CN110993958A - Current collector and preparation method and application thereof - Google Patents
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- CN110993958A CN110993958A CN201911370992.6A CN201911370992A CN110993958A CN 110993958 A CN110993958 A CN 110993958A CN 201911370992 A CN201911370992 A CN 201911370992A CN 110993958 A CN110993958 A CN 110993958A
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Images
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention provides a current collector and a preparation method and application thereof, wherein the current collector comprises a first polymer film layer, a second polymer layer and a metal layer; the second polymer layer is formed by solidifying prepolymer on the upper surface of the first polymer film layer, and the metal layer is arranged on the upper surface of the second polymer layer. When the current collector is applied to a battery, the battery is not negatively affected even if the battery is bent, and the battery can still have good conductive performance and capacity retention rate.
Description
Technical Field
The invention relates to a current collector, in particular to a current collector and a preparation method and application thereof, and belongs to the technical field of batteries.
Background
The secondary battery has the characteristics of high energy density and high power density, so that the secondary battery has wide application prospects in the fields of consumer electronics, electric vehicles, energy storage and the like. However, the secondary battery may cause an internal short circuit under some abuse conditions (e.g., needle punching, pressing, impact, etc.) to cause thermal runaway to cause safety accidents, and thus, there is an increasing interest in improving the safety performance of the secondary battery.
In a conventional secondary battery, for example, a lithium ion battery, a current collector is made of a metal foil, a positive electrode is generally made of a metal aluminum foil, and a negative electrode is generally made of a metal copper foil, so that current cannot be cut off in the case of a short circuit inside the battery, which may cause heat accumulation and ultimately cause thermal runaway. Therefore, there are researchers replacing conventional metal current collectors with a new class of current collectors. The novel current collector generally adopts a non-conductive polymer film as a substrate, and metal is evaporated on two sides of the substrate in a vacuum evaporation mode, an electroplating mode and the like. For example, plating aluminum on both sides of a PET (polyethylene terephthalate) film as a positive current collector and plating copper on both sides of the PET (polyethylene terephthalate) film as a negative current collector achieve certain effects of improving the safety performance of the battery, and simultaneously can reduce the weight of the current collector and further improve the weight energy density of the battery.
However, the current collector in the above technical solution is prone to bend the battery during use due to certain elasticity, and further negatively affects the conductivity and capacity retention rate of the battery to a certain extent.
Disclosure of Invention
The invention provides a current collector which is applied to a battery, does not have negative influence on the battery even if the battery is bent, and can still keep the battery to have good conductive performance and capacity retention rate.
The invention also provides a preparation method of the current collector, which is simple and easy to operate, does not need large-scale arrangement assistance, and can quickly obtain the current collector which enables the battery to have good bending resistance.
The invention also provides a secondary battery, which comprises the current collector, so that when the secondary battery is bent, the conductive performance and the capacity retention rate of the secondary battery are not obviously and negatively influenced.
The invention provides a current collector, which comprises a first polymer film layer, a second polymer layer and a metal layer;
the second polymer layer is formed by solidifying prepolymer on the upper surface of the first polymer film layer, and the metal layer is arranged on the upper surface of the second polymer layer;
the prepolymer is at least one of acrylic resin prepolymer, polyurethane prepolymer and silicon rubber prepolymer.
The current collector is characterized in that the acrylic resin prepolymer is at least one of epoxy acrylate prepolymer, polyether acrylate prepolymer and polyester acrylate prepolymer.
The current collector is characterized in that the polyurethane prepolymer is selected from polyester polyurethane prepolymers and polyether polyurethane prepolymers.
The current collector as described above, wherein the material of the first polymer film layer is at least one of polyethylene terephthalate, polyamide, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, poly (p-phenylene terephthalamide), polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl formal, polyvinyl butyral, polyurethane, polyacrylonitrile, polyvinyl acetate, polyoxymethylene, phenolic resin, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate, polysulfone, polyethersulfone, and polyphenylene oxide.
The current collector as described above, wherein the thickness of the second polymer layer is 1-1000 nm.
The current collector as described above, wherein the thickness of the second polymer layer is 10-100 nm.
The current collector as described above, wherein the thickness of the first polymer film layer is 1 to 15 μm.
The current collector as described above, wherein the thickness of the metal layer is 0.1 to 5 μm.
The invention also provides a preparation method of any one of the current collectors, which comprises the following steps:
1) coating a prepolymer on the upper surface of the first polymer film layer, and then curing the prepolymer to obtain a second polymer layer on the upper surface of the first polymer film layer;
2) and arranging a metal layer on the upper surface of the second polymer layer to obtain the current collector.
The invention also provides a secondary battery, which comprises any one of the current collectors.
The implementation of the invention at least comprises the following advantages:
1. according to the invention, the structure of the current collector is specially limited, so that the safety performance of a secondary battery using the current collector can be enhanced, the bending resistance of the secondary battery can be improved, and the secondary battery still has good conductivity and capacity retention rate even after being bent;
2. the current collector can be used for rigid batteries and flexible batteries, and when the current collector is applied to the rigid batteries, the serious performance reduction of the batteries and even the damage to the batteries caused by the careless bending of the batteries can be avoided; when the flexible battery is applied to the flexible battery, the application range of the flexible battery can be further developed, and the serious performance reduction of the battery caused by excessive bending times or excessive bending degree is avoided;
3. the preparation method of the current collector is simple, does not need the assistance of a large instrument, and is popularized and applied in a large range when in use.
Drawings
Fig. 1 is a schematic structural view of the current collector of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a schematic structural view of the current collector of the present invention. As shown in fig. 1, the current collector of the present invention comprises a first polymer film layer 1, a second polymer layer 2 and a metal layer 3;
the second polymer layer 2 is formed on the upper surface of the first polymer film layer 1 by prepolymer curing, and the metal layer 3 is arranged on the upper surface of the second polymer layer 2;
wherein the prepolymer is at least one of acrylic resin prepolymer, polyurethane prepolymer and silicon rubber prepolymer.
Specifically, the current collector of the invention comprises a first polymer film layer 1, a second polymer layer 2 and a metal layer 3 from bottom to top in sequence.
In the current collector of the present invention, the first polymer film layer 1 can mainly reduce the quality of the current collector, enhance the safety performance of a battery using the current collector by reducing the probability of short circuit, and ensure that the current collector has certain rigidity and strength. The first polymer film layer 1 may be obtained by directly melting, coating, and cooling a polymer compound in sequence, or may be obtained by dissolving a polymer compound in a solvent, coating the solution, and evaporating the solvent, and in one embodiment, the material of the first polymer film layer 1, that is, the polymer compound may be selected from the group consisting of poly (terephthalate), polyamide, Polyimide (PI), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), poly (vinyl chloride) (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly (paraphenylene terephthalamide), polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl formal, polyvinyl butyral, polyurethane, polyacrylonitrile, polyvinyl acetate, polyoxymethylene, phenol resin, epoxy resin, poly (ethylene terephthalate), poly (propylene glycol), poly (acrylonitrile-butadiene-co-styrene), poly (vinyl formal), poly (vinyl butyral), poly (, At least one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), silicone rubber, polycarbonate, polysulfone, polyethersulfone, polyphenylene oxide.
The second polymer film layer 2 is obtained by coating a prepolymer on the upper surface of the first polymer film layer 1 and then curing the prepolymer. Specifically, the prepolymer may be at least one selected from an acrylic resin prepolymer, a polyurethane prepolymer, and a silicone rubber prepolymer. Because the prepolymer is a liquid substance with certain viscosity, the prepolymer can be cured by a curing means to form a cured film layer after being coated on the upper surface of the first polymer film layer. In the present invention, the curing means is not particularly limited, and may be ultraviolet curing, room temperature curing, or heating curing.
The metal layer 3 is formed on the upper surface of the second polymer layer 2, and is mainly used for collecting and conducting current generated by active materials in the electrode. The material of the metal layer 3 may be aluminum, copper, nickel, titanium, silver, stainless steel, nickel-copper alloy, aluminum-zirconium alloy. The material of the metal layer 3 determines the specific application of the current collector, for example, when the metal layer is an aluminum layer, the current collector is a positive current collector; when the metal layer is positioned on the copper layer, the current collector is a negative electrode current collector.
According to the technical scheme provided by the invention, even if the limited current collector is bent by 180 degrees at the bending radius of 0.5cm and the resistance change rate is less than 0.5 percent after being repeatedly bent for 20000 times, the current collector still has good conductive performance, and when the limited current collector is used in an electrode of a secondary battery, such as a lithium ion battery, the capacity retention rate of the battery is not remarkably reduced after the battery is bent for 1000 times at the bending radius of 3cm and 90 ℃. Based on the analysis, the inventor thinks that the second polymer film layer obtained by curing the prepolymer on the surface of the first polymer film layer has more excellent elasticity, so that the second polymer film layer is beneficial to rapid recovery after being stretched or bent, and is more beneficial to increasing the flexibility of the current collector, thereby reducing the negative influence of bending on the current collector and the battery.
In one embodiment, the acrylic resin prepolymer is at least one selected from the group consisting of an epoxy acrylate prepolymer, a polyether acrylate prepolymer, and a polyester acrylate prepolymer.
In one embodiment, the polyurethane prepolymer is selected from the group consisting of polyester polyurethane prepolymers and polyether polyurethane prepolymers.
In specific application, the prepolymer and the first polymer film layer can be obtained commercially.
The thickness of the second polymer layer is not limited by the invention, and may be, for example, 1 to 1000nm, and in order to further optimize the bending resistance of the current collector and avoid other influences on the performance of the battery due to the excessively thick current collector, the thickness of the second polymer layer may be 10 to 100 nm.
In addition, the invention also defines the thickness of the first polymer film layer and the metal layer. Specifically, the thickness of the first polymer film layer may be 1 to 15 μm, further 3 to 10 μm; the thickness of the metal layer may be 0.1 to 5 μm, and further 0.5 to 2 μm.
The current collector sequentially comprises a first polymer film layer, a second polymer layer obtained by solidifying an oligomer and a metal layer from bottom to top, and the resistivity of the current collector can not be obviously changed even after the current collector is bent for many times, so that good conductive performance can be kept; when the current collector is applied to a secondary battery, the current collector contributes to a secondary battery having a high capacity retention rate even after being bent a plurality of times.
The invention also provides a preparation method of any one of the current collectors, which comprises the following steps:
1) coating a prepolymer on the upper surface of the first polymer film layer, and then curing the prepolymer to obtain a second polymer layer on the upper surface of the first polymer film layer;
2) and arranging a metal layer on the upper surface of the second polymer layer to obtain the current collector.
In step 1), after coating the prepolymer on the upper surface of the first polymer film, the liquid prepolymer having a certain viscosity may be cured by means of, for example, ultraviolet curing, room temperature curing, or heating curing, so as to form the second polymer layer on the upper surface of the first polymer film.
In step 2), a metal layer may be disposed on the upper surface of the second polymer layer by at least one of mechanical pressing, adhesion, vapor deposition, chemical plating, and electroplating, wherein the vapor deposition method may be a physical vapor deposition method, and the physical vapor deposition method may be at least one of evaporation and sputtering; the evaporation method may be at least one of a vacuum evaporation method, a thermal evaporation method, and an electron beam evaporation method, and the sputtering method may be a magnetron sputtering method.
Before the step 1), sequentially melting a high molecular polymer, coating on the surface of a support plate, and cooling to finally obtain a first polymer film layer; or dissolving the high molecular polymer in a solvent, coating the solution on the carrier plate, and evaporating the solvent to obtain the first polymer film layer.
It can be understood that the above preparation processes can be all completed on the carrier plate, and when the preparation of the metal layer is completed, the carrier plate can be separated from the current collector; or separating the first polymer film layer from the carrier plate, and then sequentially arranging a second polymer layer and a metal layer.
In the above preparation method, the materials and thicknesses of the first polymer film layer, the second polymer layer and the metal layer are the same as those described above, and are not described herein again.
The invention also provides an application of the current collector, and specifically provides a secondary battery which comprises the current collector.
In a specific application, the current collector may be used as a support of a secondary battery electrode, and a slurry containing a positive electrode active material or a slurry containing a negative electrode active material may be applied to a metal layer of the current collector to obtain a positive electrode or a negative electrode.
The positive electrode and/or the negative electrode including the current collector is assembled with an electrolyte and a separator to obtain a secondary battery, and the conductive performance and the capacity retention performance of the secondary battery are not affected even if the secondary battery is bent for a plurality of times.
Further, the secondary battery may be a lithium ion battery.
Hereinafter, the current collector of the present invention will be described in detail by way of specific examples.
The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, and are commercially available, unless otherwise specified.
Example 1
The preparation method of the current collector a1 of the present embodiment includes the following steps:
1) coating a pre-prepared PET film (average molecular weight of PET 31000) with thickness of 3 μm on the surface of the PET film by a coater to obtain a polyether polyurethane prepolymer (average molecular weight of 3000) with thickness of 10nm, and applying the prepolymer with wavelength of 365nm and strength of 100 μ W cm-2Irradiating the prepolymer with ultraviolet light for 1min to form a second polymer layer with the thickness of 10nm on the surface of the PET film;
2) a metal aluminum layer having a thickness of 2 μm was deposited on the upper surface of the second polymer layer by vacuum deposition to obtain a current collector a 1.
The preparation method of the current collector B1 of the present embodiment includes the following steps:
1) coating a pre-prepared PET film (average molecular weight of 31000) with thickness of 3 μm on the surface of the PET film by a coater to obtain a polyether polyurethane prepolymer (average molecular weight of 3000) with thickness of 10nm, and applying the prepolymer with wavelength of 365nm and strength of 100 μ W cm-2Irradiating the prepolymer with ultraviolet light for 1min to form a second polymer layer with the thickness of 10nm on the surface of the PET film;
2) and evaporating a metal copper layer with the thickness of 2 mu m on the upper surface of the second polymer layer by vacuum evaporation to obtain a current collector B1.
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
according to a conventional preparation process of the lithium ion battery anode, 95 parts of lithium cobaltate anode, 2 parts of acetylene black conductive agent, 0.5 part of carbon nano tube conductive agent, 2.5 parts of PVDF binder and 60 parts of N-methyl pyrrolidone (NMP) are stirred for 4 hours under vacuum by a double planetary stirrer under the conditions of revolution of 30r/min and rotation of 1500r/min to be dispersed into uniform slurry, then the slurry is coated on a current collector A1 and baked for 30min at 130 ℃ to be dried, rolled under the rolling pressure of 40 tons, and cut into required anode sheets;
according to the conventional preparation process of the lithium ion battery cathode, 95 parts of a graphite cathode, 1.5 parts of an acetylene black conductive agent, 0.5 part of a carbon nano tube conductive agent, 1 part of sodium carboxymethylcellulose (CMC), 2 parts of a Styrene Butadiene Rubber (SBR) binder and 100 parts of deionized water are stirred for 4 hours under vacuum by a double-planet stirrer under the conditions of revolution of 30r/min and rotation of 1500r/min to be dispersed into uniform slurry, then the slurry is coated on a current collector B1 and baked for 30min at 100 ℃ to be dried, rolled under 40 tons of rolling pressure, and cut into required cathode sheets;
the obtained positive plate and negative plate are matched with a Polyethylene (PE) porous diaphragm of a wet-process polyethylene porous diaphragm ND12 (with the thickness of 12 μm) produced by Shanghai New Material science and technology Limited and an LBC445B33 type electrolyte of Shenzhen New Zealand science and technology Limited, and the lithium ion battery 1# is prepared by a conventional preparation process of the lithium ion battery.
Comparative examples 1 to 1
The preparation method of the current collector A1-1 of the comparative example is basically the same as that of the current collector A1 of example 1, except that the step of coating polyether polyurethane prepolymer is not included, and a metal aluminum layer with the thickness of 2 microns is directly evaporated on the surface of a PET film to obtain the current collector A1-1.
The preparation method of the current collector B1-1 of the comparative example is basically the same as that of the current collector B1 of the example 1, except that the step of coating polyether polyurethane prepolymer is not included, and a metal copper layer with the thickness of 2 microns is directly evaporated on the surface of a PET film to obtain the current collector B1-1.
The method for manufacturing lithium ion battery 1-1# of this comparative example is substantially the same as the method for manufacturing lithium ion battery 1# of example 1, except that current collector a1-1 is used in place of current collector a1, and current collector B1-1 is used in place of current collector B1.
Comparative examples 1 to 2
The lithium ion battery 1-2# of this comparative example was prepared in substantially the same manner as the lithium ion battery 1# of example 1, except that the current collector a1 was replaced with an aluminum foil having a thickness of 9 μm and the current collector B1 was replaced with a copper foil having a thickness of 5 μm.
Comparative examples 1 to 3
The method for preparing current collector a1-3 of this comparative example, includes the steps of:
1) taking a PET film with the thickness of 3 mu m in example 1, and arranging a polyether polyurethane layer with the thickness of 10nm, which is prepared by polyether polyurethane prepolymer (with the average molecular weight of 3000) in advance, on the surface of the PET film in a bonding mode;
2) and evaporating a metal aluminum layer with the thickness of 2 mu m on the upper surface of the polyether polyurethane layer by vacuum evaporation to obtain a current collector A1-3.
The method for preparing current collector B1-3 of this comparative example, includes the steps of:
1) taking the PET film with the thickness of 3 microns in example 1, and arranging a polyether polyurethane layer with the thickness of 10nm, which is prepared by polyether polyurethane prepolymer (with the average molecular weight of 3000) in advance, on the surface of the PET film in a bonding mode;
2) and evaporating a metal copper layer with the thickness of 2 mu m on the upper surface of the polyether polyurethane layer by vacuum evaporation to obtain a current collector B1-3.
The method for manufacturing lithium ion battery # 1-3 of this comparative example is substantially the same as the method for manufacturing lithium ion battery # 1 of example 1, except that current collector a1-3 is used in place of current collector a1, and current collector B1-3 is used in place of current collector B1.
Example 2
The preparation method of the current collector a2 of the present embodiment includes the following steps:
1) a PET film having a thickness of 5 μm as in example 1 was coated with a polyester polyurethane prepolymer (average molecular weight: 5000) having a thickness of 100nm by a coater, and the resultant coating film was irradiated with light having a wavelength of 365nm and a strength of 100. mu.W.cm-2Irradiating the prepolymer with ultraviolet light for 5min to form a second polymer layer with the thickness of 100nm on the surface of the PET film;
2) a metal aluminum layer having a thickness of 1 μm was deposited on the upper surface of the second polymer layer by vacuum deposition to obtain a current collector a 2.
The preparation method of the current collector B2 of the present embodiment includes the following steps:
1) a PET film having a thickness of 5 μm as in example 1 was coated with a polyester polyurethane prepolymer (having an average molecular weight of 5000) having a thickness of 100nm by a coater, and the resultant coating film was irradiated with light having a wavelength of 365nm and a strength of 100. mu.W.cm-2Irradiating the prepolymer with ultraviolet light for 5min to obtain the PETForming a second polymer layer with the thickness of 100nm on the surface of the film;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the second polymer layer by vacuum evaporation to obtain a current collector B2.
The lithium ion battery 2# of the present example was prepared in substantially the same manner as the lithium ion battery 1# of example 1, except that the current collector a1 was replaced with current collector a2, and the current collector B1 was replaced with current collector B2.
Comparative example 2-1
The preparation method of the current collector A2-1 of the comparative example is basically the same as that of the current collector A2 of example 2, except that the step of coating a polyester polyurethane prepolymer is not included, and a metal aluminum layer with the thickness of 1 μm is directly evaporated on the surface of a PET film to obtain the current collector A2-1.
The preparation method of the current collector B2-1 of the comparative example is basically the same as that of the current collector B2 of example 2, except that the step of coating the polyester polyurethane prepolymer is not included, and a metal copper layer with the thickness of 1 μm is directly evaporated on the surface of the PET film to obtain the current collector B2-1.
The method for manufacturing lithium ion battery 2-1# of this comparative example is substantially the same as the method for manufacturing lithium ion battery 2# of example 2, except that current collector a2-1 is used in place of current collector a2, and current collector B2-1 is used in place of current collector B2.
Comparative examples 2 to 2
The lithium ion battery 2-2# of this comparative example was prepared in substantially the same manner as the lithium ion battery 2# of example 2, except that the current collector a2 was replaced with an aluminum foil having a thickness of 9 μm and the current collector B2 was replaced with a copper foil having a thickness of 8 μm.
Comparative examples 2 to 3
The method for preparing current collector a2-3 of this comparative example, includes the steps of:
1) taking the PET film with the thickness of 5 microns in example 1, and arranging a polyester polyurethane layer with the thickness of 100nm, which is prepared by a polyester polyurethane prepolymer (with the average molecular weight of 5000) in advance, on the surface of the PET film in a bonding mode;
2) and evaporating a metal aluminum layer with the thickness of 1 mu m on the upper surface of the polyester polyurethane layer by vacuum evaporation to obtain a current collector A2-3.
The method for preparing current collector B2-3 of this comparative example, includes the steps of:
1) taking the PET film with the thickness of 5 microns in example 1, and arranging a polyester polyurethane layer with the thickness of 100nm, which is prepared by a polyester polyurethane prepolymer (with the average molecular weight of 5000) in advance, on the surface of the PET film in a bonding mode;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the polyester polyurethane layer by vacuum evaporation to obtain the current collector B2-3.
The method for manufacturing lithium ion battery 2-3# of this comparative example is substantially the same as the method for manufacturing lithium ion battery 2# of example 2, except that current collector a2-3 is used in place of current collector a2, and current collector B2-3 is used in place of current collector B2.
Example 3
The preparation method of the current collector a3 of the present embodiment includes the following steps:
1) taking a previously prepared PBT film (average molecular weight of 38000 PBT) with thickness of 5 μm, coating a silicone rubber prepolymer (average molecular weight of 10000) with thickness of 1000nm on the surface of the PBT film by a coating machine, and then coating with a light wave length of 365nm and intensity of 200 μ W cm-2Irradiating the prepolymer with ultraviolet light for 10min to form a second polymer layer with the thickness of 1000nm on the surface of the PET film;
2) a metal aluminum layer having a thickness of 1 μm was deposited on the upper surface of the second polymer layer by vacuum deposition to obtain a current collector a 3.
The preparation method of the current collector B3 of the present embodiment includes the following steps:
1) taking a previously prepared PBT film (average molecular weight of 38000) with thickness of 5 μm, coating a silicone rubber prepolymer (average molecular weight of 10000) with thickness of 1000nm on the surface of the PBT film by a coating machine, and then coating with a light wave length of 365nm and intensity of 100 μ W cm-2Irradiating the prepolymer with ultraviolet light for 5min to form a second polymer layer with the thickness of 1000nm on the surface of the PET film;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the second polymer layer by vacuum evaporation to obtain a current collector B3.
The lithium ion battery 3# of the present example was prepared in substantially the same manner as the lithium ion battery 1# of example 1, except that the current collector a1 was replaced with current collector A3, and the current collector B1 was replaced with current collector B3.
Comparative example 3-1
The preparation method of the current collector A3-1 of the comparative example is basically the same as that of the current collector A3 of example 3, except that the step of coating a silicone rubber prepolymer is not included, and a metal aluminum layer with the thickness of 1 μm is directly evaporated on the surface of a PBT film to obtain the current collector A3-1.
The preparation method of the current collector B3-1 of the comparative example is basically the same as that of the current collector B3 of example 3, except that the step of coating silicone rubber prepolymer is not included, and a metal copper layer with the thickness of 1 μm is directly evaporated on the surface of a PBT film to obtain the current collector B3-1.
The method for manufacturing lithium ion battery 3-1# of this comparative example is substantially the same as the method for manufacturing lithium ion battery 3# of example 3, except that current collector A3-1 is used in place of current collector A3, and current collector B3-1 is used in place of current collector B3.
Comparative examples 3 to 2
The lithium ion battery 3-2# of this comparative example was prepared in substantially the same manner as the lithium ion battery 3# of example 3, except that the current collector a3 was replaced with an aluminum foil having a thickness of 9 μm and the current collector B3 was replaced with a copper foil having a thickness of 8 μm.
Comparative examples 3 to 3
The method for preparing current collector a3-3 of this comparative example, includes the steps of:
1) taking the PBT film with the thickness of 5 mu m in the embodiment 3, and arranging a silicone rubber layer with the thickness of 1000nm, which is prepared by silicone rubber prepolymer (with the average molecular weight of 10000) in advance, on the surface of the PBT film in a bonding mode;
2) and evaporating a metal aluminum layer with the thickness of 1 mu m on the upper surface of the silicon rubber layer by vacuum evaporation to obtain a current collector A3-3.
The method for preparing current collector B3-3 of this comparative example, includes the steps of:
1) taking the PBT film with the thickness of 5 mu m in the embodiment 3, and arranging a silicone rubber layer with the thickness of 1000nm, which is prepared by silicone rubber prepolymer (with the average molecular weight of 10000) in advance, on the surface of the PBT film in a bonding mode;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the silicon rubber layer by vacuum evaporation to obtain the current collector B3-3.
The method for manufacturing lithium ion battery 3-3# of this comparative example is substantially the same as the method for manufacturing lithium ion battery 3# of example 3, except that current collector A3-3 is used in place of current collector A3, and current collector B3-3 is used in place of current collector B3.
Example 4
The preparation method of the current collector a4 of the present embodiment includes the following steps:
1) taking a pre-prepared PI film (the average PI molecular weight is 45000) with the thickness of 5 mu m, coating an epoxy acrylate prepolymer (the average PI molecular weight is 8000) with the thickness of 100nm on the surface of the PI film through a coating machine, and naturally curing at room temperature for 30min to form a second polymer layer with the thickness of 100nm on the surface of the PI film;
2) a metal aluminum layer having a thickness of 1 μm was deposited on the upper surface of the second polymer layer by vacuum deposition to obtain a current collector a 4.
The preparation method of the current collector B4 of the present embodiment includes the following steps:
1) taking a pre-prepared PI film (the average PI molecular weight is 45000) with the thickness of 5 mu m, coating an epoxy acrylate prepolymer (the average PI molecular weight is 8000) with the thickness of 100nm on the surface of the PI film through a coating machine, and naturally curing at room temperature for 30min to form a second polymer layer with the thickness of 100nm on the surface of the PI film;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the second polymer layer by vacuum evaporation to obtain a current collector B4.
The lithium ion battery 4# of the present example was prepared in substantially the same manner as the lithium ion battery 1# of example 1, except that the current collector a1 was replaced with current collector a4, and the current collector B1 was replaced with current collector B4.
Comparative example 4-1
The preparation method of the current collector A4-1 of the comparative example is basically the same as that of the current collector A4 of example 4, except that the step of coating epoxy acrylate prepolymer is not included, and a metal aluminum layer with the thickness of 1 μm is directly evaporated on the surface of the PI film to obtain the current collector A4-1.
The preparation method of the current collector B4-1 of the comparative example is basically the same as that of the current collector B4 of example 4, except that the step of coating epoxy acrylate prepolymer is not included, and a metal copper layer with the thickness of 1 μm is directly evaporated on the surface of the PI film to obtain the current collector B4-1.
The lithium ion battery 4-1# of this comparative example was prepared in substantially the same manner as lithium ion battery 4# of example 4, except that current collector a4-1 was used in place of current collector a4 and current collector B4-1 was used in place of current collector B4.
Comparative examples 4 to 2
The lithium ion battery 4-2# of this comparative example was prepared in substantially the same manner as the lithium ion battery 4# of example 4, except that the current collector a4 was replaced with an aluminum foil having a thickness of 9 μm and the current collector B4 was replaced with a copper foil having a thickness of 7 μm.
Comparative examples 4 to 3
The method for preparing current collector a4-3 of this comparative example, includes the steps of:
1) taking the PI film with the thickness of 5 mu m in the embodiment 4, and arranging an epoxy acrylate layer with the thickness of 100nm, which is prepared by an epoxy acrylate prepolymer (with the average molecular weight of 8000) in advance, on the surface of the PI film in a bonding mode;
2) and evaporating a metal aluminum layer with the thickness of 1 mu m on the upper surface of the epoxy acrylate layer by vacuum evaporation to obtain a current collector A4-3.
The method for preparing current collector B4-3 of this comparative example, includes the steps of:
1) taking the PI film with the thickness of 5 mu m in the embodiment 4, and arranging an epoxy acrylate layer with the thickness of 100nm, which is prepared by an epoxy acrylate prepolymer (with the average molecular weight of 8000) in advance, on the surface of the PI film in a bonding mode;
2) and evaporating a metal copper layer with the thickness of 1 mu m on the upper surface of the epoxy acrylate layer by vacuum evaporation to obtain a current collector B4-3.
The lithium ion battery 4-3# of this comparative example was prepared in substantially the same manner as lithium ion battery 4# of example 4, except that current collector a4-3 was used in place of current collector a4 and current collector B4-3 was used in place of current collector B4.
Test examples
1. The collectors of the above examples and comparative examples were sampled at 4cm x 20cm size, respectively, and tested for initial resistance R0Then bending the steel plate 180 degrees at a bending radius of 0.5cm, repeatedly bending the steel plate 20000 times, and testing the real-time resistance R of the steel plate1The rate of change in resistance △ of the current collector was calculated according to equation 1 and the results are shown in table 1.
△＝(R1-R0)/R0100% of formula 1
2. Respectively bending the lithium ion batteries in the embodiments and the comparative examples by a repeated bending tester at a bending radius of 3cm for 90 degrees and repeatedly bending the lithium ion batteries for 1000 times, and testing the capacity retention rate of the lithium ion batteries after bending;
the capacity test value of the lithium ion battery before bending is recorded as C0And the capacity test value of the lithium ion battery after bending is recorded as C1，
Capacity retention after bending ═ C1-C0)/C0*100％
The specific test method refers to GB/T18287-2013.
3. After the lithium ion batteries in the above examples and comparative examples are fully charged, the safety performance of each lithium ion battery is tested by needling, heating and overcharging, the test method refers to GB/T31485-2015, 10 lithium ion batteries in the same example or comparative example are subjected to the above test, and the results are shown in Table 1.
TABLE 1
From table 1, it can be seen that: the current collector has excellent bending resistance, and the resistance of the current collector is hardly changed before and after bending; and the lithium ion battery using the current collector of the invention has good bending resistance, and the capacity retention rate of the lithium ion battery is not obviously reduced before and after bending.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A current collector comprising a first polymer film layer, a second polymer layer, and a metal layer;
the second polymer layer is formed by solidifying prepolymer on the upper surface of the first polymer film layer, and the metal layer is arranged on the upper surface of the second polymer layer;
the prepolymer is at least one of acrylic resin prepolymer, polyurethane prepolymer and silicon rubber prepolymer.
2. The current collector of claim 1, wherein the acrylic resin prepolymer is at least one selected from the group consisting of an epoxy acrylate prepolymer, a polyether acrylate prepolymer, and a polyester acrylate prepolymer.
3. The current collector of claim 2, wherein the polyurethane prepolymer is at least one selected from the group consisting of a polyester polyurethane prepolymer and a polyether polyurethane prepolymer.
4. The current collector of claim 1, wherein the first polymer film layer is made of at least one material selected from the group consisting of polyester terephthalate, polyamide, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, poly (paraphenylene terephthalamide), polypropylene, acrylonitrile-butadiene-styrene copolymer, polyvinyl formal, polyvinyl butyral, polyurethane, polyacrylonitrile, polyvinyl acetate, polyoxymethylene, phenolic resin, epoxy resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, polycarbonate, polysulfone, polyethersulfone, and polyphenylene oxide.
5. The current collector of claim 1, wherein the thickness of the second polymer layer is 1-1000 nm.
6. The current collector of claim 5, wherein the thickness of the second polymer layer is 10-100 nm.
7. The current collector of claim 1, wherein the thickness of the first polymer film layer is 1-15 μ ι η.
8. The current collector of claim 1, wherein the metal layer has a thickness of 0.1-5 μ ι η.
9. A method for preparing the current collector of any one of claims 1 to 8, comprising the steps of:
1) coating a prepolymer on the upper surface of the first polymer film layer, and then curing the prepolymer to obtain a second polymer layer on the upper surface of the first polymer film layer;
2) and arranging a metal layer on the upper surface of the second polymer layer to obtain the current collector.
10. A secondary battery comprising the current collector of any one of claims 1 to 8.
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| CN115939410A (en) * | 2022-12-29 | 2023-04-07 | 江阴纳力新材料科技有限公司 | Composite current collector, preparation method thereof, electrode and secondary battery |
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| WO2024138516A1 (en) * | 2022-12-29 | 2024-07-04 | 江阴纳力新材料科技有限公司 | Composite current collector, preparation method therefor, electrode and secondary battery |
| WO2024145783A1 (en) * | 2023-01-03 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Composite current collector and preparation method therefor, and electrode sheet, battery and electric apparatus |
| WO2024159493A1 (en) * | 2023-02-02 | 2024-08-08 | 扬州纳力新材料科技有限公司 | Modified composite current collector, preparation method therefor, and application thereof |
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