CN112510210A - Composite current collector, preparation method thereof and secondary battery - Google Patents
Composite current collector, preparation method thereof and secondary battery Download PDFInfo
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- CN112510210A CN112510210A CN202011461300.1A CN202011461300A CN112510210A CN 112510210 A CN112510210 A CN 112510210A CN 202011461300 A CN202011461300 A CN 202011461300A CN 112510210 A CN112510210 A CN 112510210A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The application provides a composite current collector, a preparation method thereof and a secondary battery, and belongs to the technical field of current collectors of secondary batteries. The preparation method of the composite current collector comprises the following steps: and coating the conductive polymer slurry on at least one surface of the insulating support layer to form a conductive polymer layer. And forming a metal layer on the surface of the polymer layer, which is far away from the insulating support layer. In the preparation method, the conductive polymer layer is formed on the supporting layer in a coating mode, a thin metal layer is not required to be formed in a physical vapor deposition mode, and perforation of the supporting layer can be avoided.
Description
Technical Field
The application relates to the technical field of current collectors of secondary batteries, in particular to a composite current collector, a preparation method of the composite current collector and a secondary battery.
Background
In the prior art, the negative electrode current collector generally includes an insulating support layer and copper metal layers disposed on both surfaces of the insulating support layer. The method for forming the copper metal layer on the surface of the insulating support layer comprises the following steps:
(1) and forming a copper metal layer on the insulating supporting layer by means of physical vapor deposition (such as magnetron sputtering, vacuum evaporation and the like), wherein the copper metal layer can meet the flow guide requirement of the current collector only when reaching a certain thickness. Therefore, it usually requires several physical vapor depositions to obtain a thicker copper metal layer. The method has the following disadvantages: the higher temperature of the PVD process can cause thermal damage (e.g., via-holes or substrate deformation) to the insulating support layer, which is undesirableForming a uniform copper metal layer; physical vapor deposition under vacuum (2.0X 10)-1-5.0×10-1) And then, copper splashing phenomenon is generated when copper metal is gasified and evaporated, so that the prepared negative current collector has a through hole.
(2) And firstly forming a thin copper metal layer on the insulating supporting layer in a physical vapor deposition mode, and then continuously forming a metal layer on the thin copper metal layer in an electroplating mode to obtain a thick copper metal layer so as to meet the flow guide requirement of the current collector. However, this method also requires a physical vapor deposition process, and the above-described problems still remain.
Disclosure of Invention
The application aims to provide a preparation method of a composite current collector, which can avoid thermal damage to an insulating support layer in the preparation process.
In a first aspect, the present application provides a method for preparing a composite current collector, comprising: and coating the conductive polymer slurry on at least one surface of the insulating support layer to form a conductive polymer layer. And forming a metal layer on the surface of the polymer layer, which is far away from the insulating support layer.
In the preparation method, the conductive polymer layer is formed on the supporting layer in a coating mode, a thin metal layer is not required to be formed in a physical vapor deposition mode, and perforation of the supporting layer can be avoided. And the price of the conductive polymer material is lower than that of metal copper, so that the cost can be reduced to a certain extent. And the conductive polymer layer is formed in a coating mode, so that the production efficiency is improved. And the conductive polymer layer is positioned between the metal layer and the supporting layer, so that the flow guide requirement of the current collector can be met.
In one possible embodiment, the thickness of the conductive polymer layer is 30-100nm, and the metal layer is formed by acid plating. The conductive polymer layer formed by coating is uniform, the conductive requirement of the acid plating process can be met, and then when the metal layer is formed in an acid plating mode, the metal layer can be uniformly formed on the conductive polymer layer, the diversion requirement of the current collector is met, and the cost is low.
In one possible embodiment, the thickness of the conductive polymer layer is 10-15nm, a first metal layer with a thickness of 100-120nm is formed on the surface of the conductive polymer layer by means of alkalinity, and then a second metal layer with a thickness of 0.8-2 μm is formed on the surface of the first metal layer by means of acidity.
The thickness of the conductive high molecular layer is relatively small, so that the conductive capacity is relatively poor, but the requirement of alkalinity is met, after one metal layer of alkalinity is formed, one metal thickening layer (second metal layer) of acidity is formed, the conductive requirement of a current collector can be met, and the cost is reduced as far as possible.
In one possible embodiment, the conductive polymer paste includes iodine-doped polyacetylene and a conductive paste. The conductive effect of the conductive polymer layer can be better, so that the subsequent electroplating effect is better, and the bonding force between the conductive polymer layer and the metal layer and between the conductive polymer layer and the insulating support layer is larger.
A second object of the present application is to provide a composite current collector, which is a new composite current collector capable of satisfying the conductive requirements of the current collector.
In a second aspect, the present application provides a composite current collector, including an insulating support layer, a conductive polymer layer disposed on at least one surface of the insulating support layer, and a metal layer disposed on a surface of the conductive polymer layer away from the insulating support layer.
The composite current collector is a novel composite current collector, and the conductive part of the composite current collector is also provided with a conductive polymer layer besides the metal layer, and the conductive polymer layer is positioned between the metal layer and the supporting layer, so that the flow guide requirement of the current collector can be met. And the price of the conductive polymer material is lower than that of metal copper, so that the cost can be reduced to a certain extent. In addition, excessive temperature is not needed in the process of forming the conductive polymer layer, and thermal damage to the insulating support layer in the preparation process can be effectively avoided.
In one possible embodiment, the conductive polymer material of the conductive polymer layer is iodine-doped polyacetylene. The iodine-doped polyacetylene has a good conductive effect, so that the flow guide effect of the composite current collector is better.
In one possible embodiment, the thickness of the conductive polymer layer is 30 to 100 nm. To meet the conductive requirements of the conductive polymer layer.
In a possible embodiment, the composite current collector is a negative electrode current collector, and the material of the conductive polymer layer further includes a copper-based conductive adhesive. On one hand, the copper conductive adhesive can ensure that the combination performance of the conductive polymer layer and the insulating support layer is better; on the other hand, the subsequent metal layer and the conductive polymer layer can be well combined; in the third aspect, the conductive requirement of the conductive polymer layer can be met, so that the metal layer can be prepared subsequently.
The metal layer is a negative electrode metal layer. If the cathode metal layer is quickly thickened in an electroplating mode, the cost is reduced, and the production efficiency is improved. However, the electroplated substrate needs to be a conductive substrate, so the conductive polymer layer is firstly arranged on the support layer so as to enable the substrate to have certain conductivity, and a metal layer is formed on the conductive polymer layer by electroplating. The conductive substrate is obtained without forming a thin metal layer on the support layer by means of physical vapor deposition.
Optionally, the negative electrode metal layer is a copper metal layer.
In a possible embodiment, the composite current collector is a positive current collector, and the material of the conductive polymer layer further includes an aluminum-based conductive adhesive. On one hand, the aluminum conductive adhesive can ensure that the combination performance of the conductive polymer layer and the insulating support layer is better; on the other hand, the subsequent metal layer and the conductive polymer layer can be well combined; in the third aspect, the conductive requirement of the conductive polymer layer can be met, so that the metal layer can be prepared subsequently.
The metal layer is a positive electrode metal layer. Optionally, the positive electrode metal layer is an aluminum metal layer.
In one possible embodiment, the conductive polymer layer includes a first conductive polymer layer and a second conductive polymer layer, and the metal layer includes a first metal layer and a second metal layer. The first conductive polymer layer and the second conductive polymer layer are respectively arranged on two surfaces of the insulating support layer, the first metal layer is arranged on the surface of the first conductive polymer layer, which deviates from the insulating support layer, and the second metal layer is arranged on the surface of the second conductive polymer layer, which deviates from the insulating support layer.
Two surfaces of the insulating supporting layer form a conducting layer structure, active substance layers can be coated on the two surfaces, and flow guide is carried out, so that the flow guide effect of the current collector is better, and the energy density of the battery is improved.
In a third aspect, the present application provides a secondary battery comprising the above-described composite current collector. The current-collecting body has good flow-guiding effect, reduces or even eliminates the penetrating holes of the current-collecting body, and makes the metal layer on the current-collecting body more uniform.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments are briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive efforts and also belong to the protection scope of the present application.
Fig. 1 is a schematic view of a layer structure of a composite current collector provided in an embodiment of the present application;
fig. 2 is a CCD photograph of the negative current collector provided in example 1 of the present application;
fig. 3 is a CCD photograph of the negative current collector provided in comparative example 1.
Icon: 110-an insulating support layer; 111-a first surface; 112-a second surface; 120-a first conductive polymer layer; 130-a second conductive polymer layer; 140-a first metal layer; 150-second metal layer.
Detailed Description
In the preparation of composite current collectors, a metal layer is typically formed on an insulating support layer. The material of the insulating support layer may be Biaxially Oriented Polypropylene (BOPP) film, Cast Polypropylene (CPP) film, Polyethylene (PE) film, Polymethyl methacrylate (PMMA) film, Polystyrene (PS) film, Polyethylene terephthalate (PET) film, Polyphenylene sulfide (PPS) film, one of a fluorinated ethylene propylene resin (FEP) film, a Polyethylene naphthalate (PEN) film, a Polytetrafluoroethylene terephthalate (PEN) film, a Polytetrafluoroethylene (PTFE) film, a Polyvinyl chloride (PVC) film, a Polyphenylene sulfone resin (PPSU) film, a polyether ether ketone (PEEK) film, and a polyether sulfone resin (PES) film.
The thickness of the insulating support layer is 2-30 μm. For example: the thickness of the insulating support layer 110 is 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 15 μm, 20 μm, 25 μm, or 30 μm.
If a thicker metal layer is formed on the insulating support layer by electroplating, the production cost is reduced. It is necessary to form a metal layer on the insulating support layer by Physical Vapor Deposition (PVD) to form a conductive base film, and then to form a metal layer by electroplating to increase the thickness of the metal layer. However, when a thin metal layer is formed by PVD (high temperature), thermal damage (thin thickness of the insulating support layer and high molecular material) is easily caused to the insulating support layer, thereby causing a via hole.
Therefore, fig. 1 is a schematic view of a layer structure of the composite current collector provided in the embodiment of the present application. Referring to fig. 1, in the present application, a conductive polymer layer is formed on an insulating support layer 110 by coating, and then a metal layer is formed on the conductive polymer layer by electroplating, so that a thin metal layer is not required to be formed by physical vapor deposition, and the support layer is prevented from being perforated. And the price of the conductive polymer material is lower than that of metal copper, so that the cost can be reduced to a certain extent. And the conductive polymer layer is formed in a coating mode, so that the production efficiency is improved.
In the embodiment of the present application, an electrically conductive polymer paste is coated on at least one surface of the insulating support layer 110 to form an electrically conductive polymer layer. A metal layer is formed on the surface of the conductive polymer layer facing away from the insulating support layer 110 by electroplating.
The insulating support layer 110 has a first surface 111 and a second surface 112 along the thickness direction, and in one embodiment, the first surface 111 of the insulating support layer 110 is coated with conductive polymer paste to form a conductive polymer layer, and a metal layer is formed on the surface of the conductive polymer layer facing away from the insulating support layer 110. In another embodiment, the first conductive polymer layer 120 is formed by coating the first surface 111 of the insulating support layer 110 with a conductive polymer paste, the second conductive polymer layer 130 is formed by coating the second surface 112 of the insulating support layer 110 with a conductive polymer paste, the first metal layer 140 is formed on the surface of the first conductive polymer layer 120 facing away from the insulating support layer 110, and the second metal layer 150 is formed on the surface of the second conductive polymer layer 130 facing away from the insulating support layer 110.
In the embodiment of the present application, in order to make the bonding force between the insulating support layer 110 and the conductive polymer layer and the bonding force between the conductive polymer layer and the metal layer stronger, the conductive polymer material in the conductive polymer slurry is polyacetylene doped with iodine, and the material of the insulating support layer 110 is a BOPP material. Alternatively, iodine doped polyacetylene is a material currently on the market.
In other embodiments, the conductive polymer material in the conductive polymer paste may also be polyaniline doped with protonic acid, polypyrrole doped with anions, etc., and the application is not limited as long as the conductive polymer material capable of being made into the conductive polymer paste and coated on the insulating support layer 110 to form the conductive polymer layer is within the protection scope of the application.
In the embodiment of the present invention, the conductive polymer layer is formed by coating the conductive polymer paste on the insulating support layer 110 and then drying. High-temperature treatment is not needed when the conductive polymer layer is formed, so that the insulating support layer 110 can be prevented from being thermally damaged, and the perforation of the composite current collector can be avoided.
In order to increase the bonding force between the insulating support layer 110 and the conductive polymer layer, the conductive polymer paste includes a conductive polymer material and a conductive paste. Other additives may also be included as desired, such as: plasticizer, curing agent, antioxidant, filler and antistatic agent. The mixture is put into stirring equipment and is mixed together under the mechanical actions of turning, kneading, shearing and the like generated by the equipment, and the process is uniform and stable and is suitable for a coated solid-liquid suspension system so as to be coated subsequently.
After the conductive polymer layer is formed, the conductive polymer layer and the insulating support layer 110 are jointly used as a base material for electroplating, a metal layer can be formed on the conductive polymer layer in an electroplating mode, the efficiency is high, the cost is low, the conductive polymer layer can be more uniform due to the coating mode, and the metal layer formed by subsequent electroplating is more uniform.
In the embodiment of the present application, the conductive polymer layer is formed as follows: the running speed of the insulating support layer 110 (film) at the time of coating is 20-100m/min, and the drying temperature after coating is 55-160 c, to form a dry conductive polymer layer having strong adhesion on the insulating support layer 110.
In some possible embodiments, the running speed of the membrane is 20m/min, 30m/min, 40m/min, 50m/min, 60m/min, 70m/min, 80m/min, 90m/min, or 100 m/min; the drying temperature after coating is 55 deg.C, 60 deg.C, 80 deg.C, 100 deg.C, 120 deg.C or 160 deg.C. To obtain a dried conductive polymer layer.
In the process of forming the conductive polymer layer, the insulating support layer 110 is arranged on the roller, so that the insulating support layer 110 sequentially passes through the coating device and the drying device, the conductive polymer slurry is coated on the surface of the insulating support layer 110 through the coating device, and the conductive polymer slurry on the insulating support layer 110 is dried through the drying device to form the conductive polymer layer.
In order to ensure the conductivity of the conductive polymer layer so that the conductive polymer layer and the insulating support layer 110 together serve as a base material for plating, sufficient conductivity can be provided. The thickness of the conductive polymer layer is 30-100nm, and the metal layer is formed by acid plating. When the metal layer is formed in an acid plating mode, the metal layer can be uniformly formed on the conductive polymer layer, the flow guide requirement of the current collector is met, and the cost is low.
In some possible embodiments, the thickness of the conductive polymer layer is 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100 nm.
In another embodiment, the thickness of the conductive polymer layer is 10-15nm (e.g., 10nm, 12nm or 15nm), a first metal layer with a thickness of 100-120nm (e.g., 100nm, 110nm or 120nm) is formed on the surface of the conductive polymer layer by means of alkalinity, and then a second metal layer with a thickness of 0.8-2 μm (e.g., 0.8 μm, 1 μm, 1.5 μm or 2 μm) is formed on the surface of the first metal layer by means of acidity.
In one embodiment, the composite current collector is a negative electrode current collector, the conductive paste in the conductive polymer paste is a copper-based conductive paste, and the metal layer is a negative electrode metal layer (e.g., a copper metal layer). On one hand, the copper-based conductive adhesive can make the conductive polymer layer and the insulating support layer 110 have better bonding performance; on the other hand, the copper conductive adhesive can ensure that the subsequent copper metal layer and the conductive polymer layer have better combination effect; in the third aspect, the copper-based conductive adhesive can also meet the conductive requirement of the conductive polymer layer, so that the subsequent preparation of the copper metal layer is facilitated.
Furthermore, if the cathode metal layer (for example, a copper metal layer) is rapidly thickened by electroplating, the cost is reduced, and the production efficiency is improved. However, the electroplated substrate needs to be a conductive substrate, so the conductive polymer layer is firstly arranged on the support layer so as to enable the substrate to have certain conductivity, and a metal layer is formed on the conductive polymer layer by electroplating. The conductive substrate is obtained without forming a thin metal layer on the support layer by means of physical vapor deposition.
Optionally, the thickness of the negative electrode metal layer is 1-10 μm. For example: the thickness of the negative electrode metal layer is 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, or 10 μm.
In another embodiment, the composite current collector is a positive current collector, the conductive paste in the conductive polymer paste is an aluminum conductive paste, and the metal layer is a positive metal layer (e.g., an aluminum metal layer). On one hand, the aluminum-based conductive adhesive can make the conductive polymer layer and the insulating support layer 110 have better bonding performance; on the other hand, the aluminum conductive adhesive can ensure that the subsequent aluminum metal layer and the conductive polymer layer have better combination effect; in the third aspect, the conductive requirement of the conductive polymer layer can be met, so that the preparation of the aluminum metal layer can be carried out subsequently.
Optionally, the thickness of the positive electrode metal layer is 0.2-4 μm. For example: the thickness of the positive electrode metal layer is 0.2 μm, 1 μm, 2 μm, 3 μm, or 4 μm.
In other embodiments, the metal layer may be formed in other manners, such as: in the PVD magnetron sputtering method, due to the arrangement of the polymer layer, the insulating support layer 110 may be protected to a certain extent, and in the process of forming the metal layer by the PVD magnetron sputtering method, thermal damage to the insulating support layer 110 may also be avoided to a certain extent.
The composite current collector prepared by the above method includes an insulating support layer 110, a conductive polymer layer, and a metal layer. Of course, the application is not limited to the conductive polymer layer formed by coating, and the conductive polymer layer formed by other methods may also be used, so long as the conductive polymer layer formed without causing thermal damage to the insulating support layer 110 is within the protection scope of the application.
In this application, the conductive polymer layer is disposed on at least one surface (one surface or both surfaces) of the insulating support layer 110, and the metal layer is disposed on a surface of the conductive polymer layer facing away from the insulating support layer 110.
The composite current collector is a novel composite current collector, and the conductive part of the composite current collector is also provided with a conductive polymer layer besides the metal layer, and the conductive polymer layer is positioned between the metal layer and the supporting layer, so that the flow guide requirement of the current collector can be met. And the price of the conductive polymer material is lower than that of metal copper, so that the cost can be reduced to a certain extent. And the conductive polymer layer is formed by coating (or other low-temperature treatment), so that thermal damage to the insulating support layer 110 can be avoided, and the production efficiency is improved.
The application provides a secondary battery, including above-mentioned anodal mass flow body and negative current collector. The composite current collector has good flow guiding effect, reduces or even eliminates penetrating holes of the current collector, makes a metal layer on the current collector more uniform, and makes the electrical performance of the secondary battery better.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The preparation method of the negative current collector comprises the following steps:
and arranging a BOPP insulating supporting layer on a roller, enabling the insulating supporting layer to sequentially pass through a coating device and a drying device at the running speed of 40m/min, coating conductive slurry (the conductive polymer slurry comprises iodine-doped polyacetylene, copper conductive adhesive, plasticizer-di (2-ethylhexyl) phthalate and curing agent-p-hydroxybenzene sulfonic acid) to the first surface of the insulating supporting layer through the coating device, and drying the conductive slurry on the insulating supporting layer at the temperature of 60 ℃ through the drying device to form a first conductive layer with the thickness of 40nm to obtain a semi-finished product of the electroplating base material.
And then continuously arranging the insulating support layer on the roller, enabling the insulating support layer to sequentially pass through a coating device and a drying device at the running speed of 40m/min, coating the conductive slurry on the second surface of the insulating support layer through the coating device, and drying the conductive slurry on the insulating support layer at the temperature of 60 ℃ through the drying device to form a second conductive layer with the thickness of 40nm to obtain the electroplating base material.
Placing an electroplating substrate on a coating device, carrying out tape transport by a traction film, gradually opening the internal microcirculation amount to 9 times/h, controlling the solution temperature to be 25 +/-3 ℃, controlling the cooling water temperature to be 20 +/-2 ℃, and controlling the solution components to be: the copper sulfate concentration is 80g/L, the Cl concentration is 45PPM, the additive concentration is 300ml/1000Ah, the sulfuric acid concentration is 170g/L, then, according to the current applied to each conductive roller by the film, the total current is applied to the film at 8500A, the film coating speed is 5m/min, the film has negative charges, and the copper ions of the solution receive 2 electrons on the surface of the film to be reduced into a copper simple substance, so that copper metal layers with the thickness of about 2 mu m are respectively generated on the two surfaces of the base material, and a negative electrode current collector is obtained.
Example 2
The preparation method of the negative current collector comprises the following steps:
and arranging a BOPP insulating supporting layer on a roller, enabling the insulating supporting layer to sequentially pass through a coating device and a drying device at the running speed of 100m/min, coating conductive slurry (the conductive polymer slurry comprises iodine-doped polyacetylene, copper conductive adhesive, plasticizer-di (2-ethylhexyl) phthalate and curing agent-p-hydroxybenzene sulfonic acid) to the first surface of the insulating supporting layer through the coating device, and drying the conductive slurry on the insulating supporting layer at the temperature of 80-85 ℃ through the drying device to form a first conductive layer with the thickness of 10nm to obtain a semi-finished product of the electroplating base material.
And then continuously arranging the insulating support layer on the roller, enabling the insulating support layer to sequentially pass through a coating device and a drying device at the running speed of 100m/min, coating the conductive slurry on the second surface of the insulating support layer through the coating device, and drying the conductive slurry on the insulating support layer at the temperature of 80-85 ℃ through the drying device to form a second conductive layer with the thickness of 10nm to obtain the electroplating base material.
And (3) performing an alkaline copper electroplating process on a first copper layer with the surface alkalinity thickness of 120nm on the electroplating base material, and performing an acidic copper electroplating process on a second copper layer with the surface acidity thickness of 870nm on the first copper layer to obtain a negative current collector. Preparing a copper layer with the sheet resistance of 1-5 omega on the surface, and further thickening the copper layer by using an acid copper electroplating process until the sheet resistance of the surface is about 20m omega.
Comparative example 1
The preparation method of the negative current collector comprises the following steps:
and (3) evaporation coating: placing the coil stock into a vacuum chamber of a vacuum evaporation coating machine, sealing the vacuum chamber, and gradually vacuumizing until the vacuum degree reaches 2 multiplied by 10-2Pa, adopting a crucible high-frequency heating mode as an evaporation source, wherein the evaporation source evaporation raw material is metallic copper, the purity is more than or equal to 99.9 percent, the winding speed is controlled at 200m/min, and evaporated atoms are formed on the surface of the insulating support layerA conductive layer of copper having a thickness of 40 nm. Then, a copper conductive layer having a thickness of 40nm was formed on the surface of the insulating support layer in the same manner, to obtain a plated substrate.
Placing an electroplating substrate on a coating device, carrying out tape transport by a traction film, gradually opening the internal microcirculation amount to 9 times/h, controlling the solution temperature to be 25 +/-3 ℃, controlling the cooling water temperature to be 20 +/-2 ℃, and controlling the solution components to be: the copper sulfate concentration is 80g/L, the Cl concentration is 45PPM, the additive concentration is 300ml/1000Ah, the sulfuric acid concentration is 170g/L, then, according to the current applied to each conductive roller by the film, the total current is applied to the film at 8500A, the film coating speed is 5m/min, the film has negative charges, and the copper ions of the solution receive 2 electrons on the surface of the film to be reduced into a copper simple substance, so that copper metal layers with the thickness of about 2 mu m are respectively generated on the two surfaces of the base material, and a negative electrode current collector is obtained.
Experimental example 1
The negative current collector prepared in example 1 and the negative current collector prepared in comparative example 1 are photographed in a CCD on-line detection manner, respectively, to obtain a CCD picture of the negative current collector provided in example 1 of the present application in fig. 2, and a CCD picture of the negative current collector provided in comparative example 1 in fig. 3. As can be seen from comparison between fig. 2 and 3, the negative electrode current collector provided in example 1 of the present application has no pores and the support layer is not thermally damaged, whereas the negative electrode current collector provided in comparative example 1 has pores and the support layer is thermally damaged.
The resistivity of the plating base material and the negative electrode current collector provided in example 1, example 2 and comparative example 1 was measured, respectively, wherein the resistivity was measured by the following method: and testing the sheet resistance of the negative current collector by adopting a four-probe method to obtain the sheet resistance Rs.
The sheet resistance of the electroplating substrate provided in embodiment 1 of the present application is about 10 Ω, and the sheet resistance of the negative electrode current collector is about 20m Ω; the sheet resistance of the electroplating substrate provided in embodiment 2 of the present application is about 25 Ω, the sheet resistance is about 3 Ω after alkaline copper plating, and the sheet resistance of the negative electrode current collector is about 20m Ω after acidic copper plating; the sheet resistance of the negative electrode current collector provided in comparative example 1 was also about 20m Ω, which indicates that the conductive effect of the negative electrode current collector provided in the example of the present application was not substantially affected.
The plating base materials provided in examples 1 and 2 were examined for adhesion of the conductive polymer layer to the insulating support layer. The detection method comprises the following steps: a test tape (3M; 200N/M) was attached to the adhered sample using a double-sided tape to fix the plating base on a flat surface and smoothly pressed with a roller (removal of air bubbles). The test tape was then removed from the sample at a flat angle.
Finally, no adhesive tape with the thickness of more than 2mm is observed and tested2The polymer conductive layer of (2) is remained, and it is explained that the adhesion between the conductive polymer layer and the insulating support layer is good in examples 1 and 2.
The above description is only a few examples of the present application and is not intended to limit the present application, and various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The composite current collector is characterized by comprising an insulating support layer, a conductive polymer layer arranged on at least one surface of the insulating support layer, and a metal layer arranged on the surface of the conductive polymer layer, which is far away from the insulating support layer.
2. The composite current collector of claim 1, wherein the conductive polymer material of the conductive polymer layer is iodine-doped polyacetylene.
3. The composite collector of claim 1, wherein the thickness of the conductive polymer layer is 30-100 nm.
4. The composite current collector of any one of claims 1 to 3, wherein the composite current collector is a negative electrode current collector, the material of the conductive polymer layer further comprises a copper-based conductive adhesive, and the metal layer is a negative electrode metal layer;
optionally, the negative electrode metal layer is a copper metal layer.
5. The composite current collector of any one of claims 1 to 3, wherein the composite current collector is a positive current collector, the material of the conductive polymer layer further comprises an aluminum-based conductive adhesive, and the metal layer is a positive metal layer;
optionally, the positive electrode metal layer is an aluminum metal layer.
6. The composite current collector of any one of claims 1 to 3, wherein the conductive polymer layer comprises a first conductive polymer layer and a second conductive polymer layer, and the metal layer comprises a first metal layer and a second metal layer;
the first conductive polymer layer and the second conductive polymer layer are respectively arranged on two surfaces of the insulating support layer, the first metal layer is arranged on the surface, deviating from the insulating support layer, of the first conductive polymer layer, and the second metal layer is arranged on the surface, deviating from the insulating support layer, of the second conductive polymer layer.
7. A secondary battery comprising the composite current collector of any one of claims 1 to 6.
8. A method of preparing a composite current collector as claimed in any one of claims 1 to 6, comprising:
coating conductive polymer slurry on at least one surface of the insulating support layer to form the conductive polymer layer;
and forming the metal layer on the surface of the macromolecule layer, which is far away from the insulating support layer.
9. The method for preparing an electric conduction polymer layer according to claim 8, wherein the thickness of the electric conduction polymer layer is 30 to 100nm, and the metal layer is formed by means of acidity.
10. The method as claimed in claim 9, wherein the thickness of the conductive polymer layer is 10-15nm, a first metal layer with a thickness of 100-120nm is formed on the surface of the conductive polymer layer by means of alkalinity, and a second metal layer with a thickness of 0.8-2 μm is formed on the surface of the first metal layer by means of acidity.
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