CN114899356A - Composite current collector, preparation method, electrode plate, battery and electronic equipment - Google Patents
Composite current collector, preparation method, electrode plate, battery and electronic equipment Download PDFInfo
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- CN114899356A CN114899356A CN202210764184.3A CN202210764184A CN114899356A CN 114899356 A CN114899356 A CN 114899356A CN 202210764184 A CN202210764184 A CN 202210764184A CN 114899356 A CN114899356 A CN 114899356A
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- 239000002131 composite material Substances 0.000 title claims abstract description 154
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000012779 reinforcing material Substances 0.000 claims abstract description 31
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 47
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 28
- 239000002041 carbon nanotube Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 20
- -1 polyethylene terephthalate Polymers 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 238000001771 vacuum deposition Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 50
- 239000000203 mixture Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229920000307 polymer substrate Polymers 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to a composite current collector, a preparation method, an electrode plate, a battery and electronic equipment, and belongs to the technical field of energy storage. The invention provides a composite current collector, which comprises an enhanced composite film and a conductive layer, wherein the conductive layer is formed on at least one surface of the enhanced composite film by a physical vapor deposition method; the reinforced composite film comprises the following raw materials in parts by weight: 0.1-5 parts of heat conduction reinforcing material, 0.01-1 part of coupling agent and 95-100 parts of organic supporting material. The added heat-conducting reinforcing material promotes the enhanced composite film to have better temperature resistance and mechanical property, the enhanced composite film is not easy to deform when a metal conducting layer is plated on the surface of the enhanced composite film in vacuum by using a physical vapor deposition method, the processing property of the enhanced composite film is improved, the safety of a battery is ensured, and the added heat-conducting reinforcing material improves the electrical conductivity and the thermal conductivity of the composite current collector, so that the welding efficiency of the lug is improved.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to a composite current collector, a preparation method, an electrode plate, a battery and electronic equipment.
Background
Electrochemical devices, such as lithium ion batteries, have been applied in large scale in the fields of consumer electronics, electric vehicles, etc., and the market places higher demands on the energy density, cycle life, safety in use, etc. of the electrochemical devices.
The current collector is used for supporting the active material layer, and can collect and output current generated by the active material layer, so that the current collector has an important influence on the performance of the electrochemical device. The composite current collector is a novel current collector material, is made of metal plated on two sides of a polymer substrate layer, is of a sandwich structure, has the weight reduced by 50% -80% compared with a pure metal current collector, and meanwhile, has the thickness greatly reduced relative to the pure metal current collector, so that more spaces in an electrochemical device can be given to active substances, and the energy density of the electrochemical device is improved. And the polymer base material layer in the composite current collector can reduce the temperature rise of the electrochemical device, reduce the risk of thermal runaway and improve the safety of the electrochemical device.
However, the vacuum physical vapor deposition method has high requirements on equipment, and high temperature is accompanied in the process of preparing the composite current collector, and the polymer substrate layer is easy to deform, wrinkle, bubble, perforate, become brittle and the like at high temperature, so a series of problems are brought to the processing of the composite current collector, and in addition, the existence of the polymer substrate layer also causes the welding efficiency of the composite current collector to be low.
Disclosure of Invention
The invention aims to provide a composite current collector, a preparation method, an electrode plate, a battery and electronic equipment, and aims to solve the problem that when a conductive layer of the composite current collector is formed by using a physical vapor deposition method, an enhanced composite film is affected by high temperature and is not beneficial to processing of the composite current collector.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect of the present invention, a composite current collector is provided, the composite current collector comprising a reinforced composite film and a conductive layer; at least one surface of the reinforced composite film is provided with the conductive layer by a physical vapor deposition method;
the reinforced composite film comprises the following raw materials in parts by weight: 0.1-5 parts of heat conduction reinforcing material, 0.01-1 part of coupling agent and 95-100 parts of organic supporting material.
In some embodiments, the thermally conductive reinforcing material is selected from, but not limited to, one or more of carbon nanotubes, carbon fibers, graphite, and graphene.
In some embodiments, the coupling agent is selected from, but not limited to, one or more of a silane coupling agent and a titanate coupling agent;
and/or the organic support material is selected from one or more of, but not limited to, polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyimide, polyvinyl chloride, polystyrene, derivatives thereof, and copolymers thereof.
In some embodiments, the thermally conductive reinforcing material and the organic support material are dried under vacuum at 60-120 ℃ for 4-8 hours before processing.
In some embodiments, the physical vapor deposition process is a magnetron sputtering process or a vacuum evaporation process.
In another aspect of the present invention, a method for preparing the composite current collector is provided, which includes the following steps:
s1, preparing the enhanced composite film;
and S2, forming a conducting layer on at least one surface of the enhanced composite film through a physical vapor deposition method to obtain the composite current collector.
In some embodiments, the reinforced composite film is prepared according to the following method: and pre-mixing and stirring the heat conduction reinforcing material and the coupling agent, mixing the heat conduction reinforcing material and the coupling agent with the organic supporting material, and performing melt extrusion and stretching to form a film to obtain the enhanced composite film.
In another aspect of the present invention, an electrode plate is provided, wherein the electrode plate comprises the composite current collector or the composite current collector prepared by the preparation method; and
an active material layer disposed on a surface and/or within pores of the conductive layer of the composite current collector.
In another aspect of the present invention, a battery is provided, where the battery includes a positive electrode plate, a negative electrode plate, a diaphragm and an electrolyte, and the positive electrode plate and/or the negative electrode plate is the above electrode plate.
In another aspect of the invention, an electronic device is provided, which includes the above battery.
Compared with the prior art, the invention has the following advantages:
(1) the enhanced composite film is promoted to have better temperature resistance and mechanical property by adding the heat conduction enhanced material, and the metal conducting layer is not easy to deform when being vacuum-plated on the surface of the enhanced composite film by using a physical vapor deposition method, so that the processing property is improved, and the safety of the battery is ensured.
(2) The addition of the heat conduction reinforcing material improves the electrical conductivity and the heat conductivity of the composite current collector, and further improves the welding efficiency of the tab.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect of the present invention, a composite current collector is provided, the composite current collector comprising a reinforced composite film and a conductive layer; at least one surface of the reinforced composite film is provided with the conductive layer by a physical vapor deposition method;
the reinforced composite film comprises the following raw materials in parts by weight: 0.1-5 parts of heat conduction reinforcing material, 0.01-1 part of coupling agent and 95-100 parts of organic supporting material;
the heat conduction reinforcing material is selected from one or more of carbon nano tubes, carbon fibers, graphite and graphene.
The energy density, safety and stability of the lithium ion battery are always subjected to the following problems, and the improvement of a current collector and the search for a high-capacity lithium ion battery anode and cathode material are important research directions for improving the energy density of the lithium ion battery at present. The traditional current collector is made of pure metal materials, and the weight of the traditional current collector can reach 15% or even higher in the lithium ion battery. The composite current collector is made of the metal-plated layer on the surface of the polymer base material layer, and compared with the traditional metal current collector, the weight of the composite current collector is greatly reduced, the thickness of the composite current collector can be reduced, the space in the lithium ion battery is saved, and the composite current collector gives way to active substances, so that the energy density of the lithium ion battery is improved.
Aluminum foil and copper foil are commonly used current collectors, wherein the aluminum foil serves as the positive current collector and the copper foil serves as the negative current collector. The traditional composite current collector adopts a physical vapor deposition method to form a conducting layer on the surface of a polymer substrate layer, wherein the conducting layer adopts metal materials such as aluminum, copper and the like.
Although aluminum, copper, nickel and chromium have good electrical conductivity and are suitable for preparing a composite current collector, the boiling point of aluminum is as high as 2327 ℃, the boiling point of copper is as high as 2562 ℃, the boiling point of nickel is as high as 2730 ℃ and the boiling point of chromium is as high as 2761 ℃. When the vacuum physical vapor deposition method is used for plating the conducting layer on the surface of the polymer base material layer, the requirement on the temperature resistance of equipment and the polymer base material layer is high. Because in the physical vapor deposition process, gaseous atoms of metals such as aluminum, copper, nickel and chromium contact with the polymer substrate layer, the temperature of the polymer substrate layer can be inevitably increased, and the polymer substrate layer has the problems of wrinkling, bubble channeling, perforation, embrittlement and the like, and is not beneficial to the processing of the composite current collector.
The enhanced composite film is prepared by taking the heat-conducting reinforcing material, the coupling agent and the organic supporting material as raw materials, the selected heat-conducting reinforcing material is one or more of carbon nano tubes, carbon fibers, graphite and graphene, the carbon nano tubes, the carbon fibers, the graphite and the graphene have excellent heat-conducting, electric-conducting and mechanical properties, the enhanced composite film is prepared by combining the carbon nano tubes, the carbon fibers, the graphite and the graphene with the organic supporting material, the electric conductivity, the heat-conducting property and the strength of the enhanced composite film can be improved, and the problems that the performance of the enhanced composite film is influenced and the processing of a composite current collector is not facilitated under the condition of high temperature are solved. The inventor finds that when the adding amount of the heat conduction reinforcing material is less, the strength, the electric conductivity and the heat conductivity of the reinforced composite film of the composite current collector are insufficient, the problems of deformation, wrinkling, bubble channeling, perforation, embrittlement and the like are still generated, and the processing of the composite current collector is not facilitated, and when the adding amount of the heat conduction reinforcing material is more, the cost is increased firstly, and secondly, the tensile strength of the reinforced composite film is reduced on the contrary because the heat conduction reinforcing material is agglomerated, and when the adding amount of the heat conduction reinforcing material is 0.1-5 parts, the performance of the reinforced composite film and the composite current collector is optimal.
Alternatively, in the reinforced composite film of the present invention, the thermally conductive reinforcing material may be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts, the coupling agent may be 0.01 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, and the organic support material may be 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts.
In some embodiments, the coupling agent is selected from, but not limited to, one or more of a silane coupling agent, a titanate coupling agent.
It is understood that the coupling agent used in the present invention is a silane coupling agent or a titanate coupling agent or a mixture of a silane coupling agent and a titanate coupling agent in any mass ratio, or the coupling agent used in the present invention is other coupling agents commonly used in the art to improve the adhesion strength between the thermal conductivity enhancing material of the present invention and the organic support material.
In some embodiments, the organic support material is selected from one or more of, but not limited to, polyethylene terephthalate (PET), Polyethylene (PE), polypropylene (PP), polyamide, polyimide, polyvinyl chloride (PVC), Polystyrene (PS), derivatives thereof, and copolymers thereof.
It can be understood that the organic support material of the present invention is one of polyethylene terephthalate (PET), Polyethylene (PE), polypropylene (PP), Polyamide (PA), Polyimide (PI), polyvinyl chloride (PVC), Polystyrene (PS), derivatives thereof and copolymers thereof, or a mixture of any several of polyethylene terephthalate (PET), Polyethylene (PE), polypropylene (PP), Polyamide (PA), Polyimide (PI), polyvinyl chloride (PVC), Polystyrene (PS), derivatives thereof and copolymers thereof, in any proportion, and the organic support material of the present invention may also be other polymers commonly used in the field of current collector compounding for preparing polymer substrates.
In some embodiments, the thermally conductive reinforcing material and the organic support material are dried under vacuum at 60-120 ℃ for 4-8 hours before processing.
Optionally, before the heat conduction reinforcing material and the organic supporting material are processed, the vacuum drying temperature can be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, and the vacuum drying time can be 4h, 5h, 6h, 7h or 8 h. According to the invention, the heat-conducting reinforcing material and the organic supporting material are subjected to vacuum drying before processing to remove moisture in the heat-conducting reinforcing material and the organic supporting material, so that the influence of the moisture on the melting process is avoided, and the performance of the reinforced composite film is further reduced.
In some embodiments, the physical vapor deposition method includes, but is not limited to, magnetron sputtering or vacuum evaporation.
The physical vapor deposition method is adopted in the invention to deposit the gasified metal material on the enhanced composite film to form the conducting layer, so that other physical vapor deposition methods such as a magnetron sputtering method or a vacuum evaporation method and the like which can form the conducting layer on the surface of the enhanced composite film by the metal material can be adopted besides the magnetron sputtering method or the vacuum evaporation method.
In another aspect of the present invention, a method for preparing the composite current collector is provided, which includes the following steps:
s1, preparing the enhanced composite film;
and S2, forming a conducting layer on at least one surface of the enhanced composite film through a physical vapor deposition method to obtain the composite current collector.
In some embodiments, the reinforced composite film is prepared according to the following method: and pre-mixing and stirring the heat conduction reinforcing material and the coupling agent, mixing the heat conduction reinforcing material and the coupling agent with the organic supporting material, and performing melt extrusion and stretching to form a film to obtain the enhanced composite film.
In another aspect of the present invention, an electrode plate is provided, wherein the electrode plate comprises the composite current collector or the composite current collector prepared by the preparation method; and
an active material layer disposed on a surface and/or within pores of the conductive layer of the composite current collector.
In another aspect of the present invention, a battery is provided, where the battery includes a positive electrode plate, a negative electrode plate, a diaphragm and an electrolyte, and the positive electrode plate and/or the negative electrode plate is the above electrode plate.
In some embodiments, the conductive layer of the composite current collector of the present invention may be made of aluminum, and the positive active material such as lithium iron phosphate, lithium cobaltate or lithium nickel cobalt manganese oxide, is mixed with a conductive agent, a binder and a solvent, and then coated on the conductive layer of the composite current collector of the present invention to serve as a positive electrode plate for a lithium ion battery; or the conducting layer of the composite current collector can be a copper material, and negative active materials such as graphite, soft carbon or silicon carbon and the like are mixed with a conductive agent, a binder and a solvent and then coated on the conducting layer of the composite current collector to serve as a negative pole piece for a lithium ion battery; the composite current collector can also be applied to other electrochemical devices such as lithium metal batteries and the like.
In another aspect of the invention, an electronic device is provided, which includes the above battery.
The present invention will be described in further detail with reference to specific examples and comparative examples. Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer. It is understood that the following examples are specific to the particular apparatus and materials used, and in other embodiments, are not limited thereto; the weight of the related components mentioned in the embodiments of the present specification may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the embodiments of the present specification according to the present specification. Specifically, the weight described in the description of the embodiment of the present invention may be a mass unit known in the chemical engineering field such as μ g, mg, g, kg, etc.
Example 1
The preparation method of the composite current collector comprises the following steps:
s1, drying 0.1kg of carbon nano tubes and 99.9kg of PET particles at 120 ℃ for 4 hours in vacuum, then adding 0.01kg of silane coupling agent KH550 into the dried 0.1kg of carbon nano tubes, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and dried 99.9kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to obtain a reinforced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
In step S2, the physical vapor deposition method specifically includes: and (4) heating and evaporating the metal aluminum by a vacuum evaporation method, and depositing the metal aluminum on the surface of the reinforced composite film obtained in the step (S1) to form a conductive layer.
Example 2
The preparation method of the composite current collector comprises the following steps:
s1, vacuum drying 0.1kg of carbon nano tube, 0.2kg of graphene and 99.7kg of PET particles at 120 ℃ for 6 hours, then adding 0.02kg of silane coupling agent KH550 into the dried 0.1kg of carbon nano tube and 0.2kg of graphene, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and dried 99.7kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to obtain a reinforced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Example 3
The preparation method of the composite current collector comprises the following steps:
s1, vacuum drying 0.2kg of carbon nano tube, 0.4kg of graphene and 99.4kg of PET particles at 120 ℃ for 4 hours, then adding 0.06kg of silane coupling agent KH560 into the dried 0.2kg of carbon nano tube and 0.4kg of graphene, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and dried 99.4kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to obtain a reinforced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Example 4
The preparation method of the composite current collector comprises the following steps:
s1, drying 1kg of carbon nano tubes and 98.9kg of PET particles at 120 ℃ in vacuum for 6h, then adding 0.1kg of silane coupling agent KH550 into the dried 1kg of carbon nano tubes, and mixing and stirring to obtain a uniform mixture. Uniformly mixing and stirring the mixture and the dried 98.9kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to prepare an enhanced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1.5 mu m on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Example 5
The preparation method of the composite current collector comprises the following steps:
s1, drying 1kg of carbon nano tube, 1kg of graphite and 97.8kg of PET particles at 120 ℃ in vacuum for 6 hours, then adding 0.2kg of silane coupling agent KH550 into the dried 1kg of carbon nano tube and 1kg of graphite, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and dried 97.8kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to prepare an enhanced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Example 6
The preparation method of the composite current collector comprises the following steps:
s1, drying 5kg of carbon nano tubes and 95kg of PET particles at 60 ℃ in vacuum for 8h, then adding 1kg of silane coupling agent KH560 into the dried 5kg of carbon nano tubes, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and the dried 95kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to obtain a reinforced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Example 7
The preparation method of the composite current collector comprises the following steps:
s1, drying 5kg of carbon fibers and 100kg of PET particles at 90 ℃ for 7h in vacuum, adding 1kg of silane coupling agent KH560 into the dried 5kg of carbon fibers, and mixing and stirring to obtain a uniform mixture; uniformly mixing and stirring the mixture and the dried 100kg of PET particles, and extruding and stretching the mixture into a film by using a double-screw extruder to obtain a reinforced composite film with the thickness of 8 mu m;
and S2, forming conductive layers of 1 micron on two surfaces of the enhanced composite film respectively through a physical vapor deposition method to obtain a composite current collector, wherein the conductive layers are made of aluminum.
Comparative example 1
The preparation method of the composite current collector is specifically the same as that of example 1, and only differs from that of example 1 in that: in step S1, 100kg of PET particles are dried in vacuum at 120 ℃ for 4h, and extruded and stretched into a film by using a twin-screw extruder to prepare a reinforced composite film with the thickness of 8 μm.
Comparative example 2
The preparation method of the composite current collector is specifically the same as that in example 2, and only differs from that in the following steps: in step S1, 100kg of PET particles are dried in vacuum at 120 ℃ for 6h, and extruded and stretched into a film by using a twin-screw extruder to prepare a reinforced composite film with the thickness of 8 μm.
Comparative example 3
The preparation method of the composite current collector is specifically the same as that in example 2, and only differs from that in the following steps: in step S1, 100kg of PET particles are dried in vacuum at 120 ℃ for 4h, and extruded and stretched into a film by using a twin-screw extruder to prepare a reinforced composite film with the thickness of 8 μm.
Comparative example 4
The method of preparing a composite current collector was the same as example 4 except that 1kg of carbon nanotubes and 98.9kg of PET particles were replaced with 0.08kg of carbon nanotubes and 99.82kg of PET particles.
Comparative example 5
The method of preparing a composite current collector was the same as in example 4 except that 1kg of carbon nanotubes and 98.9kg of PET particles were replaced with 6kg of carbon nanotubes and 93.9kg of PET particles.
Test example 1 Performance test of reinforced composite film
The reinforced composite films prepared in examples 1 to 7 and comparative examples 1 to 5 were subjected to tensile strength, initial decomposition temperature and surface resistance tests in the following manner, and the test results are shown in table 1.
(1) Tensile strength: the tensile speed was 50mm/min, 5 pieces were sampled per sample, and the average value was taken as the test result. During measurement, the length direction of the sample is parallel to the axis of the clamp, and the sample is kept linear, so that the sample is pulled in the jaw of the clamp; the sample edge is notched, and the experimental result is invalid.
(2) Initial decomposition temperature: the mass of the sample is 3-4mg, the heating temperature range is from room temperature to 600 ℃, the working atmosphere is nitrogen, and the heating rate is set to be 10 ℃/min.
(3) Surface resistance: the front and back sheet resistances of the samples were measured using a four-probe tester.
Table 1 performance test results of reinforced composite films
Compared with comparative examples 1-3, the reinforced composite films prepared in examples 1-7 have higher tensile strength, higher initial decomposition temperature and relatively lower surface resistance, and the heat conduction reinforcing materials added in examples 1-5 can enhance the processing performance of the composite current collector, as can be seen from table 1 above;
the carbon nano tube in the reinforced composite film prepared in the comparative example 4 is 0.08kg, the carbon nano tube in the reinforced composite film prepared in the comparative example 5 is 6kg, and the carbon nano tube in the reinforced composite film prepared in the example 4 is 1 kg; compared with example 4, the reinforced composite film of comparative example 5 has lower tensile strength and lower initial decomposition temperature, because the carbon nanotubes are added in a larger amount in comparative example 5, which causes the carbon nanotubes to agglomerate, and is not beneficial to improving the mechanical property and the thermal conductivity.
Test example 2 Performance test of composite Current collector
The composite current collectors prepared in examples 1 to 7 and comparative examples 1 to 5 were subjected to tab welding speed testing according to the following method, and the test results are shown in table 2.
Testing the tab welding speed: and welding the single-layer composite current collector with a tab foil, and testing the tab welding speed under the conditions of ultrasonic frequency of 20KHz, amplitude of 20 microns and pressure of 400 kPa.
Table 2 performance test results of composite current collectors
The physical vapor deposition methods used for the composite current collectors prepared in examples 1 to 7 and comparative examples 1 to 5 were the same. As can be seen from table 2, the composite current collectors prepared in examples 1 to 7 have the heat conduction reinforcing material added thereto, and the tab welding speed is significantly increased compared with those of comparative examples 1 to 3, which indicates that the heat conduction reinforcing material added to the composite current collector can significantly improve the tab welding efficiency. Compared with example 1, the composite current collector of comparative example 4 has lower welding efficiency, because the addition amount of the carbon nanotubes in the composite current collector of comparative example 4 is less, and the conductivity of the composite current collector is not greatly improved.
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 various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A composite current collector is characterized by comprising a reinforced composite film and a conductive layer, wherein the conductive layer is formed on at least one surface of the reinforced composite film through a physical vapor deposition method;
the reinforced composite film comprises the following raw materials in parts by weight: 0.1-5 parts of heat conduction reinforcing material, 0.01-1 part of coupling agent and 95-100 parts of organic supporting material.
2. The composite current collector of claim 1, wherein the thermally conductive reinforcing material comprises one or more of carbon nanotubes, carbon fibers, graphite, and graphene.
3. The composite current collector of claim 1 or 2, wherein the coupling agent comprises one or more of a silane coupling agent and a titanate coupling agent;
and/or the organic support material comprises one or more of polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyimide, polyvinyl chloride, polystyrene, derivatives thereof, and copolymers thereof.
4. The composite current collector of claim 1, wherein the thermal conductivity enhancement material and the organic support material are vacuum dried at 60-120 ℃ for 4-8 hours before processing.
5. The composite current collector of any one of claims 1 to 2 and 4, wherein the physical vapor deposition method is a magnetron sputtering method or a vacuum evaporation method.
6. The method for preparing a composite current collector as claimed in any one of claims 1 to 5, comprising the steps of:
s1, preparing the enhanced composite film;
and S2, forming a conducting layer on at least one surface of the enhanced composite film through a physical vapor deposition method to obtain the composite current collector.
7. The method for preparing a composite current collector as claimed in claim 6, wherein the reinforced composite film is prepared according to the following method: and pre-mixing and stirring the heat conduction reinforcing material and the coupling agent, mixing the heat conduction reinforcing material and the coupling agent with the organic supporting material, and performing melt extrusion and stretching to form a film to obtain the enhanced composite film.
8. An electrode piece, characterized in that the electrode piece comprises the composite current collector of any one of claims 1 to 5 or the composite current collector prepared by the preparation method of any one of claims 6 to 7; and
an active material layer disposed on a surface and/or within pores of the conductive layer of the composite current collector.
9. A battery, characterized in that, the battery includes positive pole piece, negative pole piece, diaphragm and electrolyte, the positive pole piece and/or the negative pole piece adopts the electrode pole piece of claim 8.
10. An electronic device characterized by comprising the battery of claim 9.
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| CN202210764184.3A CN114899356A (en) | 2022-06-30 | 2022-06-30 | Composite current collector, preparation method, electrode plate, battery and electronic equipment |
| PCT/CN2022/116771 WO2024000802A1 (en) | 2022-06-30 | 2022-09-02 | Composite current collector and preparation method therefor, electrode plate, battery, and electronic device |
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