layer polyester film as an example. The preparation method of the polyester film for the composite copper foil film comprises the following steps:
the components with the following weight ratio: 80-95 wt% of PET resin and 5-20 wt% of polyester functional master batch are respectively metered by an electronic scale and enter a mixing bunker to be mixed to prepare a mixture.
And then the mixture enters an exhaust type double-screw extruder E.
100% of PET resin is put into a pre-crystallizer, pre-crystallized for 15 minutes at the temperature of 160 ℃, and then the PET material enters a drying tower, is dried for 6 hours at the temperature of 160 ℃ and then enters a single-screw extruder F.
The temperature of the twin-screw extruder E and the twin-screw extruder F is adjusted to 270 ℃ to 280 ℃.
After materials are melted in two extruders, the materials extruded by a double-screw extruder E are used as a layer A and a layer C on the surface, the materials extruded by a single-screw extruder F are used as a layer B in the middle, and a three-layer composite thick sheet is prepared by a multilayer co-extrusion process. The thickness and the profile of the slab can be adjusted by the extrusion amount of an extruder, the rotating speed of a casting sheet roller and the opening degree of a die head.
Preheating the thick sheet at 50-90 ℃, entering an infrared heating zone at 300-500 ℃, and longitudinally stretching at a linear speed of 40-150 m/min, wherein the longitudinal stretching ratio is 4.0, thus obtaining the stretched sheet.
Preheating the stretched sheet at the temperature of 90-120 ℃, and transversely stretching the sheet at the temperature of 100-160 ℃, wherein the transverse stretching ratio is 3.8. Then shaping at 160-240 ℃, and cooling at 100-50 ℃ to obtain the three-layer polyester film.
The thickness of the prepared polyester film is 6-10 μm, wherein the thickness of the layer A is 1-2 μm, the thickness of the layer B is 2-8 μm, and the thickness of the layer C is 1-2 μm.
Examples 1 to 5
According to the weight parts of the raw materials in the following table, polyester functional master batch chips are respectively prepared and then added with common PET resin to prepare the polyester film with a single-layer structure for the composite copper foil film.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Poly (m-xylylene diamide) | 30 | 35 | 40 | 45 | 50 |
| |
1 | 1.5 | 2 | 2.5 | 3 |
| Dibutylhydroxytoluene | 3 | 3.5 | 4 | 4.5 | 5 |
| 1,4-diiodobenzene | 5 | 7 | 7.5 | 8 | 10 |
| Silicon dioxide | 20 | 22 | 25 | 27 | 30 |
| PET | 50 | 65 | 75 | 85 | 100 |
| Amount of slices to prepare a monolayer substrate layer | 5wt％ | 10wt％ | 13wt％ | 15wt％ | 20wt％ |
| Thickness of the substrate layer | 6 | 7 | 8 | 9 | 10 |
Comparative examples 6 to 10
In the same manner as in the above examples, comparative polyester films were prepared in the following raw material weight ratio.
The performance parameters of each polyester film were obtained by testing and preparing respectively, and the films with thickness of 8 μm prepared from pure PET without any functional master batch were compared, and the performance parameters are shown in the following table.
And respectively forming metal copper sputtering layers on the surfaces of the two sides of the polyester film on the upper surface by a vacuum sputtering process, controlling the thickness of the metal copper layers on the two sides of the vacuum sputtering film to be 5nm, and testing the surface crack parameters of the prepared film.
The performance parameters of the film layer and the crack condition of the metal coating are visible, the porosity, the water absorption, the oxygen transmission rate and other performances of the polyester film prepared by adding the polyester functional master batch are greatly improved, and no obvious crack propagation is observed after the metal copper conductive layer is formed.
Further, the resistivity difference of the metal copper sputtered layers on both sides of the polyester film shown in the above table was tested as shown in the following table.
The polyester film prepared by adding the polyester functional master batch has the advantages that the resistivity difference of the metal copper sputtering layer formed on the polyester film is obviously smaller than that of the film without the functional master batch, and the two-side structure of the polyester film is more excellent in consistency.
Further, since the present application requires that the metal copper sputtering layer 21 is formed on the surface of the base material layer 1 first, the base material layer 1 needs to be controlled to operate at a low temperature during sputtering. Although the mylar of the improved substrate layer 1 has excellent properties of porosity, water absorption rate, oxygen transmission rate and the like, the problem of interference of moisture released when the surface of the mylar absorbs water and then is sputtered at low temperature on the vacuum degree still needs to be prevented.
Therefore, in an embodiment not shown in the figure, in order to avoid the problem of moisture absorption and release of the substrate layer 1 during sputtering, a barrier layer may be formed on the outer side of the substrate layer 1 between the conductive layer 2 and the substrate layer 1 by sputtering, so as to form a coating isolation on the surface of the substrate layer 1, and form a hydrophobic structure on the surface of the substrate layer 1. Since the thickness of the barrier layer is small, in order to improve the adhesion of the barrier layer on the surface of the substrate layer 1, before the barrier layer is formed by sputtering, the surface of the substrate layer 1 needs to be subjected to corona treatment to form a corona layer with a thickness of 1-2nm on the surface of the substrate layer 1, and then the barrier layer is formed outside the corona layer.
The polyester films prepared in examples 1 to 5 were used as a base material layer, and were subjected to corona treatment, sputtering of a barrier layer, sputtering of a metal copper sputtering layer, electroplating of a metal copper plating layer, and electroplating of a protective layer, respectively, to prepare a composite copper foil film having the following parameters.
As can be seen from the measurement parameters, the composite copper foil film provided with the corona layer and the barrier layer has excellent electrical performance, the adhesive force of the conductive layer is extremely strong, and the conductive layer can hardly be peeled off in conventional use.
Although the performance of the composite copper film can be improved by means of corona treatment and barrier layer sputtering, the polyester film needs to be treated by corona independently, and the surface adhesion of the formed corona layer is gradually reduced along with the time. Thus, the corona treatment and subsequent sputtering of the barrier layer requires a short time interval, otherwise a controlled effect is difficult to achieve. In order to achieve the capacity of processing at short time intervals, special corona and sputtering integrated equipment is needed, the equipment cost is very high, the number of equipment owned in the whole country is only several, and the production efficiency and the yield are difficult to improve.
Fig. 3 shows a schematic structural diagram of an improved on-line coated composite copper foil film, and as shown in the figure, the on-line coated composite copper foil film of the present embodiment is composed of a substrate layer 1, on-line coating layers 12 formed on both sides of the substrate layer 1, and a conductive layer 2 attached to the outer sides of the on-line coating layers 12. As in the previous embodiment, the conductive layer 2 of the present embodiment includes a metal copper sputtering layer 21, a metal copper plating layer 22, and a protective layer 23 in this order from the inside to the outside; the metal copper sputtering layer 21 is a layer of metal copper with the thickness of 5-15nm formed on the two side surfaces of the base material layer by adopting a vacuum sputtering process, the metal copper electroplating layer 22 is a layer of metal copper with the thickness of 100-500nm formed on the outer surface of the metal copper sputtering layer 21 by adopting a water electroplating process, and the protective layer 23 is a compact protective layer formed after the outer surface of the metal copper electroplating layer 22 is passivated; the protective layer 23 is a 5-15nm metal chromium protective layer formed by an electroplating process.
The embodiment shown in fig. 3 focuses on forming the in-line coating layer 12 on both sides of the substrate layer 1, and the corona layer and the barrier layer in the embodiment not shown are replaced by the in-line coating layer 12, so that the processing process is simplified, the equipment requirement is reduced, and the equivalent performance effect can be obtained. The structure and process except for the on-line coating are the same as those of the previous embodiment, and the same contents are not repeated.
The in-line coating can directly coat chemical articles on the substrate layer through an in-line coating machine in the production process of the substrate layer so as to obtain the same technical effect as the technical effect of arranging the corona layer and the barrier layer. Different with corona layer and barrier layer setting, online coating can be directly formed in the later stage of the production process of substrate layer, need not expand the operation again with the coiled material, also need not dedicated corona and sputter integration equipment, and the coating forms evenly, fast, efficient, with low costs.
In the present application, the primer solution constituting the in-line coating layer 12 may be applied to a sheet before or during stretching of the polyester film constituting the base material layer, and then the primer solution applied to the surface of the sheet is cured at a high temperature during stretching to form the in-line coating layer 12 as the sheet is stretched to a film having a desired thickness and the thickness is reduced.
In one embodiment, the in-line coating layer 12 is formed by uniformly mixing acrylic resin, metallic copper nanoparticles having a particle size of 5-10nm, 1,4-dioxane, polyethylene oxide, and ethylene-vinyl acetate copolymer into a primer solution, and then curing by in-line coating. The in-line coating layer 12 is preferably formed to have a thickness of 0.3 to 0.5. Mu.m.
Specifically, the mass ratio of each component of the online coating layer 12 is, respectively, acrylic resin: metallic copper nanoparticles: 1,4-dioxane: polyethylene oxide: ethylene-vinyl acetate copolymer 100: (5-10): (20 to 30): (10-15): (5-10).
Wherein the ethylene-vinyl acetate copolymer can be ethylene-vinyl acetate copolymer which is sold by Mitsui corporation of Japan and has the trade name of Evaflex 550, and the mass percentage of the contained vinyl acetate polymer is 14 percent.
On-line coating layers were prepared on the substrate layers prepared in examples 1 to 5, respectively, according to the following raw material weight ratio.
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Acrylic resin | 100 | 100 | 100 | 100 | 100 |
| Metallic copper nanoparticles | 5 | 6.5 | 7.5 | 8.5 | 10 |
| 1,4-dioxane | 20 | 22 | 25 | 28 | 30 |
| Polyethylene oxide | 10 | 12 | 13 | 14 | 15 |
| Ethylene-vinyl acetate copolymer | 5 | 6 | 7.5 | 8 | 10 |
| Thickness (nm) | 300 | 350 | 400 | 450 | 500 |
The polyester films prepared in examples 1 to 5 were also used as a substrate layer, and a composite copper foil film with the following parameters was prepared by on-line coating, sputtering a metal copper sputtering layer, electroplating a metal copper electroplating layer, and electroplating a protective layer, respectively.
As can be seen from the measurement parameters, the online coating composite copper foil film has the advantages that the technical effect of the corona layer and the barrier layer is equivalent to that of the prior corona layer and barrier layer, the excellent electrical performance is achieved, the adhesive force of the conducting layer is extremely strong, and the conducting layer can be hardly peeled off in conventional use.
The preparation method of the on-line coated composite copper foil film of the present application is further described below.
As described above, the on-line coated composite copper foil film of the present invention includes a substrate layer, on-line coating layers formed on both sides of the substrate layer, and a conductive layer attached to the outer sides of the on-line coating layers, and thus the method for preparing the on-line coated composite copper foil film of the present invention includes the steps of: firstly, a substrate layer is made of a polyester film added with polyester functional master batch. The process steps for preparing the substrate layer have been described in detail above and will not be repeated here.
Forming an online coating layer on two sides of the base material layer through an online coating process while forming the base material layer; and finally forming the conductive layer on the outer side of the on-line coating layer.
Further, as described above, the conductive layer includes a metal copper sputtering layer, a metal copper electroplating layer, and a protective layer in this order from the inside to the outside. Thus, the forming of the conductive layer includes: forming a metal copper sputtering layer on the outer side of the online coating layer by adopting a vacuum sputtering process; growing a metal copper electroplating layer on the outer surface of the metal copper sputtering layer by adopting a water electroplating process; and forming a protective layer on the outer surface of the metal copper electroplating layer through an electroplating process.
It should be appreciated by those skilled in the art that while the present application is described in terms of several embodiments, not every embodiment includes only a single embodiment. The description is thus given for clearness of understanding only, and it is to be understood that all matters in the embodiments are to be interpreted as including all technical equivalents which are encompassed by the claims and are to be interpreted as combined with each other in a different embodiment so as to cover the scope of the present application.
The above description is only illustrative of the present invention and is not intended to limit the scope of the present invention. Any equivalent alterations, modifications and combinations that may be made by those skilled in the art without departing from the spirit and principles of this application shall fall within the scope of this application.
Claims (9)
1. The on-line coating composite copper foil film is composed of a base material layer (1), on-line coating layers (12) formed on two sides of the base material layer (1) and a conductive layer (2) attached to the outer sides of the on-line coating layers (12), and is characterized in that the on-line coating layers (12) are formed by uniformly mixing acrylic resin, metal copper nanoparticles with the particle size of 5-10nm, 1,4-dioxane, polyethylene oxide and ethylene-vinyl acetate copolymer into a primer solution and then carrying out on-line coating and curing.
2. The on-line coating composite copper foil film as claimed in claim 1, wherein the on-line coating layer (12) comprises the following components in percentage by mass: metallic copper nanoparticles: 1,4-dioxane: polyethylene oxide: the ethylene-vinyl acetate copolymer is 100: (5-10): (20 to 30): (10-15): (5-10).
3. The on-line coated composite copper foil film according to claim 1, wherein the thickness of the on-line coating layer (12) is 0.3 to 0.5 μm.
4. The on-line coated composite copper foil film according to any one of claims 1 to 3, wherein said conductive layer (2) comprises a sputtered layer of metal copper (21), an electroplated layer of metal copper (22), and a protective layer (23) in this order from the inside to the outside; the metal copper sputtering layer (21) is a layer of metal copper with the thickness of 5-15nm, which is formed on the two side surfaces of the base material layer by adopting a vacuum sputtering process, the metal copper electroplating layer (22) is a layer of metal copper with the thickness of 100-500nm, which is formed on the outer surface of the metal copper sputtering layer (21) by adopting a water electroplating process, and the protective layer (23) is a compact protective layer formed after the outer surface of the metal copper electroplating layer (22) is passivated; the protective layer (23) is a metal chromium protective layer with the thickness of 5-15nm formed by an electroplating process.
5. The on-line coated composite copper foil film as claimed in claim 4, wherein the thickness of the sputtered layer of metal copper is 5-8nm, the thickness of the electroplated layer of metal copper is 300-400nm, and the thickness of the protective layer of metal chromium is 5-8nm.
6. The on-line coated composite copper foil film as claimed in any one of claims 1 to 3, wherein the substrate layer is made of a polyester film added with a polyester functional masterbatch, the polyester film is a single-layer polyester film containing 5 to 20wt% of the polyester functional masterbatch, or a polyester film with a three-layer structure comprising an A layer, a B layer and a C layer, wherein the A layer and the C layer contain 5 to 20wt% of the polyester functional masterbatch, and the polyester functional masterbatch is prepared from the following raw materials in parts by weight: 30-50 parts of poly (m-xylylene diamide), 1-3 parts of cobalt neodecanoate, 3-5 parts of dibutyl hydroxy toluene, 5-10 parts of 1,4-diiodobenzene, 20-30 parts of silicon dioxide and 50-100 parts of PET.
7. The preparation method of the on-line coated composite copper foil film comprises a substrate layer (1), on-line coating layers (12) formed on two sides of the substrate layer (1) and a conductive layer (2) attached to the outer sides of the on-line coating layers (12), and comprises the following steps: preparing a substrate layer (1) from a polyester film added with polyester functional master batch; forming an online coating layer (12) on two sides of the base material layer (1) through an online coating process while forming the base material layer (1); finally, the conductive layer (2) is formed on the outer side of the in-line coating layer (12).
8. The method of claim 7, further comprising the step of preparing the polyester functional masterbatch: at normal temperature, adding 50-100 parts by weight of powdered PET, 20-30 parts by weight of nano silicon dioxide, 30-50 parts by weight of powdered poly (m-xylylene diamide), 1-3 parts by weight of powdered cobalt neodecanoate, 3-5 parts by weight of powdered dibutylhydroxytoluene and 5-10 parts by weight of powdered 1,4-diiodobenzene into a high-speed mixer for pre-dispersion and mixing, wherein the rotating speed is 1500-2000 rpm, and the mixing time is 30-60 minutes to form a mixture; and then carrying out melt extrusion through a double-screw extruder, and then carrying out water-cooling granulation or slicing to obtain the polyester functional master batch.
9. The method according to claim 7, wherein the conductive layer (2) comprises, in order from the inside to the outside, a sputtered layer of metallic copper (21), a plated layer of metallic copper (22), and a protective layer (23); wherein the forming of the conductive layer (2) comprises: forming a metal copper sputtering layer (21) on the outer side of the online coating layer (12) by adopting a vacuum sputtering process; growing a metal copper electroplating layer (22) on the outer surface of the metal copper sputtering layer (21) by adopting a water electroplating process; a protective layer (23) is formed on the outer surface of the metal copper plating layer (22) by a plating process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117276558A (en) * | 2023-11-02 | 2023-12-22 | 河北海伟电子新材料科技股份有限公司 | Composite copper foil, preparation method and lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117276558A (en) * | 2023-11-02 | 2023-12-22 | 河北海伟电子新材料科技股份有限公司 | Composite copper foil, preparation method and lithium ion battery |
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