CN115094384B - Copper composite current collector and preparation method and application thereof - Google Patents
Copper composite current collector and preparation method and application thereof Download PDFInfo
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- CN115094384B CN115094384B CN202210827217.4A CN202210827217A CN115094384B CN 115094384 B CN115094384 B CN 115094384B CN 202210827217 A CN202210827217 A CN 202210827217A CN 115094384 B CN115094384 B CN 115094384B
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- current collector
- composite current
- copper composite
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 150
- 239000010949 copper Substances 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000007747 plating Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 229920006254 polymer film Polymers 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 238000007738 vacuum evaporation Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 4
- -1 polyethylene terephthalate Polymers 0.000 claims description 39
- 239000002861 polymer material Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011231 conductive filler Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229920001940 conductive polymer Polymers 0.000 claims description 6
- 229920006037 cross link polymer Polymers 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004760 aramid Substances 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229920001197 polyacetylene Polymers 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000005011 phenolic resin Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 21
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 15
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000011883 electrode binding agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005019 vapor deposition process Methods 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001883 metal evaporation Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- KPMKEVXVVHNIEY-NTSWFWBYSA-N (1s,4r)-bicyclo[2.2.1]heptan-3-one Chemical compound C1C[C@H]2C(=O)C[C@@H]1C2 KPMKEVXVVHNIEY-NTSWFWBYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The invention relates to the field of lithium ion batteries, in particular to a copper composite current collector, and a preparation method and application thereof. The preparation method of the copper composite current collector comprises the following steps: providing a polymer film; the polymer film passes through a copper plating roller by adopting a vacuum evaporation technology, the temperature of the copper plating roller is divided into a first temperature zone and a second temperature zone along the axial direction of the copper plating roller, the temperature of the first temperature zone is 40-50 ℃, and the temperature of the second temperature zone is 10-20 ℃; and evaporating metallic copper under vacuum conditions to plate copper metal layers on both sides of the polymer film. The copper composite current collector prepared by the preparation method of the copper composite current collector has high specific surface area, and can reduce the interface resistance of the battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a copper composite current collector, and a preparation method and application thereof.
Background
The surface of the copper metal layer on the surface of the conventional copper composite current collector is flat and very smooth, and the surface roughness, the surface energy and the specific surface area are low, so that the following problems occur when the copper composite current collector is coated with electrode slurry: 1) The electrode slurry is easy to generate missing coating, the product quality is reduced, and the coating speed is limited; 2) Because the specific surface area of the copper metal layer is low, the bonding area between the active material layer in the battery and the copper metal layer is small, so that the bonding force between the active material layer in the battery and the composite current collector is low, and the powder falling phenomenon is easy to occur; meanwhile, the small bonding area also causes small conductive channels between the active substances and the composite current collector, and increases the interface resistance between the active substances and the interface of the copper metal layer of the composite current collector.
Disclosure of Invention
Based on this, it is necessary to provide a copper composite current collector capable of increasing specific surface area while reducing interfacial resistance, and a method for preparing the same and application thereof.
In one aspect of the invention, a method for preparing a copper composite current collector is provided, which comprises the following steps:
providing a polymer film;
the polymer film passes through a copper plating roller by adopting a vacuum evaporation technology, and the copper plating roller is provided with a first temperature zone and a second temperature zone along the axial direction of the copper plating roller, wherein the temperature of the first temperature zone is 40-50 ℃, and the temperature of the second temperature zone is 10-20 ℃; and
evaporating metallic copper under vacuum to plate copper metal layers on both sides of the polymer film.
In one embodiment, the copper plating roll has a length of 5mm to 10mm for each of the first temperature zone and the second temperature zone independently.
In one embodiment, the vacuum degree for evaporating the metallic copper is 10 < -4 > Pa to 10 < -5 > Pa, the temperature is 1600 ℃ to 1800 ℃, and the concentration of copper steam is maintained to be 60mol/L to 80mol/L.
In one embodiment, the movement speed of the polymer film is 10 m/min-100 m/min in the process of plating the copper metal layer.
In one embodiment, the material of the polymer film is selected from a composite formed by an insulating polymer material and an inorganic non-conductive filler, a composite formed by an insulating polymer material and a conductive filler, an insulating polymer material or a conductive polymer material, wherein the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the inorganic non-conductive filler is more than or equal to 90%, and the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the conductive filler is more than or equal to 90%.
In one embodiment, the insulating polymer material is selected from one or more of cellulose and its derivatives, starch and its derivatives, proteins and its derivatives, polyvinyl alcohol and its cross-linked polymers, polyethylene glycol and its cross-linked polymers, polyamides, polyterephthalates, polyimides, polyethylene, polypropylene, polystyrene, polyvinylchloride, aramid, polydioxanediamine, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, poly-paraphenylene terephthalamide, polypropylene, polyoxymethylene, epoxy, phenolic, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber and polycarbonate.
In one embodiment, the conductive polymer material is selected from doped polysulfide and/or doped polyacetylene.
In one embodiment, the inorganic non-conductive filler is selected from one or more of a ceramic material, a glass material, and a ceramic composite material.
In one embodiment, the conductive filler is selected from one or more of carbon black, carbon nanotubes, graphite, acetylene black, graphene, nickel, iron, copper, aluminum, alloys, nickel-coated graphite powder, and nickel-coated carbon fibers.
In one aspect of the invention, a copper composite current collector is also provided, which is prepared by the preparation method of the copper composite current collector.
In one embodiment, the copper composite current collector has at least one of the following properties:
(1) The surface roughness is more than 0.2 mu m;
(2) Specific surface area > 20m 2 /g；
(3) The number of surface holes is more than 10/m 2 The aperture is more than or equal to 10nm;
(4) The puncture strength is more than or equal to 200gf;
(5) The longitudinal tensile strength is more than or equal to 150MPa, the longitudinal elongation is more than or equal to 10%, the transverse tensile strength is more than or equal to 150MPa, and the transverse elongation is more than or equal to 10%.
In another aspect of the present invention, there is further provided a negative electrode including the above-described copper composite current collector and a negative electrode active material layer on one or both sides of the copper composite current collector.
In yet another aspect of the present invention, a lithium ion battery is provided, which includes the negative electrode described above.
In still another aspect of the present invention, an electric device is provided, which uses the lithium ion battery as a power source.
According to the preparation method of the copper composite current collector, the copper plating roller is regulated and controlled to have different temperature areas, so that the plating speeds of the copper metal layer on the surface of the polymer film are different, the growing speeds of copper crystals in the copper metal layer are different, and a pore structure is formed on the surface of the copper metal layer. The formation of the pore structure realizes the increase of the roughness and the specific surface area of the copper composite current collector, thereby increasing the contact area between the active substances in the battery and the copper composite current collector, improving the coating amount of the active substances, reducing the internal resistance of the battery, improving the capacity and the energy density of the battery and prolonging the cycle life of the battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the copper composite current collector prepared in example 1.
Detailed Description
Reference now will be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present invention cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
It can be appreciated that the conventional copper composite current collector has a relatively smooth surface, is difficult to coat more battery active materials on the surface, and has poor coating quality. Therefore, the invention provides a preparation method of a copper composite current collector, which is characterized in that the copper plating roller is regulated to have different temperature areas, so that the plating speeds of a copper metal layer on the surface of a polymer film are different, the growing speeds of copper crystals in the copper metal layer are different, and a pore structure is formed on the surface of the copper metal layer. The formation of the pore structure realizes the increase of roughness and specific surface area of the copper composite current collector (at least 20 percent compared with the traditional copper composite current collector), thereby increasing the contact area between the active substances in the battery and the copper composite current collector, improving the coating amount of the active substances (at least 5 percent compared with the traditional copper composite current collector), reducing the internal resistance of the battery, improving the capacity and energy density of the battery and prolonging the cycle life of the battery.
In one aspect, the invention relates to a method for preparing a copper composite current collector, which comprises the following steps:
providing a polymer film;
the polymer film passes through a copper plating roller by adopting a vacuum evaporation technology, wherein the copper plating roller is provided with a first temperature zone and a second temperature zone along the axial direction of the copper plating roller, the temperature of the first temperature zone is 40-50 ℃, and the temperature of the second temperature zone is 10-20 ℃; and
metallic copper is evaporated under vacuum to plate copper metal layers on both sides of the polymer film.
In some embodiments, the temperature of the first temperature zone may be any value between 40 ℃ and 50 ℃, for example, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃.
In some embodiments, the temperature of the second temperature zone may be any value between 10 ℃ and 20 ℃, for example, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃.
In some embodiments, the copper plating roll has a length of the first and second temperature zones of any value between 5mm and 10mm, respectively, independently, and may also be 6mm, 7mm, 8mm, 9mm, for example.
In some embodiments, the vacuum level for evaporating metallic copper may be 10 -4 Pa～10 -5 Pa, the temperature can be 1600-1800 ℃, and the concentration of copper steam is maintained to be 60-80 mol/L.
In some embodiments, the movement speed of the polymer film during the copper metal layer plating process may be 10m/min to 100m/min, and may be 20m/min, 30m/min, 40m/min, 50m/min, 60m/min, 70m/min, 80m/min, or 90m/min.
In some embodiments, the copper metal layer has a purity of 99.8% or greater.
In some embodiments, the polymer film is not limited to any polymer material known in the art, including, but not limited to, a composite of an insulating polymer material and an inorganic nonconductive filler, a composite of an insulating polymer material and a conductive filler, an insulating polymer material, or a conductive polymer material, wherein the mass percent of the insulating polymer material in the composite of the insulating polymer material and the inorganic nonconductive filler is greater than or equal to 90%, and the mass percent of the insulating polymer material in the composite of the insulating polymer material and the conductive filler is greater than or equal to 90%.
In some embodiments, the insulating polymeric material may be selected from one or more of cellulose and its derivatives, starch and its derivatives, proteins and its derivatives, polyvinyl alcohol and its cross-linked polymers, polyethylene glycol and its cross-linked polymers, polyamides, polyterephthalates, polyimides, polyethylene, polypropylene, polystyrene, polyvinylchloride, aramid, polydioxanediamine, acrylonitrile-butadiene-styrene copolymers, polyethylene terephthalate, polybutylene terephthalate, poly-terephthalamide, polypropylene, polyoxymethylene, epoxy, phenolic, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, and polycarbonate.
In some embodiments, the conductive polymer material may be selected from doped polysulfide and/or doped polyacetylene.
In some embodiments, the inorganic non-conductive filler may be selected from one or more of a ceramic material, a glass material, and a ceramic composite material.
In some embodiments, the conductive filler may be selected from one or more of carbon black, carbon nanotubes, graphite, acetylene black, graphene, nickel, iron, copper, aluminum, alloys, nickel-coated graphite powder, and nickel-coated carbon fibers. Wherein the alloy may comprise one or more of nickel, iron, copper and aluminum.
In some embodiments, after plating copper metal layers on both sides of the polymer film, the method further comprises a step of winding;
alternatively, the winding tension may be 5N to 25N.
In one aspect of the invention, a copper composite current collector is also provided, which is prepared by the preparation method of the copper composite current collector.
In some embodiments, the copper composite current collector has at least one of the following properties:
(1) The surface roughness is more than 0.2 mu m;
(2) Specific surface area > 20m 2 /g；
(3) The number of surface holes is more than 10/m 2 The aperture is more than or equal to 10nm;
(4) The puncture strength is more than or equal to 200gf;
(5) The tensile strength in the Machine Direction (MD) is more than or equal to 150MPa, the elongation in the Machine Direction (MD) is more than or equal to 10%, the tensile strength in the Transverse Direction (TD) is more than or equal to 150MPa, and the elongation in the Transverse Direction (TD) is more than or equal to 10%.
In some embodiments, the specific surface area of the copper composite current collector may also be 25m 2 /g、28m 2 /g、30m 2 /g、35m 2 Per gram, the number of surface holes is more than 100 per m 2 For example, 150/m 2 200/m 2 300/m 2 400/m 2 500/m 2 。
In some embodiments, the copper composite current collector may have a thickness of 1.6 μm to 31 μm, preferably, the polymer thin film may have a thickness of 1 μm to 25 μm, and the copper metal layer may have a thickness of 0.3 μm to 3 μm. More preferably, the thickness of the polymer film is 2 μm to 8 μm. The thickness of the polymer film is regulated in the range, so that the production cost of the copper composite current collector can be reduced, and the problem of belt breakage of the polymer film in the processing process can be avoided.
In some embodiments, the polymer film meets at least one of the following properties:
(1) The puncture strength is more than or equal to 200gf;
(2) The tensile strength in the Machine Direction (MD) is more than or equal to 160MPa, the elongation in the Machine Direction (MD) is more than or equal to 30%, the tensile strength in the Transverse Direction (TD) is more than or equal to 160MPa, and the elongation in the Transverse Direction (TD) is more than or equal to 30%.
In another aspect of the present invention, there is further provided a negative electrode including the above-described copper composite current collector and a negative electrode active material layer on one or both sides of the copper composite current collector.
In some embodiments, the material of the anode active material layer is not limited, and may be composed of a common anode active material, a conductive agent, and an anode binder; the negative electrode active material can be graphite, lithium titanate and lithium, the negative electrode binder can be at least one of styrene-butadiene latex, acrylic ester and sodium carboxymethyl cellulose, and the conductive agent can be at least one of carbon nano tube and conductive carbon black.
In yet another aspect of the present invention, a lithium ion battery is provided, which includes the negative electrode described above.
In some embodiments, the lithium ion battery may further include a positive electrode and an electrolyte.
The positive electrode comprises a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, wherein the positive electrode current collector can be an aluminum current collector, and the material of the positive electrode active material layer is not limited and can be composed of a common positive electrode active material, a conductive agent and a positive electrode binder; the positive electrode active material may be any positive electrode active material commonly used in the art, such as lithium cobaltate, lithium iron phosphate, NCA, NCM, lithium manganate, lithium nickelate, NCMA, or cobalt-free positive electrode; the positive electrode binder can be at least one of PVDF and acrylic ester, and the conductive agent can be at least one of carbon nano tube and conductive carbon black; .
In some embodiments, the electrolyte may be a solid electrolyte, a semi-solid electrolyte, or a liquid electrolyte, wherein the solid electrolyte and the semi-solid electrolyte may be oxide or sulfide electrolytes, and the solute in the liquid electrolyte may be lithium hexafluorophosphate.
In some embodiments, the lithium ion battery described above may further comprise a separator, wherein the separator may be any separator known in the art, such as a PE wet separator, a PP dry separator, or a double layer PE/PP coated separator.
The shape of the lithium ion battery is not limited, and may be, for example, cylindrical or square.
In still another aspect of the present invention, an electric device is provided, which uses the lithium ion battery as a power source.
In some embodiments, specific types of electrical devices include, but are not limited to, mobile terminals (cell phones, mobile computers, etc.), smart wear, power tools (drills, motors, etc.), electric vehicles, mobile power sources, etc.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
1. Preparation of copper composite current collector
The copper composite current collector is prepared by adopting a vacuum evaporation process, and the polymer film is a biaxially oriented polypropylene (BOPP) film. The method comprises the following specific steps:
1) Vacuumizing an evaporation chamber of the vacuum ion evaporation equipment until the vacuum degree is 10 -5 After Pa, passing a BOPP film having a thickness of 4 μm through a copper plating roll, wherein the copper plating roll has a first temperature zone having a temperature of 45 ℃ and a second temperature zone having a temperature of 15 ℃, and the copper plating roll having the first temperature zone and the second temperature zone has a length of 6mm;
2) Copper metal with purity of 99.9% in the evaporation boat is evaporated at 1800 ℃ and the concentration of copper vapor is maintained to be 70mol/L so as to vapor-deposit copper metal layers with thickness of 1 μm on both sides of the BOPP film in the step 1), wherein the movement speed of the BOPP film is 30m/min in the vapor-deposition process. And then rolling under the acting force of 5N, and unreeling the BOPP film evaporated with the copper metal layer under 20N to prepare the copper composite current collector. The surface morphology of the copper composite current collector is shown in fig. 1, and the related performance of the copper composite current collector is shown in table 1.
2. Battery assembly
And (3) a positive electrode: lithium iron phosphate;
and (3) a negative electrode: the method comprises the steps of (1) preparing a copper composite current collector and a graphite layer positioned on the surface of the copper composite current collector;
electrolyte solution: liquid electrolyte with lithium hexafluorophosphate as solute;
a diaphragm: polyethylene (PE) microporous separator;
the above components were assembled into a ternary lithium ion battery model 100Ah, and relevant performance tests were performed, and the test results are shown in table 2.
Example 2
The preparation method of this example is basically the same as that of example 1, except that: the copper plating roller temperature and copper metal evaporation parameters are different. The method comprises the following specific steps:
the copper composite current collector is prepared by adopting a vacuum evaporation process, and the polymer film is a biaxially oriented polypropylene (BOPP) film. The method comprises the following specific steps:
1) Vacuumizing an evaporation chamber of the vacuum ion evaporation equipment until the vacuum degree is 10 -5 After Pa, passing a BOPP film having a thickness of 4 μm through a copper plating roll, wherein the copper plating roll has a first temperature zone having a temperature of 40 ℃ and a second temperature zone having a temperature of 10 ℃, and the copper plating roll having the first temperature zone and the second temperature zone has a length of 8mm;
2) Copper metal with purity of 99.9% in the evaporation boat is evaporated at 1600 ℃ and the concentration of copper vapor is maintained to be 60mol/L so as to vapor-deposit copper metal layers with thickness of 1 μm on both sides of the BOPP film in the step 1), wherein the movement speed of the BOPP film is 20m/min in the vapor-deposition process. And then rolling under the acting force of 5N, and unreeling the BOPP film evaporated with the copper metal layer under 20N to prepare the copper composite current collector.
Example 3
The preparation method of this example is basically the same as that of example 1, except that: the polymer film is polyethylene terephthalate film, and the thickness of the polymer film and the thickness of the copper metal layer are different, and the temperature of the copper plating roller and the copper metal evaporation parameters are different. The method comprises the following specific steps:
the copper composite current collector is prepared by adopting a vacuum evaporation process, and the polymer film is a polyethylene terephthalate film. The method comprises the following specific steps:
1) After the evaporation chamber of the vacuum ion evaporation equipment is vacuumized to 10 < -5 > Pa, a polyethylene terephthalate film with the thickness of 6 mu m passes through a copper plating roller, wherein the copper plating roller is provided with a first temperature zone with the temperature of 50 ℃ and a second temperature zone with the temperature of 20 ℃, and the lengths of the copper plating roller with the first temperature zone and the copper plating roller with the second temperature zone are 10mm;
2) Copper metal with purity of 99.9% in the evaporation boat was evaporated at 1800 ℃ and the concentration of copper vapor was maintained at 80mol/L to vapor-deposit copper metal layers with thickness of 2 μm on both sides of the polyethylene terephthalate film in step 1), wherein the movement speed of the polyethylene terephthalate film during the vapor deposition was 80m/min. And then rolling under the action of 5N tension, and unreeling the polyethylene terephthalate film evaporated with the copper metal layer under 20N tension to prepare the copper composite current collector.
Comparative example 1
1. Preparation of copper composite current collector
The copper composite current collector is prepared by adopting a vacuum evaporation process, and the polymer film is a biaxially oriented polypropylene (BOPP) film. The method comprises the following specific steps:
1) Vacuumizing an evaporation chamber of the vacuum ion evaporation equipment until the vacuum degree is 10 -5 After Pa, passing a BOPP film having a thickness of 4 μm through a copper plating roll, wherein the copper plating roll has a temperature of 30 ℃;
2) Copper metal with purity of 99.9% in the evaporation boat is evaporated at 1700 ℃ and the concentration of copper vapor is maintained to be 150mol/L so as to vapor-deposit copper metal layers with thickness of 1 μm on both sides of the BOPP film in the step 1), wherein the movement speed of the BOPP film is 50m/min in the vapor-deposition process. And then rolling under the acting force of 5N, and unreeling the BOPP film evaporated with the copper metal layer under 20N to prepare the copper composite current collector. The relevant properties of the copper composite current collector are shown in table 1.
2. Battery assembly
And (3) a positive electrode: lithium iron phosphate;
and (3) a negative electrode: the method comprises the steps of (1) preparing a copper composite current collector and a graphite layer positioned on the surface of the copper composite current collector;
electrolyte solution: liquid electrolyte with lithium hexafluorophosphate as solute;
a diaphragm: polyethylene (PE) microporous separator;
the above components were assembled into a ternary lithium ion battery model 100Ah, and relevant performance tests were performed, and the test results are shown in table 2.
TABLE 1
| Results of Performance test | Example 1 | Comparative example 1 |
| Thickness (μm) | 6 | 6 |
| Specific surface area (m) 2 /g) | 28 | 10 |
| MD elongation (%) | 95 | 92 |
| TD elongation (%) | 90 | 88 |
| Number of surface pore structures (number/m) 2 ) | 500 | 0 |
Related performance test of ternary lithium ion battery:
the peel force test, the internal resistance test and the charge-discharge cycle performance test are shown in the national standard GB18287_2000, and the test results are shown in Table 2.
1) Peel force test: the peel force between the aluminum composite current collector and the positive electrode active material layer in the lithium iron phosphate batteries assembled in example 1 and comparative examples 1 to 3 were respectively tested 10PCS, and the average value was taken;
2) And (3) testing the internal resistance of the battery: the internal resistances of the lithium iron phosphate batteries assembled in example 1 and comparative examples 1 to 3 were respectively tested 10PCS, and the average value was taken;
3) And (3) testing charge-discharge cycle performance: at a capacity retention of 80%, the cycle performance of the lithium iron phosphate batteries assembled in 10PCS example 1 and comparative examples 1 to 3 were each tested at 1C rate charge and 1C rate discharge (1C/1C), respectively, and the average value was taken.
TABLE 2
| Test index | Example 1 | Comparative example 1 |
| Stripping force (N/m) | 35 | 25 |
| Internal resistance (mΩ) | 10 | 18 |
| Cycle number of charge and discharge (week) | 2000 | 1400 |
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (11)
1. The preparation method of the copper composite current collector is characterized by comprising the following steps of:
providing a polymer film;
the polymer film passes through a copper plating roller by adopting a vacuum evaporation technology, and the copper plating roller is provided with a first temperature zone and a second temperature zone along the axial direction of the copper plating roller, wherein the temperature of the first temperature zone is 40-50 ℃, and the temperature of the second temperature zone is 10-20 ℃; and
evaporating metallic copper under vacuum to plate copper metal layers on both sides of the polymer film.
2. The method for producing a copper composite current collector according to claim 1, wherein the copper plating roll has a length of 5mm to 10mm, respectively, independently of the first temperature zone and the second temperature zone.
3. The method for manufacturing a copper composite current collector according to claim 1, wherein a vacuum degree for evaporating the metallic copper is 10 -4 Pa～10 -5 Pa, the temperature is 1600-1800 ℃, and the concentration of copper steam is maintained to be 60-80 mol/L.
4. The method for preparing a copper composite current collector according to claim 3, wherein the movement speed of the polymer thin film is 10m/min to 100m/min in the process of plating the copper metal layer.
5. The method for preparing the copper composite current collector according to claim 1, wherein the material of the polymer film is selected from a composite formed by an insulating polymer material and an inorganic non-conductive filler, a composite formed by an insulating polymer material and a conductive filler, an insulating polymer material or a conductive polymer material, wherein the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the inorganic non-conductive filler is more than or equal to 90%, and the mass percentage of the insulating polymer material in the composite formed by the insulating polymer material and the conductive filler is more than or equal to 90%.
6. The method of preparing a copper composite current collector according to claim 5, wherein the insulating polymer material is selected from one or more of cellulose and its derivatives, starch and its derivatives, protein and its derivatives, polyvinyl alcohol and its cross-linked polymers, polyethylene glycol and its cross-linked polymers, polyamides, polyethylene terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, aramid, polydimethyl-phenylenediamine, acrylonitrile-butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate, poly-paraphenylene terephthalamide, polypropylene, polyoxymethylene, epoxy, phenolic resin, polytetrafluoroethylene, polyvinylidene fluoride, silicone rubber, and polycarbonate; and/or
The conductive polymer material is selected from doped polysulfide and/or doped polyacetylene; and/or
The inorganic non-conductive filler is selected from one or more of ceramic materials, glass materials and ceramic composite materials; and/or
The conductive filler is selected from one or more of carbon black, carbon nano tube, graphite, acetylene black, graphene, nickel, iron, copper, aluminum, alloy, nickel-coated graphite powder and nickel-coated carbon fiber.
7. A copper composite current collector, characterized in that it is manufactured by the manufacturing method of the copper composite current collector according to any one of claims 1 to 6.
8. The copper composite current collector of claim 7, wherein said copper composite current collector has at least one of the following properties:
(1) The surface roughness is more than 0.2 mu m;
(2) Specific surface area > 20m 2 /g；
(3) The number of surface holes is more than 10/m 2 The aperture is more than or equal to 10nm;
(4) The puncture strength is more than or equal to 200gf;
(5) The longitudinal tensile strength is more than or equal to 150MPa, the longitudinal elongation is more than or equal to 10%, the transverse tensile strength is more than or equal to 150MPa, and the transverse elongation is more than or equal to 10%.
9. A negative electrode comprising the copper composite current collector of claim 7 or 8 and a negative electrode active material layer on one or both sides of the copper composite current collector.
10. A lithium ion battery comprising the negative electrode of claim 9.
11. An electric device, characterized in that the lithium ion battery of claim 10 is used as a power source.
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| US5522955A (en) * | 1994-07-07 | 1996-06-04 | Brodd; Ralph J. | Process and apparatus for producing thin lithium coatings on electrically conductive foil for use in solid state rechargeable electrochemical cells |
| JP2009280868A (en) * | 2008-05-22 | 2009-12-03 | Panasonic Corp | Film deposition apparatus and film deposition method |
| JP2017174827A (en) * | 2017-05-22 | 2017-09-28 | 京セラ株式会社 | Sodium secondary battery |
| JP2020180351A (en) * | 2019-04-25 | 2020-11-05 | 大同メタル工業株式会社 | Method and apparatus for manufacturing metal layer, and orientation control method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5522955A (en) * | 1994-07-07 | 1996-06-04 | Brodd; Ralph J. | Process and apparatus for producing thin lithium coatings on electrically conductive foil for use in solid state rechargeable electrochemical cells |
| JP2009280868A (en) * | 2008-05-22 | 2009-12-03 | Panasonic Corp | Film deposition apparatus and film deposition method |
| JP2017174827A (en) * | 2017-05-22 | 2017-09-28 | 京セラ株式会社 | Sodium secondary battery |
| JP2020180351A (en) * | 2019-04-25 | 2020-11-05 | 大同メタル工業株式会社 | Method and apparatus for manufacturing metal layer, and orientation control method |
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