WO2024000802A1 - 一种复合集流体、制备方法、电极极片、电池和电子设备 - Google Patents
一种复合集流体、制备方法、电极极片、电池和电子设备 Download PDFInfo
- Publication number
- WO2024000802A1 WO2024000802A1 PCT/CN2022/116771 CN2022116771W WO2024000802A1 WO 2024000802 A1 WO2024000802 A1 WO 2024000802A1 CN 2022116771 W CN2022116771 W CN 2022116771W WO 2024000802 A1 WO2024000802 A1 WO 2024000802A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- current collector
- composite current
- reinforced composite
- conductive layer
- composite
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000012779 reinforcing material Substances 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 44
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 29
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 29
- 239000002041 carbon nanotube Substances 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 27
- -1 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000003466 welding Methods 0.000 abstract description 10
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 6
- 239000010410 layer Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000203 mixture Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 229920000307 polymer substrate Polymers 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 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
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium 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
Definitions
- the present invention relates to the field of energy storage technology, and in particular to a composite current collector, a preparation method, an electrode pole piece, a battery and an electronic device.
- Electrochemical devices such as lithium-ion batteries have been widely used in consumer electronics, electric vehicles and other fields.
- the market has put forward higher requirements for the energy density, cycle life, safety and other performance of electrochemical devices.
- the current collector is used to carry the active material layer and can collect the current generated by the active material layer and output it. Therefore, the current collector has an important influence on the performance of the electrochemical device.
- Composite current collector is a new type of current collector material. It is made of a polymer substrate layer plated with metal on both sides and has a "sandwich structure". Its weight is 50%-80% lower than that of a pure metal current collector. At the same time, its thickness is also lower than that of a pure metal current collector. The metal current collector is greatly reduced, which allows more space in the electrochemical device to be given to active materials and increases the energy density of the electrochemical device. Moreover, the polymer substrate 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.
- the vacuum physical vapor deposition method has high requirements on equipment, and the process of preparing composite current collectors is accompanied by high temperatures. Since the polymer substrate layer is easily deformed, wrinkled, bubbled, perforated, brittle, etc. at high temperatures, it causes problems. The processing of composite current collectors brings a series of problems. In addition, the existence of the polymer substrate layer also makes the welding efficiency of composite current collectors low.
- the object of the present invention is to provide a composite current collector, a preparation method, an electrode pole piece, a battery and an electronic device, so as to solve the problem that when the conductive layer of a composite current collector is formed by physical vapor deposition, the reinforced composite film is affected by high temperature and is not conducive to Problems in composite current collector processing.
- One aspect of the present invention provides a composite current collector, which includes a reinforced composite film and a conductive layer; at least one surface of the reinforced composite film is formed with the conductive layer by a physical vapor deposition method;
- the reinforced composite film includes the following raw materials in parts by weight: 0.1-5 parts of thermally conductive reinforcing materials, 0.01-1 parts of coupling agent and 95-100 parts of organic support materials.
- the thermally conductive enhancement material is selected from one or more of, but not limited to, carbon nanotubes, carbon fibers, graphite and graphene.
- the coupling agent is selected from but not limited to one or more of silane coupling agents and titanate coupling agents;
- the organic support material is selected from but not limited to polyethylene terephthalate, polyethylene, polypropylene, polyamide, polyimide, polyvinyl chloride, polystyrene, and their derivatives and one or more of their copolymers.
- the thermal conductivity enhancement material and the organic support material are vacuum dried at 60-120°C for 4-8 hours before processing.
- the physical vapor deposition method is magnetron sputtering or vacuum evaporation.
- Another aspect of the present invention provides a method for preparing the above-mentioned composite current collector, which includes the following steps:
- the reinforced composite film is prepared according to the following method: the thermally conductive reinforcing material and the coupling agent are mixed and stirred in advance, then mixed with the organic support material, melted, extruded and stretched into film to obtain the enhanced composite film.
- an electrode piece is provided, which electrode piece includes the above-mentioned composite current collector or the composite current collector produced by the above-mentioned preparation method;
- An active material layer is provided on the surface and/or in the pores of the conductive layer of the composite current collector.
- a battery in another aspect of the present invention, includes a positive electrode piece, a negative electrode piece, a separator and an electrolyte.
- the positive electrode piece and/or the negative electrode piece is the above-mentioned electrode piece.
- Another aspect of the present invention provides an electronic device, including the above-mentioned battery.
- the present invention has the following advantages:
- the thermally conductive reinforcing materials added to the above-mentioned enhanced composite film make it have better temperature resistance and mechanical properties, and the physical vapor deposition method is used to prevent deformation when the metal conductive layer is vacuum-plated on the surface, improving the processing performance. , while ensuring the safety of the battery.
- thermal conductivity enhancement materials improves the electrical conductivity and thermal conductivity of the composite current collector, thereby improving the welding efficiency of the tab.
- One aspect of the present invention provides a composite current collector, which includes a reinforced composite film and a conductive layer; at least one surface of the reinforced composite film is formed with the conductive layer by physical vapor deposition;
- the reinforced composite film includes the following raw materials in parts by weight: 0.1-5 parts of thermally conductive reinforcing materials, 0.01-1 parts of coupling agent and 95-100 parts of organic support materials;
- the thermally conductive reinforcing material is selected from, but is not limited to, one or more of carbon nanotubes, carbon fibers, graphite, and graphene.
- the energy density, safety and stability of lithium-ion batteries have always been criticized. Improving current collectors and finding high-capacity positive and negative electrode materials for lithium-ion batteries are currently important research directions to improve the energy density of lithium-ion batteries.
- Traditional current collectors are made of pure metal, and their weight can account for 15% or more of the lithium-ion battery.
- the composite current collector is made of a polymer substrate layer coated with a metal layer on the surface. Compared with the traditional metal current collector, the weight of the composite current collector is greatly reduced. At the same time, the thickness of the composite current collector can be reduced, saving space in the lithium-ion battery. Giving it up to active materials increases the energy density of lithium-ion batteries.
- Aluminum foil and copper foil are commonly used current collectors, with aluminum foil serving as the positive current collector and copper foil serving as the negative current collector.
- Traditional composite current collectors use physical vapor deposition to form a conductive layer on the surface of the polymer substrate layer.
- the conductive layer uses metal materials such as aluminum and copper.
- the boiling points of aluminum are as high as 2327°C, that of copper is as high as 2562°C, that of nickel is as high as 2730°C, and that of chromium is as high as 2761°C.
- the vacuum physical vapor deposition method to plate a conductive layer on the surface of a polymer substrate layer, there are higher requirements for the temperature resistance of the equipment and the polymer substrate layer.
- the present invention uses thermally conductive reinforcing materials, coupling agents and organic support materials as raw materials to prepare enhanced composite films.
- the selected thermally conductive reinforcing materials are one or more of carbon nanotubes, carbon fibers, graphite and graphene. Carbon nanotubes, Carbon fiber, graphite and graphene have excellent thermal conductivity, electrical conductivity and mechanical properties. Combining them with organic support materials to prepare reinforced composite films can improve the electrical conductivity, thermal conductivity and strength of the reinforced composite films and avoid high temperature
- the conductive layer of the present invention is made of aluminum, copper, nickel, chromium, titanium, silver and other metals.
- the thermally conductive reinforcing material can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts or 5 parts
- the coupling agent can be 0.01 part, 0.1 part, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part
- the organic support material can be 95 parts, 96 parts, 97 parts, 98 parts, 99 parts or 100 parts.
- the coupling agent is selected from, but is not limited to, one or more of silane coupling agents and titanate coupling agents.
- 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.
- the coupling agent can be other commonly used coupling agents in this technical field that can improve the bonding strength between the thermally conductive reinforcing material of the present invention and the organic support material.
- the organic support material is selected from, but is not limited to, polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide, polyimide, poly One or more of vinyl chloride (PVC), polystyrene (PS), their derivatives and their copolymers.
- PET polyethylene terephthalate
- PE polyethylene
- PP polypropylene
- polyamide polyamide
- polyimide poly One or more of vinyl chloride (PVC), polystyrene (PS), their derivatives and their copolymers.
- PVC vinyl chloride
- PS polystyrene
- the organic support material of the present invention is polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyamide (PA), polyimide (PI) , one of polyvinyl chloride (PVC), polystyrene (PS), their derivatives and their copolymers, or polyethylene terephthalate (PET), polyethylene (PE) , polypropylene (PP), polyamide (PA), polyimide (PI), polyvinyl chloride (PVC), polystyrene (PS), any of their derivatives and their copolymers according to any
- the organic support material of the present invention can also be used to prepare other polymers commonly used in the field of composite current collectors to prepare polymer substrates.
- the thermal conductivity enhancement material and the organic support material are vacuum dried at 60-120°C for 4-8 hours before processing.
- the vacuum drying temperature can be 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105 °C, 110°C, 115°C or 120°C
- the vacuum drying time can be 4h, 5h, 6h, 7h or 8h.
- the thermally conductive reinforcing material and the organic support material are vacuum-dried before processing to remove moisture, so as to avoid the influence of moisture on the melting process and thereby reduce the performance of the reinforced composite film.
- the physical vapor deposition method includes but is not limited to magnetron sputtering or vacuum evaporation.
- the present invention adopts the physical vapor deposition method in order to deposit the vaporized metal material on the reinforced composite film to form a conductive layer. Therefore, in addition to the magnetron sputtering method or vacuum evaporation method, molecular beam epitaxy, etc. can also be used to form a conductive layer. Other physical vapor deposition methods in which metal materials form conductive layers on the surface of reinforced composite films.
- Another aspect of the present invention provides a method for preparing the above-mentioned composite current collector, which includes the following steps:
- the reinforced composite film is prepared according to the following method: the thermally conductive reinforcing material and the coupling agent are mixed and stirred in advance, then mixed with the organic support material, melted, extruded and stretched into film to obtain the enhanced composite film.
- an electrode piece is provided, which electrode piece includes the above-mentioned composite current collector or the composite current collector produced by the above-mentioned preparation method;
- An active material layer is provided on the surface and/or in the pores of the conductive layer of the composite current collector.
- a battery in another aspect of the present invention, includes a positive electrode piece, a negative electrode piece, a separator and an electrolyte.
- the positive electrode piece and/or the negative electrode piece is the above-mentioned electrode piece.
- the conductive layer of the composite current collector of the present invention can be made of aluminum.
- the positive electrode active material such as lithium iron phosphate, lithium cobalt oxide or lithium nickel cobalt manganate is mixed with a conductive agent, a binder and a solvent. Coated on the conductive layer of the composite current collector of the present invention, it can be used as a positive electrode in a lithium-ion battery; or the conductive layer of the composite current collector of the present invention can be made of copper, and graphite, soft carbon or silicon carbon can be used as negative electrode active material.
- the substance 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 as a negative electrode plate for use in lithium ion batteries; the composite current collector of the present invention can also be applied to lithium metal batteries and other electrochemical devices.
- Another aspect of the present invention provides an electronic device, including the above-mentioned battery.
- the weight described in the description of the embodiments of the present invention may be mass units well known in the field of chemical engineering such as ⁇ g, mg, g, kg, etc.
- the preparation method of composite current collector includes the following steps:
- step S2 the specific steps of the physical vapor deposition method are: heating and evaporating the metal aluminum through a vacuum evaporation method, so that it is deposited on the surface of the enhanced composite film obtained in step S1 to form a conductive layer.
- the preparation method of composite current collector includes the following steps:
- the preparation method of composite current collector includes the following steps:
- the preparation method of composite current collector includes the following steps:
- the preparation method of composite current collector includes the following steps:
- the preparation method of composite current collector includes the following steps:
- the preparation method of composite current collector includes the following steps:
- the preparation method of the composite current collector is specifically the same as in Example 1. The only difference is that in step S1, 100kg PET particles are vacuum-dried at 120°C for 4 hours, and extruded and stretched into a film using a twin-screw extruder to prepare a reinforcement with a thickness of 8 ⁇ m. type composite film.
- step S1 The preparation method of the composite current collector is the same as that of Example 2. The only difference is that in step S1, 100kg PET particles are vacuum dried at 120°C for 6 hours, and then extruded and stretched into a film using a twin-screw extruder to prepare a reinforcement with a thickness of 8 ⁇ m. type composite film.
- step S1 The preparation method of the composite current collector is the same as in Example 2. The only difference is that in step S1, 100kg PET particles are vacuum dried at 120°C for 4 hours, and then extruded and stretched into a film using a twin-screw extruder to prepare a reinforced film with a thickness of 8 ⁇ m. type composite film.
- the preparation method of the composite current collector is the same as in Example 4. The only difference is that 1kg carbon nanotubes and 98.9kg PET particles are replaced by 0.08kg carbon nanotubes and 99.82kg PET particles.
- the preparation method of the composite current collector is the same as in Example 4. The only difference is that 1kg carbon nanotubes and 98.9kg PET particles are replaced by 6kg carbon nanotubes and 93.9kg PET particles.
- Tensile strength The tensile speed is 50mm/min. Take 5 pieces of each sample and take the average value as the test result. When measuring, the length direction of the sample should be parallel to the axis of the clamp, and the sample should be kept straight so that the sample is pulled within the jaws of the clamp; if there is a gap on the edge of the sample, the experimental results will be invalid.
- Example 1 Group Tensile strength/MPa Initial decomposition temperature/°C Surface resistance/ ⁇ Example 1 227 409 1000 Example 2 245 411 312 Example 3 238 414 120 Example 4 237 417 160 Example 5 224 412 150 Example 6 189 410 110 Example 7 183 414 120
- Comparative example 1 199 403 >10 16 Comparative example 2 208 405 >10 16 Comparative example 3 202 402 >10 16 Comparative example 4 217 410 10 4 -10 6 Comparative example 5 152 419 100
- the reinforced composite films prepared in Examples 1 to 7 are added with thermal conductive reinforcing materials.
- the reinforced composite films prepared in Examples 1 to 5 have The tensile strength is large, the initial decomposition temperature is high, and the surface resistance is relatively low, indicating that the thermal conductive reinforcing materials added in Examples 1 to 5 can enhance the processing performance of the composite current collector;
- the carbon nanotubes in the enhanced composite film prepared in Comparative Example 4 are 0.08kg, the carbon nanotubes in the enhanced composite film prepared in Comparative Example 5 are 6kg, the carbon nanotubes in the enhanced composite film prepared in Example 4 are 1kg; and Compared with Example 4, the tensile strength of the reinforced composite film of Comparative Example 5 is smaller and the initial decomposition temperature is lower. This is because the addition amount of carbon nanotubes in Comparative Example 5 is relatively large, resulting in the agglomeration of carbon nanotubes and not Conducive to the improvement of mechanical properties and thermal conductivity.
- Tab welding speed test Weld the single-layer composite current collector to the tab foil, and perform the tab welding speed test under the conditions of ultrasonic frequency of 20KHz, amplitude of 20 ⁇ m, and pressure of 400kPa.
- Example 1 Group Tab welding speed/s Example 1 1
- Example 2 0.5
- Example 3 0.5
- Example 4 0.5
- Example 5 0.5
- Example 6 0.5
- Example 7 0.5 Comparative example 1 3 Comparative example 2 3 Comparative example 3 3 Comparative example 4 2 Comparative example 5 0.5
- the composite current collectors prepared in Examples 1 to 7 and Comparative Examples 1 to 5 adopt the same physical vapor deposition method.
- Table 2 compared with Comparative Examples 1 to 3, the composite current collectors prepared in Examples 1 to 7 have thermal conductive reinforcing materials added, and the tab welding speed is significantly faster, indicating that the thermal conductive reinforcing materials added to the composite current collector can significantly Improve the welding efficiency of the tab.
- the welding efficiency of the composite current collector of Comparative Example 4 is lower. This is because the added amount of carbon nanotubes in the composite current collector of Comparative Example 4 is less, and the conductivity of the composite current collector has not been significantly improved. promote.
Landscapes
- 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
本发明涉及一种复合集流体、制备方法、电极极片、电池和电子设备，属于储能技术领域。本发明提供了一种复合集流体，复合集流体包括增强型复合薄膜和导电层，增强型复合薄膜的至少一个表面通过物理气相沉积法形成有导电层；增强型复合薄膜按照重量份数计，包括以下原料：0.1-5份导热增强材料、0.01-1份偶联剂和95-100份有机支撑材料。本发明加入的导热增强材料促使增强型复合薄膜具有更好的耐温性和力学性能，利用物理气相沉积法在其表面真空镀金属导电层时不易发生变形，提升了增强型复合薄膜的加工性能，同时保证了电池的安全性，并且加入的导热增强材料提高了复合集流体的导电性和导热性，进而提升了极耳的焊接效率。
Description
本发明涉及储能技术领域，特别是涉及一种复合集流体、制备方法、电极极片、电池和电子设备。
电化学装置，例如锂离子电池，已经在消费电子、电动车等领域大规模应用，市场对电化学装置的能量密度、循环寿命、使用安全等性能提出了更高的要求。
集流体用于承载活性物质层，能够将活性物质层产生的电流汇集后向外输出，因此，集流体对于电化学装置的性能具有重要影响。复合集流体是一种新型的集流体材料，由高分子基材层两面镀金属制成，呈“三明治结构”，重量比纯金属集流体降低50％-80％，同时，厚度也相对于纯金属集流体有大幅减少，从而能够将电化学装置内更多的空间让渡给活性物质，提高了电化学装置的能量密度。且复合集流体中的高分子基材层可以减小电化学装置温升，降低热失控的发生风险，提高了电化学装置的安全性。
然而，真空物理气相沉积法对设备的要求高，并且制备复合集流体的过程中伴随着高温，由于高分子基材层在高温下容易变形、起皱、窜泡、穿孔、变脆等，给复合集流体的加工带来了一系列问题，另外，高分子基材层的存在也使得复合集流体的焊接效率较低。
发明内容
本发明的目的在于提供一种复合集流体、制备方法、电极极片、电池和电子设备，以解决利用物理气相沉积法形成复合集流体的导电层时，增强型复合薄膜受高温影响，不利于复合集流体加工的问题。
为实现上述目的，本发明采取以下技术方案：
本发明的一个方面，提供了一种复合集流体，所述复合集流体包括增强型 复合薄膜和导电层；所述增强型复合薄膜的至少一个表面通过物理气相沉积法形成有所述导电层；
所述增强型复合薄膜按照重量份数计，包括以下原料：0.1-5份导热增强材料、0.01-1份偶联剂和95-100份有机支撑材料。
在一些实施方式中，所述导热增强材料选自但不限于碳纳米管、碳纤维、石墨和石墨烯中的一种或多种。
在一些实施方式中，所述偶联剂选自但不限于硅烷偶联剂和钛酸酯偶联剂中的一种或多种；
和/或，所述有机支撑材料选自但不限于聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚氯乙烯、聚苯乙烯、它们的衍生物及它们的共聚物中的一种或多种。
在一些实施方式中，所述导热增强材料和所述有机支撑材料进行加工前，于60-120℃真空干燥4-8h。
在一些实施方式中，所述物理气相沉积法为磁控溅射法或真空蒸镀法。
本发明的另一个方面，提供了上述复合集流体的制备方法，包括以下步骤：
S1.制备所述增强型复合薄膜；
S2.在所述增强型复合薄膜的至少一个表面上通过物理气相沉积法形成导电层，得到所述复合集流体。
在一些实施方式中，所述增强型复合薄膜按照以下方法制备：将所述导热增强材料与所述偶联剂进行预先混合搅拌，再与所述有机支撑材料进行混合、熔融挤出拉伸成膜，得到所述增强型复合薄膜。
本发明的再一个方面，提供了一种电极极片，所述电极极片包括上述复合集流体或上述制备方法制得的复合集流体；及
活性物质层，所述活性物质层设置于所述复合集流体的导电层的表面上和/或孔隙内。
本发明的还一个方面，提供了一种电池，所述电池包括正极极片、负极极片、隔膜及电解液，所述正极极片和/或所述负极极片为上述电极极片。
本发明的又一个方面，提供了一种电子设备，包括上述电池。
与传统技术相比，本发明具有如下优点：
(1)上述增强型复合薄膜中加入的导热增强材料促使增其具有更好的耐温性和力学性能，利用物理气相沉积法在其表面真空镀金属导电层时不易发生变形，提升了加工性能，同时保证了电池的安全性。
(2)上述导热增强材料的添加提高了复合集流体的导电性和导热性，进而提升了极耳的焊接效率。
为了便于理解本发明，下面将结合具体的实施例对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本发明的一个方面，提供了一种复合集流体，所述复合集流体包括增强型复合薄膜和导电层；所述增强型复合薄膜的至少一个表面通过物理气相沉积法形成有所述导电层；
所述增强型复合薄膜按照重量份数计，包括以下原料：0.1-5份导热增强材料、0.01-1份偶联剂和95-100份有机支撑材料；
所述导热增强材料选自但不限于碳纳米管、碳纤维、石墨、石墨烯中的一种或多种。
锂离子电池的能量密度、安全性和稳定性一直饱受诟病，改进集流体、寻找高容量的锂离子电池正负极材料是目前提高锂离子电池的能量密度的重要研究方向。传统的集流体为纯金属材质，其重量在锂离子电池中占比可达15％甚至更高。复合集流体由高分子基材层表面镀金属层制成，相对于传统的金属集流体，复合集流体的重量大幅降低，同时可以减小复合集流体的厚度，节省锂 离子电池中的空间，将其让与活性物质，从而提高锂离子电池的能量密度。
铝箔和铜箔是常用的集流体，其中铝箔作为正极集流体，铜箔作为负极集流体。传统的复合集流体采用物理气相沉积法在高分子基材层表面形成导电层，其中，导电层采用铝、铜等金属材料。
虽然铝、铜、镍和铬的导电性较好，适合制备复合集流体，然而铝的沸点高达2327℃，铜的沸点高达2562℃，镍的沸点高达2730℃，铬的沸点高达2761℃。利用真空物理气相沉积法在高分子基材层表面镀导电层时，对设备和高分子基材层的耐温性的要求较高。由于在物理气相沉积过程中，铝、铜、镍和铬等金属的气态原子与高分子基材层接触，无法避免地会引起高分子基材层的温度升高，导致高分子基材层产生起皱、窜泡、穿孔、变脆等问题，不利于复合集流体的加工。
本发明以导热增强材料、偶联剂和有机支撑材料为原料制备增强型复合薄膜，选用的导热增强材料为碳纳米管、碳纤维、石墨和石墨烯中的一种或多种，碳纳米管、碳纤维、石墨和石墨烯具有优异的导热、导电和力学性能，将其与有机支撑材料共同制备增强型复合薄膜，可以提高增强型复合薄膜的导电性、导热性及强度，避免了温度较高的情况下影响增强型复合薄膜的性能及不利于复合集流体加工的问题，本发明的导电层采用铝、铜、镍、铬、钛和银等金属制成。发明人发现，当导热增强材料加入量较少时，复合集流体的增强型复合薄膜的强度、导电性和导热性不够，仍会产生变形、起皱、窜泡、穿孔、变脆等问题，不利于复合集流体的加工，而当导热增强材料加入量较多时，首先成本会增加，其次由于导热增强材料发生团聚，反而降低了增强型复合薄膜的拉伸强度，当导热增强材料为0.1-5份时，增强型复合薄膜和复合集流体的性能最优。
可选地，本发明的增强型复合薄膜中，导热增强材料可以为0.1份、0.5份、1份、2份、3份、4份或5份，偶联剂可以为0.01份、0.1份、0.2份、0.3份、0.4份、0.5份、0.6份、0.7份、0.8份、0.9份或1份，有机支撑材料可以为95份、96份、97份、98份、99份或100份。
在一些实施方式中，所述偶联剂选自但不限于硅烷偶联剂、钛酸酯偶联剂 中的一种或多种。
可以理解的是，本发明使用的偶联剂为硅烷偶联剂或钛酸酯偶联剂或硅烷偶联剂与钛酸酯偶联剂以任意质量比例的混合物，或者本发明使用的偶联剂为本技术领域常用的其他能够提高本发明导热增强材料与有机支撑材料的粘接强度的偶联剂即可。
在一些实施方式中，所述有机支撑材料选自但不限于聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺、聚酰亚胺、聚氯乙烯(PVC)、聚苯乙烯(PS)、它们的衍生物及它们的共聚物中的一种或多种。
可以理解的是，本发明的有机支撑材料为聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚酰亚胺(PI)、聚氯乙烯(PVC)、聚苯乙烯(PS)、它们的衍生物和它们的共聚物中的一种，也可以为聚对苯二甲酸乙二醇酯(PET)、聚乙烯(PE)、聚丙烯(PP)、聚酰胺(PA)、聚酰亚胺(PI)、聚氯乙烯(PVC)、聚苯乙烯(PS)、它们的衍生物和它们的共聚物中任意几种按照任意比例组成的混合物，本发明的有机支撑材料还可以为复合集流体领域制备高分子基材常用的其他聚合物。
在一些实施方式中，所述导热增强材料和所述有机支撑材料进行加工前，于60-120℃真空干燥4-8h。
可选地，导热增强材料和所述有机支撑材料进行加工前，真空干燥温度可以为60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃或120℃，真空干燥的时间可以为4h、5h、6h、7h或8h。本发明将导热增强材料与有机支撑材料在加工前进行真空干燥以去除其中的水分，避免水分对熔融过程产生影响进而降低增强型复合薄膜的性能。
在一些实施方式中，所述物理气相沉积法包括但不仅限于为磁控溅射法或真空蒸镀法。
本发明采用物理气相沉积法是为了将气化的金属材料沉积于增强型复合薄膜上形成导电层，因此，除了采用磁控溅射法或真空蒸镀法，还可以采用分子束外延等能够将金属材料在增强型复合薄膜表面形成导电层的其他物理气相沉积法。
本发明的另一个方面，提供了上述复合集流体的制备方法，包括以下步骤：
S1.制备所述增强型复合薄膜；
S2.在所述增强型复合薄膜的至少一个表面上通过物理气相沉积法形成导电层，得到所述复合集流体。
在一些实施方式中，所述增强型复合薄膜按照以下方法制备：将所述导热增强材料与所述偶联剂进行预先混合搅拌，再与所述有机支撑材料进行混合、熔融挤出拉伸成膜，得到所述增强型复合薄膜。
本发明的再一个方面，提供了一种电极极片，所述电极极片包括上述复合集流体或上述制备方法制得的复合集流体；及
活性物质层，所述活性物质层设置于所述复合集流体的导电层的表面上和/或孔隙内。
本发明的还一个方面，提供了一种电池，所述电池包括正极极片、负极极片、隔膜及电解液，所述正极极片和/或所述负极极片为上述电极极片。
在一些实施方式中，本发明的复合集流体的导电层可以为铝材质，将磷酸铁锂、钴酸锂或镍钴锰酸锂等正极活性物质，与导电剂、粘结剂和溶剂混合后涂覆于本发明的复合集流体的导电层上作为正极极片用于锂离子电池中；或者本发明的复合集流体的导电层可以为铜材质，将石墨、软炭或硅碳等负极活性物质，与导电剂、粘结剂和溶剂混合后涂覆于本发明的复合集流体的导电层上作为负极极片用于锂离子电池中；本发明的复合集流体还可应用于锂金属电池等其他电化学装置。
本发明的又一个方面，提供了一种电子设备，包括上述电池。
以下结合具体实施例和对比例对本发明做进一步详细的说明。以下具体实施例中未写明的实验参数，优先参考本申请文件中给出的指引，还可以参考本领域的实验手册或本领域已知的其它实验方法，或者参考厂商推荐的实验条件。可理解，以下实施例所用的仪器和原料较为具体，在其他具体实施例中，可不限于此；本发明说明书实施例中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本发明实施例说明书相关组分的含量按比例放大或缩小均在本发明说明书实施例公 开的范围之内。具体地，本发明实施例说明书中所述的重量可以是μg、mg、g、kg等化学化工领域公知的质量单位。
实施例1
复合集流体的制备方法，包括以下步骤：
S1.将0.1kg碳纳米管和99.9kg PET粒子于120℃真空干燥4h，然后将0.01kg硅烷偶联剂KH550加入到干燥后的0.1kg碳纳米管中，混合搅拌，获得均匀混合物；将上述混合物与干燥后的99.9kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜，得到厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
步骤S2中，物理气相沉积法的具体步骤为：通过真空蒸镀法将金属铝加热蒸发，使其在步骤S1得到的增强型复合薄膜表面沉积形成导电层。
实施例2
复合集流体的制备方法，包括以下步骤：
S1.将0.1kg碳纳米管、0.2kg石墨烯和99.7kg PET粒子于120℃真空干燥6h，然后将0.02kg硅烷偶联剂KH550加入到干燥后0.1kg碳纳米管和0.2kg石墨烯中，混合搅拌，获得均匀混合物；将上述混合物与干燥后的99.7kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜，得到厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
实施例3
复合集流体的制备方法，包括以下步骤：
S1.将0.2kg碳纳米管、0.4kg石墨烯和99.4kg PET粒子于120℃真空干燥4h，然后将0.06kg硅烷偶联剂KH560加入到干燥后的0.2kg碳纳米管和0.4kg石墨 烯中，混合搅拌，获得均匀混合物；将上述混合物与干燥后的99.4kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜，得到厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
实施例4
复合集流体的制备方法，包括以下步骤：
S1.将1kg碳纳米管和98.9kg PET粒子于120℃真空干燥6h，然后将0.1kg硅烷偶联剂KH550加入到干燥后的1kg碳纳米管中，混合搅拌，获得均匀混合物。将上述混合物与干燥后的98.9kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜制备厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1.5μm的导电层，得到复合集流体，其中，导电层为铝材质。
实施例5
复合集流体的制备方法，包括以下步骤：
S1.将1kg碳纳米管、1kg石墨和97.8kg PET粒子于120℃真空干燥6h，然后将0.2kg硅烷偶联剂KH550加入到干燥后的1kg碳纳米管和1kg石墨中，混合搅拌，获得均匀混合物；将上述混合物与干燥后的97.8kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜制备厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
实施例6
复合集流体的制备方法，包括以下步骤：
S1.将5kg碳纳米管和95kg PET粒子于60℃真空干燥8h，然后将1kg硅烷偶联剂KH560加入到干燥后的5kg碳纳米管中，混合搅拌，获得均匀混合物； 将上述混合物与干燥后的95kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜，得到厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
实施例7
复合集流体的制备方法，包括以下步骤：
S1.将5kg碳纤维和100kg PET粒子于90℃真空干燥7h，然后将1kg硅烷偶联剂KH560加入到干燥后的5kg碳纤维中，混合搅拌，获得均匀混合物；将上述混合物与干燥后的100kg PET粒子混合搅拌均匀，使用双螺杆挤出机，挤出拉伸成膜，得到厚度为8μm的增强型复合薄膜；
S2.在增强型复合薄膜的两个表面分别通过物理气相沉积法形成1μm的导电层，得到复合集流体，其中，导电层为铝材质。
对比例1
复合集流体的制备方法具体同实施例1，区别仅在于：步骤S1中，将100kg PET粒子于120℃真空干燥4h，使用双螺杆挤出机，挤出拉伸成膜制备厚度为8μm的增强型复合薄膜。
对比例2
复合集流体的制备方法具体同实施例2，区别仅在于：步骤S1中，将100kg PET粒子于120℃真空干燥6h，使用双螺杆挤出机，挤出拉伸成膜制备厚度为8μm的增强型复合薄膜。
对比例3
复合集流体的制备方法具体同实施例2，区别仅在于：步骤S1中，将100kg PET粒子于120℃真空干燥4h，使用双螺杆挤出机，挤出拉伸成膜制备厚度为8μm的增强型复合薄膜。
对比例4
复合集流体的制备方法具体同实施例4，区别仅在于，将1kg碳纳米管和98.9kg PET粒子替换为将0.08kg碳纳米管和99.82kg PET粒子。
对比例5
复合集流体的制备方法具体同实施例4，区别仅在于，将1kg碳纳米管和98.9kg PET粒子替换为将6kg碳纳米管和93.9kg PET粒子。
试验例1增强型复合薄膜的性能测试
将实施例1～7和对比例1～5制备的增强型复合薄膜按照以下方法进行拉伸强度、初始分解温度和表面电阻测试，测试结果如表1所示。
(1)拉伸强度：拉伸速度50mm/min，每个样品取5个片样，取平均值作为测试结果。测量时样品的长度方向与夹具轴线平行，并保持样品直线状，使样品在夹具钳口内拉；样品边缘有缺口，实验结果无效。
(2)初始分解温度：样品质量为3-4mg，加热温度区间为室温至600℃，工作气氛为氮气，升温速率设定为10℃/min。
(3)表面电阻：使用四探针测试仪测量样品正反两面膜片电阻。
表1增强型复合薄膜的性能测试结果
| 组别 | 拉伸强度/MPa | 初始分解温度/℃ | 表面电阻/Ω |
| 实施例1 | 227 | 409 | 1000 |
| 实施例2 | 245 | 411 | 312 |
| 实施例3 | 238 | 414 | 120 |
| 实施例4 | 237 | 417 | 160 |
| 实施例5 | 224 | 412 | 150 |
| 实施例6 | 189 | 410 | 110 |
| 实施例7 | 183 | 414 | 120 |
| 对比例1 | 199 | 403 | ＞10 16 |
| 对比例2 | 208 | 405 | ＞10 16 |
| 对比例3 | 202 | 402 | ＞10 16 |
| 对比例4 | 217 | 410 | 10 4-10 6 |
| 对比例5 | 152 | 419 | 100 |
实施例1～7制备的增强型复合薄膜相对于对比例1～3添加了导热增强材料，从上表1可知，与对比例1～3相比，实施例1～5制备的增强型复合薄膜的拉伸强度较大且初始分解温度较高，表面电阻相对较低，说明实施例1～5加入的导热增强材料能够增强复合集流体的加工性能；
对比例4制备的增强型复合薄膜中碳纳米管为0.08kg，对比例5制备的增强型复合薄膜中碳纳米管为6kg，实施例4制备的增强型复合薄膜中碳纳米管为1kg；与实施例4相比，对比例5的增强型复合薄膜的拉伸强度较小并且初始分解温度较低，这是由于对比例5中碳纳米管的加入量比较多，导致碳纳米管团聚，不利于力学性能和导热性的提升。
试验例2复合集流体的性能测试
将实施例1～7和对比例1～5制备的复合集流体按照以下方法进行极耳焊接速度测试，测试结果如表2所示。
极耳焊接速度测试：将单层复合集流体与极耳箔材焊接，在超声频率为20KHz，振幅为20μm，压力为400kPa的条件下进行极耳焊接速度测试。
表2复合集流体的性能测试结果
| 组别 | 极耳焊接速度/s |
| 实施例1 | 1 |
| 实施例2 | 0.5 |
| 实施例3 | 0.5 |
| 实施例4 | 0.5 |
| 实施例5 | 0.5 |
| 实施例6 | 0.5 |
| 实施例7 | 0.5 |
| 对比例1 | 3 |
| 对比例2 | 3 |
| 对比例3 | 3 |
| 对比例4 | 2 |
| 对比例5 | 0.5 |
实施例1～7和对比例1～5制备的复合集流体所采用的物理气相沉积方法相同。由表2可以看出，实施例1～7制备的复合集流体与对比例1～3相比添加了导热增强材料，极耳焊接速度显著加快，表明复合集流体中加入的导热增强材料能够明显提高极耳的焊接效率。与实施例1相比，对比例4的复合集流体的焊接效率较低，这是由于对比例4的复合集流体中碳纳米管的添加量较少，该复合集流体的导电性未得到大幅提升。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (10)
- 一种复合集流体，其特征在于，所述复合集流体包括增强型复合薄膜和导电层，所述增强型复合薄膜的至少一个表面通过物理气相沉积法形成有所述导电层；所述增强型复合薄膜按照重量份数计，包括以下原料：0.1-5份导热增强材料、0.01-1份偶联剂和95-100份有机支撑材料。
- 根据权利要求1所述的复合集流体，其特征在于，所述导热增强材料包括碳纳米管、碳纤维、石墨和石墨烯中的一种或多种。
- 根据权利要求1或2所述的复合集流体，其特征在于，所述偶联剂包括硅烷偶联剂和钛酸酯偶联剂中的一种或多种；和/或，所述有机支撑材料包括聚对苯二甲酸乙二醇酯、聚乙烯、聚丙烯、聚酰胺、聚酰亚胺、聚氯乙烯、聚苯乙烯、它们的衍生物及它们的共聚物中的一种或多种。
- 根据权利要求1所述的复合集流体，其特征在于，所述导热增强材料和所述有机支撑材料进行加工前，于60-120℃真空干燥4-8h。
- 根据权利要求1～2及4任一项所述的复合集流体，其特征在于，所述物理气相沉积法为磁控溅射法或真空蒸镀法。
- 如权利要求1～5任一项所述的复合集流体的制备方法，其特征在于，包括以下步骤：S1.制备所述增强型复合薄膜；S2.在所述增强型复合薄膜的至少一个表面上通过物理气相沉积法形成导电层，得到所述复合集流体。
- 根据权利要求6所述的复合集流体的制备方法，其特征在于，所述增强型复合薄膜按照以下方法制备：将所述导热增强材料与所述偶联剂进行预先混合搅拌，再与所述有机支撑材料进行混合、熔融挤出拉伸成膜，得到所述增强型复合薄膜。
- 一种电极极片，其特征在于，所述电极极片包括权利要求1～5任一项所述的复合集流体或权利要求6～7任一项所述的制备方法制得的复合集流体；及活性物质层，所述活性物质层设置于所述复合集流体的导电层的表面上和/ 或孔隙内。
- 一种电池，其特征在于，所述电池包括正极极片、负极极片、隔膜及电解液，所述正极极片和/或所述负极极片采用权利要求8所述的电极极片。
- 一种电子设备，其特征在于，包括权利要求9所述的电池。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210764184.3 | 2022-06-30 | ||
| CN202210764184.3A CN114899356A (zh) | 2022-06-30 | 2022-06-30 | 一种复合集流体、制备方法、电极极片、电池和电子设备 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024000802A1 true WO2024000802A1 (zh) | 2024-01-04 |
Family
ID=82729267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2022/116771 WO2024000802A1 (zh) | 2022-06-30 | 2022-09-02 | 一种复合集流体、制备方法、电极极片、电池和电子设备 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114899356A (zh) |
| WO (1) | WO2024000802A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114899356A (zh) * | 2022-06-30 | 2022-08-12 | 扬州纳力新材料科技有限公司 | 一种复合集流体、制备方法、电极极片、电池和电子设备 |
| WO2024011537A1 (zh) * | 2022-07-14 | 2024-01-18 | 扬州纳力新材料科技有限公司 | 复合集流体及其制备方法和应用 |
| CN115312971A (zh) * | 2022-08-18 | 2022-11-08 | 江阴纳力新材料科技有限公司 | 聚合物膜及其制备方法、复合集流体 |
| CN115425234A (zh) * | 2022-08-29 | 2022-12-02 | 浙江柔震科技有限公司 | 复合集流体及其制备方法 |
| WO2024087127A1 (zh) * | 2022-10-28 | 2024-05-02 | 扬州纳力新材料科技有限公司 | 低热收缩率复合集流体及其制备方法和应用 |
| WO2024088417A1 (zh) * | 2022-10-28 | 2024-05-02 | 扬州纳力新材料科技有限公司 | 低热收缩率复合集流体及其制备方法和应用 |
| CN115594872B (zh) * | 2022-12-12 | 2023-03-28 | 安徽元琛环保科技股份有限公司 | 一种复合集流体基膜及其制备方法、集流体及其制备方法 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008140552A (ja) * | 2006-11-29 | 2008-06-19 | Nissan Motor Co Ltd | 双極型電池用電極 |
| CN111048789A (zh) * | 2019-12-26 | 2020-04-21 | 珠海冠宇电池有限公司 | 一种集流体及其制备方法和应用 |
| CN114243028A (zh) * | 2021-11-15 | 2022-03-25 | 浙江柔震科技有限公司 | 一种集流体及其制备方法 |
| CN114361461A (zh) * | 2022-01-10 | 2022-04-15 | 上海恩捷新材料科技有限公司 | 柔性集流体芯层、集流体、极片和电池及其制备方法 |
| CN114824290A (zh) * | 2022-05-13 | 2022-07-29 | 扬州纳力新材料科技有限公司 | 二次电池的高导热集流体及其制备方法 |
| CN114899356A (zh) * | 2022-06-30 | 2022-08-12 | 扬州纳力新材料科技有限公司 | 一种复合集流体、制备方法、电极极片、电池和电子设备 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110943201B (zh) * | 2019-04-15 | 2021-02-26 | 宁德时代新能源科技股份有限公司 | 一种正极极片和电化学装置 |
| CN110311091B (zh) * | 2019-07-01 | 2023-04-11 | 东莞维科电池有限公司 | 一种导热极片、及其制备方法和用途 |
-
2022
- 2022-06-30 CN CN202210764184.3A patent/CN114899356A/zh active Pending
- 2022-09-02 WO PCT/CN2022/116771 patent/WO2024000802A1/zh unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008140552A (ja) * | 2006-11-29 | 2008-06-19 | Nissan Motor Co Ltd | 双極型電池用電極 |
| CN111048789A (zh) * | 2019-12-26 | 2020-04-21 | 珠海冠宇电池有限公司 | 一种集流体及其制备方法和应用 |
| CN114243028A (zh) * | 2021-11-15 | 2022-03-25 | 浙江柔震科技有限公司 | 一种集流体及其制备方法 |
| CN114361461A (zh) * | 2022-01-10 | 2022-04-15 | 上海恩捷新材料科技有限公司 | 柔性集流体芯层、集流体、极片和电池及其制备方法 |
| CN114824290A (zh) * | 2022-05-13 | 2022-07-29 | 扬州纳力新材料科技有限公司 | 二次电池的高导热集流体及其制备方法 |
| CN114899356A (zh) * | 2022-06-30 | 2022-08-12 | 扬州纳力新材料科技有限公司 | 一种复合集流体、制备方法、电极极片、电池和电子设备 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114899356A (zh) | 2022-08-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2024000802A1 (zh) | 一种复合集流体、制备方法、电极极片、电池和电子设备 | |
| WO2022267538A1 (zh) | 钠离子电池的负极极片、电化学装置及电子设备 | |
| JP2020503639A (ja) | 集電体、その極シートと電気化学デバイス | |
| CN107154499A (zh) | 一种含有新型集流体的锂电池及其制备方法 | |
| CN112151806A (zh) | 一种超轻多层复合集流体及其制备方法 | |
| CN115447248B (zh) | 复合聚合物膜、其制造方法、金属化复合聚合物膜与应用 | |
| CN113422062A (zh) | 一种集流体、极片、电池及设备 | |
| WO2023221932A1 (zh) | 聚酯基膜及其制备方法和应用、极片和锂电池单体 | |
| JP2018190527A (ja) | 蓄電デバイス用集電体、その製造方法、およびその製造に用いる塗工液 | |
| WO2023216348A1 (zh) | 二次电池的高导热集流体及其制备方法 | |
| Shi et al. | Ultrastable Interfacial Contacts Enabling Unimpeded Charge Transfer and Ion Diffusion in Flexible Lithium‐Ion Batteries | |
| CN115763829A (zh) | 一种可增强导电性的复合集流体 | |
| WO2024036936A1 (zh) | 聚合物膜及其制备方法、复合集流体 | |
| Zhang et al. | Metallized Plastic Foils: A Promising Solution for High‐Energy Lithium‐Ion Battery Current Collectors | |
| CN115763828A (zh) | 聚合物复合膜及其制备方法、复合集流体、极片、二次电池和用电装置 | |
| CN114156486B (zh) | 一种轻量阻燃型集流体及其制备方法、电极、电池 | |
| CN111848892A (zh) | 碳纳米管负载二维共价有机框架电极材料的制备方法 | |
| WO2024104393A1 (zh) | 多层复合聚丙烯材料及其制备方法和应用 | |
| CN116376280A (zh) | 聚对苯撑苯并二噁唑多孔膜及其制备方法和应用、复合隔膜及电池 | |
| CN112467086A (zh) | 一种基于聚酰胺酸基电极粘结剂的硅基负极材料的制备方法 | |
| CN114122395B (zh) | 一种钠离子电池用负极极片的制备及其应用 | |
| CN115275211A (zh) | 一种复合集流体及其制备方法、电极极片、电池和终端 | |
| WO2024131980A1 (zh) | 复合集流体及其制备方法和其在锂离子电池中的应用 | |
| CN117577855A (zh) | 一种低方阻复合集流体及其制备方法与应用 | |
| WO2024000803A1 (zh) | 复合集流体的制备方法及复合集流体 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22948892 Country of ref document: EP Kind code of ref document: A1 |