CN115207366A - Composite current collector and preparation method and application thereof - Google Patents
Composite current collector and preparation method and application thereof Download PDFInfo
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- CN115207366A CN115207366A CN202210854305.3A CN202210854305A CN115207366A CN 115207366 A CN115207366 A CN 115207366A CN 202210854305 A CN202210854305 A CN 202210854305A CN 115207366 A CN115207366 A CN 115207366A
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Images
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a composite current collector and a preparation method and application thereof. The composite current collector comprises a first metal layer, a second metal layer and a polymer material layer, wherein the polymer material layer is positioned between the first metal layer and the second metal layer, and the composite current collector is provided with a through hole structure penetrating through the first metal layer, the second metal layer and the polymer material layer; the aperture of the through hole structure is 0.1 mm-1 mm, and the porosity is 0.1% -5%. The composite current collector can conduct ions, reduce the internal polarization of the battery and improve the electrochemical performance of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite current collector and a preparation method and application thereof.
Background
The current metal composite current collector is mainly a copper current collector or an aluminum current collector. The copper current collector or the aluminum current collector is composed of two parts, and comprises metal layers and a polymer layer positioned between the metal layers. However, the polymer layer in the middle of the conventional metal composite current collector is of a non-porous structure, that is, the porosity is 0, and the upper and lower metal layers cannot conduct ions on the upper and lower layers of the current collector, so that the resistivity of the upper and lower metal layers is different, and the formed ion field is not uniform, thereby causing the internal polarization of the battery to be large and affecting the electrochemical performance of the battery.
Disclosure of Invention
Therefore, a need exists for a composite current collector capable of conducting ions, reducing polarization inside a battery and improving electrochemical performance of the battery, and a preparation method and an application thereof.
In one aspect of the present invention, a composite current collector is provided, which includes a first metal layer, a second metal layer, and a polymer material layer, where the polymer material layer is located between the first metal layer and the second metal layer, and the composite current collector has a through hole structure penetrating through the first metal layer, the second metal layer, and the polymer material layer; the aperture of the through hole structure is 0.1 mm-1 mm, and the porosity is 0.1% -5%.
In some embodiments, the through-hole structure has a pore diameter of 0.5mm to 1mm and a porosity of 0.1% to 5%.
In some embodiments, the composite current collector has a thickness of 2 to 28 μm, wherein the first and second metal layers may have a thickness of 0.5 to 1.5 μm, respectively, and the polymer material layer may have a thickness of 1 to 25 μm.
In some embodiments, the material of the polymer material layer is selected from a composite formed by an insulating polymer material and an inorganic non-conductive filler, a composite formed by an insulating polymer material and a conductive filler, an insulating polymer material or a conductive polymer material, wherein the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the inorganic non-conductive filler is greater than or equal to 90%, and the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the conductive filler is greater than or equal to 90%.
In some embodiments, the insulating polymer material is selected from one or more of cellulose and derivatives thereof, starch and derivatives thereof, proteins and derivatives thereof, polyvinyl alcohol and cross-linked polymers thereof, polyethylene glycol and cross-linked polymers thereof, polyamides, polyterephthalate, polyimides, polyethylene, polypropylene, polystyrene, polyvinyl chloride, aramid, polydiformyl phenylenediamine, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, poly (p-phenylene terephthalamide), polypropylene, polyoxymethylene, epoxy resins, phenolic resins, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, and polycarbonate; and/or
The conductive polymer material is selected from doped sulfur nitride and/or doped polyacetylene; and/or
The inorganic non-conductive filler is selected from one or more of ceramic materials, glass materials and ceramic composite materials; and/or
The conductive filler is selected from one or more of carbon black, carbon nano tube, graphite, acetylene black, graphene, nickel, iron, copper, aluminum, alloy, nickel-coated graphite powder and nickel-coated carbon fiber.
In one aspect of the present invention, there is also provided a method for preparing the composite current collector, including the following steps:
and respectively forming the first metal layer and the second metal layer on two sides of the polymer material layer, and perforating the polymer material layer, the first metal layer and the second metal layer according to the distribution principle of the through hole structure.
In some embodiments, the method of plating is vacuum evaporation, and/or the method of drilling is laser drilling;
optionally, the evaporation temperature of the plating material for vacuum evaporation is 600-1600 ℃, and the vacuum degree is less than 1 x 10 -2 Pa, the evaporation rate is 10 m/min-100 m/min;
optionally, the wavelength of the laser drilling is 400nm to 700nm.
In another aspect of the present invention, a positive electrode is further provided, which includes the composite current collector described above and a positive electrode active material layer located on the surface of the composite current collector.
In another aspect of the invention, a battery is provided, which includes the positive electrode described above.
In another aspect of the present invention, an electric device is further provided, which includes the battery described above.
The porous composite current collector is prepared by arranging the through holes and regulating and controlling the aperture and the distance of the through holes. When the resistivity of the first metal layer and the second metal layer of the composite current collector is different and the ion field is inconsistent, the through hole structure can allow ions to pass through, so that the ion concentration of the surface of the first metal layer and the surface of the second metal layer gradually tend to be consistent, the polarization of the surface of the first metal layer and the surface of the second metal layer of the composite current collector is reduced, the electrical property of the battery is improved, and particularly, the multiplying power performance of the battery is improved while the internal resistance of the battery is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural view of a porous composite current collector made in one embodiment of the present invention;
fig. 2 is a top view of the porous composite current collector of fig. 1.
Description of reference numerals: 100. a first metal layer; 200. a second metal layer; 300. a layer of polymeric material; 400. a duct.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other than as shown in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The invention provides a composite current collector, which comprises a first metal layer, a second metal layer and a polymer material layer, wherein the polymer material layer is positioned between the first metal layer and the second metal layer; wherein, the aperture of the through hole structure is 0.1 mm-1 mm, and the porosity is 0.1% -5%.
The porous composite current collector is prepared by arranging the through holes and regulating and controlling the aperture and the distance of the through holes. When the resistivity of the first metal layer and the second metal layer of the composite current collector is different and the ion field is inconsistent, the through hole structure can allow ions to pass through, so that the ion concentration of the surface of the first metal layer and the surface of the second metal layer tend to be consistent, the polarization of the surface of the first metal layer and the surface of the second metal layer of the composite current collector is reduced, the electrical property of the battery is improved, and particularly, the multiplying power performance of the battery is improved while the internal resistance of the battery is reduced.
In one embodiment, the aperture of the through hole structure may be any value between 0.1mm and 1mm, preferably any value between 0.5mm and 1mm, for example, 0.6mm, 0.7mm, 0.8mm, 0.9mm;
in one embodiment, the porosity may be any value between 0.1% and 5%, for example, 0.5%, 1%, 2%, 3%, 4%, 4.5%.
In one embodiment, the distance between centers of two adjacent through holes may be any value between 5mm and 10mm, for example, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, 8mm, 8.5mm, 9mm, 9.5mm, and preferably any value between 8mm and 10mm.
In one embodiment, the thickness of the composite current collector may be 2 μm to 28 μm, and may be, for example, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm. Preferably, the first metal layer and the second metal layer may have a thickness of 0.5 μm to 1.5 μm, respectively and the polymer material layer may have a thickness of 1 μm to 25 μm.
In one embodiment, the material of the polymer material layer may be any material commonly used in the art, including but not limited to a composite formed by insulating polymer material and inorganic non-conductive filler, a composite formed by insulating polymer material and conductive filler, insulating polymer material or conductive polymer material, wherein the mass percentage of the insulating polymer material in the composite formed by insulating polymer material and inorganic non-conductive filler is greater than or equal to 90%, and the mass percentage of the insulating polymer material in the composite formed by insulating polymer material and conductive filler is greater than or equal to 90%.
The insulating polymer material can be selected from one or more of cellulose and derivatives thereof, starch and derivatives thereof, protein and derivatives thereof, polyvinyl alcohol and cross-linked polymers thereof, polyethylene glycol and cross-linked polymers thereof, polyamide, polyterephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, aramid, polydiformyl phenylenediamine, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyterephthalamide, polypropylene, polyformaldehyde, epoxy resin, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber and polycarbonate;
the conductive polymer material may be selected from doped polysulphide and/or doped polyacetylene.
The inorganic non-conductive filler may be selected from one or more of a ceramic material, a glass material, and a ceramic composite material;
the conductive filler can be selected from at least one of a conductive carbon material, a metal material and a composite conductive material, wherein the carbon material can be selected from carbon black, carbon nano tubes, graphite, acetylene black and graphene, the metal material can be selected from nickel, iron, copper, aluminum and an alloy, the alloy contains one or more of nickel, iron, copper and aluminum, and the composite conductive material can be selected from one or more of nickel-coated graphite powder and nickel-coated carbon fibers.
In one embodiment, the layer of polymeric material has a puncture strength of 100gf or more, a Machine Direction (MD) tensile strength of 180MPa or more, a Machine Direction (MD) elongation of 10% or more, a Transverse Direction (TD) tensile strength of 180MPa or more, and a Transverse Direction (TD) elongation of 10% or more.
In one embodiment, the composite current collector is a positive electrode current collector, the puncture strength is more than or equal to 50gf, the longitudinal (MD) tensile strength is more than or equal to 180MPa, the longitudinal (MD) elongation is more than or equal to 10%, the Transverse (TD) tensile strength is more than or equal to 180MPa, and the Transverse (TD) elongation is more than or equal to 10%.
In one embodiment, the peel force between the first and second metal layers and the polymeric material layer is ≧ 5N/m.
In one embodiment, the first metal layer and the second metal layer may be a copper metal layer or an aluminum metal layer. Preferably, the purity of the first metal layer and the second metal layer is more than or equal to 99.8 percent.
In one aspect of the present invention, there is also provided a method for preparing the composite current collector, including the following steps:
and respectively forming a first metal layer and a second metal layer on two sides of the polymer material layer, and perforating the polymer material layer, the first metal layer and the second metal layer according to the distribution principle of the through hole structure.
In one embodiment, the plating method may be vacuum evaporation, wherein the parameters of the vacuum evaporation are required to satisfy any one of the following conditions: the evaporation temperature of the plating material can be 600-1600 ℃, and the vacuum degree is less than 1 multiplied by 10 -2 Pa, the evaporation rate is 10 m/min-100 m/min. For example, the degree of vacuum may be 0.1X 10 -2 Pa～0.8×10 -2 Pa. Wherein, the evaporation rate is the moving speed of the polymer material layer.
In one embodiment, the method of drilling may be laser drilling; preferably, the wavelength of the laser drilling may be 400nm to 700nm.
In one embodiment, the preparation method further comprises the steps of rolling and vacuum packaging.
In another aspect of the present invention, a positive electrode is further provided, which includes the composite current collector described above and a positive active material layer located on the surface of the composite current collector.
In one embodiment, the positive electrode active material in the positive electrode active material layer may be any positive electrode active material known in the art, and may be, for example, lithium cobaltate, lithium iron phosphate, NCA, NCM, lithium manganate, lithium nickelate, NCMA, or a cobalt-free positive electrode.
In another aspect of the invention, a battery is provided, which includes the positive electrode described above.
In one of the embodiments, the battery may further include a negative electrode and an electrolyte.
The negative electrode may be any negative electrode commonly used in the art, such as graphite, lithium, and lithium titanate.
In one embodiment, the electrolyte may be a solid electrolyte, a semi-solid electrolyte, or a liquid electrolyte, wherein the solid electrolyte and the semi-solid electrolyte may be oxide or sulfide electrolytes, and the solute in the liquid electrolyte may be lithium hexafluorophosphate.
In one embodiment, the battery may further include a separator, wherein the separator may be any separator known in the art, such as a PE wet separator, a PP dry separator, or a double layer PE/PP coated separator.
The shape of the battery is not limited, and the battery can be cylindrical or square, and can also be a soft package of an aluminum plastic film.
In one embodiment, the battery may be a lithium ion battery.
In another aspect of the present invention, an electric device is also provided, which includes the battery described above.
In one embodiment, specific types of powered devices include, but are not limited to, mobile terminals (cell phones, mobile computers, etc.), smart wear, power tools (electric drills, motors, etc.), electric cars, mobile power sources, and the like.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
Preparation of porous composite current collector
As shown in fig. 1 and 2, in the present embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a PET film, and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively carrying out vacuum evaporation on a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9% on two sides of a PET film with the thickness of 6 mu m to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: vacuum degree of 0.5X 10 -2 Pa, the temperature of the plating material is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector with a pore passage 400; wherein the depth of the pore passage 400 is 8 μm, the pore diameter is 0.5mm, and the distance between the centers of adjacent circular holes is 8mm; the wavelength of laser drilling is 600nm.
Measuring the puncture strength of the porous composite current collector to be 200gf; a Machine Direction (MD) tensile strength of 210MPa and a Machine Direction (MD) elongation of 35%; the Transverse Direction (TD) tensile strength was 190MPa, and the Transverse Direction (TD) elongation was 15%.
The peel force between the polymer material layers 300 of the first metal layer 100 or the second metal layer 200 was measured to be 5N/m.
(II) Battery Assembly
And (3) positive electrode: the lithium iron phosphate current collector consists of the porous composite current collector prepared in the step one and a lithium iron phosphate active material coated on the porous composite current collector;
negative electrode: graphite;
electrolyte solution: liquid electrolyte taking lithium hexafluorophosphate as solute;
a diaphragm: a Polyethylene (PE) microporous separator;
the components are assembled into a lithium iron phosphate battery with the model of 50Ah, relevant performance tests are carried out, and the test results are shown in Table 1.
Example 2
The method of preparing a porous composite current collector in this example is substantially the same as in example 1, except that: the aperture is 1mm. The method comprises the following specific steps:
as shown in fig. 1 and 2, in the present embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a PET film, and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively carrying out vacuum evaporation on a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9% on two sides of a PET film with the thickness of 6 mu m to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: the vacuum degree is 0.5 multiplied by 10 -2 Pa, the plating material temperature is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector; wherein the depth of the pore passage 400 is 8 μm, the pore diameter is 1mm, and the distance between centers of adjacent circular holes is 8mm; the wavelength of laser drilling is 600nm.
Example 3
The method of preparing a porous composite current collector in this example is substantially the same as in example 1, except that: the distance between centers of adjacent round holes is 5mm. The method comprises the following specific steps:
as shown in fig. 1 and 2, in the present embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a PET film, and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively carrying out vacuum evaporation on a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9% on two sides of a PET film with the thickness of 6 mu m to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: the vacuum degree is 0.5 multiplied by 10 -2 Pa, the temperature of the plating material is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector; wherein the depth of the pore passage 400 is 8 μm, the pore diameter is 0.5mm, and the distance between the centers of adjacent circular holes is 5mm; the wavelength of laser drilling is 500nm.
Example 4
The method of preparing a porous composite current collector in this example is substantially the same as in example 1, except that: the distance between centers of adjacent round holes is 10mm. The method comprises the following specific steps:
as shown in fig. 1 and 2, in the present embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a PET film, and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively carrying out vacuum evaporation on a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9% on two sides of a PET film with the thickness of 6 mu m to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: the vacuum degree is 0.5 multiplied by 10 -2 Pa, the temperature of the plating material is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector; wherein, the depth of the pore canal 400 is 8 μm, the aperture is 0.5mm, and the distance between the centers of the adjacent round holes is 10mm; the wavelength of laser drilling is 600nm.
Example 5
The method of preparing a porous composite current collector in this example is substantially the same as in example 1, except that: the layer of polymer material 300 is a conductive film composed of polyethylene and graphite in a mass ratio of 9:1. The method comprises the following specific steps:
as shown in fig. 1 and 2, in this embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a conductive film composed of polyethylene and graphite (with a mass ratio of 9:1), and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively performing vacuum evaporation on two surfaces of a conductive film consisting of 6 mu m polyethylene and graphite (the mass ratio is 9:1) to form a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9 percent to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: vacuum degree of 0.5X 10 -2 Pa, the plating material temperature is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector; wherein, the depth of the pore canal 400 is 8 μm, the aperture is 0.5mm, and the distance between the centers of the adjacent round holes is 8mm; the laser drilling parameters are as follows: the wavelength was 600nm.
Comparative example 1
This comparative example was prepared substantially the same as example 1, except that: the current collector is not perforated, i.e., the pore passages 400 are not formed. The method comprises the following specific steps:
preparation of composite current collector
1) A PET film having a thickness of 6 μm was vacuum-deposited on both surfaces thereof to give a film having a thickness of 1 μm and a purity of 999% of a first metallic aluminum layer and a second metallic aluminum layer, preparing a composite current collector with a thickness of 8 μm; the parameters of vacuum evaporation are as follows: vacuum degree of 0.5X 10 -2 Pa, the temperature of the plating material is 650 ℃, and the evaporation rate is 100m/min.
Measuring the puncture strength of the composite current collector to be 190gf; a Machine Direction (MD) tensile strength of 220MPa and a Machine Direction (MD) elongation of 43%; the Transverse Direction (TD) tensile strength was 200MPa, and the Transverse Direction (TD) elongation was 21%.
The peel force between the polymer material layers 300 of the first metal layer 100 or the second metal layer 200 was measured to be 5N/m.
(II) Battery Assembly
And (3) positive electrode: the lithium iron phosphate current collector consists of the composite current collector prepared in the step one and a lithium iron phosphate active material coated on the composite current collector;
negative electrode: graphite;
electrolyte solution: liquid electrolyte taking lithium hexafluorophosphate as solute;
a diaphragm: a Polyethylene (PE) microporous membrane;
the components are assembled into a lithium iron phosphate battery with the model number of 50Ah, and relevant performance tests are carried out, wherein the test results are shown in Table 1.
Comparative example 2
This comparative example was prepared substantially the same as example 1, except that: the aperture is 2mm. The method comprises the following specific steps:
preparation of porous composite current collector
As shown in fig. 1 and 2, in the present embodiment, the first metal layer 100 and the second metal layer 200 are both metal aluminum layers, the polymer material layer 300 is a PET film, and the pore structure penetrates through the thickness direction of the porous composite current collector to form a pore channel 400. The preparation method comprises the following specific steps:
1) Respectively carrying out vacuum evaporation on a first metal aluminum layer and a second metal aluminum layer with the thickness of 1 mu m and the purity of 99.9% on two sides of a PET film with the thickness of 6 mu m to prepare a composite current collector with the thickness of 8 mu m; the parameters of vacuum evaporation are as follows: vacuum degree of 0.5X 10 -2 Pa, the plating material temperature is 650 ℃, and the evaporation rate is 100m/min.
2) Punching in the thickness direction of the composite current collector prepared in the step 1) by adopting a laser punching mode to prepare a porous composite current collector with a pore passage 400; wherein the depth of the pore passage 400 is 8 μm, the pore diameter is 2mm, and the distance between centers of adjacent circular holes is 8mm; the laser drilling parameters are as follows: the wavelength is 600nm.
(II) Battery Assembly
And (3) positive electrode: the lithium iron phosphate current collector consists of the porous composite current collector prepared in the step one and a lithium iron phosphate active material coated on the porous composite current collector;
negative electrode: graphite;
electrolyte: liquid electrolyte taking lithium hexafluorophosphate as solute;
a diaphragm: a Polyethylene (PE) microporous membrane;
the components are assembled into a lithium iron phosphate battery with the model number of 50Ah, and relevant performance tests are carried out, wherein the test results are shown in Table 1.
And (3) performance testing:
the polarization internal resistance test, the capacity retention rate and the charge-discharge cycle performance test are shown in the national standard GB 18287-2000, and the test results are shown in Table 1.
1) Capacity retention ratio: the capacity retention rates of the lithium iron phosphate batteries assembled in example 1 and comparative examples 1 to 2 were tested at 25 ℃ and with a cycle of 3C rate for 1000 weeks, with the test results shown in table 1;
2) And (3) testing charge and discharge cycle performance: the lithium iron phosphate batteries assembled in example 1 and comparative examples 1 to 2 were tested for cycle performance at a 1C rate charge and 1C rate discharge (1C/1C) at a capacity retention rate of 80%, and the cycle number is shown in table 1.
TABLE 1
| Serial number | Polarization internal resistance (m omega) | 3C capacity retention (%) | 1C/1C cycle (week) |
| Example 1 | 2 | 99.5 | 1800 |
| Comparative example 1 | 6 | 97 | 1400 |
| Comparative example 2 | 5 | 96.5 | 1350 |
According to the test results, the ion concentrations of the upper metal layer and the lower metal layer of the current collector tend to be consistent by arranging the porous structure on the composite current collector, so that the polarization of the upper metal layer and the lower metal layer of the porous composite current collector is reduced, and the electrical property of the battery, especially the internal resistance and the multiplying power of the battery are improved. And the parameters of the pore structure, such as the pore diameter, the center distance between pores and the like, are further regulated and controlled, so that the polarizability of the porous composite current collector can be reduced on the basis of excellent mechanical strength. And the larger the pore size, the larger the number of pores also reduces the strength of the composite current collector.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A composite current collector, comprising a first metal layer, a second metal layer and a polymer material layer, wherein the polymer material layer is located between the first metal layer and the second metal layer, and the composite current collector has a via structure penetrating through the first metal layer, the second metal layer and the polymer material layer; the aperture of the through hole structure is 0.1 mm-1 mm, and the porosity is 0.1% -5%.
2. The composite current collector of claim 1, wherein the through-hole structure has a pore diameter of 0.5mm to 1mm and a porosity of 0.1% to 5%.
3. The composite collector of claim 1, wherein the composite collector has a thickness of 2 μ ι η to 28 μ ι η, wherein the first metal layer and the second metal layer may have a thickness of 0.5 μ ι η to 1.5 μ ι η, respectively, and the polymer material layer may have a thickness of 1 μ ι η to 25 μ ι η.
4. The composite current collector of any one of claims 1 to 3, wherein the polymer material layer is made of a material selected from a composite of an insulating polymer material and an inorganic non-conductive filler, a composite of an insulating polymer material and a conductive filler, an insulating polymer material or a conductive polymer material, wherein the mass percentage of the insulating polymer material in the composite of the insulating polymer material and the inorganic non-conductive filler is greater than or equal to 90%, and the mass percentage of the insulating polymer material in the composite of the insulating polymer material and the conductive filler is greater than or equal to 90%.
5. The composite current collector of claim 4, wherein the insulating polymer material is selected from one or more of cellulose and its derivatives, starch and its derivatives, proteins and its derivatives, polyvinyl alcohol and its crosslinked polymers, polyethylene glycol and its crosslinked polymers, polyamides, polyterephthalate, polyimides, polyethylene, polypropylene, polystyrene, polyvinyl chloride, aramid, polydiformyl phenylenediamine, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyterephthalamide, polypropylene, polyoxymethylene, epoxy resins, phenolic resins, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, and polycarbonate; and/or
The conductive polymer material is selected from doped sulfur nitride and/or doped polyacetylene; and/or
The inorganic non-conductive filler is selected from one or more of ceramic materials, glass materials and ceramic composite materials; and/or
The conductive filler is selected from one or more of carbon black, carbon nano tube, graphite, acetylene black, graphene, nickel, iron, copper, aluminum, alloy, nickel-coated graphite powder and nickel-coated carbon fiber.
6. A method for preparing a composite current collector as claimed in any one of claims 1 to 5, characterized in that it comprises the following steps:
and respectively forming the first metal layer and the second metal layer on two sides of the polymer material layer, and perforating and penetrating the polymer material layer, the first metal layer and the second metal layer according to the distribution principle of the through hole structures.
7. The method for preparing a composite current collector according to claim 6, wherein the plating method is vacuum evaporation and/or the hole drilling method is laser drilling;
optionally, the evaporation temperature of the plating material for vacuum evaporation is 600-1600 ℃, and the vacuum degree is less than 1 x 10 -2 Pa, the evaporation rate is 10 m/min-100 m/min;
optionally, the wavelength of the laser drilling is 400nm to 700nm.
8. A positive electrode comprising the composite current collector according to any one of claims 1 to 5 and a positive electrode active material layer on a surface of the composite current collector.
9. A battery comprising the positive electrode according to claim 8.
10. An electric device comprising the battery according to claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115832195A (en) * | 2022-11-03 | 2023-03-21 | 天津力神电池股份有限公司 | Porous composite foil, positive pole piece, negative pole piece, semi-solid lithium ion battery and preparation method |
| CN117199393A (en) * | 2023-11-08 | 2023-12-08 | 江苏正力新能电池技术有限公司 | Composite current collector, preparation method thereof, electrode plate and secondary ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115832195A (en) * | 2022-11-03 | 2023-03-21 | 天津力神电池股份有限公司 | Porous composite foil, positive pole piece, negative pole piece, semi-solid lithium ion battery and preparation method |
| CN117199393A (en) * | 2023-11-08 | 2023-12-08 | 江苏正力新能电池技术有限公司 | Composite current collector, preparation method thereof, electrode plate and secondary ion battery |
| CN117199393B (en) * | 2023-11-08 | 2024-01-30 | 江苏正力新能电池技术有限公司 | Composite current collector, preparation method thereof, electrode plate and secondary ion battery |
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